WO2019095405A1 - Method for directly producing aromatic hydrocarbons from syngas and for producing low carbon olefins in parallel - Google Patents

Abstract

Disclosed by the present invention is a method for preparing aromatic hydrocarbons from syngas and for producing low-carbon olefins in parallel, the method comprising: contacting a raw material comprising syngas and a catalyst in a reaction zone under reaction conditions sufficient to convert at least a part of the raw material so as to obtain a reaction effluent comprising aromatic hydrocarbons, low-carbon olefins, and unconverted raw material; then isolating the aromatic hydrocarbons, the low-carbon olefins and the unconverted raw material from the reaction effluent; the catalyst comprises a high dispersion metal oxide material having an inert carrier limitation region, an acidic molecular sieve, and at least one optionally selected from among graphite powder and a dispersing agent; in the high dispersion metal oxide material having an inert carrier limitation region, the inert carrier is at least one from among silicon oxide and aluminum oxide, and the content of the metal oxide calculated according to metal is lower than or equal to 10% by mass; on the basis of the weight of the high dispersion metal oxide material having an inert carrier region, the acidic molecule sieve is selected from among a modified acidic ZSM-5 molecular sieve, a modified acidic ZSM-11 molecular sieve and a mixture thereof.

Description

Method for directly producing aromatic hydrocarbons from syngas and producing low carbon olefins in parallel Technical field

The present invention relates to a process for the direct production of aromatic hydrocarbons from syngas to produce lower olefins in parallel.

Background technique

Aromatic hydrocarbons (especially Benzene, Toluene and Xylene) and low-carbon olefins (ethylene, propylene, various butenes) are important basic organic chemical materials. At present, aromatic hydrocarbons are mainly produced from petroleum as a raw material, and their production techniques include, for example, catalytic reforming of naphtha, gasoline hydrogenation, aromatic hydrocarbon extraction, heavy aromatic lightening, and light hydrocarbon aromatization. Currently, low carbon olefins are produced primarily by steam cracking or catalytic cracking of petroleum or its fractions.

However, due to the depletion of petroleum resources, it is very important to develop other production routes such as coal chemical routes to produce aromatics and low-carbon olefins. For example, the technology for producing aromatic hydrocarbons from coal chemical products (MTA) and the production of low-carbon olefins (MTO) from methanol and/or dimethyl ether have been extensively studied, and some technologies have been commercialized. Chemical.

The process of directly producing aromatic hydrocarbons from syngas omits the intermediate methanol and/or dimethyl ether production steps and is therefore highly attractive.

Chinese patent application CN105944751A teaches a catalyst for the direct preparation of aromatic hydrocarbons from synthesis gas, the catalyst consisting of a metal active component, an auxiliary agent and a hydrogen-type ZSM-5 molecular sieve material, the metal active component being iron, molybdenum, An oxide of one or more of cobalt, zinc, and gallium, and the adjuvant is an oxide of one or more of sodium, potassium, calcium, magnesium, vanadium, chromium, manganese, and copper.

Catalysts suitable for the direct preparation of aromatic hydrocarbons from syngas are also disclosed in Chinese Patent Application Nos. CN101422743A, CN106215972A, CN106540740A and CN106268924A.

There remains a need for a catalyst suitable for the direct production of aromatic hydrocarbons from syngas to produce lower olefins in parallel, which catalysts have high aromatic and low carbon olefin selectivity and stable properties.

Summary of the invention

In order to overcome the problems existing in the prior art, the inventors conducted diligent research. Result It has been found that a catalyst comprising at least one of a highly dispersed metal oxide material limited to an inert support, an acidic molecular sieve, and optionally a graphite powder and a dispersant is well suited for the direct preparation of aromatic hydrocarbons from syngas in parallel to produce lower olefins. The process, which uses the catalyst to directly produce aromatic hydrocarbons from syngas to produce lower olefins in parallel, can achieve high feedstock conversion and overall product selectivity. The present invention has been completed on the basis of the above findings.

Accordingly, it is an object of the present invention to provide a process for the direct production of aromatic hydrocarbons from a synthesis gas in parallel to produce lower olefins, the process comprising:

Contacting a feed stream comprising syngas with a catalyst in a reaction zone under reaction conditions sufficient to convert at least a portion of the feedstock to an aromatic hydrocarbon to provide a reaction effluent comprising an aromatic hydrocarbon, a lower olefin, and an unconverted feedstock;

Separating aromatic hydrocarbons, light olefins, and unconverted feedstock from the reaction effluent,

Wherein the catalyst comprises at least one of an inert carrier-limited high-dispersion metal oxide material, an acidic molecular sieve, and optionally a graphite powder and a dispersant, wherein the inert carrier-limited high-dispersion metal oxide material The inert carrier is at least one of silica and alumina, and the metal oxide is present in an amount of less than or equal to 10% by mass based on the weight of the inert carrier-limited high-dispersion metal oxide material. And wherein the acidic molecule is selected from the modified acidic ZSM-5 molecular sieve, the modified acidic ZSM-11 molecular sieve, and mixtures thereof.

In one embodiment, the reaction zone contains a fixed bed reactor, or a plurality of fixed bed reactors in series and/or in parallel.

In one embodiment, the reaction conditions include: a reaction temperature of 300 to 450 ° C, a reaction pressure of 0.5 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in the synthesis gas of 1:9 to 9:1, and 1000 to 20000 h. Syngas volume hourly space velocity in the standard state of ^-1 .

Description of the preferred embodiment

The term "lower olefin" as used herein, unless otherwise indicated, refers to an olefin having from 2 to 4 carbon atoms.

The term "BTX" as used herein, unless otherwise indicated, refers to benzene, toluene and xylene.

In a first aspect, the present invention provides a method for the direct production of aromatic hydrocarbons from a synthesis gas in parallel to produce a lower olefin, the method comprising:

Contacting a feed stream comprising syngas with a catalyst in a reaction zone under reaction conditions sufficient to convert at least a portion of the feedstock to an aromatic hydrocarbon to provide a reaction effluent comprising an aromatic hydrocarbon, a lower olefin, and an unconverted feedstock;

Separating aromatic hydrocarbons, light olefins, and unconverted feedstock from the reaction effluent,

Wherein the catalyst comprises at least one of an inert carrier-limited high-dispersion metal oxide material, an acidic molecular sieve, and optionally a graphite powder and a dispersant, wherein the inert carrier-limited high-dispersion metal oxide material The inert carrier is at least one of silica and alumina, and the metal oxide is present in an amount of less than or equal to 10% by mass based on the weight of the inert carrier-limited high-dispersion metal oxide material. And wherein the acidic molecule is selected from the modified acidic ZSM-5 molecular sieve, the modified acidic ZSM-11 molecular sieve, and mixtures thereof.

Catalyst for direct production of aromatic hydrocarbons from syngas to produce lower olefins in parallel

As stated above, the catalyst used in the process of the invention comprises at least one of an inert support-limited high-dispersion metal oxide material, an acidic molecular sieve, and optionally a graphite powder and a dispersant, wherein the inert support is limited In the highly dispersed metal oxide material, the inert carrier is at least one of silicon oxide and aluminum oxide, and the content of the metal oxide in terms of metal is less than or equal to 10% by mass, based on the high dispersion of the inert carrier. The weight of the metal oxide material, and wherein the acidic molecules are selected from the modified acidic ZSM-5 molecular sieve, the modified acidic ZSM-11 molecular sieve, and mixtures thereof.

In one embodiment, the metal oxide in the inert support-limited high dispersion metal oxide material is an oxide that removes at least one of aluminum and a metal other than the radioactive element. Preferably, the metal oxide in the inert carrier-limited high-dispersion metal oxide material is an oxide of at least one of zinc, chromium, zirconium, copper, manganese, platinum, and palladium. More preferably, the metal oxide in the inert carrier-limited high-dispersion metal oxide material is an oxide of at least one of zinc, chromium, and zirconium.

In one embodiment, the metal oxide content of the metal oxide in the inert carrier-limited high-dispersion metal oxide material is less than or equal to 10% by weight; preferably less than or equal to 5% by weight; more preferably less than Or equal to 2% by weight, based on the weight of the inert carrier-limited high dispersion metal oxide material. The term "metal oxide" as used herein, unless otherwise indicated The content "does not include the content of alumina, if alumina is present.

In one embodiment, the average particle size of the metal oxide in the inert carrier-limited highly dispersed metal oxide material is less than or equal to 100 nm, preferably less than or equal to 50 nm, more preferably less than or equal to 20 nm.

In a preferred embodiment, the X-ray powder diffraction pattern of the inert support-limited high dispersion metal oxide material does not exhibit characteristic diffraction peaks of the metal oxide.

The inert support limited high dispersion metal oxide material is different from conventional metal composite oxide materials known in the art. For example, the former has a high metal oxide dispersion (characteristic XRD diffraction peak without metal oxide), a small metal oxide mass fraction (generally less than 10%), and a small metal oxide average particle size (generally less than 100 nm) And usually has a large specific surface area (generally greater than 400 m ² /g). Conventional composite metal oxide materials such as copper zinc aluminum composite oxide material (CuZnAlO _x ) for low temperature methanol synthesis, zinc chromium aluminum composite oxide material (ZnCrAlO _x ) for high temperature methanol synthesis, and zinc known in the art The zirconium composite oxide material (ZnZrO _x ) has a metal oxide mass fraction generally greater than 80%, has a significant metal oxide characteristic XRD diffraction peak, and has a specific surface area generally less than 100 m ² /g.

Without wishing to be bound by any particular theory, it is believed that the inert carrier which is abundantly present in the highly dispersed metal oxide material of the inert carrier of the present invention can provide both a large specific surface area and stability due to the confinement effect. Acts as a metal oxide that catalyzes the active component.

In one embodiment, the inert carrier-limited high dispersion metal oxide material has an average particle size of less than or equal to 5 mm, preferably less than or equal to 1 mm, more preferably less than or equal to 0.5 mm, still more preferably less than or equal to 0.1 mm. Still more preferably less than or equal to 0.05 mm.

In some embodiments, the inert support limited high dispersion metal oxide material can be prepared by a coprecipitation-calcination process. For example, in the case of using alumina as a carrier, the inert carrier-limited high-dispersion metal oxide material can be prepared as follows: a salt of a catalytically active metal and an aluminum salt are mixed into a mixed metal salt aqueous solution; The mixed metal salt aqueous solution is contacted with the aqueous solution of the precipitating agent to coprecipitate the metal ions in the mixed metal salt aqueous solution; aging; and the precipitate is washed, dried, and calcined. Examples of such precipitating agents include, but are not limited to, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide, and mixtures thereof.

In one embodiment, the temperature during the coprecipitation is from 0 ° C to 90 ° C, coprecipitated The pH in the process is 7.0 to 8.5, the aging time is not less than 1 hour, and the calcination temperature is 300 ° C to 700 ° C.

In a specific embodiment, the inert carrier-limited high-dispersion metal oxide material is prepared by formulating a salt of an aluminum salt and a catalytically active metal to a total metal ion concentration of from 0.1 mol/L to 3.5 mol/L. Mixing a metal salt aqueous solution; then, the mixed metal salt aqueous solution is contacted with a precipitating aqueous solution having a molar concentration of 0.1 mol/L to 3.5 mol/L at a temperature of 0 ° C to 90 ° C under stirring to coprecipitate the metal salt The metal ions are then aged for a period of time, the pH of the solution during the coprecipitation may be 7.0 to 8.5, and the aging time is not less than 1 hour; the obtained precipitate is filtered and washed and calcined at a temperature of, for example, 300 ° C to 700 ° C. A highly dispersed metal oxide material having an inert carrier confinement is obtained.

There is no particular restriction on the kind of the aluminum salt and the salt of the catalytically active metal as long as they are water-soluble, for example, having a water solubility of more than 1 g/L at 25 °C. Examples of the aluminum salt and the salt of the catalytically active metal include, but are not limited to, hydrochloride, sulfate, and nitrate.

There is no particular limitation on the manner in which the mixed metal salt aqueous solution is contacted with the aqueous precipitant solution. In a particular embodiment, the contacting can be accomplished by cocurrent, feed or reverse feed.

In other embodiments, the inert carrier-limited, highly dispersed metal oxide material can be prepared by a sol-gel process. For example, in the case of using at least silica as a carrier, the inert carrier-limited high-dispersion metal oxide material can be prepared as follows: an aqueous solution of a salt of a catalytically active metal is added to a silicon oxychloride together with an aqueous solution of a precipitant. In the alkyl compound, and allowing the coprecipitation and the sol-gel reaction to proceed, the obtained gel is washed, dried, and calcined to obtain an inert carrier-limited high-dispersion metal oxide material. Examples of the precipitating agent include, but are not limited to, one or more of ammonium carbonate, aqueous ammonia, ammonium hydrogencarbonate, ammonium dihydrogen phosphate, and urea.

In one embodiment, the siloxane-based compound is an alkyl orthosilicate, examples of which include, but are not limited to, methyl orthosilicate, tetraethyl orthosilicate, n-propyl orthosilicate, orthosilicate Propyl ester, n-butyl orthosilicate, isobutyl orthosilicate, tert-butyl orthosilicate, and mixtures thereof.

The acidic molecular sieve component of the catalyst of the present invention is selected from the group consisting of modified acidic ZSM-5 molecular sieves, modified acidic ZSM-11 molecular sieves, and mixtures thereof.

In some embodiments, the modification of the acidic molecular sieve is one or more of phosphorus modification, boron modification, silicon modification, alkaline earth metal modification, and rare earth metal modification.

In some embodiments, the original of silicon and aluminum in the acidic ZSM-5 and ZSM-11 molecular sieves The subratio is Si/Al = 3 to 200, preferably Si/Al = 100 to 150.

In some embodiments, the crystals of the acidic ZSM-5 and ZSM-11 molecular sieves are microscale or nanoscale, and the crystals contain a microporous structure or a mesoporous-microporous structure. The modified acidic molecular sieves are either commercially available or can be prepared by methods known per se. There is no particular limitation on the specific method of preparing the modified acidic molecular sieve. For example, the modified acidic molecular sieve can be obtained by modifying a commercially available acidic ZSM-5 molecular sieve or an acidic ZSM-11 molecular sieve.

In a specific embodiment, the acidic molecular sieve may be impregnated with, for example, H ₃ PO ₄ , NH ₄ H ₂ PO ₄ or an aqueous solution of (NH ₄ ) ₂ HPO ₄ , and then the impregnated acidic molecular sieve is dried and then calcined. A phosphorus-modified acidic molecular sieve containing 0.5 to 10.0% by weight of phosphorus based on the weight of the modified molecular sieve is obtained.

In another embodiment, the acidic molecular sieve may be impregnated with, for example, an aqueous solution of H ₃ BO ₃ , and then the impregnated acidic molecular sieve is dried and then calcined to obtain 0.5 to 10.0% by weight based on the weight of the modified molecular sieve. Boron modified acidic molecular sieves of boron.

In yet another embodiment, the silicon modified acidic molecular sieve can be prepared by treatment with a siloxane compound by liquid phase deposition and/or treatment with a silane compound by vapor deposition. The siloxane compound and the silane compound which can be used are respectively represented by the following structural formula:

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a C _1-10 alkyl group. An example of the siloxane compound is tetraethyl orthosilicate, and an example of the silane compound is tetramethylsilane.

In a specific embodiment, the liquid phase deposition process is carried out by dissolving a silicone compound in an inert organic solvent to provide a solution of the siloxane compound, then soaking or impregnating the acidic molecular sieve with the solution, drying and then calcining A silicon modified acidic molecular sieve is obtained. The silicon-modified acidic molecular sieve may have a silicon loading of 0.5 to 10.0% by weight based on the weight of the modified molecular sieve, and the silicon loading does not include the original silicon in the acidic molecular sieve. The inert organic solvent may be any solvent that does not react with the siloxane compound and the molecular sieve, such as n-hexane or cyclohexane. Alkane, n-heptane.

In a specific embodiment, the vapor deposition process is carried out by passing a silane compound gas through an acidic molecular sieve and then calcining the treated acidic molecular sieve to obtain a silicon-modified acidic molecular sieve. The silicon-modified acidic molecular sieve may have a silicon loading of 0.5 to 10.0% by weight based on the weight of the modified molecular sieve. The silicon loading does not include the original silicon in the acidic molecular sieve.

In a specific embodiment, the acidic molecular sieve may be impregnated with an alkaline earth or a rare earth metal salt aqueous solution, and then the impregnated acidic molecular sieve is filtered, dried and calcined to obtain a weight of 0.5 to 10.0% by weight based on the weight of the modified molecular sieve. Alkaline earth or rare earth metal modified acidic molecular sieve of alkaline earth or rare earth metal.

In one embodiment, the acidic molecular sieve has an average particle size of less than or equal to 5 mm, preferably less than or equal to 0.5 mm, more preferably less than or equal to 0.1 mm, still more preferably less than or equal to 0.05 mm.

In some embodiments, the dispersing agent is selected from the group consisting of alumina, silica, and mixtures thereof. There are no particular restrictions on alumina, silica or alumina-silica which can be used as a dispersant, and they are commercially available from many suppliers.

There are no particular limitations on the graphite powders usable in the present invention, and they are commercially available from many suppliers. In some embodiments, the graphite powder has an average particle size of from 0.05 to 5 microns.

In one embodiment, the catalyst used in the process of the invention may be prepared by a process comprising the following steps:

(1) providing a highly dispersed metal oxide material having an inert carrier confinement;

(2) providing a modified acidic molecular sieve;

(3) mixing at least one of the inert carrier-limited high-dispersion metal oxide material obtained in the step (1), the modified acidic molecular sieve obtained in the step (2), and optionally graphite powder and a dispersant, and The resulting mixture was molded into a shape.

In some embodiments, the catalyst of the present invention comprises from 10 to 90% by weight of an inert carrier-limited, highly dispersed metal oxide material. The lower limit of the content of the highly dispersed metal oxide material limited by the inert carrier may be 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, or 50 weight. %, and the upper limit may be 88, 85, 82, 80, 78, 75, 72, 70, 68, 65, 62, 60, 58, 55, 52 or 50% by weight, based on the weight of the catalyst.

In some embodiments, the catalyst of the present invention comprises from 10 to 90% by weight of an acidic molecular sieve. The lower limit of the content of the acidic molecular sieve may be 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, or 50% by weight, and the upper limit may be 88, 85. , 82, 80, 78, 75, 72, 70, 68, 65, 62, 60, 58, 55, 52, or 50% by weight, based on the weight of the catalyst.

In some embodiments, the catalyst of the present invention comprises 0 to 10% by weight, such as 0 to 8% by weight, 0 to 7% by weight, 0 to 6% by weight, or 0 to 5% by weight, based on the weight of the catalyst. meter.

In some embodiments, the catalyst of the present invention comprises 0 to 40% by weight, such as 0 to 38% by weight, 0 to 35% by weight, 0 to 30% by weight, or 0 to 25% by weight, based on the weight of the catalyst. meter.

In some embodiments, the catalyst of the present invention comprises 10 to 90% by weight of an inert carrier-limited high-dispersion metal oxide material, 10 to 90% by weight of an acidic molecular sieve, 0 to 10% by weight of graphite powder, and 0 to 40% by weight of the dispersant, wherein the total content of the inert carrier-limited high-dispersion metal oxide material and the acidic molecular sieve is from 60 to 100% by weight, based on the total weight of the catalyst. In some preferred embodiments, the catalyst of the present invention comprises 20 to 80% by weight of an inert carrier-limited high-dispersion metal oxide material, 20 to 80% by weight of an acidic molecular sieve, 0 to 5% by weight of graphite powder, and 0 to 30% by weight of a dispersant, the weight percentage being based on the total weight of the catalyst.

There is no particular limitation on the shape of the catalyst, only that it is suitable for the process intended for application. In a specific embodiment, the particle shape of the catalyst may be spherical, strip, cylindrical, semi-cylindrical, prismatic, clover, ring, pellet, regular or irregular grain or sheet.

In the present invention, the terms "powder", "particle" and "powdered particles" are used interchangeably. Method for directly preparing aromatic hydrocarbons from syngas to produce low carbon olefins

As previously mentioned, in the process of the present invention, the feed stream comprising synthesis gas is contacted with the catalyst in the reaction zone under reaction conditions sufficient to convert at least a portion of the feedstock to aromatics to provide aromatics, light olefins and unconverted The reaction effluent of the raw material.

In the process of the invention, syngas is used as the feedstock. The term "synthesis" as used herein "Gas" means a mixture of hydrogen and carbon monoxide. In the synthesis gas feed, the molar ratio of hydrogen to carbon monoxide may be from 1:9 to 9:1, preferably from 1:9 to 1:1.

In the process of the invention, the reaction zone may be one or more fixed bed reactors. The fixed bed reactor can be operated in a continuous mode. When multiple fixed bed reactors are employed, the plurality of reactors can be in series, parallel, or a combination of series and parallel.

In the method of the present invention, the reaction conditions include: a reaction temperature of 300 to 450 ° C, a reaction pressure of 0.5 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in the synthesis gas of 1:9 to 9:1, and 1000 to Syngas volume hourly space velocity in the standard state of 20000 h ^-1 .

In a preferred embodiment, the reaction conditions include: a reaction temperature of 320 to 400 ° C, a molar ratio of hydrogen to carbon monoxide in a synthesis gas of 1:9 to 1:1, a reaction pressure of 5.0 to 10.0 MPa, and 1000 Syngas volume hourly space velocity in the standard state of ~5000 h ^-1 .

In the process of the invention, the contacting step produces a reaction effluent comprising an aromatic hydrocarbon, a lower olefin, and an unconverted feedstock.

In one embodiment, the aromatic hydrocarbon is at least one selected from the group consisting of monocyclic aromatic hydrocarbons having 6 to 11 carbon atoms. Examples of the monocyclic aromatic hydrocarbon having 6 to 11 carbon atoms include, but are not limited to, benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, mesitylene, and tetramethylbenzene.

In one embodiment, the lower olefin is at least one selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, and isobutylene.

Separation of reaction effluent

In the process of the present invention, the separation of aromatic hydrocarbons, light olefins and unconverted starting materials from the reaction effluent can be carried out according to methods known per se.

Preferably, the separated unconverted feedstock can be recycled to the contacting step as part of the feed stream.

The beneficial effects that can be produced by the present invention include:

1) The process of the present invention directly converts synthesis gas to aromatic hydrocarbons, especially BTX, using a catalyst comprising at least one of an inert carrier-limited high-dispersion metal oxide material, an acidic molecular sieve, and optionally graphite powder and a dispersant. Co-production of low-carbon olefins.

2) The catalyst used in the method of the present invention has stable performance, long life, and no significant decrease in performance of the catalyst after repeated regeneration.

3) The process of the invention reduces energy consumption compared to processes known in the art for producing aromatic hydrocarbons from syngas via methanol and/or dimethyl ether.

4) The ratio of aromatic hydrocarbons to lower olefins as a product of the process of the invention is flexibly adjustable.

5) The inert carrier-limited high-dispersion metal oxide material used in the method of the present invention has a higher specific surface activity, higher catalytic activity, and relatively expensive active metal oxide component than the conventional metal composite oxide material. The advantages of less heavy metal ion emissions during preparation and easier to form into industrial catalysts.

DRAWINGS

1 is an XRD pattern of material A in Example 1 of the present application.

2 is an XRD pattern of the material REF-1 in Comparative Example 1 of the present application.

Detailed ways

The invention will be described in detail below with reference to examples, but the invention is not limited to the examples.

The raw materials in the examples of the present invention are all commercially available unless otherwise indicated.

In the examples, automatic gas composition analysis was performed using two Agilent 7890 gas chromatographs with a gas autosampler, a TCD detector coupled to a TDX-1 packed column, and an FID detector coupled to an FFAP and PLOT-Q capillary column.

In the examples, the conversion and selectivity are calculated based on the number of moles of carbon:

Carbon monoxide conversion = [( moles of carbon monoxide carbon in the feed) - (molar carbon monoxide carbon in the discharge)] ÷ (moles of carbon monoxide in the feed) × 100%

Aromatic selectivity = (moles of aromatic hydrocarbons in the discharge) ÷ (carbon moles of all hydrocarbon products in the discharge) × 100%

Low carbon olefin selectivity = (mole of low carbon olefin carbon in the discharge) ÷ (carbon moles of all hydrocarbon products in the discharge) × 100%

BTX selectivity = (number of moles of BTX carbon in the discharge) ÷ (molar moles of all hydrocarbon products in the discharge) × 100%

Inert carrier limited high dispersion metal oxide material

Example 1

Prepare 1L of 0.05 mol/L Zn ²⁺ and 1.0 mol/L Al ³⁺ mixed nitrate solution, slowly add 0.5 mol/L ammonia solution to control the coprecipitation reaction temperature to 70 ° C, pH 7.2, so that The metal ions were co-precipitated and aged at this temperature for 4 h, filtered, washed and dried, and calcined at 500 ° C for 4 h to obtain a highly dispersed zinc oxide material bound by an alumina inert carrier, numbered A. The mass fraction of A containing zinc is 8.3%, and the XRD pattern is shown in Fig. 1.

Example 2

Prepare 1L of 0.02mol/L Zn ²⁺ , 0.02mol/L Cr ³⁺ and 1.0mol/L Al ³⁺ mixed nitrate solution, slowly add 1.0mol/L ammonium carbonate solution to control the coprecipitation reaction temperature. 70 ° C, pH 7.5, the metal ions co-precipitate, and aged at this temperature for 4h, filtered, washed and dried, calcined at 500 ° C for 4h, to obtain a high dispersion zinc chromium oxide material limited by the alumina inert carrier, number For B. B has a zinc content of 3.1% and a chromium content of 2.5%.

Example 3

Prepare 1L of mixed nitrate solution containing 0.01mol/L Zn ²⁺ , 0.01mol/L Zr ⁴⁺ and 1.0mol/L Al ³⁺ , and slowly add 1.2mol/L sodium carbonate solution to control the coprecipitation reaction temperature. 70 ° C, pH 7.3, the metal ions co-precipitate, and aged at this temperature for 4h, filtered, washed and dried, calcined at 500 ° C for 4h, to obtain a high dispersion zinc zirconium oxide material limited by alumina inert carrier, number For C. The mass fraction of C-containing zinc is 1.5%, and the mass fraction containing zirconium is 2.1%.

Example 4

Prepare 1L of 0.01 mol/L Zn ²⁺ , 0.02 mol/L Cu ²⁺ and 1.0 mol/L Al ³⁺ mixed nitrate solution, and slowly add 1.5 mol/L potassium carbonate solution to control the co-precipitation reaction temperature. 70 ° C, pH 7.9, the metal ions co-precipitate, and aging at this temperature for 4h, filtered, washed and dried, calcined at 500 ° C for 4h, to obtain a high-dispersion zinc-copper oxide material limited by alumina inert carrier, number For D. D has a mass fraction of 1.5% and a copper content of 3.1%.

Example 5

Prepare 100mL containing 0.2mol/L Zn ²⁺ and 0.2mol/L Cr ³⁺ mixed nitrate solution, prepare 100mL of 1.0mol/L urea aqueous solution, add the above two solutions to 1mol of tetraethyl orthosilicate, room temperature After reacting for 24 hours, a gel was obtained, dried at 100 ° C, and calcined at 500 ° C for 4 h to obtain a highly dispersed zinc-chromium oxide material having a silica inert carrier confinement, numbered E. The mass fraction of E-containing zinc is 1.8%, and the mass fraction of chromium is 1.5%.

Example 6

Prepare 100mL containing 0.2mol/L Zn ²⁺ and 0.2mol/L Zr ⁴⁺ mixed nitrate solution, prepare 100mL of 1.0mol/L urea aqueous solution, add the above two solutions to 1mol of tetraethyl orthosilicate, room temperature After reacting for 24 hours, a gel was obtained, dried at 100 ° C, and calcined at 500 ° C for 4 h to obtain a highly dispersed zinc-chromium oxide material having a silica inert carrier confinement, numbered F. The mass fraction of F-containing zinc is 1.8%, and the mass fraction containing zirconium is 2.5%.

Comparative example 1

Prepare 1L of mixed nitrate solution containing 1.0mol/L Zn ²⁺ , 0.50mol/L Cr ³⁺ and 0.20mol/L Al ³⁺ , and slowly add 1.0mol/L ammonium carbonate solution to control the coprecipitation reaction temperature. 70 ° C, pH 7.5, metal ions co-precipitate, and aged at this temperature for 4h, filtered, washed, dried, calcined at 500 ° C for 4h, to obtain zinc chromium composite oxide, numbered REF-1. The XRD pattern of REF-1 is shown in Figure 2.

Modified acidic molecular sieve preparation

Example 7

A sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al=25 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. After calcination at °C for 4 h, it was immersed in an equal volume at room temperature for 24 hours with an aqueous solution of (NH ₄ ) ₂ HPO ₄ , dried, and then calcined at 550 ° C for 4 h in an air atmosphere to obtain an acidic ZSM-5 having a P content of 4%. Molecular sieve, numbered G.

Example 8

A sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al=200 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. After calcination at °C for 4 h, it was immersed in an equal volume at room temperature for 24 hours with H ₃ BO ₃ aqueous solution, dried, and then calcined at 550 ° C for 4 h in an air atmosphere to obtain an acidic ZSM-5 molecular sieve containing B mass fraction of 8%. H.

Example 9

A sodium type ZSM-11 (Aotech) having Si/Al = 40 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-11 molecular sieve, which was 550 ° C in an air atmosphere. After calcination for 4 h, it was immersed in an equal volume of H ₃ BO ₃ aqueous solution at room temperature for 24 hours, dried, and then calcined at 550 ° C for 4 h in an air atmosphere to obtain an acidic ZSM-11 molecular sieve containing B mass fraction of 8%, numbered I.

Example 10

A sodium type ZSM-5 (Ako Corporation) having Si/Al=3 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, which was 550 ° C in an air atmosphere. After calcination for 4 h, it was reacted with cyclohexane solution of tetraethyl orthosilicate at 50 ° C for 4 hours, evaporated to dryness, and then calcined at 550 ° C for 4 h in an air atmosphere to obtain a mass fraction of Si containing 8% (excluding molecular sieves). Some of the acidic ZSM-5 molecular sieves of Si) are numbered J.

Example 11

A sodium type ZSM-5 (Fuxu Company) having Si/Al=80 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, which was 550 ° C in an air atmosphere. Calcined for 4 h, then carried with 5% volume fraction of tetramethylsilane with nitrogen, treated at 200 ° C for 3 hours, and then calcined at 550 ° C for 4 h in an air atmosphere to obtain a Si content of 2% (excluding the original molecular sieve) Acidic ZSM-5 molecular sieve of Si), numbered K.

Example 12

A sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al=60 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. After calcination at °C for 4 h, it was immersed in an equal volume at room temperature for 24 hours using a mixed aqueous solution of magnesium nitrate and lanthanum nitrate. After drying, it was calcined at 550 ° C for 4 h in an air atmosphere to obtain a mass fraction of Mg and Ce of 4% and 1%, respectively. Acidic ZSM-5 molecular sieve, numbered L.

Mixed catalyst preparation

Example 13

The inert carrier-limited high-dispersion metal oxide material A in Example 1 and the acidic molecular sieve G in Example 7 were uniformly mixed and crushed in an inert carrier-limited high-dispersion metal oxide material mass fraction of 75%. The powder was less than 0.05 mm, and then sieved to make a 1 mm particle catalyst, numbered M, and the preparation scheme is summarized in Table 1.

Examples 14-18

The preparation method is similar to that of Example 13, and the specific scheme is shown in Table 1.

Comparative example 2

The metal composite oxide REF-1 in Comparative Example 1 and the acidic molecular sieve G in Example 7 The metal composite oxide was uniformly mixed and crushed to a powder of less than 0.05 mm in a mass fraction of 75%, and then sieved to form a 1 mm pellet catalyst, numbered REF-2.

Table 1 mixed catalyst preparation scheme

Catalyst performance test

Example 19

The catalyst M 5g was placed in a stainless steel reaction tube having an inner diameter of 8 mm, and activated with 50 ml/min of hydrogen at 300 ° C for 4 h under the following conditions: reaction temperature (T) = 400 ° C, reaction pressure (P) = 4.0 MPa, The volumetric space velocity (GHSV) = 6000 h ^-1 under standard conditions, and the volume fraction of hydrogen in the synthesis gas (CO and H ₂ mixture) is V(H ₂ )% = 40%. After reacting for 500 hours, the product was analyzed by gas chromatography, and the results are shown in Table 2.

Example 20-24

The reaction conditions and reaction results are shown in Table 2. The other operation is the same as in the embodiment 19.

Comparative example 3

5 g of catalyst REF-2 was placed in a stainless steel reaction tube with an inner diameter of 8 mm, and activated with 50 ml/min of hydrogen at 300 ° C for 4 h under the following conditions: reaction temperature (T) = 400 ° C, reaction pressure (P) = 4.0 MPa, volumetric space velocity (GHSV) = 6000h ^-1 under standard conditions, volume fraction of hydrogen in synthesis gas (CO and H ₂ mixture) V(H ₂ )%=40%. After reacting for 500 hours, the product was analyzed by gas chromatography, and the results are shown in Table 2.

Table 2 Results of catalytic reactions in Examples 19-24 and Comparative Example 3

Catalyst regeneration test

Example 25

The catalyst deactivated in Example 19 was treated with a mixture of a volume fraction of 2% oxygen and 98% nitrogen at 550 ° C for 10 h to cause the catalyst to regenerate for one round and reacted under the conditions of Example 19. Five rounds were regenerated in the same manner, and the catalytic activity data after 500 hours of each reaction was selected for comparison. The results are shown in Table 3.

Table 3 Results of the catalytic reaction in Example 25

The above is only a few embodiments of the present invention, and is not intended to limit the present invention. The present invention is disclosed by the preferred embodiments, but is not intended to limit the present invention. It is within the scope of the technical solution to make a slight change or modification with the technical content disclosed above, which is equivalent to the equivalent embodiment, without departing from the scope of the present invention.

Claims (14)

A method for producing aromatic hydrocarbons from a syngas to produce low carbon olefins in parallel, the method comprising: a) contacting the feed comprising synthesis gas with a catalyst in a reaction zone under reaction conditions sufficient to convert at least a portion of the feed to provide a reaction effluent comprising aromatics, lower olefins, and unconverted feedstock; b) separating said aromatic hydrocarbons, light olefins and unconverted starting materials from said reaction effluent, Wherein the catalyst comprises at least one of an inert carrier-limited high-dispersion metal oxide material, an acidic molecular sieve, and optionally a graphite powder and a dispersant, wherein the inert carrier-limited high-dispersion metal oxide material The inert carrier is at least one of silica and alumina, and the metal oxide is present in an amount of less than or equal to 10% by mass based on the weight of the inert carrier-limited high-dispersion metal oxide material. And wherein the acidic molecule is selected from the modified acidic ZSM-5 molecular sieve, the modified acidic ZSM-11 molecular sieve, and mixtures thereof. The method of claim 1 having at least one of the following features: The reaction zone comprises a fixed bed reactor or a plurality of fixed bed reactors connected in series and / or in parallel; - the reaction conditions include: a reaction temperature of 300 to 450 ° C, a reaction pressure of 0.5 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in a synthesis gas of 1:9 to 9:1, and a standard state of 1000 to 20000 h ^-1 Lower syngas volume hourly space velocity; The metal oxide is an oxide of at least one of zinc, chromium, zirconium, copper, manganese, platinum and palladium; The content of the metal oxide in the inert carrier-limited high-dispersion metal oxide material in terms of metal is less than or equal to 5% by weight, based on the weight of the inert carrier-limited high-dispersion metal oxide material; The particle size of the metal oxide in the inert carrier-limited high-dispersion metal oxide material is less than or equal to 100 nm; - the modification of the acidic molecular sieve is one or more of phosphorus modification, boron modification, silicon modification, alkaline earth metal modification and rare earth metal modification; - the atomic ratio of silicon to aluminum in the acidic ZSM-5 and ZSM-11 molecular sieves is Si / Al = 3 ~ 200; - The shape of the catalyst is spherical, strip, cylindrical, semi-cylindrical, prismatic, clover, ring, pellet, regular or irregular grain or flake. The method of claim 1 wherein said catalyst comprises from 10 to 90% by weight of an inert carrier-limited, highly dispersed metal oxide material, from 10 to 90% by weight of an acidic molecular sieve, from 0 to 10% by weight of graphite powder, and 0 to 40% by weight of the dispersant, wherein the total content of the inert carrier-limited high-dispersion metal oxide material and the acidic molecular sieve is from 60 to 100% by weight, based on the total weight of the catalyst. The method of claim 1 wherein said catalyst comprises from 20 to 80% by weight of an inert carrier-limited, highly dispersed metal oxide material, from 20 to 80% by weight of an acidic molecular sieve, from 0 to 5% by weight of graphite powder, and 0 to 30% by weight of a dispersant, the weight percentage being based on the total weight of the catalyst. The method of claim 1 wherein said inert support-limited high-dispersion metal oxide material has an average particle size of less than or equal to 5 mm and said acidic molecular sieve particles have an average particle size of less than or equal to 5 mm; preferably said inert The carrier-limited high-dispersion metal oxide material has an average particle diameter of less than or equal to 0.05 mm, and the acidic molecular sieve particles have an average particle diameter of less than or equal to 0.05 mm. The method of claim 1 wherein said catalyst is prepared by a process comprising the steps of: (1) providing a highly dispersed metal oxide material having an inert carrier confinement; (2) providing a modified acidic molecular sieve; (3) mixing at least one of the inert carrier-limited high-dispersion metal oxide material obtained in the step (1), the modified acidic molecular sieve obtained in the step (2), and optionally the graphite powder and the dispersant, The resulting mixture was molded into shape. The method of claim 6 wherein said method for preparing a catalyst has at least one of the following features: - in step (1), preparing the inert carrier-limited high-dispersion metal oxide material by a precipitation-calcination method, or preparing the inert carrier-limited high-dispersion metal oxide material by a sol-gel method; - the modified acidic molecule is screened from a ZSM-5 molecular sieve and a ZSM-11 molecular sieve modified by phosphorus modification, boron modification, silicon modification, alkaline earth metal modification and/or rare earth metal modification; - In the step (3), the mixture is molded into catalyst particles by an extrusion method or a molding method. The method of claim 6, wherein in the step (1) of the method for preparing a catalyst, the inert carrier-limited high-dispersion metal oxide material is provided by a method comprising the steps of: catalytically active metal a salt and an aluminum salt are mixed into a mixed metal salt solution; contacting the mixed metal salt aqueous solution with an aqueous solution of a precipitating agent to coprecipitate the metal ions in the mixed metal salt aqueous solution; aging; and washing and drying the precipitate Calcination produces a highly dispersed metal oxide material that is inert to the carrier. The method of claim 8 having at least one of the following features: a salt of said catalytically active metal and said aluminum salt being selected from the group consisting of hydrochlorides, sulfates and nitrates; The precipitating agent is selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and mixtures thereof; - the coprecipitation is carried out at 0 ° C to 90 ° C; - the pH value during the coprecipitation is 7.0 to 8.5; - the aging time is not less than 1 hour; - the calcination is carried out at 300 ° C to 700 ° C. The method of claim 6, wherein in the step (1) of the method for preparing a catalyst, the inert carrier-limited high-dispersion metal oxide material is provided by a method comprising the steps of: catalytically active metal The aqueous solution of the salt is added to the siloxane-based compound together with the aqueous solution of the precipitating agent, and the coprecipitation and the sol-gel reaction are allowed to proceed, and then the obtained gel is washed, dried, and calcined to obtain a high inert carrier. Disperse metal oxide materials. The method of claim 10 having at least one of the following features: The precipitating agent is selected from the group consisting of ammonium carbonate, aqueous ammonia, ammonium hydrogencarbonate, ammonium dihydrogen phosphate, urea, and mixtures thereof; - the siloxane-based compound is an alkyl orthosilicate, preferably selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, n-butyl orthosilicate Ester, isobutyl orthosilicate, tert-butyl orthosilicate, and mixtures thereof. The method of claim 1 wherein said reaction conditions comprise: a reaction temperature of from 320 to 400 ° C, a reaction pressure of from 5.0 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in the synthesis gas of from 1:9 to 1:1, and Syngas volume airspeed in the standard state of 1000 to 5000 h ^-1 . The method of claim 1, wherein the aromatic hydrocarbon is at least one selected from the group consisting of monocyclic aromatic hydrocarbons having 6 to 11 carbon atoms, and the lower olefin is selected from the group consisting of ethylene, propylene, and 1-butene. At least one of 2-butene and isobutylene. The method of claim 1 further comprising: c) recycling the unconverted starting material from step b) to step a).

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