WO2019128867A1 - Hydrolysis hydrogenation process for biomass - Google Patents

Abstract

A hydrolysis hydrogenation process for a biomass or coal and a biomass, the preparation steps for a slurry therein are as follows: sequentially drying, preliminarily pulverizing, compressing and secondarily pulverizing a biomass, then mixing with a catalyst to obtain a mixture, and adding the mixture to an oil product/water for grinding and to make a slurry so as to obtain a biomass/coal slurry. In the process, the biomass is first compressed and then secondarily pulverized; by means of compressing the biomass, the loose biomass successively undergoes stages of rearrangement, mechanical denaturation, shaping rheology and so on such that the volume of the biomass is greatly reduced, thereby reducing the porosity of the biomass, increasing the density and specific gravity of the biomass to enable the biomass to disperse in an oil product more easily, thus increasing the content thereof in the oil product, increasing the concentration of a reaction material, increasing the amount of biomass which a pump delivers per unit time, and ensuring the smooth operation and delivery of the pump, while increasing the conversion rate of the biomass.

Description

Hydrogenation hydrogenation process of biomass Technical field

The invention relates to the field of bioenergy, in particular to a process for hydrolyzing hydrogenation of biomass.

Background technique

Coal, oil, natural gas, oil shale and other non-renewable fossil With the rapid development of social economy and depleting, and their post-combustion generating CO _2, SO _2, NO _x and other pollutants caused serious environmental pollution This has made it necessary for humans to seriously consider ways to obtain energy and ways to improve the environment. Biomass refers to all organic substances formed directly or indirectly by photosynthesis of green plants, including plants, animals, microorganisms and their excretions and metabolites. It is renewable, low in pollution and widely distributed, therefore, from energy security. Starting from environmental protection, the development and utilization of biomass has become the strategic focus of the current development of renewable energy.

Biomass liquefaction technology is an important part of biomass resource utilization. The liquefaction mechanism of biomass is as follows: biomass is first cleaved into oligomers, then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecules. The compound, the small molecule compound, is then reacted by condensation, cyclization, polymerization or the like to form a new compound. At present, it can be mainly divided into two categories: indirect liquefaction and direct liquefaction. Among them, biomass direct liquefaction technology refers to hydrolysis, supercritical liquefaction or introduction of hydrogen, inert gas, etc. at the appropriate temperature under the action of solvent or catalyst. The biomass is directly liquefied from a solid to a liquid under pressure. Biomass direct liquefaction technology mainly includes pyrolysis liquefaction, catalytic liquefaction and pressurized hydroliquefaction, especially for pressurized hydro-liquefaction products with high yield and good quality, which generally include drying, pulverizing, pulping and heating of solid materials. Complex processes such as pressurization, reaction, and separation. For example, Chinese Patent Publication No. CN103242871A discloses a heavy oil-biomass hydrogenation co-liquefaction process which comprises pre-pulverizing dried biomass to 40-100 mesh and then mixing with heavy oil to form a slurry, and to the slurry The catalyst and the vulcanizing agent are added, and then placed in a slurry bed hydrogenation reactor, the reaction temperature is controlled from 370 ° C to 430 ° C, the partial pressure of hydrogen is 4-8 MPa, and the hydrothermal pyrolysis reaction is carried out, and the reaction product is fractionated to obtain Bio-oil and coke.

The above process enables the conversion of biomass to bio-oil, but in the above technique, on the one hand, the slurry formed from biomass and heavy oil needs to be pumped into the slurry bed hydrogenation reactor, while most biomass (for example) Straw) has a low specific gravity due to its rich porosity, making it less soluble in the biomass liquefaction solvent, resulting in a lower concentration of biomass in the slurry (the biomass in the above technology only accounts for 5-20% by weight of the heavy oil). ), which results in a limited amount of biomass transport per unit time, resulting in lower production efficiency, higher industrial costs, and higher energy consumption of the hydrogenation co-liquefaction process; on the other hand, biomass with porosity It is easy to float on the surface of the liquefied solvent, and the heavy oil as the solvent of the slurry has a large viscosity, so that the above slurry is not easy to flow, and it is easy to cause blockage of the conveying pipe, thereby making it difficult to achieve smooth transportation of the pump. Although the prior art attempts to increase the concentration and dispersibility of biomass in the slurry by adding a dispersant to the slurry, the addition of the dispersant tends to affect the quality of the produced bio-oil. In addition, the biomass conversion rate is low in the above technology (the conversion rate is only about 90%).

To this end, how to improve the existing biomass liquefaction process to increase the concentration of biomass in the slurry, increase the pumping capacity of the biomass per unit time, achieve smooth pumping, reduce energy consumption, and increase biomass conversion rate. This is still a technical problem to be solved by those skilled in the art.

Summary of the invention

Therefore, the technical problem to be solved by the present invention is to overcome the defects of the prior biomass liquefaction process, that the pump conveys less biomass and the transportation is not stable, the biomass conversion rate is low, and the energy consumption is high, thereby providing a kind of health. A hydrolyzed hydrogenation process of matter or coal and biomass.

In order to solve the above technical problem, the present invention adopts the following technical solutions:

The first technical solution provided by the present invention: a process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Preparing a slurry containing a catalyst and biomass, introducing hydrogen into the slurry to react, controlling the reaction pressure to 15-20 MPa, and reacting at a temperature of 380-420 ° C to finally obtain a bio-oil;

The biomass is straw, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw, then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil for grinding. The slurry is obtained to obtain the slurry having a straw concentration of 30 to 60% by weight.

The straw raw material in the invention may be straw of cereals such as wheat, rice, corn, reed, sorghum, millet, etc., or legumes such as soybean, adzuki bean, mung bean, broad bean, pea, etc., and may also be cotton, linen, The fiber crop straw such as ramie and hemp can be a straw or a biomass material composed of a variety of straws.

In the preparation step of the slurry, the straw is compressed at a pressure of 0.5 to 3 MPa and a temperature of 30 to 60 °C.

In the preparation step of the slurry, the drying temperature of the straw is 50-70 ° C, the time is 3-5 h, the moisture content of the straw after drying is less than 2 wt%; the median particle size after the initial pulverization is 100-300 μm After the secondary pulverization, the median particle size is 30-50 μm, and the secondary pulverization has a bulk density of 400-500 kg/m ³ .

In the slurry, the viscosity of the slurry is 500-1400 mPa. s (50 ° C).

In the slurry, the biomass is contained in an amount of 55 to 60% by weight.

In the step of preparing the slurry, the oil is one or more of waste animal and vegetable oil, waste mineral oil, mineral oil or distillate oil.

Further, the waste animal and vegetable oil is one or more of waste oil, hydrophobic oil or rancid oil;

The waste mineral oil is one or two of waste lubricating oil or waste lubricating oil;

The mineral oil is one or more of heavy oil, residual oil, eucalyptus oil or washing oil.

The grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping or homogenizing pulping.

In the slurry, the catalyst is contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; the catalyst has a particle diameter of 5 μm to 500 μm;

The specific method of introducing hydrogen into the slurry is:

Injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a reaction raw material;

The reaction raw material is sent to a slurry bed reactor to generate hydrolysis, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor. The speed is 0.02 ~ 0.2m / s, preferably 0.05 ~ 0.08m / s;

Wherein, the pressure of the high-pressure hydrogen gas and the high-pressure cold hydrogen is 15-22 MPa, and the temperature of the high-pressure cold hydrogen is 50-135 °C.

The high pressure hydrogen gas is injected into the slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the slurry for a first time, heat-treating the slurry to 380-420 ° C, and then injecting high-pressure high-temperature hydrogen into the slurry a second time;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 360-420 ° C, and the temperature of the high-pressure high-temperature hydrogen gas is 430-510 ° C.

The cold hydrogen is injected through 3 to 5 injection ports on the side wall of the slurry bed reactor.

The inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor.

The reaction time is 30-120 min.

The catalyst is a vulcanized bioactive carbon loaded with an active component, and the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide, and the active component and the biomass carbon The total mass of the active component is 10 to 50% by weight;

The preparation method of the biomass carbon loaded with active component comprises:

(1) taking biomass carbon as a biomass carbon carrier;

(2) The active component is supported on the biomass carbon support to prepare the catalyst.

The specific method of supporting the active component on the biomass carbon carrier is:

Mixing the biomass carbon carrier and the aqueous solution of the active component into a suspension, adding a precipitating agent to precipitate the active component on the biomass carbon carrier, washing and drying to obtain the catalyst; wherein the precipitate The agent is an aqueous solution of at least one of ammonia carbonate or alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 to 9.

Or the catalyst is a vulcanized amorphous iron oxyhydroxide.

The invention also provides a second technical solution:

A process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Preparing a slurry containing a catalyst and biomass, introducing hydrogen into the slurry to react, controlling the reaction pressure to 15-20 MPa, and reacting at a temperature of 380-440 ° C to finally obtain a bio-oil;

The biomass is vegetable oil residue, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil. The slurry is ground to obtain the slurry having a vegetable oil residue concentration of 50 to 65 wt%.

The vegetable oil residue in the present invention may be one or more of palm oil residue, soybean oil residue, peanut oil residue, saponin oil residue, linseed oil residue, castor oil residue, rapeseed oil residue or olive oil residue.

In the preparation step of the slurry, the vegetable oil residue is compressed at a pressure of 3 to 5 MPa and a temperature of 40 to 60 °C.

In the preparation step of the slurry, the drying temperature of the vegetable oil residue is 80-110 ° C, the time is 2-6 h, the moisture content of the vegetable oil residue after drying is less than 2 wt%; the median particle size after the initial crushing is 100 -300 μm; after secondary pulverization, the median particle size is 30-50 μm, and after secondary pulverization, the bulk density is 1500-1600 kg/m ³ .

In the slurry, the viscosity of the slurry is 300-700 mPa. s (50 ° C).

Wherein, the type of the oil, the method of grinding and pulping, the amount of the catalyst, the particle size, the specific method of introducing hydrogen into the slurry, the stock of the catalyst in the slurry bed reactor, and the reaction time The cold hydrogen injection mode, the composition of the catalyst, and the preparation method of the biomass carbon loaded with the active component are the same as those of the first technical solution.

The high pressure hydrogen gas is injected into the slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the slurry for the first time, heat-treating the slurry to 380-440 ° C, and then injecting high-pressure high-temperature hydrogen into the slurry a second time;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 360-440 ° C, and the temperature of the high-pressure high-temperature hydrogen gas is 450-510 ° C.

The invention also provides a third technical solution:

A multi-stage liquefaction process for biomass comprising the following steps:

(1) preparing a slurry containing the first catalyst and the biomass, introducing hydrogen into the slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure to be 15 to 25 MPa, and the reaction temperature to be 280 to 350 ° C to obtain a first-order addition. Hydrogen product;

The biomass is straw, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw, and then mixing with the first catalyst to obtain a mixture, and adding the mixture to the oil. The slurry is ground to obtain the slurry having a straw concentration of 30 to 60% by weight.

(2) adding a second catalyst to the primary hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure to be 15 to 25 MPa, and the reaction temperature to be 400 to 480 ° C to obtain a secondary hydrogenation product. The secondary hydrogenation product is separated and the oil phase is collected to obtain a bio-oil.

Wherein, in the preparation step of the slurry, the source of the straw, the contraction force of the straw, the temperature, the drying temperature of the straw, the time, the moisture content control, the particle size control in the pulverization, the bulk density of the straw, the viscosity of the slurry, the straw in the slurry The content, the type of oil, the grinding and pulping method, etc. are the same as those of the first technical solution.

In the slurry, the first catalyst is contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; the first catalyst has a particle diameter of 5 μm to 500 μm;

The second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 μm to 500 μm;

Before the adding the second catalyst to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically:

The catalyst slurry is prepared by mixing the second catalyst and the solvent oil in a mass ratio of (1 to 2): 10; the solvent oil is waste animal and vegetable oil, waste mineral oil, mineral oil, and fraction One or more of oil or bio-oil produced by the process.

The specific method for introducing hydrogen into the slurry in the step (1) is:

Injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a primary reaction raw material;

And sending the first-stage reaction raw material into the first slurry-bed reactor to generate a first-stage hydrogenation reaction, and simultaneously injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the first slurry bed. The total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;

Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen are both 15 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C;

The method of introducing hydrogen into step (2) is:

The mixture of the primary hydrogenation product and the second catalyst is heated to 400 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas. To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and The volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is (1000-1500): 1;

Wherein, the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 15-27 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C, and the temperature of the high-pressure cold hydrogen is 50-135 ° C.

In the step (1), the high-pressure hydrogen gas is injected into the slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the slurry for a first time, heat-treating the slurry to 280-350 ° C, and then injecting high-pressure high-temperature hydrogen into the slurry a second time;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 260-350 ° C, and the temperature of the second-injected high-pressure high-temperature hydrogen gas is 360-510 ° C.

The high pressure cold hydrogen is injected through the first slurry bed reactor or three to five injection ports on the side wall of the second slurry bed reactor.

The amount of the first catalyst in the first slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry The inventory in the bed reactor is controlled in the range of 5 to 30% by weight of the liquid phase in the second slurry bed reactor.

The time of the first hydrogenation reaction is 30 to 60 minutes, and the time of the second hydrogenation reaction is 30 to 90 minutes.

Further, the step of subjecting the secondary hydrogenation product to hydro-reforming under conditions of a pressure of 7 to 23 MPa and a temperature of 250 to 460 ° C is also included.

The first catalyst is a vulcanized biomass char loaded with a first active component, and the first active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide, The first active component is contained in an amount of 10 to 50% by weight based on the total mass of the active component and the biomass carbon; and the second catalyst is a vulcanized biochar which is loaded with the second active component, The second active component is one or more of oxides of Mo, Mn, W, Fe, Co, Ni or Pd, and the content of the active component is based on the total mass of the second active component and the biomass carbon. 1 to 5 wt%;

The preparation method of the biomass carbon loaded with the first active component comprises:

(1) taking biomass carbon as the first biomass carbon carrier;

(2) The first active component is supported on the first biomass carbon support to prepare the first catalyst.

A specific method of supporting the first active component on the first biomass carbon carrier is:

The first biomass carbon carrier and the first active component aqueous solution are mixed and formulated into a suspension, and the first active component is precipitated on the first biomass carbon carrier by adding a precipitating agent, and is washed and dried to obtain a solution. The first catalyst; wherein the precipitating agent is an aqueous solution of at least one of ammonia water or an alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 ~9.

The preparation method of the biomass carbon loaded with the second active component comprises:

S1, the biomass carbon is acidified or alkalized to obtain a second biomass carbon carrier;

S2, mixing and grinding the second active component and the second biomass carbon carrier to prepare a second catalyst.

The step of mixing the second active component and the second biomass carbon carrier is performed by vibrating and/or planar grinding and/or planar grinding and/or polishing the second active component and the second biomass carbon carrier. Ball milling yielded a second catalyst having a particle size of from 5 μm to 500 μm.

The acid concentration of the H+ substance in the acidified acid medium is 0.5 mol/L to 5 mol/L; the volume ratio of the biomass carbon to the acidic medium is 1:5 to 1:15, and the acidification temperature is 30 ～. 80 ° C, acidification time is 1h ~ 10h; the amount of the substance of OH- in the alkalized alkaline medium is 0.5mol / L ~ 5mol / L; the volume ratio of the biomass carbon to the alkaline medium The ratio is 1:5 to 1:15, the alkalization temperature is 30 ° C to 80 ° C, and the alkalization time is 1 h to 10 h.

Or the first catalyst is vulcanized amorphous iron oxyhydroxide, the second catalyst is a vulcanized amorphous alumina loaded with a third active component, and the third active component is selected from the periodic table of elements. One or more of the oxides of Group VIB, VIIB or VIII metals.

The invention also provides a fourth technical solution:

A multi-stage liquefaction process for biomass comprising the following steps:

(1) preparing a slurry containing the first catalyst and the biomass, introducing hydrogen into the slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure to be 15 to 25 MPa, and the reaction temperature to be 250 to 350 ° C to obtain a first-order addition. Hydrogen product;

The biomass is vegetable oil residue, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the first catalyst to obtain a mixture, and adding the mixture to the oil. Grinding and pulping in the product to obtain the slurry having a vegetable oil residue concentration of 30 to 60% by weight;

(2) adding a second catalyst to the primary hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure to be 15 to 25 MPa, and the reaction temperature to be 380 to 480 ° C to obtain a secondary hydrogenation product. The secondary hydrogenation product is separated and the oil phase is collected to obtain a bio-oil.

Wherein, in the preparation step of the slurry, the source of the vegetable oil residue, the compression and contraction force of the vegetable oil residue, the temperature, the drying temperature, the time, the particle size control during the crushing, the bulk density, the viscosity of the slurry, the oil type, the grinding and pulping The method and the like are the same as the second technical solution.

Wherein, in the slurry, the content of the first catalyst, the particle diameter, the dosage of the second catalyst, the particle size, the manner of dosing, and the introduction of hydrogen into the slurry in the step (1) The specific method, the method of introducing hydrogen into the step (2), the standards of the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen are the same as the third technical scheme.

Further, in the step (1), the high-pressure hydrogen gas is injected into the slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the slurry for the first time, heat-treating the slurry to 250-350 ° C, and then injecting high-pressure high-temperature hydrogen into the slurry a second time;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 230-350 ° C, and the temperature of the second-injected high-pressure high-temperature hydrogen gas is 360-510 ° C.

Wherein the stock of the first catalyst in the first slurry bed reactor, the inventory of the second catalyst in the second slurry bed reactor, the primary and secondary hydrogenation reaction time, The conditions of the hydro-reforming, the composition of the first catalyst, the preparation method, the composition of the second catalyst, the preparation method of the biomass carbon loaded with the second active component, and the like are the same as those of the third technical solution.

The invention also provides a fifth technical solution,

A co-liquefaction process of coal and biomass, comprising the following steps:

Preparation of biomass coal slurry:

Collecting biomass and controlling the water content to less than 2% by weight, and then pulverizing to a median particle diameter of 100 to 300 μm;

The pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C;

The biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain a biomass powder;

Collecting coal and controlling the water content to less than 2wt%, and then pulverizing to a median particle size of 50-100μm;

Compressing the pulverized coal, the compression pressure is 5-15 MPa, and the compression temperature is 30-60 ° C;

The coal after compression molding is pulverized again, and pulverized to a median diameter of 30-50 μm to obtain coal powder;

Mixing the biomass powder, the pulverized coal, the catalyst and the oil in proportion, and grinding and pulping to obtain a biomass coal slurry, the biomass powder and the pulverized coal occupying the biomass coal 60 to 70% by weight of the slurry;

Liquefaction reaction: hydrogen is introduced into the biomass coal slurry to react, and the reaction pressure is controlled to 15 to 25 MPa, and the reaction temperature is 380 to 480 ° C to obtain a bio-oil;

In the preparation step of the biomass coal slurry, when the mixing is performed, the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The oil is mixed, or the biomass powder, the pulverized coal, the catalyst, and the oil are directly mixed.

In the biomass coal slurry, the concentration of the biomass is 20 to 30% by weight, and the concentration of the coal powder is 30 to 45% by weight.

The moisture content is controlled by drying and dehydrating, the drying and dehydrating temperature is 50-70 ° C, and the drying and dehydrating time is 3 to 5 h.

The compression molding is press forming, tablet forming or bead forming.

In the preparation step of the biomass coal slurry, the bulk density of the biomass powder is controlled to be 300 to 500 kg/m ³ , and the bulk density of the coal powder is controlled to be 1000 to 1200 kg/m ³ .

The pulverization is a hammer mill pulverization, a ball mill pulverization, a rod mill pulverization, an ultrafine pulverization or a jet pulverization.

The grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping, homogenizing pulping or colloidal grinding pulping.

The grinding and pulping time is 2 to 8 minutes.

The biomass coal slurry has a viscosity of 550 to 1000 mPa·s (50 ° C).

The coal is low rank coal; the oil is made of hydrophobic oil, waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or the process. One or more of the bio-oils.

In the biomass coal slurry, the catalyst is contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; and the catalyst has a particle diameter of 5 to 500 μm.

The specific method for introducing hydrogen into the gas is:

Injecting high-pressure hydrogen into the biomass coal slurry, and controlling a volume ratio of the high-pressure hydrogen to the biomass coal slurry to be (600-1000): 1, thereby forming a reaction raw material;

The reaction raw material is sent into a slurry bed reactor to undergo liquefaction, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor. The speed is 0.02 ~ 0.2m / s, preferably 0.05 ~ 0.08m / s;

Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen is 13-27 MPa, and the temperature of the high pressure cold hydrogen is 50-135 °C.

The high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the biomass coal slurry for the first time, heat-treating the biomass coal slurry to 300-400 ° C, and then second to the biomass coal slurry Secondary injection of high pressure and high temperature hydrogen;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 300 to 400 ° C, and the temperature of the high-pressure high-temperature hydrogen gas is 410 to 510 ° C.

The cold hydrogen is injected through 3 to 5 injection ports on the side wall of the slurry bed reactor.

The inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor.

The reaction time is 30 to 90 min.

The preparation step of the biomass coal slurry further includes an operation of screening the biomass powder and the coal powder, and returning the solid material exceeding a defined particle size to the compression or the crushing step The operation is performed again; the defined particle size is from 80 μm to 100 μm.

The catalyst is a vulcanized biological carbon loaded with an active component, and the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide;

Or the catalyst is a vulcanized amorphous iron oxyhydroxide.

The biomass used in the present invention may be solid, such as straw of crops such as wheat, rice, corn, cotton, etc., or may be economic crops such as reed, bamboo yellow grass, trees, leaves, fruits and vegetables, or algae. Industrial wood, paper waste, etc.; can also be liquid, such as liquid manure, etc. When liquid biomass is used, the compression and pulverization of the biomass material is omitted in the step of preparing the biomass coal slurry. The process can also be a biomass material which is composed of one kind of biomass or a plurality of kinds of biomass.

The preparation method of the biomass carbon loaded with the active component in the invention comprises:

(1) selecting biomass charcoal as a biomass carbon carrier;

(2) The active component is supported on the biomass carbon support to prepare the catalyst.

The specific method of supporting the active component on the biomass carbon carrier is:

Mixing the biomass carbon carrier and the aqueous solution of the active component into a suspension, adding a precipitating agent to precipitate the active component on the biomass carbon carrier, washing and drying to obtain the catalyst; wherein the precipitate The agent is an aqueous solution of at least one of ammonia carbonate or alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 to 9.

Or the catalyst is a vulcanized amorphous iron oxyhydroxide.

The invention also provides a sixth technical solution:

A co-hydrolysis hydrogenation process of coal and biomass, comprising the following steps:

Preparation of biomass coal slurry:

Collecting biomass and controlling the water content to less than 2% by weight, and then pulverizing to a median particle diameter of 100 to 300 μm;

The pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C;

The biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain a biomass powder;

Collecting coal and controlling the water content to less than 2wt%, and then pulverizing to a median particle size of 50-100μm, a compression temperature of 30-60 ° C;

Compressing the pulverized coal, the compression pressure is 5-15 MPa;

The coal after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain coal powder;

Mixing the biomass powder, the pulverized coal, the catalyst with water, and grinding and pulping to obtain a biomass coal slurry, the biomass powder and the pulverized coal occupying 55 to 65 wt of the biomass coal slurry %;

Liquefaction reaction: hydrogen is introduced into the biomass coal slurry to react, and the reaction pressure is controlled to 15 to 25 MPa, and the reaction temperature is 300 to 420 ° C to obtain a bio-oil;

In the preparation step of the biomass coal slurry, when the mixing is performed, the biomass powder and the pulverized coal are degreased and premixed with the catalyst, and then the premixed is obtained. The material is mixed with the water, or alternatively, the biomass powder, the pulverized coal, the catalyst, and the water are directly mixed.

In the biomass coal slurry, the concentration of the biomass is 15 to 30% by weight, and the concentration of the coal powder is 35 to 50% by weight.

In the preparation step of the biomass coal slurry, the biomass density of the biomass powder is controlled to be 300 to 500 kg/m ³ , and the bulk density of the coal powder is controlled to be 1200 to 1300 kg/m ³ .

Wherein the drying temperature, time, the time of the grinding and pulping, the content of the catalyst in the slurry, the particle size, the type of coal, the specific method of introducing hydrogen, the source of biomass, the type of catalyst, and the preparation The methods are the same as the fifth technical solution.

The high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the biomass coal slurry for the first time, heat-treating the biomass coal slurry to 300-400 ° C, and then second to the biomass coal slurry Secondary injection of high pressure and high temperature hydrogen;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 300 to 400 ° C, and the temperature of the high-pressure high-temperature hydrogen gas is 410 to 510 ° C.

The inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor.

The reaction time is 30 to 60 min.

The invention also provides a seventh technical solution:

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Preparation of biomass kerosene paddles:

Collecting biomass and controlling the water content to less than 2% by weight, and then pulverizing to a median particle diameter of 100 to 300 μm;

The pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C;

The biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain a biomass powder;

Collecting coal and controlling the water content to less than 2wt%, and then pulverizing to a median particle size of 50-100μm;

Compressing the pulverized coal, the compression pressure is 5-15 MPa, and the compression temperature is 30-60 ° C;

The coal after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain coal powder;

The biomass powder, the pulverized coal, the catalyst and the oil are proportion-mixed and ground to obtain a biomass coal slurry, and the biomass powder and the pulverized coal together comprise the biomass coal 60 to 70% by weight of the slurry;

First-stage hydrogenation reaction: hydrogen is introduced into the biomass coal slurry to generate a first-stage hydrogenation reaction, and the reaction pressure is 15-25 MPa, and the reaction temperature is 280-350 ° C to obtain a first-stage hydrogenation product;

Secondary hydrogenation reaction: adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure to be 15-25 MPa, and the reaction temperature being 400-480 ° C, to obtain a secondary a hydrogenation product, the second hydrogenated product is finally separated to obtain a bio-oil;

In the preparation step of the biomass coal slurry, when the mixing is performed, the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The oil is mixed, or the biomass powder, the pulverized coal, the catalyst, and the oil are directly mixed.

Wherein, the biomass coal slurry, the concentration of biomass, the concentration of coal powder, the drying time, the temperature, the compression mode, the biomass density of the compressed biomass powder, the pulverized coal, the pulverization method, the grinding and pulping method, and the time The slurry viscosity, coal and oil varieties are equal to the fifth technical solution.

The preparation step of the biomass kerosene paddle further includes an operation of screening the biomass powder and the pulverized coal, and returning the solid material exceeding a defined particle size to the compression or the pulverization step The operation is performed again; the defined particle size is from 80 μm to 100 μm.

In the biomass coal slurry, the content of the first catalyst is 0.1 to 10% by weight, preferably 2% by weight; the particle diameter of the first catalyst is 5 μm to 500 μm;

The second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 μm to 500 μm;

Before the adding the second catalyst to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically:

The catalyst slurry is prepared by mixing the second catalyst with a solvent oil (water) in a mass ratio of (1 to 2):10.

The specific method for introducing hydrogen into the first-stage hydrogenation reaction step is:

Injecting high-pressure hydrogen into the biomass coal slurry, and controlling a volume ratio of the high-pressure hydrogen to the biomass coal slurry to be (600-1000): 1, thereby forming a primary reaction raw material;

And sending the first-stage reaction raw material into the first slurry-bed reactor to generate a first-stage hydrogenation reaction, and simultaneously injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the first slurry bed. The total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;

Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen is 13 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C;

The method of introducing hydrogen into the second-stage reaction step is:

The mixture of the primary hydrogenation product and the second catalyst is heated to 380 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas. To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and The volume ratio of hydrogen to the primary hydrogenation product is (1000 to 1500): 1;

Wherein, the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 13-27 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C, and the temperature of the high-pressure cold hydrogen is 50-135 ° C.

The high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:

After injecting high-pressure medium-temperature hydrogen into the biomass coal slurry for the first time, heat-treating the biomass coal slurry to 200-350 ° C, and then second to the biomass coal slurry Secondary injection of high pressure and high temperature hydrogen;

Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 180 to 350 ° C, and the temperature of the second injection high-pressure high-temperature hydrogen gas is 360 to 510 ° C.

The high pressure cold hydrogen is injected through the first slurry bed reactor or three to five injection ports on the side wall of the second slurry bed reactor.

The amount of the first catalyst in the first slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry The inventory in the bed reactor is controlled in the range of 5 to 30% by weight of the liquid phase in the second slurry bed reactor.

The time of the first hydrogenation reaction is 30 to 60 minutes, and the time of the second hydrogenation reaction is 30 to 90 minutes.

Further, the step of subjecting the secondary hydrogenation product to hydro-reforming under conditions of a pressure of 7 to 23 MPa and a temperature of 250 to 460 ° C is also included.

The first catalyst is a vulcanized biomass char loaded with a first active component, and the first active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide; The second catalyst is a vulcanized biochar carrying a second active component, and the second active component is one or more of oxides of Mo, W, Fe, Co, Ni or Pd;

Or the first catalyst is vulcanized amorphous iron oxyhydroxide, the second catalyst is a vulcanized amorphous alumina loaded with a third active component, and the third active component is selected from the periodic table of elements. One or more of the oxides of Group VIB, VIIB or VIII metals.

The biomass raw material in the present invention may be straw of solid crops such as wheat, rice, corn, cotton, etc., or may be economic crops such as reed, bamboo yellow grass, trees, leaves, fruits and vegetables, or algae, industrially. Wood, paper waste, etc.; it can also be liquid feces, etc.; it can be a biomass or a biomass material composed of a variety of biomass.

The preparation method of the biomass carbon loaded with the first active component comprises:

(1) selecting biomass charcoal as the first biomass carbon carrier;

(2) The first active component is supported on the first biomass carbon support to prepare the first catalyst.

A specific method of supporting the first active component on the first biomass carbon carrier is:

The first biomass carbon carrier and the first active component aqueous solution are mixed and formulated into a suspension, and the first active component is precipitated on the first biomass carbon carrier by adding a precipitating agent, and is washed and dried to obtain a solution. The first catalyst; wherein the precipitating agent is an aqueous solution of at least one of ammonia water or an alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 ~9.

The preparation method of the biomass carbon loaded with the second active component comprises:

(1) After the biomass carbon is acidified or alkalized, a second biomass carbon carrier is obtained;

(2) mixing and grinding the second active component and the second biomass carbon carrier to prepare a second catalyst.

The step of mixing the second active component and the second biomass carbon carrier is performed by vibrating and/or planar grinding and/or planar grinding and/or polishing the second active component and the second biomass carbon carrier. Ball milling yielded a second catalyst having a particle size of from 5 μm to 500 μm.

The amount of the substance of H ⁺ in the acidified acidic medium is 0.5 mol / L ~ 5 mol / L; the volume ratio of the biomass carbon to the acidic medium is 1: 5 ~ 1:15, the acidification temperature is 30 ～80° C., the acidification time is 1 h to 10 h; the amount of the OH ⁻ substance in the alkalized alkaline medium is 0.5 mol/L to 5 mol/L; the biomass carbon and the alkaline medium volume The ratio is 1:5 to 1:15, the alkalization temperature is 30 ° C to 80 ° C, and the alkalization time is 1 h to 10 h.

The invention also provides an eighth technical solution:

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Preparation of biomass coal slurry:

Collecting biomass and controlling the water content to less than 2% by weight, and then pulverizing to a median particle diameter of 100 to 300 μm;

The pulverized biomass is compression-molded, and the compression pressure is 2 to 5 MPa;

The biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain a biomass powder;

Collecting coal and controlling the water content to less than 2wt%, and then pulverizing to a median particle size of 50-100μm;

Compressing the pulverized coal, the compression pressure is 5-15 MPa;

The coal after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain coal powder;

Mixing the biomass powder, the pulverized coal, the catalyst with water, and grinding and slurrying to obtain a biomass coal slurry, the biomass powder and the pulverized coal occupying 60 to 70 wt of the biomass coal slurry %;

First-stage hydrogenation reaction: introducing hydrogen into the biomass coal slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure to 15-20 MPa, and reacting at a temperature of 220-300 ° C to obtain a first-stage hydrogenation product;

Secondary hydrogenation reaction: adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a second-stage hydrogenation reaction, controlling the reaction pressure to be 15-20 MPa, and the reaction temperature is 380-420 ° C, and obtaining the second stage a hydrogenation product, the second hydrogenated product is finally separated to obtain a bio-oil;

In the preparation step of the biomass coal slurry, when the mixing is performed, the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The water is mixed or, alternatively, the biomass powder, the pulverized coal, the catalyst, and the water are directly mixed.

Wherein, the biomass coal slurry, the concentration of biomass, the concentration of coal powder, the drying time, the temperature, the compression mode, the biomass density of the compressed biomass powder, the pulverized coal, the pulverization method, the grinding and pulping method, and the time The viscosity of the slurry, the type of coal and biomass are the same as the sixth technical solution.

Wherein, in the biomass coal slurry, the content of the first and second catalysts, the particle size, the manner of adding the second catalyst, the specific method of introducing hydrogen into the first hydrogenation reaction step, and the second-stage reaction step a method of introducing hydrogen into the medium, a method of injecting high-pressure cold hydrogen, a stock of the first and second catalysts in the first and second slurry beds, a first hydrogenation reaction time, a hydrogenation reforming condition, and a first First, the composition and preparation method of the second catalyst are the same as those of the seventh technical solution.

The above technical solution of the present invention has the following advantages:

1. The hydrolyzed hydrogenation process of biomass provided by the present invention, wherein the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the biomass, and then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil. The slurry is obtained by grinding and pulping. The first process of the invention is that the biomass is firstly compressed and then secondarily pulverized. The biomass is subjected to compression treatment, so that the loose biomass undergoes re-alignment such as collapse and closure. The stage of mechanical deformation greatly reduces the volume of biomass, thereby reducing the porosity of the biomass, increasing its density and specific gravity, making it advantageous for dispersion in the flowing medium, and improving its presence in the flowing medium. The content of the reaction material increases the concentration of the reaction material, and the content of the straw in the oil slurry can be as high as 30-60 wt%, which is much higher than 5-16 wt% in the prior art; the content of the vegetable oil residue in the slurry can be Up to 50-65wt%, and due to the increase of biomass concentration in the slurry, it will inevitably increase the amount of biomass transported by the pump per unit time, thereby improving the whole organism. The efficiency of the liquefaction process reduces the industrial cost and energy consumption; in addition, the increase in the specific gravity of the biomass also facilitates the suspension and dispersion of the biomass in the slurry, thereby reducing the viscosity of the biomass slurry and achieving biomass pulping. The smooth flow of the slurry in the pipeline avoids the blockage of the pipeline, realizes the smooth operation and transportation of the pump, and also makes the high-viscosity waste oil which cannot be used as a biomass liquefaction solvent in the prior art, such as waste engine oil and waste oil. , rancid oil, etc., can also be used.

The invention prepares a bio-oil by preparing a slurry containing a catalyst and a biomass, and then introducing hydrogen into the slurry to generate a primary or secondary reaction, and finally controlling the reaction pressure and the reaction temperature, and the process of the invention is in the presence of hydrogen. Under the action of the catalyst, the biomass is cracked and hydrogenated to realize the conversion from biomass to bio-oil, and the conversion rate of biomass is improved. In the process of the invention, the biomass conversion rate can be as high as 95-99. %. The process of the invention, under the action of hydrogen and the first catalyst and the second catalyst, causes the biomass to undergo cracking hydrogenation reaction, thereby realizing the conversion from biomass to bio-oil, in the process of the invention, the biomass conversion rate can be Up to 98-99%.

2. The hydrolyzation hydrogenation process of biomass provided by the present invention can significantly enhance the rheology of the straw and reduce the viscosity of the biomass slurry by controlling the compression temperature at 30-60 ° C, and then compressing the straw at this temperature. The viscosity of the slurry formed by the straw and the oil in the process of the invention is 500-1400 mPa. s (50 ° C), thereby achieving smooth flow of the slurry after biomass slurrying, avoiding blockage of the pipeline, achieving smooth operation and transportation of the pump; by controlling the compression temperature at 40-60 ° C, Further compressing the vegetable oil residue at this temperature can significantly enhance the rheology of the vegetable oil residue and reduce the viscosity of the biomass slurry. The viscosity of the slurry formed by the vegetable oil residue and the oil in the process of the present invention is 300-700 mPa. s (50 ° C), thereby achieving the smooth flow of the slurry after the slurry of the vegetable oil residue in the pipeline, avoiding the blockage of the pipeline, and achieving smooth operation and transportation of the pump.

3. The inventive first realization of the mixing and liquefaction of coal, biomass and oil provides a common liquefaction process of coal and biomass. The invention successfully prepares biomass and coal by dehydrating, pulverizing, compressing, re-pulverizing, primary slurrying, grinding and pulping of biomass and coal, and by optimizing the pulverized particle size and compression conditions. Biomass kerosene with a content of 60-70 wt% and a viscosity of only 550-1000 mPa·s (50 ° C); biomass and coal content of 55-65 wt%, and viscosity of only 450-1100 mPa·s (50 ° C) Biomass coal water slurry.

The compression treatment can cause the pore structure inside the coal and biomass material to collapse and close, and plastic rheology and plastic deformation occur, thereby greatly increasing the density of the coal and biomass raw materials, so that it can be well dispersed in the solvent oil; The collapse and closure of the pore structure avoids the adsorption of solvent oil by coal and biomass, so that the solvent oil can fully exert its function as a dispersant; we have found that the compression temperature has a great influence on the degree of plastic rheology and plastic deformation. The higher the temperature, the higher the density. However, if the temperature is too high, the material will be decomposed or cause other problems. Therefore, 30 to 60 ° C is used as the temperature at the time of compression. The re-pulverization operation after compression increases the contactable area of the raw material, so that the raw material can be in better contact with the catalyst and the solvent oil, and the hydrogen transfer can be enhanced, and the raw material is in contact with the hydrogen and the catalyst due to being in the pore structure. Thus the situation of the reaction.

The "crushing + compression + re-crushing" provided by the invention can be applied to all coal materials and biomass materials having pore structure inside, especially low-rank coal materials such as lignite, and porous and porous biomass materials such as straw and rice husk. The prepared high-concentration biomass kerosene slurry has good slurryability and high fluidity, and can be directly transported by the pump, which can effectively improve the running stability of the conveying system, the utilization efficiency of the liquefaction device and the liquefaction efficiency, and meet the subsequent processing technology. The feed requirement also realizes the clean and efficient utilization of inferior coal and biomass; the close proximity of coal and biomass makes the hydrogen produced by biomass pyrolysis a part of hydrogen source for pyrolysis of coal, reducing hydrogen Consumption. The common liquefaction process provided by the present invention enables high-viscosity waste oils, such as waste engine oil, waste oil, and rancid oil, which cannot be used as coal and biomass liquefaction solvents in the prior art, can also be utilized.

The reaction is carried out by introducing hydrogen into the biomass kerosene slurry, and the reaction pressure is 15-25 MPa, and the reaction temperature is 380-480 ° C, thereby finally producing a bio-oil; the process of the invention makes the coal and the biomass at a high pressure Liquefaction under high temperature conditions, and further cracking and hydrogenation reaction under the action of hydrogen and catalyst, thereby realizing the conversion of coal and biomass to bio-oil. In the process of the present invention, the conversion ratio of coal to biomass can reach 90-95%, the yield of bio-oil can reach 40-75%, and the residue amount is not higher than 3%.

The reaction is carried out by introducing hydrogen into the biomass coal water slurry, and controlling the reaction pressure to be 15 to 25 MPa and the reaction temperature to be 300 to 420 ° C to finally obtain a bio-oil; the process of the present invention is in the presence of an appropriate amount of water. The high-temperature and high-temperature hydrolysis of coal and biomass is carried out, and under the action of hydrogen and catalyst, the hydrolyzed product is further cracked and hydrogenated to realize the conversion from coal and biomass to bio-oil. In the process of the present invention, the conversion ratio of coal to biomass can reach 85-95%, the yield of bio-oil can reach 60-80%, and the amount of residue is less than 5%.

The multi-stage liquefaction process of coal and biomass provided by the invention liquefies coal and biomass under high temperature and high pressure conditions, and the liquefied products successively occur under the action of hydrogen and the first catalyst and the second catalyst. Cracking, hydrogenation and deep cracking, hydrogenation reactions to achieve the conversion of coal and biomass to bio-oil and the refining of bio-oil. In the process of the present invention, the biomass and coal conversion rate can reach 95 to 99%, the bio-oil yield can reach 70-80%, and the residue amount is less than 2.5%.

The multi-stage liquefaction process of coal and biomass provided by the invention generates hydrolysis of coal and biomass by high pressure and high temperature, and primary cracking of hydrolyzed products in the presence of hydrogen and the first catalyst and the second catalyst. Hydrogenation reaction and deep cracking, hydrogenation reaction, thereby realizing the conversion of coal and biomass to bio-oil and the purification of bio-oil. In the process of the present invention, the conversion rate of biomass and coal can reach 97 to 99%, the yield of bio-oil can reach 70-80%, and the amount of residue is less than 3%.

In the secondary reaction, amorphous alumina loaded with a metal oxide of Group VIB, VIIB or VIII is used as the second catalyst, and hydrogen gas is introduced to refine the bio-oil, which is better obtained by vulcanization with a noble metal. The hydrogenation performance further avoids coke formation, and the amorphous alumina has an acidity, which makes the cracking more sufficient.

4. The co-liquefaction process of coal and biomass provided by the invention, combined with the process of screening solid materials, can ensure uniform particle size of solid particles used for preparing biomass oil coal slurry, so that the stability of the obtained biomass coal slurry is more stable. Well, it is not easy to settle during transportation, avoiding blockage of the transportation pipeline and damage to the liquefaction equipment. The solid biomass is pretreated by drying, pulverizing and ash removal, and then mixed with the catalyst to better utilize the surface energy of the coal and biomass powder to cause the catalyst to adhere to the surface, so that the catalyst can be timely Hydrogen transfer is provided for coal and biomass liquefaction products, thereby ensuring that coke polycondensation does not occur during the entire process, thereby reducing the amount of residue.

3. The hydrolyzed hydrogenation process of biomass provided by the present invention, by using a slurry bed reactor, the reaction raw material is first sent from the bottom of the reactor to the slurry bed reactor to react, and then the reactor is injected into the reactor. Hydrogen, so in the reactor can rely on the different specific gravity of gas, liquid, solid materials and the change in specific gravity caused by the production of light oil after the reaction, to achieve differential control of the flow velocity of each phase, so that biomass raw materials Hydrolysis, cracking, and hydrogenation reactions occur from bottom to top in the reactor. In this process, even if the biomass and catalyst solid particles rise with gas and light oil, they return to the upper cold hydrogen. Re-involved in the reaction to the bottom, and appropriately adjust the hydrogen content and the cold hydrogen injection amount into the slurry of the reactor according to the material density of the upper, middle and lower parts of the reactor, thereby realizing the circulation of the unconverted biomass inside the reactor and the catalyst. The equilibrium discharge is performed, thereby ensuring sufficient progress of the reaction such as hydrolyzing hydrogenation, thereby contributing to improvement of biomass conversion rate and bio-oil yield.

4. The hydrolyzation hydrogenation process of biomass provided by the present invention, in the first-stage reaction, by injecting high-pressure hydrogen into the slurry twice, that is, injecting high-pressure hydrogen gas before and after heating the slurry, the injection of the previous high-pressure hydrogen gas may be Increase the disturbance of the slurry in the heat exchanger to avoid deposition of solid biomass and catalyst. In the secondary reaction, high pressure hydrogen is injected into the slurry three times, that is, high pressure hydrogen is injected once before and after the slurry is heated, and then before the mixture of the first hydrogenation product and the second catalyst enters the second slurry bed reactor. The high-pressure hydrogen gas is injected again, and the injection of the first high-pressure hydrogen gas can increase the disturbance of the slurry in the heat exchanger, thereby avoiding the deposition of biomass and catalyst. By injecting high-pressure hydrogen three times, the gas velocity can be supplied to various liquids, solids, and catalysts, and the difference in phase and density of the mixture can be achieved by the difference in phase and density of the mixture, and can be based on the layers in the reactor. The density difference is adjusted by the hydrogen injection port on the outer wall of the reactor to ensure sufficient hydrolysis, cracking and hydrogenation reactions.

5. The hydrolyzed hydrogenation process of biomass provided by the invention, the catalyst added in the slurry is subjected to vulcanization treatment, and the catalyst after vulcanization has better hydrogenation performance, can further avoid coke formation, and further hydrolyze hydrogenation reaction. full.

Detailed ways

The technical solutions of the present invention will be described clearly and completely hereinafter, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention. Further, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not constitute a conflict with each other.

Example 1

A process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Biomass pretreatment

The rice straw and the reed straw are sent to a dryer and dried at 50 ° C for 5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for initial pulverization. The median diameter after the initial pulverization is 100 μm, and then the initial The pulverized rice straw and the reed straw are sent to a briquetting machine for compression extrusion at a temperature of 30 ° C and a pressure of 3 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 30 μm. The bulk density after the secondary pulverization was 500 kg/m ³ , which was used.

Catalyst preparation

(1) taking biomass carbon as a biomass carbon carrier;

(2) The iron oxide is supported on the above-mentioned biomass carbon carrier and vulcanized to obtain a catalyst.

The specific method of supporting iron oxide on the above biomass carbon carrier is:

The biological carbon carrier and the aqueous solution of iron oxide are mixed and formulated into a suspension, and an aqueous solution of sodium carbonate and ammonia water as a precipitating agent is added, and the iron oxide is precipitated on the biomass carbon carrier, and the catalyst is obtained by washing, drying and vulcanization. The temperature of the precipitation process was 90 ° C, and the pH was 7, and the iron oxide content was 50% by weight based on the total mass of the iron oxide and the biomass carbon carrier.

Preparation of biomass slurry

The pretreated biomass and the catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of a hydrophobic oil and a residual oil to be stirred and slurried to form a slurry. The total content of the rice straw and the reed straw in the slurry is 60 wt. %, the viscosity of the slurry is 500mPa. s (50 ° C), the content of the catalyst in the above slurry was 10% by weight, and the particle diameter of the catalyst to be charged was 5 μm.

Hydrolysis hydrogenation reaction:

Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 20 MPa, and the reaction temperature is 380 ° C to prepare a bio-oil;

The specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 600:1, thereby forming a reaction raw material; feeding the above-mentioned reaction raw material into the slurry bed reactor to cause hydrolysis, Cracking and hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas velocity in the slurry-bed reactor to be 0.2 m/s; wherein the pressures of high-pressure hydrogen and high-pressure cold hydrogen are both 22 MPa. , the temperature of the high pressure cold hydrogen is 135 ° C;

The high pressure cold hydrogen is injected through three injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the reaction time was 30 min.

Example 2

A process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Biomass pretreatment

The linseed oil residue and the peanut oil residue are sent to a dryer and dried at 110 ° C for 2 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization, and the median diameter after initial pulverization is 300 μm, and then The initially pulverized linseed oil slag and peanut oil slag are sent to a briquetting machine for compression extrusion at a temperature of 60 ° C and a pressure of 3 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 50 μm. After the second pulverization, the bulk density was 1500 kg/m ³ and was used.

Catalyst preparation

(1) taking biomass carbon as a biomass carbon carrier;

(2) The iron oxyhydroxide is supported on the above-mentioned biomass carbon carrier and vulcanized to obtain a catalyst.

The specific method for supporting the iron oxyhydroxide on the above biomass carbon carrier is:

The biological carbon carrier and the aqueous solution of iron oxyhydroxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydrogencarbonate and potassium hydroxide as a precipitating agent is added, and the iron oxyhydroxide is precipitated on the biomass carbon carrier, washed, dried, The catalyst was prepared by vulcanization, the temperature of the precipitation process was 30 ° C, and the pH was 9, and the content of iron oxyhydroxide was 10 wt% based on the total mass of the iron oxyhydroxide and the biomass carbon support.

Preparation of biomass slurry

The pretreated biomass and the catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of waste lubricating oil and waste engine oil to be dispersed and slurried to form a slurry, and the total content of linseed oil residue and peanut oil residue in the slurry is detected. 50wt%, the viscosity of the slurry is 700mPa. s (50 ° C), the content of the catalyst in the above slurry was 0.1% by weight, and the particle diameter of the catalyst to be charged was 500 μm.

Hydrolysis hydrogenation reaction:

Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 15 MPa and the reaction temperature is 420 ° C to prepare a bio-oil;

The specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 1000:1 to form a reaction raw material; feeding the above-mentioned reaction raw material into the slurry bed reactor to cause hydrolysis, Cracking and hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas velocity in the slurry-bed reactor to be 0.02 m/s; wherein the pressures of high-pressure hydrogen and high-pressure cold hydrogen are both 15 MPa. , the temperature of the high pressure cold hydrogen is 50 ° C;

The high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounted for 5 wt% of the liquid phase mass in the slurry bed reactor, and the reaction time was 120 min.

Example 3

A multi-stage liquefaction process for biomass comprising the following steps:

Biomass pretreatment

The cotton straw is sent to a dryer and dried at 60 ° C for 4 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization. The median diameter after the initial pulverization is 200 μm, and then the initial pulverization is carried out. The cotton straw is sent to a briquetting machine for compression extrusion molding at a temperature of 50 ° C and a pressure of 2 MPa, followed by secondary pulverization, and the median diameter after secondary pulverization is 40 μm, and the cotton after secondary pulverization The bulk density of the straw is 450kg/m ³ , which is reserved.

Preparation of the first catalyst

(1) taking biomass carbon as the first biomass carbon carrier;

(2) The iron hydroxide and the iron oxide are supported on the first biomass carbon carrier and vulcanized to obtain a first catalyst.

The specific method of supporting iron hydroxide and iron oxide on the first biomass carbon carrier is as follows:

The first biomass carbon carrier, an aqueous solution of iron hydroxide and iron oxide is mixed to prepare a suspension, and an aqueous solution of ammonia water and potassium hydroxide as a precipitating agent is added to precipitate iron hydroxide and iron oxide in the first biomass carbon carrier. First, the first catalyst is prepared by washing, drying and vulcanization, the temperature of the precipitation process is 60 ° C, the pH is 8, and the iron hydroxide is determined by the total mass of the iron hydroxide, the iron oxide and the first biomass carbon carrier. The total content of iron oxide and iron oxide is 30% by weight; the particle diameter of the first catalyst is 5 to 500 μm.

Preparation of second catalyst

S1, after the acid carbon is acidified, the second biomass carbon carrier is prepared, wherein the acid concentration of the H ⁺ substance in the acidified acid medium is 3 mol/L, and the volume ratio of the biomass carbon to the acidic medium is 1: 10, the acidification temperature is 50 ° C, the acidification time is 6 h;

S2, mixing Pd oxide, Ni oxide and second biomass carbon carrier, vibrating and ball milling the above mixture to a particle size of 100-400 μm, and vulcanizing to obtain a second catalyst; using Pd oxide, Ni The total content of the Pd oxide and the Ni oxide is 5% by weight based on the total mass of the oxide and the second biomass carbon support.

Preparation of biomass slurry

The pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of heavy oil and washing oil to be emulsified and pulped to form a slurry. The total content of the cotton straw in the slurry is 55 wt%. The viscosity of the slurry is 600mPa. s (50 ° C), in the above slurry, the content of the first catalyst was 2% by weight.

Liquefaction reaction:

(1) introducing hydrogen into the biomass slurry to generate a first-stage hydrogenation reaction, the reaction pressure is 20 MPa, and the reaction temperature is 300 ° C to obtain a first-stage hydrogenation product;

(2) adding a second catalyst to the primary hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, the reaction pressure is 20 MPa, the reaction temperature is 420 ° C, and a secondary hydrogenation product is obtained, and the secondary hydrogenation is added. The hydrogen product is subjected to hydrogenation reforming at a pressure of 23 MPa and a temperature of 250 ° C to collect the oil phase to obtain a bio-oil; wherein the second catalyst is added in an amount of 1 wt% of the mass of the first-stage hydrogenation product;

In the step (1), the specific method of introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 700:1, thereby forming a first-stage reaction raw material; Into the first slurry bed reactor to generate a first-stage hydrogenation reaction, while injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the total gas velocity in the first slurry-bed reactor to be 0.1 m/s Wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen is 22 MPa, and the temperature of the high pressure cold hydrogen is 95 ° C;

In the step (2), the specific method of introducing hydrogen gas is: raising the mixture of the primary hydrogenation product and the second catalyst to 420 ° C, and then feeding the mixture into the second slurry bed reactor and passing the high pressure. The high-temperature hydrogen gas is subjected to the second-stage hydrogenation reaction, and at the same time, the high-pressure cold hydrogen is injected into the second slurry-bed reactor, and the total gas velocity in the second slurry-bed reactor is controlled to be 0.08 m/s, and the high-pressure high-temperature hydrogen gas is The volume ratio of the first-stage hydrogenation product is 1200:1; wherein the pressures of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen are both 22 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 450 ° C, and the temperature of the high-pressure cold hydrogen is 85 °C.

The high pressure cold hydrogen is injected through four injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor. The first catalyst in the first slurry bed reactor accounts for 10% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 20 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 40 min, and the time of the second hydrogenation reaction is 45 min.

Example 4

A multi-stage liquefaction process for biomass comprising the following steps:

Biomass pretreatment

The olive oil residue is sent to a dryer and dried at 85 ° C for 4.5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization treatment. The median diameter after the initial pulverization is 150 μm, and then the initial The pulverized olive oil slag is sent to a plodder and subjected to compression extrusion at a temperature of 45 ° C and a pressure of 3.5 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 35 μm. The bulk density after the secondary pulverization was 1,535 kg/m ³ , and was used.

Preparation of biomass slurry

The pretreated biomass is mixed with the vulcanized amorphous iron oxyhydroxide (having a particle diameter of 50 to 500 μm) as a first catalyst to obtain a mixture, and the mixture is added to an rancid oil to be sheared and formed. The slurry, after testing, the total content of the olive oil residue in the slurry is 62% by weight, and the viscosity of the slurry is 600 mPa. s (50 ° C), the content of amorphous iron oxyhydroxide in the above slurry was 2% by weight.

Liquefaction reaction:

(1) introducing hydrogen into the biomass slurry to generate a first-stage hydrogenation reaction, the reaction pressure is 16 MPa, and the reaction temperature is 320 ° C to obtain a first-stage hydrogenation product;

(2) mixing the amorphous alumina loaded with W oxide and Ni oxide as the second catalyst with the rancid oil at a mass ratio of 2:10 to prepare a catalyst slurry to the primary hydrogenation product The catalyst slurry is added and hydrogen is introduced to generate a secondary hydrogenation reaction, the reaction pressure is 16 MPa, the reaction temperature is 430 ° C, and a secondary hydrogenation product is obtained, and the secondary hydrogenation product is separated to collect the oil phase. Obtaining bio-oil;

Wherein, the amount of the amorphous alumina supported as the second catalyst with W oxide and Ni oxide is 0.5% by weight of the mass of the primary hydrogenation product, and the particle size of the second catalyst to be added is 50 -400μm;

In the step (1), the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, and heat-treating the slurry to 250 ° C. And then injecting high-pressure high-temperature hydrogen into the slurry for a second time; wherein, the temperature of the high-pressure medium-temperature hydrogen is 350 ° C, the temperature of the high-pressure high-temperature hydrogen is 360 ° C; the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen introduced into the slurry a volume ratio of 800:1 to form a primary reaction feedstock; the primary reaction feedstock is fed to a first slurry bed reactor to effect a primary hydrogenation reaction while simultaneously to the first slurry bed reactor Injecting high-pressure cold hydrogen into the reactor, controlling the total gas velocity in the first slurry-bed reactor to be 0.05 m/s; wherein, the pressures of the high-pressure hydrogen and the high-pressure cold hydrogen are both 22 MPa, and the temperature of the high-pressure cold hydrogen is 65 ° C;

In the step (2), the specific method of introducing hydrogen gas is: heating the mixture of the primary hydrogenation product and the second catalyst to 430 ° C, and then feeding the mixture into the second slurry bed reactor and passing the high pressure. The high-temperature hydrogen gas is subjected to the second-stage hydrogenation reaction, and at the same time, the high-pressure cold hydrogen is injected into the second slurry-bed reactor, and the total gas velocity in the second slurry-bed reactor is controlled to be 0.07 m/s, and the high-pressure high-temperature hydrogen gas is The volume ratio of the first-stage hydrogenation product is 1450:1; wherein the pressures of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen are both 25 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 470 ° C, and the temperature of the high-pressure cold hydrogen is 120 °C.

The high pressure cold hydrogen is injected through five injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor. The first catalyst in the first slurry bed reactor accounts for 10% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 15 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 50 min, and the time of the second hydrogenation reaction is 50 min.

Example 5

A process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Biomass pretreatment

The pea straw, the sorghum straw and the rice straw are sent to a dryer and dried at 50 ° C for 3 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization, and the median diameter after the initial pulverization is 250 μm. Then, the initially pulverized pea straw, sorghum straw and rice straw are fed into a plodder at a temperature of 55 ° C and a pressure of 1.5 MPa for compression extrusion molding, followed by secondary pulverization, and the median after secondary pulverization. The particle size was 45 μm, and the bulk density after secondary pulverization was 440 kg/m ³ , which was used.

Preparation of biomass slurry

Mixing the pretreated biomass with the sulfurized amorphous iron oxyhydroxide as a catalyst to obtain a mixture, and adding the above mixture to a mixed oil of hydrophobic oil and residual oil to homogenize pulping to form a slurry, which is tested. The total content of pea straw, sorghum straw and rice straw in the slurry is 40wt%, and the viscosity of the slurry is 820mPa. s (50 ° C), the content of amorphous iron oxyhydroxide was 8 wt%, and the particle size of the amorphous iron oxyhydroxide added was 300 μm.

Hydrolysis hydrogenation reaction:

Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 17 MPa and the reaction temperature is 420 ° C to prepare a bio-oil;

The specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, and heat-treating the slurry to 420 ° C, and then to the slurry. The second injection of high-pressure high-temperature hydrogen; wherein, the temperature of the high-pressure medium-temperature hydrogen is 420 ° C, the temperature of the high-pressure high-temperature hydrogen is 430 ° C; the volume ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the slurry is 900: 1, thereby forming a reaction feedstock; the reaction feedstock fed to the hydrogenation reaction of the hydrolysis slurry bed reactor occurs while injecting hydrogen into the cold high pressure above the slurry bed reactor, control of the total gas in the slurry bed reactor The speed is 0.08 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen is 20 MPa, the temperature of the high pressure cold hydrogen is 95 ° C;

The high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounted for 25 wt% of the liquid phase mass in the slurry bed reactor, and the reaction time was 50 min.

Example 6

A process for hydrolyzing hydrogenation of biomass, comprising the following steps:

Biomass pretreatment

The soybean oil residue is sent to a dryer and dried at 95 ° C for 2.5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization. The median diameter after the initial pulverization is 300 μm, and then the initial pulverization is performed. The soybean oil residue is sent to a plodder for compression extrusion at a temperature of 58 ° C and a pressure of 3.1 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 48 μm, after secondary pulverization The bulk density is 1512 kg/m ³ and is ready for use.

Preparation of biomass slurry

Mixing the pretreated biomass with the sulfurized amorphous iron oxyhydroxide as a catalyst to obtain a mixture, adding the above mixture to a mixed oil of eucalyptus oil and circulating distillate, stirring and slurrying to form a slurry; The content of soybean oil residue in the slurry is 65 wt%, and the viscosity of the slurry is 691 mPa. s (50 ° C), the content of amorphous iron oxyhydroxide was 0.3% by weight, and the particle size of the amorphous iron oxyhydroxide to be added was 20 μm.

Hydrolysis hydrogenation reaction:

Hydrogen was introduced into the biomass slurry to react, and the reaction pressure was 19 MPa and the reaction temperature was 390 ° C to prepare a bio-oil;

The specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, heat-treating the slurry to 390 ° C, and then to the slurry. The second injection of high-pressure high-temperature hydrogen; wherein, the temperature of the high-pressure medium-temperature hydrogen is 400 ° C, the temperature of the high-pressure high-temperature hydrogen is 490 ° C; the volume ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the slurry is 800: 1, thereby forming a reaction raw material; feeding the above-mentioned reaction raw material into a slurry bed reactor to generate a hydrolyzation hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas in the slurry-bed reactor The speed is 0.07 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen is 22 MPa, the temperature of the high pressure cold hydrogen is 105 ° C;

The high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounted for 23% by weight of the liquid phase mass in the slurry bed reactor, and the reaction time was 100 min.

Example 7

A multi-stage liquefaction process for biomass comprising the following steps:

Biomass pretreatment

The hemp stalk and the broad bean stalk are sent to a dryer and dried at 65 ° C for 3 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for initial pulverization. The median diameter after the initial pulverization is 260 μm, and then the initial The pulverized hemp stalk and the broad bean stalk are sent to a plodder for compression extrusion at a temperature of 50 ° C and a pressure of 0.5 MPa, followed by secondary pulverization, and the median diameter of the biomass after secondary pulverization It is 30 μm, and the bulk density after secondary pulverization is 410 kg/m ³ , which is reserved.

Preparation of the first catalyst

(1) selecting biomass charcoal as the first biomass carbon carrier;

(2) The iron oxide is supported on the first biomass carbon carrier and vulcanized to obtain a first catalyst.

The specific method of supporting iron oxide on the above first biomass carbon carrier is:

The first biomass carbon carrier and the aqueous solution of iron oxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydroxide and ammonia water as a precipitating agent is added, and the iron oxide is precipitated on the first biomass carbon carrier, washed, dried, and vulcanized. The first catalyst is prepared, the temperature of the precipitation process is 80 ° C, the pH is 7.5, and the content of iron oxide is 50 wt% based on the total mass of the iron oxide and the first biomass carbon carrier; the particle diameter of the first catalyst is 10-450 μm.

Preparation of second catalyst

After the alkalizing treatment of the biomass carbon, the second biomass carbon carrier is prepared, and the amount of the OH- substance in the alkalized alkaline medium is 0.5 mol/L, and the biomass carbon and the alkaline medium are used. The volume ratio is 1:15, the alkalization temperature is 30 ° C, and the acidification time is 10 h;

S2, mixing Pd oxide, Mo oxide and second biomass carbon carrier, vibrating and ball milling the above mixture to a particle size of 100-500 μm, and vulcanizing to obtain a second catalyst; using Pd oxide, Mo The total content of the Pd oxide and the Mo oxide is 4% by weight based on the total mass of the oxide and the second biomass carbon carrier.

Preparation of biomass slurry

The pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to the trench oil to be dispersed and pulped to form a slurry. The total content of the cannabis straw and the broad bean straw in the slurry is determined to be 40% by weight. The viscosity is 1200mPa. s (50 ° C), the content of the first catalyst in the above slurry was 0.2% by weight.

Liquefaction reaction:

(1) introducing hydrogen into the biomass slurry to generate a first-stage hydrogenation reaction, the reaction pressure is 25 MPa, and the reaction temperature is 350 ° C to obtain a first-stage hydrogenation product;

(2) adding a second catalyst to the primary hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction at a reaction pressure of 25 MPa and a reaction temperature of 400 ° C to obtain a secondary hydrogenation product, the secondary After the hydrogenation product is separated, the oil phase is collected to obtain a bio-oil;

Wherein, the dosage of the second catalyst is 0.8 wt% of the mass of the first-stage hydrogenation product; in the step (1), the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry, and controlling the high-pressure hydrogen and the slurry. The volume ratio is 600:1 to form a first-stage reaction raw material; the first-stage reaction raw material is sent to the first slurry-bed reactor to generate a primary hydrogenation reaction, and at the same time, a high pressure is injected into the first slurry-bed reactor. Cold hydrogen, controlling the total gas velocity in the first slurry bed reactor is 0.2 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen are 27 MPa, the temperature of high pressure cold hydrogen is 50 ° C;

In the step (2), the specific method of introducing hydrogen gas is: heating the mixture of the primary hydrogenation product and the second catalyst to 400 ° C, and then feeding the mixture to the second slurry bed reactor. And introducing high-pressure high-temperature hydrogen gas to generate a second-stage hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the second slurry-bed reactor, and controlling the total gas velocity in the second slurry-bed reactor to be 0.06 m/s, and the volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is 1500:1; wherein the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen have a pressure of 27 MPa, and the high-pressure high-temperature hydrogen has a temperature of 430 °C, the temperature of the high pressure cold hydrogen is 50 °C.

The high pressure cold hydrogen is injected through three injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor. The first catalyst in the first slurry bed reactor accounts for 5% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 30 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 30 min, and the time of the second hydrogenation reaction is 90 min.

Example 8

A multi-stage liquefaction process for biomass comprising the following steps:

Biomass pretreatment

The peanut oil residue is sent to a dryer and dried at 80 ° C for 2 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization. The median diameter after initial pulverization is 160 μm, and then the initial pulverization is performed. Peanut oil residue is sent to a briquetting machine for compression extrusion at a temperature of 40 ° C and a pressure of 3 MPa, followed by secondary pulverization treatment. The median diameter of the biomass after secondary pulverization is 45 μm, twice. The pulverized bulk density was 1510 kg/m ³ and was used.

Preparation of the first catalyst

(1) selecting biomass charcoal as the first biomass carbon carrier;

(2) The iron oxyhydroxide is supported on the first biomass carbon carrier and vulcanized to obtain a first catalyst.

The specific method for supporting the iron oxyhydroxide on the first biomass carbon carrier is as follows:

The first biomass carbon carrier and the aqueous solution of iron oxyhydroxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydroxide and ammonia water as a precipitating agent is added, and the iron oxyhydroxide is precipitated on the first biomass carbon carrier, washed and dried. And vulcanization treatment to obtain a first catalyst, the temperature of the precipitation process is 40 ° C, the pH value is 8.5, and the content of iron oxyhydroxide is 50 wt% based on the total mass of the iron oxyhydroxide and the first biomass carbon carrier; the first catalyst The particle size is 110-250 μm.

Preparation of second catalyst

S1, the biomass carbon is alkalized to obtain a second biomass carbon carrier, wherein the alkalinized alkaline medium has a concentration of OH ^- 5 mol / L, dry distillation biomass carbon and alkaline medium The volume ratio is 1:5, the alkalization temperature is 80 ° C, and the acidification time is 1 h;

S2, mixing Pd oxide, Mo oxide and second biomass carbon carrier, vibrating and ball milling the above mixture to a particle size of 30-250 μm, and vulcanizing to obtain a second catalyst; Pd oxide, Mo The total content of the Pd oxide and the Mo oxide is 1.5% by weight based on the total mass of the oxide and the second biomass carbon carrier.

Preparation of biomass slurry

The pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to the trench oil to be emulsified and pulped to form a slurry. The total content of the peanut oil residue in the slurry is 65 wt%, and the viscosity of the slurry is 690mPa. s (50 ° C), the content of the first catalyst in the above slurry was 4% by weight.

Liquefaction reaction:

(1) introducing hydrogen into the biomass slurry to generate a first-stage hydrogenation reaction, the reaction pressure is 25 MPa, and the reaction temperature is 300 ° C to obtain a first-stage hydrogenation product;

(2) mixing the second catalyst with the waste oil in a ratio of 1.5:10 by mass to prepare a catalyst slurry, adding the catalyst slurry to the primary hydrogenation product and introducing hydrogen to generate secondary hydrogenation The reaction has a reaction pressure of 25 MPa and a reaction temperature of 450 ° C to obtain a secondary hydrogenation product, and the secondary hydrogenation product is separated to collect an oil phase to obtain a bio-oil;

Wherein the dosage of the second catalyst is 1.4 wt% of the mass of the first-stage hydrogenation product;

In the step (1), the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen gas to the slurry to be 800:1, thereby forming a first-stage reaction raw material; a first-stage hydrogenation reaction occurs in a slurry-bed reactor, and high-pressure cold hydrogen is injected into the first slurry-bed reactor to control the total gas velocity in the first slurry-bed reactor to be 0.1 m/s; The pressure of high pressure hydrogen and high pressure cold hydrogen is 26 MPa, and the temperature of high pressure cold hydrogen is 70 ° C;

In the step (2), the specific method of introducing hydrogen gas is: raising the mixture of the primary hydrogenation product and the second catalyst to 450 ° C, and then feeding the mixture to the second slurry bed reactor. And introducing high-pressure high-temperature hydrogen gas to generate a second-stage hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the second slurry-bed reactor, and controlling the total gas velocity in the second slurry-bed reactor to be 0.09 m/s, and the volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is 1100:1; wherein the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen have a pressure of 27 MPa, and the high-pressure high-temperature hydrogen has a temperature of 460 °C, the temperature of the high pressure cold hydrogen is 60 °C.

The high pressure cold hydrogen is injected through three injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor. The first catalyst in the first slurry bed reactor accounts for 23% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 30 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 50 min, and the time of the second hydrogenation reaction is 85 min.

Test example 1

The distribution of the products prepared by the methods of Examples 1-8 of the present invention was compared as shown in Table 1 below.

Table 1 Comparison of product distribution of Examples 1-8

It can be seen from Table 1 that the biomass conversion obtained by the method of the present invention is 95-99%, the oil phase yield is 71-86%, the residue amount is less than 0.1 wt%, and the carbon content in the obtained oil phase is 73-90 wt%, a hydrogen content of 5-17 wt%, and an oxygen content of 0.1-10 wt%. And the two-stage reaction can further reduce the oxygen content in the oil phase.

The following are examples of the co-liquefaction process of coal and biomass provided by the present invention. The calculation formulas of coal and biomass conversion, bio-oil yield and residue content in the following examples and comparative examples are as follows:

Coal to biomass conversion = (quality of liquefied reaction product - mass of catalyst - quality of solvent oil) / (mass and biomass of coal and biomass)

Bio-oil yield = mass of oil phase obtained after separation of liquefied reaction product / (mass and biomass of coal and biomass)

Residue content = residue quality / (mass and biomass quality).

Example 9

A co-liquefaction process of coal and biomass, comprising the following steps:

The lignite was taken, dried and dehydrated, and pulverized to a median diameter of 50 μm, and then extruded at 30 ° C to a molding pressure of 15 MPa to obtain a brown coal compressed material. The lignite compressed material was pulverized to obtain a lignite pulverized material having a particle diameter of 30 μm. The above-mentioned lignite pulverized material is added to the mixture of liquid slag and waste engine oil together with the amorphous iron oxyhydroxide after vulcanization in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry to occur. The reaction was controlled to a reaction pressure of 16 MPa and a reaction temperature of 480 ° C to finally obtain a bio-oil.

Example 10

A co-hydrolysis hydrogenation process of coal and biomass, comprising the following steps:

Straw pretreatment:

(1) The straw is taken, dried and dehydrated, pulverized to a median particle size of 100 μm, and then sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 2 MPa to obtain a straw compressed material.

(2) The straw compressed material is sent to a hammer mill to be pulverized to obtain a straw pulverized material having a median diameter of 30 μm, which is ready for use.

Pretreatment of coal raw materials:

(1) The lignite is taken, dried and dehydrated, pulverized to a median particle size of 100 μm, and then sent to a briquetting machine for extrusion molding at a molding pressure of 5 MPa to obtain a brown coal compressed material.

(2) The lignite compressed material is sent to a ball mill and pulverized to obtain a lignite pulverized material having a median diameter of 100 μm, which is ready for use.

Preparation and Hydrolysis Hydrogenation of Biomass Coal Water Slurry:

The straw pulverized material and the lignite pulverized material are subjected to ash removal, and then mixed with the oxidized iron oxide-loaded biomass carbon to obtain a mixture, and the mixture is added to water to form the biomass coal water slurry. The biomass coal water slurry is subjected to hydrogen gas to react, and the reaction pressure is controlled to 15 MPa, the reaction temperature is 300 ° C, and the reaction is carried out for 30 minutes to finally obtain a bio-oil.

In this embodiment, the biomass carbon loaded with iron oxide is prepared by the following method:

(1) selecting biomass charcoal as a biomass carbon carrier;

(2) The sulfurized iron oxide is supported on the biomass carbon carrier to prepare the catalyst.

The specific method of supporting the sulfurized iron oxide on the biomass carbon carrier is:

The biomass carbon carrier and the sulfurized iron oxide aqueous solution are mixed and formulated into a suspension, and the sulfided iron oxide is precipitated on the biomass carbon carrier by adding a precipitating agent, and the catalyst is obtained by washing and drying. Wherein the precipitating agent is aqueous ammonia and sodium carbonate solution, and the temperature of the precipitation process is controlled to 30 ° C and the pH is 7.

The iron oxide content is 10% by weight based on the total mass of the iron oxide and the biomass carbon.

Example 11

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Pretreatment of biomass feedstock:

(1) The reed is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment to obtain a repulver primary pulverized material having a particle diameter D ₅₀ of 300 μm.

(2) The reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 5 MPa to obtain a reed compressed material.

(3) The reed compressed material is sent to a jet mill to be subjected to secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D ₅₀ is 50 μm, which is ready for use.

Pretreatment of coal raw materials:

(1) Take the Shendong long flame coal, dry it and dehydrate it, then send it to the ball mill for pulverization treatment, and obtain the first pulverized material of Shendong long flame coal with a particle diameter D ₅₀ of 80 μm.

(2) The smashing material of Shendong Changyan coal is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 12 MPa, and the Shendong long flame coal compressed material is obtained.

(3) The Shendong long flame coal compressed material is sent to the ball mill for secondary pulverization, and the second pulverized material of Shendong Changyan coal is obtained, and the particle diameter D ₅₀ is 40 μm, which is ready for use.

Of course, as an alternative to the embodiment, the reed compressed material and the Shendong long flame coal compressed material may be separately mixed with a portion of the waste engine oil and then sent to the ball mill for the second pulverization.

Preparation and hydrogenation of biomass kerosene slurry:

The secondary pulverized material of the reed and the coal is mixed with the carbon oxyhydroxide-loaded biomass carbon after the sulfidation treatment in the reactor to obtain a mixture, and the mixture is added to the waste engine oil to form the biomass. Kerosene slurry; as a preferred mode, the above-mentioned biomass kerosene slurry can continue to be treated by a colloid mill, and the slurryability of the biomass kerosene slurry can be continuously improved.

Hydrogen is introduced into the biomass kerosene slurry to generate a primary hydrogenation reaction to obtain a primary hydrogenation product; and a primary hydrogenation product is added to the reactor to be vulcanized and loaded with Pd oxide and Ni oxide. The biomass carbon is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is separated to finally obtain a bio-oil.

Among them, the pressure for controlling the two reactions was 17 MPa, the temperature of the first hydrogenation reaction was 310 ° C, the reaction time was 45 min, the temperature of the second hydrogenation reaction was 460 ° C, and the reaction time was 70 min. In the biomass kerosene slurry, the content of the reed is 25 wt%, the content of the coal is 45 wt%, the content of the first catalyst is 0.1 wt%, and the particle diameter of the first catalyst is 500 μm; The second catalyst is added in an amount of 0.5% by weight of the first-stage hydrogenated product, the second catalyst has a particle diameter of 500 μm; and the second catalyst is added to the first-stage hydrogenated product. The method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mixing the second catalyst with the waste engine oil at a mass ratio of 1:10 to prepare the catalyst slurry. .

Example 12

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Pretreatment of biomass feedstock:

(1) Take the leaves and melons, dry them and dehydrate them, and then send them to a jet mill for pulverization treatment to obtain primary pulverized materials of leaves and melons, and the particle diameter D ₅₀ is 240 μm.

(2) The pulverized material of leaves and melons is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 2 MPa, and the leaves and melon and fruit compressed materials are obtained.

(3) The leaves and melons and compressed materials are sent to a jet mill for secondary pulverization to obtain secondary pulverized materials of leaves and melons, and the particle diameter D ₅₀ is 30 μm, which is ready for use.

Pretreatment of coal raw materials:

(1) Take the Shendong long flame coal, dry it and dehydrate it, then send it to the ball mill for pulverization treatment, and obtain the first pulverized material of Shendong long flame coal with a particle diameter D ₅₀ of 100 μm.

(2) The smashing material of Shendong Changyan coal is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 12 MPa, and the Shendong long flame coal compressed material is obtained.

(3) The Shendong long flame coal compressed material is sent to the ball mill for secondary pulverization, and the second pulverized material of Shendong Changyan coal is obtained, and the particle diameter D ₅₀ is 30 μm, which is ready for use.

Preparation and Hydrolysis Hydrogenation of Biomass Coal Water Slurry:

After the ash is removed from the secondary pulverized material of the leaves and the melon, the mixture is mixed with the carbonic acid-loaded biomass carbon in the reactor to obtain a mixture, and the mixture is added to the water to form the biomass coal water slurry. ;

Hydrogen is introduced into the biomass coal water slurry to generate a primary hydrogenation reaction to obtain a first-stage hydrogenation product; and then a Mo-oxide and a Co oxide supported in the reactor are vulcanized to the primary hydrogenation product. The biomass carbon is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, which is separated to finally obtain a bio-oil.

Among them, the pressure for controlling the two reactions is 18 MPa, the temperature of the first hydrogenation reaction is 240 ° C, the reaction time is 50 min, the temperature of the second hydrogenation reaction is 380 ° C, and the reaction time is 30 min. In the biomass coal water slurry, the content of the leaves and melons is 20% by weight, the content of the coal is 40% by weight, the content of the first catalyst is 2% by weight, and the particle size of the first catalyst 400 μm; the second catalyst is added in an amount of 0.8% by weight of the first-stage hydrogenated product, the second catalyst has a particle diameter of 400 μm; and the second catalyst is added to the first stage Before the hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mixing the second catalyst with water at a mass ratio of 2:10 to prepare the catalyst slurry. .

Example 13

A co-liquefaction process of coal and biomass, comprising the following steps:

Pretreatment of biomass feedstock:

(1) The algae is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment to obtain an algal primary pulverized material having a particle diameter D ₅₀ of 200 μm.

(2) The algae primary pulverized material is sent to a briquetting machine or a beading machine for extrusion molding at 45 ° C, and the molding pressure is 2 MPa to obtain an algae compressed material.

(3) The algae compressed material was sent to a jet mill to be subjected to secondary pulverization to obtain an algal secondary pulverized material having a particle diameter D ₅₀ of 40 μm, which was used.

Pretreatment of coal raw materials:

(1) The lignite is taken, dried and dehydrated, and then sent to a ball mill for pulverization treatment to obtain a lignite primary pulverized material having a particle diameter D ₅₀ of 80 μm.

(2) The lignite primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding at 60 ° C, and the molding pressure is 15 MPa to obtain a brown coal compressed material.

(3) The brown coal compressed material is sent to a ball mill for secondary pulverization to obtain a brown coal secondary pulverized material having a particle diameter D ₅₀ of 30 μm, which is ready for use.

The above-mentioned algae and lignite secondary pulverized material are screened, and the >100 μm algae is separated from the lignite, and then put into the compression section or the second pulverization step to be treated again with the subsequent feed to obtain a more uniform particle size. Thereby obtaining a more stable biomass kerosene slurry.

Preparation and liquefaction of biomass kerosene slurry:

The secondary pulverized material of the algae and lignite is subjected to ash removal and mixed with the amorphous iron oxyhydroxide after vulcanization in the reactor to obtain a mixture, and the mixture is added to the bio-oil prepared by the process, thereby forming a The biomass kerosene slurry is introduced into the biomass kerosene slurry to generate a reaction, and the reaction pressure is controlled to 20 MPa and the reaction temperature is 390 ° C to obtain a bio-oil. Among them, sulfur and amorphous iron oxyhydroxide were mixed at a mass ratio of 0.4:1 to obtain a catalyst. In the biomass kerosene slurry, the content of the algae is 20% by weight, the content of the coal is 40% by weight, the content of the catalyst is 4% by weight, and the particle diameter of the catalyst is 300 μm.

The specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the biomass kerosene slurry, and controlling a volume ratio of the high-pressure hydrogen gas to the biomass kerosene slurry to be 600:1, thereby forming a reaction raw material; The reaction raw material is sent to the slurry bed reactor to generate liquefaction, cracking and hydrogenation reaction, and high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor. 0.2 m/s; wherein the pressures of the high pressure hydrogen gas and the high pressure cold hydrogen are both 13 MPa, and the temperature of the high pressure cold hydrogen is 135 °C.

Example 14

A co-hydrolysis hydrogenation process of coal and biomass, comprising the following steps:

Pretreatment of biomass feedstock:

(1) Soybean oil slag is taken, dried and dehydrated, and then sent to an ultrafine pulverizer for pulverization treatment to obtain a primary pulverized material of soybean oil slag, and the particle diameter D ₅₀ is 150 μm.

(2) The soybean slag oil slag primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 4 MPa, and the soybean oil slag compressed material is obtained.

(3) The soybean oil slag compressed material is sent to an ultrafine pulverizer for secondary pulverization to obtain a secondary pulverized material of soybean oil slag, and the particle diameter D ₅₀ is 45 μm, which is ready for use.

Pretreatment of coal raw materials:

(1) Take the Shendong long flame coal, dry it and dehydrate it, then send it to the ball mill for pulverization treatment, and obtain the first pulverized material of Shendong long flame coal with a particle diameter D ₅₀ of 90 μm.

(2) The first pulverized material of Shendong Changyan coal is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 10 MPa, and the Shendong long flame coal compressed material is obtained.

(3) The Shendong long flame coal compressed material is sent to the ball mill for secondary pulverization, and the second pulverized material of Shendong long flame coal is obtained, and the particle diameter D ₅₀ is 60 μm, which is ready for use.

The secondary pulverized material of Shendong Changyan coal and soybean oil slag is added to water together with the amorphous iron oxyhydroxide after vulcanization treatment in the reactor to form the biomass coal water slurry. As a further preferred mode, the above The biomass coal water slurry can continue to be treated by a colloid mill, and the slurryability of the biomass coal water slurry can be continuously improved.

Hydrogen was introduced into the biomass coal water slurry to react, and the reaction pressure was 22 MPa, the reaction temperature was 410 ° C, and the reaction time was 60 min, and finally a bio-oil was obtained. Among them, sulfur and amorphous iron oxyhydroxide are mixed at a mass ratio of 0.8:1 to obtain a catalyst. In the biomass coal water slurry, the soybean oil slag content is 25 wt%, the coal content is 40 wt%, the catalyst content is 6 wt%, and the catalyst has a particle diameter of 200 μm.

The specific method for introducing hydrogen gas is: after injecting high-pressure medium-temperature hydrogen gas with a pressure of 18 MPa and a temperature of 350 ° C for the first time into the biomass coal water slurry, and heat-heating the biomass coal water slurry Up to 200 ° C, and then injecting a high pressure and high temperature hydrogen gas having a pressure of 18 MPa and a temperature of 510 ° C into the biomass coal water slurry for a second time, and controlling the volume of the twice injected high pressure hydrogen gas and the biomass coal water slurry The ratio is 700:1 to form a reaction raw material; the reaction raw material is sent to a slurry bed reactor to undergo hydrolysis, cracking and hydrogenation reaction, and a pressure of 18 MPa and a temperature are injected into the slurry bed reactor. For high pressure cold hydrogen at 100 ° C, the cold hydrogen was injected via 5 injection ports on the side wall of the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.08 m/s.

Example 15

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Treatment of biomass and coal raw materials:

Take rice straw, palm oil residue and lignite, dry and dehydrate it, pulverize to a median particle size of 100μm, and then send it to a briquetting machine or a plodder for extrusion molding. The molding pressure is 5MPa, and the rice straw is obtained. Palm oil residue and compressed material of lignite. The compressed material was sent to a ball mill and pulverized to obtain rice straw and palm oil slag having a median diameter of 35 μm and a pulverized material of lignite, which were used.

Preparation and liquefaction hydrogenation of biomass kerosene slurry:

After the pulverized material is degreased, it is mixed with the amorphous iron oxyhydroxide which has been vulcanized in the reactor to obtain a mixture, and the mixture is added to the mixed coal tar and petroleum to form the biomass kerosene slurry. Hydrogen is introduced into the biomass kerosene slurry to generate a first-stage hydrogenation reaction to obtain a first-stage hydrogenation product; then, the first-stage hydrogenation product is added to the first-stage hydrogenation product, and the W-oxide and Ni oxide are oxidized in the reactor. The amorphous alumina of the material is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is finally separated to obtain a bio-oil; the pressure is 7 MPa and the temperature is 460. The step of hydro-reforming the secondary hydrogenation product under the conditions of °C.

Among them, the pressure for controlling the two reactions is 23 MPa, the temperature for the first hydrogenation reaction is 290 ° C, the temperature for the secondary hydrogenation reaction is 400 ° C, the time for the first hydrogenation reaction is 40 min, and the secondary hydrogenation reaction is carried out. The first catalyst was prepared by mixing sulfur and amorphous iron oxyhydroxide in a mass ratio of 0.6:1 for 35 minutes. In the biomass kerosene slurry, the content of the palm oil slag is 10% by weight, the content of the rice straw is 15% by weight, the content of the coal is 40% by weight, and the content of the first catalyst is 8% by weight. The first catalyst has a particle diameter of 100 μm; the second catalyst is added in an amount of 1.8 wt% of the first-stage hydrogenated product, and the second catalyst has a particle diameter of 100 μm; Before the second catalyst is added to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mass ratio of the second catalyst to the solvent oil is 1: The catalyst slurry is prepared by mixing in proportion to 10; the solvent oil is animal oil and bio-oil prepared by the process.

The specific method for introducing hydrogen into the first-stage hydrogenation reaction in this embodiment is: after injecting high-pressure medium-temperature hydrogen gas having a pressure of 23 MPa and a temperature of 260 ° C for the first time into the biomass kerosene slurry, the raw The heat exchange of the material kerosene slurry is heated to 280 ° C, and then the second high pressure high temperature hydrogen gas having a pressure of 23 MPa and a temperature of 430 ° C is injected into the biomass kerosene slurry, and the two injected high pressure hydrogen gas and the biomass are controlled. The volume ratio of the kerosene slurry is 800:1, thereby forming a first-stage reaction raw material; the first-stage reaction raw material is sent into the first slurry-bed reactor to generate a primary hydrogenation reaction, and simultaneously to the first slurry state The bed reactor is filled with high pressure cold hydrogen having a pressure of 23 MPa and a temperature of 80 ° C, and the high pressure cold hydrogen is injected through four injection ports on the side wall of the first slurry bed reactor to control the first slurry state. The total gas velocity in the bed reactor was 0.05 m/s.

In the present embodiment, the hydrogen is introduced into the second hydrogenation reaction by heating the mixture of the primary hydrogenation product and the second catalyst to 440 ° C, and then feeding the mixture to the second slurry state. A high-pressure high-temperature hydrogen gas having a pressure of 23 MPa and a temperature of 440 ° C is introduced into the bed reactor to generate a secondary hydrogenation reaction, and a high pressure of 23 MPa and a temperature of 80 ° C is injected into the second slurry bed reactor. Cold hydrogen, the high pressure cold hydrogen is injected through four injection ports on the side wall of the second slurry bed reactor, and controls the total gas velocity in the second slurry bed reactor to be 0.07 m/s, and hydrogen gas The volume ratio to the primary hydrogenation product was 1350:1. The inventory of the first catalyst in the first slurry bed reactor is controlled at 5% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry bed The inventory in the reactor was controlled at 30 wt% of the liquid phase mass in the second slurry bed reactor.

Example 16

A multi-stage liquefaction process for coal and biomass, comprising the following steps:

Pretreatment of biomass feedstock:

(1) The reed is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment to obtain a repulver primary pulverized material having a particle diameter D ₅₀ of 300 μm.

(2) The reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 3 MPa to obtain a reed compressed material.

(3) The reed compressed material is sent to a jet mill to be subjected to secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D ₅₀ is 50 μm, which is ready for use.

Pretreatment of coal raw materials:

(1) The brown coal is taken, dried and dehydrated, and then sent to a ball mill for pulverization treatment to obtain a lignite primary pulverized material having a particle diameter D ₅₀ of 100 μm.

(2) The lignite primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 12 MPa to obtain a brown coal compressed material.

(3) The brown coal compressed material is sent to a ball mill for secondary pulverization to obtain a brown coal secondary pulverized material having a particle diameter D ₅₀ of 100 μm, which is ready for use.

Preparation and hydrolyzed hydrogenation process of biomass coal water slurry:

Mixing the secondary pulverized material of reed and lignite with the amorphous iron oxyhydroxide after vulcanization in the reactor to obtain a mixture, and adding the mixture to water to form the biomass coal water slurry; to the biomass Hydrogen is introduced into the coal water slurry to generate a first-stage hydrogenation reaction to obtain a first-stage hydrogenation product; then, to the first-stage hydrogenation product, a Pd-containing oxide and a Co-oxide-free oxide which are vulcanized in the reactor are added. The aluminum oxide is shaped and hydrogen is introduced to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is finally separated to obtain a bio-oil; and the conditions include a pressure of 23 MPa and a temperature of 250 ° C. The step of hydro-reforming the secondary hydrogenation product is carried out.

Among them, the pressure for controlling the two reactions is 20 MPa, the temperature of the first hydrogenation reaction is 280 ° C, the temperature of the second hydrogenation reaction is 400 ° C, the time of the first hydrogenation reaction is 60 min, and the second hydrogenation reaction The first catalyst was prepared by mixing sulfur and amorphous iron oxyhydroxide in a mass ratio of 1:1 for 30 min. In the biomass coal water slurry, the content of the first catalyst is 10 wt%, the particle diameter of the first catalyst is 5 μm; the dosage of the second catalyst is the mass of the first-stage hydrogenation product. 2 wt%, the second catalyst has a particle diameter of 5 μm; and before the addition of the second catalyst to the primary hydrogenation product, further comprising the step of formulating the second catalyst into a catalyst slurry, Specifically, the catalyst slurry is prepared by mixing the second catalyst with water at a mass ratio of 2:10.

The specific method for introducing hydrogen into the first-stage hydrogenation reaction in the present embodiment is: after injecting high-pressure medium-temperature hydrogen gas having a pressure of 27 MPa and a temperature of 180 ° C for the first time into the biomass coal water slurry, The heat transfer of the biomass coal water slurry is heated to 350 ° C, and then a second high pressure high temperature hydrogen gas with a pressure of 27 MPa and a temperature of 360 ° C is injected into the biomass coal water slurry, and the two injected high pressure hydrogen gas is controlled. The volume ratio of the biomass coal water slurry is 1000:1, thereby forming a first-stage reaction raw material; the first-stage reaction raw material is sent into the first slurry-bed reactor to generate a primary hydrogenation reaction, and at the same time In the first slurry bed reactor, a high pressure cold hydrogen having an injection pressure of 27 MPa and a temperature of 50 ° C is injected, and the high pressure cold hydrogen is injected through three injection ports on the side wall of the first slurry bed reactor, and the control station The total gas velocity in the first slurry bed reactor was 0.02 m/s.

The specific method of introducing hydrogen into the secondary hydrogenation reaction in this embodiment is: heating the mixture of the primary hydrogenation product and the second catalyst to 480 ° C, and then feeding the mixture to the second A high-pressure high-temperature hydrogen gas having a pressure of 27 MPa and a temperature of 430 ° C is introduced into the slurry bed reactor to generate a secondary hydrogenation reaction, and a pressure of 27 MPa and a temperature of 50 ° C are injected into the second slurry bed reactor. High pressure cold hydrogen, which is injected through three injection ports on the side wall of the second slurry bed reactor, and controls the total gas velocity in the second slurry bed reactor to be 0.06 m/s, And the volume ratio of hydrogen to the primary hydrogenation product is 1500:1. The inventory of the first catalyst in the first slurry bed reactor is controlled at 30 wt% of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry bed The inventory in the reactor was controlled at 5% by weight of the liquid phase mass in the second slurry bed reactor.

Comparative example 1

A co-liquefaction process of coal and biomass, comprising the following steps:

The lignite is taken, dried and dehydrated, and pulverized to a median particle size of 50 μm, and then sent to a briquetting machine or a plodder for extrusion molding at a molding pressure of 15 MPa to obtain a brown coal compressed material. The lignite compressed material was sent to a hammer mill to be pulverized to obtain a lignite pulverized material having a particle diameter of 30 μm. The above-mentioned lignite pulverized material is added to the mixture of liquid slag and waste engine oil together with the amorphous iron oxyhydroxide after vulcanization in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry to occur. The reaction was carried out, and the reaction pressure was controlled to 4 MPa, and the reaction temperature was 430 ° C to finally obtain a bio-oil.

Comparative example 2

A co-liquefaction process of coal and biomass, comprising the following steps:

The lignite is taken, dried and dehydrated, and pulverized to a median particle size of 50 μm, and then sent to a briquetting machine or a plodder for extrusion molding at a molding pressure of 15 MPa to obtain a brown coal compressed material. The lignite compressed material was sent to a hammer mill to be pulverized to obtain a lignite pulverized material having a particle diameter of 30 μm. The lignite pulverized material is added to a mixture of liquid slag and waste engine oil together with the oil-soluble dispersive hydrogenation catalyst which has been vulcanized in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry. The reaction was carried out, and the reaction pressure was controlled to 16 MPa, and the reaction temperature was 480 ° C to finally obtain a bio-oil.

The process effects of the examples of the present invention and the comparative examples were compared, and the results are shown in Table 2 below.

Table 2 Comparison of process effects of various examples and comparative examples

It can be seen from Table 2 that the co-conversion rate and the bio-oil yield of the biomass obtained by the process of the present invention are higher than those of the comparative examples 1-2, and the amount of residue is significantly reduced, thereby knowing The method of the invention can significantly improve the biomass conversion rate and the yield of bio-oil, and reduce the amount of residue. The secondary reaction can significantly reduce the residue content and the oxygen content in the oil phase.

It is apparent that the above-described embodiments are merely illustrative of the examples, and are not intended to limit the embodiments. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Obvious changes or variations resulting therefrom are still within the scope of the invention.

Claims (27)

A process for hydrolyzing hydrogenation of biomass, comprising the steps of: Preparing a slurry containing a catalyst and biomass, introducing hydrogen into the slurry to react, and controlling the reaction pressure and the reaction temperature to finally obtain a bio-oil; The slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the biomass, and then mixing with the catalyst to obtain a mixture, and adding the mixture to an oil to grind and slurry to obtain the slurry. ; The reaction is a first-order reaction, when the biomass is straw, the control reaction pressure is 15-20 MPa, the reaction temperature is 380-420 ° C; the concentration of the obtained slurry is 30-60 wt%; When the biomass is vegetable oil residue, the reaction pressure is controlled to be 15-20 MPa, the reaction temperature is 380-440 ° C; and the concentration of the obtained slurry is 50-65 wt%. The hydrolytic hydrogenation process of biomass according to claim 1, wherein the reaction is a secondary reaction comprising the following steps: (1) preparing a slurry containing the first catalyst and biomass, introducing hydrogen into the slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure and the reaction temperature to obtain a first-stage hydrogenation product; (2) adding a second catalyst to the primary hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure and the reaction temperature to obtain a secondary hydrogenation product, the secondary hydrogenation product After separation, the oil phase is collected to obtain a bio-oil; When the biomass is straw, the first hydrogenation reaction control reaction pressure is 15-25 MPa, the reaction temperature is 280-350 ° C; the secondary hydrogenation reaction control reaction pressure is 15-25 MPa, and the reaction temperature is 400-480 ° C. ; When the biomass is vegetable oil residue, the primary hydrogenation reaction control reaction pressure is 15-25 MPa, the reaction temperature is 250-350 ° C; the secondary hydrogenation reaction control reaction pressure is 15-25 MPa, and the reaction temperature is 380-480. °C. The process for hydrolyzing hydrogenation of biomass according to claim 1 or 2, wherein in the step of preparing the slurry, the straw is compressed at a pressure of 0.5 to 3 MPa and a temperature of 30 to 60 ° C; The vegetable oil residue is compressed at a pressure of 3 to 5 MPa and a temperature of 40 to 60 °C. The process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 3, wherein in the step of preparing the slurry, The drying temperature of the straw is 50-70 ° C, the time is 3-5 h, the moisture content of the straw after drying is less than 2 wt%; the median particle size after initial pulverization is 100-300 μm; the median after secondary pulverization The particle size is 30-50 μm, and the bulk density after secondary pulverization is 400-500 kg/m ³ ; The vegetable oil residue has a drying temperature of 80-110 ° C and a time of 2-6 h, and the water content of the vegetable oil residue after drying is less than 2 wt%; the median particle size after the initial pulverization is 100-300 μm; After the pulverization, the median particle size is 30 to 50 μm, and the secondary pulverization has a bulk density of 1,500 to 1600 kg/m ³ . The process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 4, characterized in that, in the slurry, the content of the straw is 55 to 60% by weight. The process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 5, wherein in the step of preparing the slurry, the oil is waste animal oil, waste mineral oil, mineral oil or fraction. One or more of the oils. The hydrolyzed hydrogenation process of the biomass according to any one of claims 1 to 6, wherein, in the slurry, when the reaction is a first-order reaction, the content of the catalyst is 0.1 to 10 wt%; The catalyst has a particle diameter of 5 μm to 500 μm; When the reaction is a secondary reaction, the content of the first catalyst is 0.1 to 10% by weight; the particle diameter of the first catalyst is 5 μm to 500 μm; The second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 μm to 500 μm; Before the adding the second catalyst to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically: The catalyst slurry is prepared by mixing the second catalyst and the solvent oil in a mass ratio of (1 to 2): 10; the solvent oil is waste animal and vegetable oil, waste mineral oil, mineral oil, and fraction One or more of oil or bio-oil produced by the process. A process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 7, wherein When the reaction is a first-order reaction, a specific method of introducing hydrogen into the slurry is: Injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a reaction raw material; The reaction raw material is sent to a slurry bed reactor to generate hydrolysis, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor. The speed is 0.02 ~ 0.2m / s, preferably 0.05 ~ 0.08m / s; Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen are both 15 to 22 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C; When the reaction is a secondary reaction, the specific method of introducing hydrogen into the slurry in the step (1) is: Injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a primary reaction raw material; And sending the first-stage reaction raw material into the first slurry-bed reactor to generate a first-stage hydrogenation reaction, and simultaneously injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the first slurry bed. The total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s; Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen are both 15 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C; The method of introducing hydrogen into step (2) is: The mixture of the primary hydrogenation product and the second catalyst is heated to 400 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas. To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and The volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is (1000-1500): 1; Wherein, the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 15-27 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C, and the temperature of the high-pressure cold hydrogen is 50-135 ° C. The hydrolytic hydrogenation process of biomass according to claim 8, wherein when the reaction is a first-order reaction, the high-pressure hydrogen gas is injected into the slurry twice, specifically: After injecting high-pressure medium-temperature hydrogen into the slurry for a first time, heat-treating the slurry to 380-420 ° C, and then injecting high-pressure high-temperature hydrogen into the slurry a second time; Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 360-420 ° C, and the temperature of the high-pressure high-temperature hydrogen gas is 430-510 ° C. The process for hydrolyzing hydrogenation of biomass according to claim 8 or 9, wherein when the reaction is a first-order reaction, the amount of the catalyst in the slurry bed reactor is controlled in the slurry 5 to 30 wt% of the liquid phase mass in the bed reactor; When the reaction is a secondary reaction, the amount of the first catalyst in the first slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the first slurry bed reactor. The amount of the second catalyst in the second slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the second slurry bed reactor. The process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 10, wherein when the reaction is a first-order reaction, the reaction time is 30-120 min; when the reaction is two In the stage reaction, the time of the first-stage hydrogenation reaction is 30 to 60 minutes, and the time of the second-stage hydrogenation reaction is 30 to 90 minutes. The process for hydrolyzing hydrogenation of biomass according to any one of claims 1 to 11, wherein when the reaction is a first-order reaction, the catalyst is a vulcanized biomass loaded with active components. Carbon, the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide; Or the catalyst is a vulcanized amorphous iron oxyhydroxide; When the reaction is a secondary reaction, the first catalyst is a vulcanized biomass char loaded with a first active component, the first active component being iron oxide, iron oxyhydroxide or iron hydroxide. One or more of the second catalysts; the vulcanized biochar loaded with a second active component, the second active component being Mo, Mn, W, Fe, Co, Ni or One or more of the oxides of Pd; Or the first catalyst is vulcanized amorphous iron oxyhydroxide, the second catalyst is a vulcanized amorphous alumina loaded with a third active component, and the third active component is selected from the periodic table of elements. One or more of the oxides of Group VIB, VIIB or VIII metals. The process for hydrolyzing hydrogenation of biomass according to any one of claims 2 to 11, wherein when the reaction is a secondary reaction, the pressure is 7 to 23 MPa and the temperature is 250 to 460 °C. The step of hydro-reforming the secondary hydrogenation product under conditions. The hydrolytic hydrogenation process of biomass according to claim 1, wherein the slurry further comprises coal, and specifically comprises the following steps: Preparation of biomass coal slurry: Collecting biomass and controlling the water content to less than 2% by weight, and then pulverizing to a median particle diameter of 100 to 300 μm; The pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C; The biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 μm to obtain a biomass powder; Collecting coal and controlling the water content to less than 2wt%, and then pulverizing to a median particle size of 50-100μm; Compressing the pulverized coal, the compression pressure is 5-15 MPa, and the compression temperature is 30-60 ° C; The coal after compression molding is pulverized again to obtain pulverized coal; Mixing the biomass powder, the pulverized coal, the catalyst with a flowing medium, and grinding and slurrying to obtain a biomass coal slurry, the flowing medium being oil or water; Liquefaction reaction: introducing hydrogen into the biomass coal slurry to react, and controlling the reaction pressure and the reaction temperature to finally obtain a bio-oil; In the preparation step of the biomass coal slurry, when the mixing is performed, the biomass powder and the pulverized coal are degreased and premixed with the catalyst, and then the premixed is obtained. Mixing with the flowing medium, or directly mixing the biomass powder, the pulverized coal, the catalyst and the oil; The reaction is a first-order reaction. When the flowing medium is an oil, the pulverized coal is pulverized again to a median diameter of 30 to 50 μm, and the biomass powder and the pulverized coal together occupy the biomass coal slurry. 60 to 70wt% of the material; and control the reaction pressure is 15 ~ 25MPa, the reaction temperature is 380 ~ 480 ° C; When the flowing medium is water, the pulverized coal is pulverized again to a median diameter of 30 to 100 μm, and the biomass powder and the pulverized coal together account for 55 to 65 wt% of the biomass coal slurry; The reaction pressure is 15 to 25 MPa, and the reaction temperature is 300 to 420 °C. The hydrolytic hydrogenation process of biomass according to claim 14, wherein the reaction is a secondary reaction, and when the flowing medium is an oil, the reaction comprises the following steps: First-stage hydrogenation reaction: introducing hydrogen into the biomass coal slurry to generate a first-stage hydrogenation reaction, and controlling the reaction pressure to be 15-25 MPa and a reaction temperature of 280-350 ° C to obtain a first-stage hydrogenation product; Secondary hydrogenation reaction: adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure to be 15-25 MPa, and the reaction temperature being 400-480 ° C, to obtain a secondary a hydrogenation product, the second hydrogenated product is finally separated to obtain a bio-oil; When the flowing medium is water, the reaction comprises the following steps: First-stage hydrogenation reaction: introducing hydrogen into the biomass coal slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure to 15-20 MPa, and reacting at a temperature of 220-300 ° C to obtain a first-stage hydrogenation product; Secondary hydrogenation reaction: adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a second-stage hydrogenation reaction, controlling the reaction pressure to be 15-20 MPa, and the reaction temperature is 380-420 ° C, and obtaining the second stage The hydrogenation product, which is separated to finally obtain a bio-oil. The process for hydrolyzing hydrogenation of biomass according to claim 14 or 15, wherein when the flowing medium is an oil, the concentration of biomass in the biomass coal slurry is 20 to 30% by weight. The concentration of pulverized coal is 30 to 45 wt%; When the medium is water, the biomass coal slurry has a biomass concentration of 15 to 30% by weight and a coal powder concentration of 35 to 50% by weight. The hydrolytic hydrogenation process of biomass according to any one of claims 14-16, characterized in that the moisture content is controlled by drying and dehydrating, the drying and dehydrating temperature is 50-70 ° C, and the drying and dehydrating time is 3 ~ 5h. The process for hydrolyzing hydrogenation of biomass according to any one of claims 14-17, wherein when the flowing medium is an oil, the biomass powder is controlled in a preparation step of the biomass coal slurry. The bulk density is 300-500 kg/m ³ , and the bulk density of the pulverized coal is controlled to be 1000-1200 kg/m ³ When the flowing medium is water, the bulk density of the biomass powder is controlled to be 300-500 kg/m ³ in the preparation step of the biomass coal slurry, and the bulk density of the pulverized coal is controlled to be 1200-1300 kg/m ^{3 .} . The process for hydrolyzing hydrogenation of biomass according to any one of claims 14 to 18, wherein the grinding and pulping time is 2 to 8 min. The process for hydrolyzing hydrogenation of biomass according to any one of claims 14 to 19, wherein the coal is low rank coal; when the flowing medium is oil, the oil is hydrophobic oil, One or more of waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or bio-oil prepared by the process. The hydrolytic hydrogenation process of coal and biomass according to any one of claims 14 to 20, wherein when the reaction is a first-order reaction, in the biomass coal slurry, the catalyst a content of 0.1 to 10% by weight, preferably 2% by weight; the catalyst has a particle size of 5 μm to 500 μm; When the reaction is a secondary reaction, the content of the first catalyst in the biomass coal slurry is 0.1 to 10% by weight, preferably 2% by weight; and the particle diameter of the first catalyst is 5 μm to 500 μm. ; The second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 μm to 500 μm; Before the adding the second catalyst to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically: The catalyst slurry is prepared by mixing the second catalyst with water in a mass ratio of (1 to 2):10. The process for hydrolyzing hydrogenation of biomass according to any one of claims 14 to 21, wherein when the reaction is a first-order reaction, the specific method for introducing hydrogen into the gas is: Injecting high-pressure hydrogen into the biomass coal slurry, and controlling a volume ratio of the high-pressure hydrogen to the biomass coal slurry to be (600-1000): 1, thereby forming a reaction raw material; The reaction raw material is sent into a slurry bed reactor to undergo liquefaction, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor. The speed is 0.02 ~ 0.2m / s, preferably 0.05 ~ 0.08m / s; Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen is 13 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C; When the reaction is a secondary reaction, the specific method for introducing hydrogen into the primary hydrogenation reaction step is: Injecting high-pressure hydrogen into the biomass coal slurry, and controlling a volume ratio of the high-pressure hydrogen to the biomass coal slurry to be (600-1000): 1, thereby forming a primary reaction raw material; And sending the first-stage reaction raw material into the first slurry-bed reactor to generate a first-stage hydrogenation reaction, and simultaneously injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the first slurry bed. The total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s; Wherein, the pressure of the high pressure hydrogen and the high pressure cold hydrogen is 13 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C; The method of introducing hydrogen into the second-stage reaction step is: The mixture of the primary hydrogenation product and the second catalyst is heated to 380 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas. To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and The volume ratio of hydrogen to the primary hydrogenation product is (1000 to 1500): 1; Wherein, the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 13-27 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C, and the temperature of the high-pressure cold hydrogen is 50-135 ° C. The hydrolytic hydrogenation process of biomass according to claim 22, wherein the high-pressure hydrogen gas is injected into the biomass coal slurry twice, specifically: When the reaction is a first-order reaction, when the flowing medium is an oil, after the first high-pressure medium-temperature hydrogen is injected into the biomass coal slurry, the biomass coal slurry is heated and heated to a temperature of 300 to 400 ° C, and then injected a second high pressure high temperature hydrogen into the biomass coal slurry; Wherein the high-pressure medium-temperature hydrogen gas has a temperature of 300 to 400 ° C, and the high-pressure high-temperature hydrogen gas has a temperature of 410 to 510 ° C; When the reaction is a first-order reaction, when the flowing medium is water, after the first high-pressure medium-temperature hydrogen is injected into the biomass coal slurry, the biomass coal slurry is heated and heated to 300. ～400° C., and then injecting high-pressure high-temperature hydrogen into the biomass coal slurry for a second time; Wherein the high-pressure medium-temperature hydrogen gas has a temperature of 300 to 400 ° C, and the high-pressure high-temperature hydrogen gas has a temperature of 410 to 510 ° C; When the reaction is a secondary reaction, when the flowing medium is an oil, after the first injection of high-pressure medium-temperature hydrogen into the biomass coal slurry, the biomass coal slurry is heated and heated to a temperature of 200-350 ° C, and then inject high-pressure high-temperature hydrogen into the biomass coal slurry for the second time; Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 180-350 ° C, and the temperature of the second-injected high-pressure high-temperature hydrogen gas is 360-510 ° C; When the reaction is a secondary reaction, when the flowing medium is water, after the first injection of high-pressure medium-temperature hydrogen into the biomass coal slurry, the biomass coal slurry is heated and heated to 200. ～350° C., and then injecting high-pressure high-temperature hydrogen into the biomass coal slurry for a second time; Wherein, the temperature of the high-pressure medium-temperature hydrogen gas is 180 to 350 ° C, and the temperature of the second injection high-pressure high-temperature hydrogen gas is 360 to 510 ° C. A process for hydrolyzing hydrogenation of biomass according to claim 22 or 23, wherein the inventory of said catalyst in said slurry bed reactor is controlled in the liquid phase mass of said slurry bed reactor ~ 30wt%. The hydrolytic hydrogenation process of biomass according to any one of claims 14 to 24, wherein when the reaction is a first-order reaction and the flowing medium is an oil, the reaction time is 30 ～. 90 min, when the flowing medium is water, the reaction time is 30 to 60 min; When the reaction is a secondary reaction, when the flowing medium is an oil, the time of the first hydrogenation reaction is 30 to 60 min, and the time of the second hydrogenation reaction is 30 to 90 min; the flowing medium When it is water, the time of the first hydrogenation reaction is 30 to 60 minutes, and the time of the second hydrogenation reaction is 30 to 60 minutes. The process for hydrolyzing hydrogenation of biomass according to any one of claims 24 to 25, wherein when the reaction is a secondary reaction, the pressure is 7 to 23 MPa and the temperature is 250 to 460 °C. The step of hydro-reforming the secondary hydrogenation product under conditions. The process for hydrolyzing hydrogenation of biomass according to any one of claims 24 to 26, wherein when the reaction is a first-order reaction, the catalyst is a vulcanized biomass loaded with active components. Carbon, the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide; Or the catalyst is a vulcanized amorphous iron oxyhydroxide; When the reaction is a secondary reaction, the first catalyst is a vulcanized biomass char loaded with a first active component, the first active component being iron oxide, iron oxyhydroxide or iron hydroxide. One or more of the second catalysts; the vulcanized biochar with a second active component loaded, the second active component being Mo, W, Fe, Co, Ni or Pd One or more of the oxides; Or the first catalyst is vulcanized amorphous iron oxyhydroxide, the second catalyst is a vulcanized amorphous alumina loaded with a third active component, and the third active component is selected from the periodic table of elements. One or more of the oxides of Group VIB, VIIB or VIII metals.