CN113736509B - A treatment method for residual oil in slurry bed hydrogenation - Google Patents

Abstract

The invention provides a treatment method for residual oil in a slurry bed hydrogenation residue, which comprises: mixing the residue oil slurry bed hydrogenation residue with solvent oil and a porous material to obtain a mixture; separating the mixture , to obtain the adsorption porous material and mixed oil; separate the mixed oil to obtain recovered solvent oil and treated residual oil. The treatment method provided by the present invention is simple and easy to implement, not only can remove heavy metals in the slurry bed hydrogenation residue oil with high selectivity; but also can realize the hydrogenation metal components in the residue to turn waste into treasure, as a hydrogenation catalyst further use efficiently. At the same time, solvent oil can be obtained by distilling and separating the mixed oil, which can be recycled and used, and the residual oil after metal removal can be used as a raw material for coking or hydrotreating for further processing.

Description

A method for treating residual oil in a residual oil slurry bed hydrogenation

Technical Field

The invention relates to a method for treating residual oil in a residual oil slurry bed hydrogenation process and application of an adsorption porous material obtained thereby.

Background Art

At present, residue oil slurry bed hydrogenation is one of the effective ways to process inferior residue oil. This process is positioned to process inferior heavy oil and extra-thick crude oil with high metal, high residual carbon and high asphaltene content. It uses a dispersed catalyst and processes inferior heavy oil or extra-thick crude oil under the conditions of catalyst addition of 0.1% to 3%, reaction temperature of 420℃ to 470℃, reaction pressure of 14Mpa to 20Mpa, and space velocity of 0.07h ^-1 to 0.20h ^-1 , and can achieve a crude oil conversion rate of 85% to 95%.

Although the slurry bed residue oil hydrogenation technology can achieve a residue oil conversion rate of 90%, there is still 5% to 10% or even more unconverted oil, which is the vacuum residue oil or deasphalted oil of the slurry bed hydrogenation reformed oil, which contains a certain amount of oil, but also contains more colloids, asphaltene, toluene insolubles, heavy metals in the raw materials and all metal catalysts. The slurry bed residue oil hydrogenation catalyst mainly includes solid powder catalyst, water-soluble catalyst and oil-soluble catalyst. Solid powder catalyst has a high processing volume (generally 2% to 5% of the raw material) due to its low dispersion and the use of Fe-containing minerals with low hydrogenation activity, so the catalyst content in its tail oil is relatively high, greater than 20%. Tail oil is currently used as a raw material for delayed coking, but due to its high metal content, the quality of delayed coking petroleum coke is unqualified, so the subsequent processing and utilization of unconverted oil is difficult.

Some technologies also use Mo-based catalysts with high hydrogenation activity and low catalyst addition. Although the Mo metal content in the catalyst tailings is low, due to the high price of Mo, they all use solvent dissolution, liquid-solid cyclone separation, and filter cake two-step pyrolysis and gasification to recover metal oxides. Although this method can achieve metal recovery and has good economic benefits, it has many steps and the two-step pyrolysis and gasification has high energy consumption.

Summary of the invention

The purpose of the method of the present invention is to treat slurry bed hydrogenation residual oil by a simple and easy method, remove metals in the residual oil, and make it easier to perform secondary processing; at the same time, the metals in the slurry bed residual oil are transformed into treasures and used as a catalyst for distillate oil hydrogenation processing.

The present invention provides a method for treating residual oil in a residual oil slurry bed hydrogenation process, the method comprising:

Mixing the residual oil from the residual oil slurry bed hydrogenation with solvent oil and a porous material to obtain a mixture;

separating the mixture to obtain an adsorbent porous material and a mixed oil;

The mixed oil is separated to obtain recovered solvent oil and treated residual oil.

In one embodiment, the residue oil slurry bed hydrogenation residue oil is mixed with solvent oil and porous material at a mixing temperature, wherein the mixing temperature is 50° C. to 200° C. higher than the softening point of the residue oil slurry bed hydrogenation residue oil.

In one embodiment, when mixed, the mass ratio of the solvent oil to the residue oil slurry bed hydrogenation residual oil is 2:1 to 10:1, and the porous material accounts for 2% to 10% based on the total weight of the solvent oil and the residue oil slurry bed hydrogenation residual oil.

In one embodiment, the metal content in the mixed oil is lower than 10 μg/g, preferably lower than 5 μg/g, and more preferably lower than 1 μg/g.

In one embodiment, the solvent naphtha is a distillate oil with a boiling point below 524°C.

In one embodiment, the porous material includes a mesoporous material and a macroporous material.

In one embodiment, the porous material is selected from one or more of kaolin, alumina, silica, molecular sieves, and activated carbon.

In one embodiment, at least a portion of the solvent naphtha is the recovered solvent naphtha.

In one embodiment, the adsorbent porous material is used as a distillate oil hydroprocessing catalyst.

On the other hand, the present invention provides the use of an adsorbent porous material as a catalyst for distillate oil hydroprocessing, wherein the adsorbent porous material is obtained as follows: the residual oil slurry bed hydrogenation residual oil is mixed with solvent oil and a porous material to obtain a mixture; and the mixture is separated to obtain the adsorbent porous material.

The treatment method provided by the present invention is simple and easy to implement. It can not only remove heavy metals in slurry bed hydrogenation residual oil with high selectivity, but also realize the transformation of hydrogenation metal components in the residue into valuables, which can be further effectively utilized as hydrogenation catalysts. At the same time, solvent oil can be obtained by distilling and separating the mixed oil, and the solvent oil can be recycled for use. The residual oil from which the metal is removed can be further processed as a raw material for coking or hydrogenation treatment.

DETAILED DESCRIPTION

The method of the present invention uses a porous material to carry out adsorption separation on a mixture of residual oil and solvent oil obtained by hydrogenation of residual oil slurry bed, thereby obtaining a porous material (adsorption porous material) adsorbing metals and metal sulfides and tail oil (mixed oil) free of metals. The porous material (adsorption porous material) adsorbing metals and metal sulfides can be directly used as a catalyst for hydrogenation treatment of distillate oil; meanwhile, the solvent oil in the method of the present invention can be recycled.

In one aspect, the present invention provides a method for treating residual oil in a residual oil slurry bed hydrogenation process, the method comprising:

Mixing the residual oil from the residual oil slurry bed hydrogenation with solvent oil and a porous material to obtain a mixture;

separating the mixture to obtain an adsorbent porous material and a mixed oil;

The mixed oil is separated to obtain recovered solvent oil and treated residual oil.

The method of the present invention creatively uses a combination of solvent oil and porous materials to treat residual oil, wherein the porous material can be used as an adsorbent to adsorb metals and metal sulfides present in the residual oil, and the solvent oil can reduce the viscosity of the residual oil, increase its fluidity, increase the possibility of contact between the residual oil and the porous material, and enhance its mass transfer effect. Compared with the method of using only porous materials to treat residual oil, the combination of solvent oil and porous materials has the following advantages: 1. The viscosity of the liquid material is reduced, the fluidity is enhanced, and the contact between the residual oil and the porous material can be strengthened; 2. The efficiency and effect of the porous material in adsorbing metals and their sulfides in the residual oil are significantly improved.

In one embodiment of the present invention, the residual oil from the residual oil slurry bed hydrogenation is mixed with solvent oil and porous material at a mixing temperature, wherein the mixing temperature is 50° C. to 200° C. higher than the softening point of the residual oil slurry bed hydrogenation. Mixing at this mixing temperature has the following advantages: the viscosity of the mixed raw material is small, the fluidity is good, and the mass transfer efficiency between the residual oil and the porous material is high.

In one embodiment, when mixed, the mass ratio of the solvent oil to the residual oil slurry bed hydrogenation residue is 2:1 to 10:1, and the porous material accounts for 2% to 10%, based on the total weight of the solvent oil and the residual oil slurry bed hydrogenation residue. For the method of the present invention, the amount of the solvent oil and the porous material is important. If the mass ratio of the solvent oil to the residual oil slurry bed hydrogenation residue is lower than 2:1, the mixed raw material has the disadvantages of high viscosity, poor fluidity, and low mass transfer efficiency between the residual oil and the porous material; if the mass ratio of the solvent oil to the residual oil slurry bed hydrogenation residue is higher than 10:1, the process has the disadvantages of high material consumption and high energy consumption. If the amount of porous material is lower than 2%, the recovery rate of metals and metal sulfides in the residual oil is low; if the amount of porous material is higher than 10%, the porous material has the disadvantages of large solid content of the system and increased difficulty in operation; high solid content, reduced transfer efficiency between the residual oil and the porous material, and low recovery rate of metals and metal sulfides in the residual oil.

In one embodiment, the solvent oil is a distillate oil or a pure solvent with a boiling point below 524°C, which has a high solubility for heavy oil, residual oil, and slurry bed hydrogenation residual oil. Pure aromatic solvents, light and heavy aromatic mixtures, raffinate oil, catalytic cracking cycle oil, catalytic cracking slurry or one or more mixtures of catalytic cracking slurry narrow fractions can be selected. In one embodiment, the porous material is a porous material with a pore structure, which can be selected from mesoporous materials and macroporous materials such as kaolin, alumina, silica, molecular sieves, and activated carbon. In the present application, mesoporous materials refer to a class of porous materials with a pore size between 2-50nm. Macroporous materials refer to a class of porous materials with a pore size greater than 50nm.

After the residue oil slurry bed hydrogenation residual oil is mixed with solvent oil and porous material, the porous material is allowed to adsorb the residue oil slurry bed hydrogenation residual oil for a period of time, which may be 1-10 hours, such as 1-5 hours.

Afterwards, the mixture of the residual oil, solvent oil and porous material from the residual oil slurry bed hydrogenation is separated to obtain the adsorbed porous material and the mixed oil. The separation method can be carried out by filtration separation or cyclone separation. The obtained adsorbed porous material adsorbs the metals and metal sulfides present in the residual oil. It is particularly important that the adsorbed porous material can be directly used as a distillate oil hydroprocessing catalyst without further processing. The hydrogenation metal components in the residual oil can be turned into treasure and further effectively utilized as a hydrogenation catalyst.

The mixture of solvent oil and tail oil (mixed oil) treated by adsorption has a metal (Ni+V+Fe+Mo) content of less than 10 μg/g, preferably less than 5 μg/g, and more preferably less than 1 μg/g.

At the same time, the mixed oil can be distilled and separated to obtain recovered solvent oil, which can be recycled as part of the solvent oil; and the metal-free residual oil (treated residual oil) can be further processed as a raw material for coking or hydrogenation.

As confirmed by the present invention, the adsorbent porous material obtained by the method of the present invention adsorbs metals and metal sulfides present in the residual oil, and can be directly used as a distillate hydroprocessing catalyst without further processing. Therefore, the present invention also relates to the use of the adsorbent porous material as a distillate hydroprocessing catalyst. The process of obtaining the adsorbent porous material can refer to the above description of the present invention specification, and will not be repeated here.

Compared with the material adsorbed with metals and metal sulfides obtained by treating the residual oil slurry bed hydrogenation residual oil with only porous materials, the adsorbed porous material obtained by the method of the present invention has the following advantages: 1. The viscosity of the system is reduced by adding solvent oil, which can strengthen the mass transfer between the residual oil slurry bed hydrogenation residual oil and the porous material, strengthen the diffusion of metals and metal sulfides in the residual oil to the porous material, and realize the adsorption of metals and metal sulfides in the slurry bed hydrogenation residual oil by the porous material; 2. The metals Mo, Ni, and V in the slurry bed residual oil can be highly selectively removed, and the content of metals Mo, Ni, and V in the mixed oil is less than 10 μg/g, so that it can be further processed as a coking or hydrogenation raw material; 3. The porous material containing metals and metal sulfides and the residual oil are effectively separated, and the catalyst can be used as a catalyst for distillate oil hydrogenation; 4. The solvent oil in the method of the present invention can be recycled, and the use effect is good. The entire invention method has no solid waste or liquid waste discharge.

The technical solution of the present invention is further described below according to specific embodiments. The protection scope of the present invention is not limited to the following embodiments, which are listed only for illustrative purposes and do not limit the present invention in any way.

In the following examples, the residual oil from the residual oil slurry bed hydrogenation is the treatment object. The residual oil is mixed with solvent oil and porous material, mixed and dispersed at a certain temperature, and the adsorbed porous material adsorbed with metals and/or metal sulfides and the mixture of solvent oil and tail oil without metals are separated by cyclone separation or filtration separation. The adsorbed porous material adsorbed with metals and metal sulfides is used as a catalyst for distillate oil hydrogenation treatment; the solvent oil obtained by separation of the metal-free mixed oil can be recycled, and the tail oil without metals can be used as a coking raw material, and the ash content of the generated petroleum coke meets the requirements.

Examples 1 to 3 show the effects of the present invention on treating residual oil by using porous materials and solvent oil in a slurry bed hydrogenation treatment of residual oil. Table 4 shows the test results of LCO hydrogenation treatment catalyzed by the adsorbed porous material adsorbing metal sulfides obtained in Example 3.

Example 1

In this embodiment, the residual oil is treated by externally discarding the residual oil after hydrogenation in a residue oil slurry bed, wherein Table 1-1 shows the properties of the residual oil after hydrogenation in a residue oil slurry bed, and Table 1-2 shows the conditions and effects of treating the hydrogenated residual oil without solvent circulation.

Table 1-1 Properties of Residue Oil from Slurry Bed Hydrogenation

nature Residue oil slurry bed hydrogenation residue oil element Mo/(μg·g ^–1 ) 2800 Ni/(μg·g ^–1 ) 1500 V/(μg·g ^–1 ) 4600 Physical properties Density (20℃)/(g·cm ^–3 ) 1.24 Dynamic viscosity (160℃)/(cP) 8000

Table 1-3 Hydrogenation residue oil treatment (solvent not recycled) conditions and effects

Residue treatment solvent/% Heavy aromatics mixture Solvent oil to residue ratio 8:1 Porous Materials Kaolin Porous material content/% 3 Residue treatment temperature/℃ 200 Residue processing time/h 4 Solid yield of porous materials/% 9 Metal content in mixed oil after treatment/(μg/g) Mo <1 Ni <1 V <1

After the residual oil is treated with solvent oil + porous material adsorption, the filter cake solid and liquid parts (including the added porous material) are obtained. The yield of solid containing porous material refers to the mass percentage of the filter cake solid including the added porous material in the filter cake solid and liquid parts.

Example 2

This embodiment treats the residual oil after residue oil slurry bed hydrogenation. Table 2-1 shows the properties of the residual oil after residue oil slurry bed hydrogenation, and Table 2-2 shows the conditions and effects of treating the hydrogenated residual oil without solvent circulation.

Table 2-1 Properties of Residue Oil from Slurry Bed Hydrogenation

nature Residue oil slurry bed hydrogenation residue oil element Mo/(μg·g ^–1 ) 1400 Ni/(μg·g ^–1 ) 750 V/(μg·g ^–1 ) 2300 Physical properties Density (20℃)/(g·cm ^–3 ) 1.17 Dynamic viscosity (100℃)/(cP) 5400

Table 2-2 Conditions and effects of hydrogenation residue oil treatment (solvent not recycled)

Residue treatment solvent/% FCC Light Distillate Solvent oil to residue ratio 2:1 Porous Materials SAPO Molecular Sieve Porous material content/% 2 Residue treatment temperature/℃ 280 Residue processing time/h 3 Solid yield of porous materials/% 8 Metal content in mixed oil after treatment/(μg/g) Mo <2 Ni <2 V <3

Example 3

This embodiment treats the residual oil after residue oil slurry bed hydrogenation. Table 3-1 shows the properties of the residual oil after residue oil slurry bed hydrogenation, and Table 3-2 shows the conditions and effects of treating the hydrogenated residual oil with solvent circulation.

Table 3-1 Properties of Residue Oil from Slurry Bed Hydrogenation

nature Residue oil slurry bed hydrogenation residue oil element Mo/(μg·g ^–1 ) 2500 Ni/(μg·g ^–1 ) 1300 V/(μg·g ^–1 ) 3900 Physical properties Density (20℃)/(g·cm ^–3 ) 1.19 Dynamic viscosity (100℃)/(cP) 3037

Table 3-2 Hydrogenation residue oil treatment (solvent circulation) conditions and effects

Residue treatment solvent/% Catalytic cracking cycle oil Solvent oil to residue ratio 5:1 Porous Materials Y molecular sieve Porous material content/% 5 Residue treatment temperature/℃ 240 Residue processing time/h 5 Solid yield of porous materials/% 10 Yield of solvent oil mixture/% 90 Mixture recovery solvent operating conditions Operating temperature/℃ 100 Operating vacuum/mmHg 500 Solvent recovery rate/% >85 Recycling the solvent treatment residue for 5 times to obtain the metal content in the circulating solvent (μg/g) Mo <3 Ni <4 V <4

It can be seen from the results of Table 1-1 to Table 3-2 that, compared with the prior art, the method of the present invention has the following outstanding features:

(1) The method of the present invention uses porous materials and organic solvents to jointly treat the residue slurry bed hydrogenation residue, which can not only remove metal Mo, Ni, and V from the residue slurry bed residue with high selectivity, but also make the content of metal Mo, Ni, and V in the mixed oil less than 10 μg/g, so that it can be further processed as a coking or hydroprocessing raw material;

(2) Compared with the existing method for recovering metals from slurry bed residue, the method of the present invention is simple and easy to operate;

(3) The solvent oil in the method of the present invention can be recycled and has a good use effect. The entire method of the present invention has no solid waste or liquid waste discharge.

Comparative Example

Since the viscosity of the slurry bed hydrogenation tail oil is high, with a viscosity greater than 3000 cP (centipoise) at 100°C, when the porous material is directly added to the slurry bed hydrogenation tail oil under the conditions of the present invention, effective mass transfer cannot be achieved, and the metals and metal sulfides in the tail oil cannot diffuse into the porous material; moreover, under conventional filtration and separation conditions, the separation of the porous material and the tail oil cannot be achieved.

Example 4

The adsorbing porous material obtained in Example 3 was used as a catalyst to catalyze the hydrogenation of LCO. The conditions are listed in Table 4.

Table 4 Conditions for LCO hydrogenation catalyzed by adsorbed porous materials in Example 3

The results in Table 4 of Example 4 show that the porous material catalyzed LCO hydrogenation test that adsorbed metal sulfides (MoxSy, NixSy, VxSy) in the slurry bed hydrogenation residue oil increased the hydrogen content of the product by 1.05 percentage points compared with the raw material. The data show that the molecular sieve material adsorbed with metal sulfides has catalytic hydrogenation activity, which can realize the conversion of metals in the hydrogenation residue oil into valuables and value-added utilization.

Those skilled in the art should note that the embodiments described in the present invention are merely exemplary, and various other substitutions, changes and improvements may be made within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but only to the claims.

Claims (11)

1. A process for treating a residuum in a slurry bed of residuum, the process comprising:

mixing the residual oil slurry bed hydrogenated residual oil with solvent oil and porous materials to obtain a mixture;

separating the mixture to obtain a porous material and mixed oil, wherein the porous material is adsorbed with metal and metal sulfide;

separating the mixed oil to obtain recovered solvent oil and treated residual oil,

wherein, when mixing, the mass ratio of the solvent oil to the residual oil slurry bed hydrogenated residual oil is 2:1-10:1, the porous material accounts for 2-10 percent, based on the total weight of the solvent oil and the residual oil slurry bed hydrogenated residual oil,

wherein the porous material is selected from one or more of kaolin and molecular sieve.

2. The process of claim 1, wherein the residuum slurry bed hydrogenated residuum is mixed with solvent oil, porous material at a mixing temperature, wherein the mixing temperature is 50 ℃ to 200 ℃ higher than a softening point of the residuum slurry bed hydrogenated residuum.

3. The process according to claim 1, wherein the metal content of the mixed oil is less than 10 μg/g.

4. The process according to claim 1, wherein the metal content of the mixed oil is less than 5 μg/g.

5. The process according to claim 1, wherein the metal content of the mixed oil is less than 1 μg/g.

6. The process according to claim 1, wherein the solvent oil is a distillate oil having a boiling point lower than 524 ℃.

7. The process of claim 1, wherein the porous material comprises a mesoporous material and a macroporous material.

8. The process of claim 1, wherein at least a portion of the mineral spirits are the recovered mineral spirits.

9. The process according to claim 1, wherein the porous material having adsorbed metals and metal sulfides is used as a distillate hydrotreating catalyst.

10. Use of a porous material having adsorbed metal and metal sulphide as a catalyst for the hydroprocessing of distillate oils, wherein the porous material having adsorbed metal and metal sulphide is obtained as follows:

mixing the residue oil slurry bed hydrogenated residual oil with solvent oil and porous materials to obtain a mixture;

separating the mixture to obtain the porous material adsorbed with the metal and the metal sulfide,

wherein, when mixing, the mass ratio of the solvent oil to the residual oil slurry bed hydrogenated residual oil is 2:1-10:1, the porous material accounts for 2-10 percent, based on the total weight of the solvent oil and the residual oil slurry bed hydrogenated residual oil,

wherein the porous material is selected from one or more of kaolin and molecular sieve.

11. The use according to claim 10, wherein the residuum slurry bed hydrogenated residuum is mixed with solvent oil, porous material at a mixing temperature, wherein the mixing temperature is 50 ℃ to 200 ℃ higher than the softening point of the residuum slurry bed hydrogenated residuum.