CN110743606A

CN110743606A - Catalyst for preparing aromatic hydrocarbon by carbon dioxide hydrogenation and synthetic method of aromatic hydrocarbon

Info

Publication number: CN110743606A
Application number: CN201810811469.1A
Authority: CN
Inventors: 李�灿; 曲圆直; 李泽龙; 王集杰
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2018-07-23
Filing date: 2018-07-23
Publication date: 2020-02-04
Anticipated expiration: 2038-07-23
Also published as: CN110743606B

Abstract

The invention relates to a preparation method of a catalyst for directly preparing aromatic hydrocarbon by carbon dioxide hydrogenation and a synthetic method of aromatic hydrocarbon. The invention compounds the oxide catalyst and the molecular sieve catalyst to realize the direct catalysis of CO₂And (3) hydrogenation to prepare aromatic hydrocarbon. CO 2₂The conversion rate can reach 14%, and the selectivity of aromatic hydrocarbon (carbon-based selectivity) in hydrocarbon products can reach 80%. Compared with the existing process for preparing the aromatic hydrocarbon by the carbon dioxide, the method has the advantage of high aromatic hydrocarbon selectivity.

Description

Catalyst for preparing aromatic hydrocarbon by carbon dioxide hydrogenation and synthetic method of aromatic hydrocarbon

Technical Field

The invention relates to a catalyst for directly preparing aromatic hydrocarbon by carbon dioxide hydrogenation, a preparation method of the catalyst and a synthetic method of the aromatic hydrocarbon.

Background

After the industrial revolution, mankind began to use a great deal of fossil energy, CO in the atmosphere₂The content of (A) is continuously increasing. Due to CO₂Has greenhouse effect, the global temperature is continuously increased, and the environment and the climate on which human beings and other animals and plants live are greatly influenced. Thus, CO is reduced₂The amount of emissions appears to be of critical importance and becomes a long and arduous task. Aromatic hydrocarbons are produced and scaled up onlySecond to the important organic chemical basic raw materials of ethylene and propylene, monocyclic aromatic hydrocarbons such as benzene, toluene and xylene are the main raw materials in the chemical fields of chemical fiber production, plastic preparation, synthetic rubber and the like, and the domestic demand is very large. Currently, over 90% of the world's total aromatics production comes from petroleum. However, global petroleum resources are increasingly tense, and it is urgent to find new ways to produce aromatics to ensure diversification of the aromatic production process. Thus, by CO₂Preparation of aromatic hydrocarbons can not only remove CO₂Carbon cycle is realized by using C1 resource, and CO in air can be reduced₂In an amount to improve the environment upon which humans depend for survival; on the other hand, a new path is opened up for the synthesis of the aromatic hydrocarbon, and the energy crisis caused by the shortage of petroleum resources is effectively relieved.

At present, CO₂The hydrogenation to aromatics can be achieved by a two-step process and a direct process, wherein the two-step process is the primary synthesis process. The main process of the two-step process is CO₂Hydrogenation to methanol on a copper-based catalyst, and then methanol through an MTA process to produce aromatics on a molecular sieve catalyst. The companies such as Qinghua university, Shanxi coal chemical institute of Chinese academy of sciences, Shanghai petrochemical research institute of China petrochemical, and American Mobil and Sater basic industry company abroad successively develop the process for preparing the aromatic hydrocarbon from the methanol with independent intellectual property rights. However, the MTA process suffers from poor catalyst life. CO 2₂The reports of preparing aromatic hydrocarbon by direct hydrogenation are less, and the patent [ CN 107840778A ] uses a composite catalyst of an iron-based catalyst and a molecular sieve catalyst to obtain 33 percent of CO₂Conversion and aromatics selectivity (of the hydrocarbons) of 41%. At present, CO₂The research work of hydrogenation reaction is mainly based on CO₂Fischer-Tropsch (F-T) process for the production of hydrocarbons and CO₂The process for preparing hydrocarbon by hydrogenation of methanol and methanol comprises preparing a catalyst mainly from Fe-based catalyst and metal oxide catalyst, such as In, and mixing with molecular sieve catalyst₂O₃H-ZSM-5. Nature Communications,2017,8:15174, reports a Fe-based catalyst/molecular sieve composite catalyst system, which can directly convert CO₂Hydrogenation for preparing gasoline, the selectivity of aromatic hydrocarbon in hydrocarbon products is only enoughReaching 38 percent. In such catalyst systems, CO₂CO predominantly on Fe-based catalysts₂F-T reaction causes generation of a large amount of alkane in the product, and aromatic hydrocarbon is difficult to obtain with high selectivity. The literature [ Nature Chemistry 2017, 9, 1019-1024 ] reports the application of the compound in CO₂Preparation of metal oxide In of gasoline by direct hydrogenation₂O₃The selectivity of aromatic hydrocarbon in hydrocarbon products of the molecular sieve composite catalyst system only reaches 20 percent. Due to In₂O₃The catalyst has good hydrogenation performance, a large amount of alkane exists in the product, and the aromatic hydrocarbon is difficult to obtain with high selectivity. In general, CO is currently available₂The research report of directly preparing aromatic hydrocarbon by hydrogenation reports that the selectivity of aromatic hydrocarbon is still low. Thus, CO is realized₂The research and development of the catalyst for preparing the aromatic hydrocarbon with high selectivity by direct hydrogenation is to realize CO₂The key point of the hydrogenation synthesis of aromatic hydrocarbon industrialization.

Disclosure of Invention

One of the technical problems to be solved by the invention is to solve the problem of the catalyst for preparing aromatic hydrocarbon by carbon dioxide hydrogenation, and provide a novel catalyst for preparing aromatic hydrocarbon by carbon dioxide hydrogenation, which has the characteristics of high activity and high aromatic hydrocarbon selectivity.

The second technical problem to be solved by the present invention is a method for preparing the catalyst described in one of the above technical problems.

The third technical problem to be solved by the invention is to realize the catalytic reaction process from carbon dioxide hydrogenation to aromatic hydrocarbon by adopting the catalyst in one of the technical problems.

In order to solve one of the above technical problems, the technical solution of the present invention is as follows: the catalyst is formed by physically mixing an oxide catalyst M and a molecular sieve catalyst Z, and is expressed by M/Z. The mass content of the oxide catalyst M in the catalyst is 20-80%, and the preferred mass content is 30-70%; the metal oxide catalyst M is composed of metal oxide or metal oxide and a carrier; the metal oxide comprises one or more of oxides of group IIIA, IIB, IVB and VIB elements; the mass percentage of the oxide in M is 20-100%, preferably 60-100%.

In the above technical scheme, the vector is characterized in that the vector is：SiO₂、Al₂O₃But the vector is not limited to the above two.

To solve the second technical problem, the technical solution of the present invention is as follows: the method for preparing the metal oxide catalyst M in any of the above technical problems comprises the following steps:

a. preparing a primary catalyst (the process can adopt one or more of an impregnation method, a coprecipitation method, a step precipitation method, a deposition precipitation method and a mechanical mixing method);

b. aging;

c. drying;

d. and (4) roasting.

In the above production method, in the step a, the element may be directly impregnated on the support or the oxide containing the desired element by drying.

In the above preparation method, in the step a, the element may be uniformly precipitated on the carrier using a precipitant. In the preparation method, a carrier is not needed, and the needed elements can be coprecipitated by a precipitator according to a certain proportion in the step a.

In the preparation method, in the step a, the element compounds can be uniformly precipitated on the carrier in sequence by adopting a precipitating agent.

In the above production method, in the step a, a compound containing the desired element and a carrier may be mixed to form a suspension, and the element may be precipitated on the carrier by controlling the pH.

In the preparation method, in the step a, the final pH value of the system in the precipitation process is controlled to be about 6-10.

In the above production method, one or more oxides containing the desired element may be directly produced by mechanical mixing.

The method comprises the following steps: precipitating one element contained in the oxide with required amount onto the oxide of the other element by a precipitator, drying and roasting to obtain the catalyst;

the second method comprises the following steps: precipitating one element contained in a required amount of oxide by using a precipitant, precipitating the other element contained in the oxide, drying and roasting to obtain a catalyst;

the third method comprises the following steps: mixing a solution containing one element and the other element in the required amount of oxide by a precipitant, coprecipitating, drying and roasting to obtain a catalyst;

the method four comprises the following steps: mixing the solution containing the required amount of one element and the other element in the oxide, coprecipitating on the carrier, drying, and calcining to obtain the catalyst.

In the above preparation method, a plurality of metal oxides containing the desired element may be directly mixed by mechanical mixing or ball milling.

The compound containing the metal element in the oxide described in the above-mentioned methods one to four is preferably a nitrate, but not limited to, for example, one or more of acetate, halide, sulfate (oxy) salt, and metal alkoxide.

As an example of the first method, for example, ZrO is added in a desired amount₂(commercially available) dispersed in a quantity of water, the desired amount of zinc nitrate solution and precipitant solution (ammonium carbonate) are added dropwise to the ZrO₂In the system, the final pH value of the system is controlled to be 6-10. After the dropwise addition, standing for 1-24 hours at 20-100 ℃, drying the solid product at 70-120 ℃ for 10-24 hours after suction filtration, and roasting the dried sample at 300-800 ℃ for 3-10 hours to obtain the catalyst.

As an example of the second method, the required amounts of zirconium nitrate solution and precipitant solution (ammonium carbonate) are respectively and slowly dripped into a certain amount of water, after the dripping is finished, the required amounts of chromium nitrate solution and precipitant solution (ammonium carbonate) are dripped into the system, after the dripping is finished, the required amounts of zinc nitrate solution and precipitant solution (ammonium carbonate) are dripped into the system, the final pH value of the system is controlled to be 6-10, after the dripping is finished, the system is kept stand at 20-100 ℃ for 1-24 hours, the solid product after suction filtration is dried at 70-120 ℃ for 10-24 hours, and the dried sample is calcined at 300-800 ℃ for 3-10 hours to obtain the catalyst.

As an example of the third method, the required amount of zirconium nitrate, zinc nitrate and chromium nitrate solution are mixed and added with the precipitant solution (ammonium carbonate) into a certain amount of water at the same time, the final pH value of the system is controlled to be 6-10, after the addition is finished, the mixture is kept stand for 1-24 hours at 20-100 ℃, the solid product after suction filtration is dried for 10-24 hours at 70-120 ℃, and the dried sample is calcined for 3-10 hours at 800 ℃ to obtain the catalyst.

As an example of the fourth method, for example, the required amount of carrier is dispersed in a certain amount of water, the required amount of zirconium nitrate, zinc nitrate and chromium nitrate solution is mixed and added with the precipitant solution (ammonium carbonate) dropwise into a certain amount of water, the pH value of the final system is controlled to be 6-10, after the dropwise addition is finished, the mixture is kept stand at 20-100 ℃ for 1-24 hours, the solid product after suction filtration is dried at 70-120 ℃ for 10-24 hours, and the dried sample is calcined at 300-800 ℃ for 3-10 hours to obtain the catalyst.

In the above technical scheme, the aging temperature in the step b is 40-100 ℃, preferably 80-100 ℃.

In the above technical solution, the aging time in the step b is preferably 6 to 24 hours, preferably 15 to 20 hours.

In the above technical solution, the drying temperature in the step c is 80-110 ℃, preferably 100-. In the above technical scheme, the drying time in the step c is 10-20 hours, preferably 15-20 hours. In the above technical solution, the temperature for the calcination in the step d is preferably 400-.

In order to solve the second technical problem, in the technical scheme of the invention, Z is a molecular sieve (one or more of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and MCM-22 molecular sieves). The silicon-aluminum ratio of the molecular sieve is 20-300. The molecular sieve Z may be optionally modified or unmodified. The modification can be carried out by using one or more of Zn, Ga, Mo, Ag, Mn, P and Si elements. The metal element accounts for 0.1-20% of the modified molecular sieve, preferably 0.5-10%.

To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the modified molecular sieve catalyst Z in the technical scheme of any one of the technical problems comprises the following steps:

a. loading one or more of the needed active elements Zn, Ga, Mo, Ag, Mn, P and Si on one or more molecular sieves (the process can adopt one or more of an impregnation method, an ion exchange method, a physical mixing method or a chemical liquid phase deposition method);

b. drying;

c. and (4) roasting.

In the above preparation method, in step a, the element may be impregnated on the molecular sieve by mixing the compound containing the desired active element prepared in a solution of a certain concentration with one or more molecular sieves and then directly drying by heating.

In the above preparation method, in step a, the compound containing the desired active element is prepared into a solution with a certain concentration and mixed with one or more molecular sieves, and then the element is ion-exchanged onto the molecular sieve. In the above preparation method, in the step a, the element may be supported on the molecular sieve by physically mixing the compound containing the desired active element directly with one or more molecular sieves.

In the above preparation method, in the step a, the element may be supported on the molecular sieve by mixing the compound containing the active element, one or more molecular sieves, and an organic solvent (such as hexane but not limited to hexane). The method five comprises the following steps: the Zn, Ga, Mo, Ag, Mn and P elements with required amounts are impregnated on one or more molecular sieves, and the catalyst is obtained by drying and roasting.

The method six: exchanging the Zn, Ga, Mo, Ag, Mn and P element ions with required amount to one or more molecular sieves, drying and roasting to obtain the catalyst.

The method comprises the following steps: physically mixing a compound containing Zn, Ga, Mo, Ag, Mn and P elements in required amount with one or more molecular sieves, and roasting to obtain the catalyst.

The method eight: depositing the required amount of Si element on one or more molecular sieves in a chemical liquid phase, drying and roasting to obtain the catalyst.

The compound of the element required in the above-mentioned methods five to eight is preferably a nitrate, but not limited to, such as zinc nitrate, gallium nitrate, ammonium molybdate, silver nitrate, manganese sulfate, phosphoric acid, ethyl orthosilicate.

As an example of the fifth method, for example, the required amount of zinc nitrate solution is mixed well with a certain amount of H-ZSM-5, then evaporated to dryness at 30-95 ℃, the solid product is dried at 70-120 ℃ for 10-24 hours, and the dried sample is calcined at 300-800 ℃ for 3-15 hours to obtain the catalyst.

As an example of the sixth method, for example, the required amount of zinc nitrate solution is mixed well with certain amount of H-ZSM5, H-ZSM-11, then stirred at 30-95 ℃ for 0.5-5 hours, the solid product after suction filtration is dried at 70-120 ℃ for 10-24 hours, and the dried sample is calcined at 300-800 ℃ for 3-15 hours to obtain the catalyst.

As an example of method seven, for example, desired amounts of ZnO and Ga are mixed₂O₃Fully grinding and mixing with a certain amount of H-ZSM-5, and then roasting the sample at the temperature of 300 ℃ and 800 ℃ for 3-15 hours to obtain the catalyst.

As an example of the method eight, for example, the desired amount of ethyl orthosilicate is thoroughly mixed with a certain amount of H-ZSM-5, MCM-22 and hexane, stirred at 30-150 ℃ for 0.5-24 hours, the solid product after suction filtration is dried at 70-120 ℃ for 10-24 hours, and the dried sample is calcined at 300-800 ℃ for 3-15 hours to obtain the catalyst.

In the above technical solution, the drying temperature in the step c is preferably 80-110 ℃.

In the above technical solution, the drying time in the step c is preferably 10 to 20 hours.

In the above technical solution, the temperature for the calcination in the step d is preferably 400-.

In order to solve the second technical problem, in the technical solution of the present invention, the mixing of the M and Z components can be performed by mechanical mixing, but is not limited to mechanical mixing.

To solve the third technical problem, the technical scheme of the invention is as follows: the method for synthesizing the aromatic hydrocarbon takes carbon dioxide and hydrogen as raw materials, and the aromatic hydrocarbon is prepared by reaction in the presence of the catalyst in any technical scheme of one of the technical problems.

For the synthesis reaction of aromatic hydrocarbon, the key of the invention lies in the selection of catalyst, and other process conditions such as reaction temperature and reaction pressureForce, raw material ratio, space velocity and the like can be reasonably determined by a person skilled in the art. By way of example, the reaction temperature may be 260-450 ℃; the reaction pressure can be 0.5-6 MPa; the volume ratio of hydrogen to carbon dioxide may be from 1 to 4; the space velocity of the raw material can be 200-30000 mL/(g)_catH). In order to smooth the hydrogenation reaction for better control or to improve selectivity, an inert diluent may also be added, for example, an inert diluent may be, but is not limited to, nitrogen.

When the catalyst is used for preparing aromatic hydrocarbon by carbon dioxide hydrogenation, the conversion rate of carbon dioxide can reach 14%, wherein the selectivity of CO can be reduced to below 40%, and the selectivity (carbon-based selectivity) of the aromatic hydrocarbon in the total hydrocarbon can reach 80%. The space-time yield of the aromatic hydrocarbon can reach 159.9 mg/(g)_cat·h)。

The present invention will be described in detail below by way of specific embodiments:

Detailed Description

[ example 1 ]

Catalyst preparation

54.1 g of 80-120 mesh ZrO₂(commercially available) powder was dispersed in 500 g of water, and 250 g of an aqueous zinc nitrate solution (containing 7.15 g of zinc) and an ammonium carbonate solution (0.1mmol/mL) were added dropwise to ZrO₂In the system, controlling the pH value of the system at 8-9, standing for 12 hours, filtering, washing with water, drying, roasting at 450 ℃ for 3 hours in an air atmosphere, and naturally cooling to obtain the catalyst M.

Respectively grinding M and H-ZSM-5(Si/Al is 100) with equal mass, tabletting under 30MPa, crushing and sieving to obtain particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 340 ℃, the reaction pressure is 5MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 2 ]

Catalyst preparation

54.1 g of 80-120 mesh ZrO₂The powders were mixed and dispersed in 500 g of water, and 250 g of an aqueous zinc nitrate solution (containing 28.8 g of zinc) and an ammonium carbonate solution (0.2mmol/mL) were added dropwise to ZrO₂In the system, the pH value of the system is controlled to be 9-10, the system is kept stand for 12 hours, filtered, washed by water, dried, roasted for 5 hours at the temperature of 400 ℃ in the air atmosphere, and naturally cooled to obtain the catalyst M.

Respectively grinding M and H-ZSM-5(Si/Al is 40) with equal mass, tabletting under 30MPa, crushing and sieving to obtain particles of 40-60 meshes to obtain the catalyst.

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 3 ]

Catalyst preparation

Adding 500 g of zirconium nitrate aqueous solution (containing 40.2 g of zirconium) and 0.2mmol/mL of ammonium carbonate aqueous solution dropwise into 300g of water, controlling the pH of the system to be about 6-7, after the dropwise addition is finished, slowly adding 500 g of zinc nitrate aqueous solution (containing 28.8 g of zinc) and ammonium carbonate solution dropwise into the system respectively, controlling the pH of the system to be 7-8, standing for 12 hours, filtering, washing with water, drying, roasting at 600 ℃ for 8 hours under an air atmosphere, and naturally cooling to obtain the catalyst M.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 360 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 4 ]

Catalyst preparation

500 g of zinc nitrate aqueous solution (containing 28.8 g of zinc) and 0.5mmol/mL of ammonium carbonate aqueous solution are dropwise added into 300g of water, the pH value of the system is controlled to be 6-7, after the dropwise addition is finished, 500 g of zirconium nitrate aqueous solution (containing 40.2 g of zirconium) and 0.5mmol/mL of ammonium carbonate aqueous solution are dropwise added into the system, the pH value of the system is controlled to be 6-7, the system is kept stand for 12 hours, the filtration is carried out, the washing with water and the drying are carried out, the roasting is carried out for 6 hours at 550 ℃ under the air atmosphere, and the natural cooling is carried out, so that the catalyst M is.

Respectively grinding M and H-ZSM-5(Si/Al is 150) with equal mass, tabletting under 30MPa, crushing and sieving to obtain particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 20:80:0, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 5 ]

Catalyst preparation

Respectively dripping 500 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate solution into 300g of water, controlling the pH value of the system at 9-10, standing for 12 hours, filtering, washing with water, drying, roasting at 400 ℃ for 10 hours in an air atmosphere, and naturally cooling to obtain the catalyst M.

Respectively grinding M and H-ZSM-5(Si/Al is 80) with equal mass, tabletting under 30MPa, crushing and sieving to obtain particles of 40-60 meshes to obtain the catalyst.

And (3) synthesizing aromatic hydrocarbon.

Synthesis of aromatic hydrocarbonsIn a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 270 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 6 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 300 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 7 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 320 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 8 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 340 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 9 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 360 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 10 ]

Catalyst preparation

600 g of zirconium nitrate and zinc nitrate aqueous solution (containing 40.2 g of zirconium and 52.4 g of zinc) and 0.2mmol/mL of ammonium carbonate solution are dropwise added into 200g of water, the pH value of the system is controlled to be 9-10, the mixture is kept stand for 12 hours, filtered, washed by water, dried, roasted for 8 hours at 500 ℃ in an air atmosphere, and naturally cooled to obtain the catalyst M.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 380 ℃, the reaction pressure is 2MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 20:80:0, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 11 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 440 ℃, the reaction pressure is 2MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 20:80:0, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 12 ]

Catalyst preparation

Dispersing 50g of silicon dioxide (sold on the market) in an aqueous solution, dropwise adding 600 g (40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate and zinc nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate solution into a silicon dioxide system, controlling the pH of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 8 hours in an air atmosphere, and naturally cooling to obtain the catalyst M.

Respectively grinding M and H-ZSM-5(Si/Al is 300) with equal mass, tabletting under 30MPa, crushing and sieving to obtain particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, and GHSV is 3000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 13 ]

Catalyst preparation

Respectively dripping 400 g (containing 10.4 g of chromium and 28.8 g of zinc) of chromium nitrate aqueous solution and 200g of ammonium carbonate aqueous solution (0.2mmol/mL) into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 150) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 0.5MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 14 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 2MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 15 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 16 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 5MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 17 ]

Catalyst preparation

Respectively dripping 400 g (13.9 g containing gallium and 36.4 g containing zirconium) of gallium nitrate and zirconium nitrate aqueous solution and 0.2mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 150) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 18 ]

Catalyst preparation

Respectively dripping 400 g (13.9 g containing gallium and 36.4 g containing zirconium) of gallium nitrate and zirconium nitrate aqueous solution and 0.2mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 200) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into 40-60 mesh particles to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 19 ]

Catalyst preparation

Respectively dripping 400 g (13.9 g containing gallium and 36.4 g containing zirconium) of gallium nitrate and zirconium nitrate aqueous solution and 0.2mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 300) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 20 ]

Catalyst preparation

Adding 400 g (containing 22.9 g of chromium and 36.4 g of zirconium) of indium nitrate and zirconium nitrate aqueous solution and 0.2mmol/mL of ammonium carbonate aqueous solution into 200g of water respectively in a dropwise manner, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 150) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 21 ]

Catalyst preparation

Respectively dripping 400 g (containing 10.4 g of chromium and 19.1 g of titanium) of indium nitrate and titanium trichloride aqueous solution and 0.2mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system to be 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 6 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 150) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbonHydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 22 ]

Catalyst preparation

400 g of aqueous solution of chromium nitrate, zinc nitrate and zirconium nitrate (10.4 g of chromium, 28.8 g of zinc and 40.5 g of zirconium) and 0.2mmol/mL of aqueous solution of ammonium carbonate are respectively added dropwise into 200g of water, the pH value of the system is controlled to be 6-7, the mixture is kept stand for 12 hours, filtered, washed by water, dried, roasted for 6 hours at 500 ℃ in the air atmosphere, and naturally cooled to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 100) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into 40-60 mesh particles to obtain the catalyst.

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 4MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, and GHSV is 3000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 23 ]

Catalyst preparation

Respectively dripping 400 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 600 ℃ for 3 hours in an air atmosphere, and naturally cooling to obtain the catalyst M.

Respectively taking M and H-ZMS-11(40) molecular sieves with equal mass, grinding uniformly, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbonsThe synthesis reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 24 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, and GHSV is 3000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 25 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 6000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 26 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 10000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 27 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 25000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ example 28 ]

Catalyst preparation

Respectively grinding M and H-ZMS-11(40) molecular sieves with the mass ratio of 5:1 uniformly, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 29 ]

Catalyst preparation

Respectively taking M and H-ZMS-11(40) molecular sieves with the mass ratio of 2:1, uniformly grinding, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 30 ]

Catalyst preparation

Respectively taking M and H-ZMS-11(40) molecular sieves with the mass ratio of 1:2, grinding uniformly, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 31 ]

Catalyst preparation

Respectively taking M and H-ZMS-11(40) molecular sieves with the mass ratio of 1:5, uniformly grinding, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ example 32 ]

Catalyst preparation

Respectively dripping 400 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 600 ℃ for 3 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. 200g of zinc nitrate aqueous solution (containing 0.6 g of zinc) and 30 g of H-ZSM-5(Si/Al is 100) molecular sieve are fully mixed, stirred and evaporated to dryness at 90 ℃, a solid product is dried for 10 hours at 120 ℃, roasted for 15 hours at 600 ℃ in an air atmosphere, and naturally cooled to obtain the catalyst Z. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 280 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 500 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 33 ]

Catalyst preparation

Respectively dripping 400 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 550 ℃ for 3 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. 200g of zinc nitrate aqueous solution (containing 0.6 g of zinc) and 30 g of MCM-22(Si/Al is 80) molecular sieve are fully mixed, stirred for 4 hours at 70 ℃, filtered, washed, dried at 120 ℃ for 10 hours, roasted at 800 ℃ for 15 hours in air atmosphere, and naturally cooled to obtain the catalyst Z. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 4MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 34 ]

Catalyst preparation

600 g of zirconium nitrate and zinc nitrate aqueous solution (containing 40.2 g of zirconium and 52.4 g of zinc) and 0.2mmol/mL of ammonium carbonate solution are dropwise added into 200g of water, the pH value of the system is controlled to be 9-10, the mixture is kept stand for 12 hours, filtered, washed by water, dried, roasted for 8 hours at 500 ℃ in an air atmosphere, and naturally cooled to obtain the catalyst M. 200g of zinc nitrate aqueous solution (containing 0.6 g of zinc), 10 g of phosphoric acid aqueous solution (containing 0.3 g of phosphorus) and 30 g of H-ZMS-5(Si/Al is 300) molecular sieve are fully mixed, stirred and evaporated to dryness at 90 ℃, a solid product is dried for 10 hours at 120 ℃, calcined for 15 hours at 600 ℃ in an air atmosphere, and naturally cooled to obtain the catalyst Z. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃ and the reaction pressure is 3MPa, carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 20:80:0, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 35 ]

Adding 500 g of zirconium nitrate aqueous solution (containing 40.2 g of zirconium) and 0.2mmol/mL of ammonium carbonate aqueous solution dropwise into 300g of water, controlling the pH of the system to be about 6-7, after the dropwise addition is finished, slowly adding 500 g of zinc nitrate aqueous solution (containing 28.8 g of zinc) and ammonium carbonate solution dropwise into the system respectively, controlling the pH of the system to be 7-8, standing for 12 hours, filtering, washing with water, drying, roasting at 500 ℃ for 8 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Catalyst Z was obtained by thoroughly grinding and mixing 30 g of H-ZMS-5(Si/Al ═ 80) molecular sieve and 30 g of H-ZSM-11(Si/Al ═ 40) molecular sieve. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 2MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, and GHSV is 2400 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 36 ]

Catalyst preparation

Respectively dripping 400 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 800 ℃ for 3 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Catalyst Z was obtained by thoroughly grinding and mixing 30 g of H-ZMS-5(Si/Al ═ 40) molecular sieve and 1 g of gallium oxide powder. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 360 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, and GHSV is 1500 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ example 37 ]

Catalyst preparation

Respectively dripping 400 g (containing 40.2 g of zirconium and 28.8 g of zinc) of zirconium nitrate aqueous solution and 0.1mmol/mL of ammonium carbonate aqueous solution into 200g of water, controlling the pH value of the system at 6-7, standing for 12 hours, filtering, washing with water, drying, roasting at 400 ℃ for 5 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. 3 g of ethyl orthosilicate, 50g of hexane and 10 g of H-ZMS-5(Si/Al ═ 80) molecular sieve are fully mixed, stirred for 4 hours at 50 ℃, filtered, washed by ethanol, dried for 10 hours at 120 ℃, roasted for 15 hours at 600 ℃ in an air atmosphere, and naturally cooled to obtain the catalyst Z. Respectively grinding M and Z with equal mass uniformly, tabletting under 30MPa, crushing and screening into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, the reaction pressure is 3MPa, and the carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ practical comparative example 38 ]

400 g of aqueous solution of ferric nitrate, zinc nitrate and zirconium nitrate (containing 22.4 g of iron, 40.2 g of zirconium and 28.8 g of zinc) and 0.3mmol/mL of aqueous solution of ammonium carbonate are respectively added dropwise into 300g of water, the pH value of the system is controlled to be 8-9, the mixture is kept stand for 12 hours, filtered, washed by water, dried, roasted for 3 hours at 600 ℃ in the air atmosphere, and naturally cooled to obtain the catalyst M. Respectively of equal massAnd (3) uniformly grinding the M and an H-ZSM-5(Si/Al is 0.2) molecular sieve, tabletting under 10MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst. The synthesis of aromatics is carried out in a fixed bed reactor. 2 aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). Before the introduction of the feed gas, the catalyst is in H₂The atmosphere was treated for 1 hour. For comparison, the composition of the catalyst and the results of the aromatic synthesis reaction are shown in Table 1.

[ practical comparative example 39 ]

Catalyst preparation

Respectively dripping 400 g (51.2 g of copper, 28.8 g of zinc and 3.5 g of aluminum) of copper nitrate, zinc nitrate and aluminum nitrate aqueous solution and 0.1mmol/mL of sodium carbonate aqueous solution into 300g of water, controlling the pH value of the system at 9-10, standing for 12 hours, filtering, washing with water, drying, roasting at 350 ℃ for 10 hours in an air atmosphere, and naturally cooling to obtain the catalyst M. Respectively grinding M and H-ZSM-5(Si/Al is 0.2) molecular sieves with equal mass, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 3MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 900 mL/(g)_catH). Before the introduction of the feed gas, the catalyst is in H₂The atmosphere was treated for 1 hour.

[ COMPARATIVE EXAMPLE 40 ] OF EXPERIMENTAL USE

Catalyst preparation

500 g of zinc nitrate aqueous solution (containing 28.8 g of zinc) and 0.5mmol/mL of ammonium carbonate aqueous solution are dropwise added into 300g of water, the pH value of the system is controlled to be 6-7, after the dropwise addition is finished, 500 g of zirconium nitrate aqueous solution (containing 40.2 g of zirconium) and 0.5mmol/mL of ammonium carbonate aqueous solution are dropwise added into the system, the pH value of the system is controlled to be 6-7, the system is kept stand for 12 hours, the filtration is carried out, the washing with water and the drying are carried out, the roasting is carried out for 6 hours at 550 ℃ under the air atmosphere, and the natural cooling is carried out, so that the catalyst M is. Tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ practical comparative example 41 ]

Catalyst preparation

H-ZSM-5 (Si/Al-150) is tableted under 30MPa, crushed and sieved into 40-60 mesh particles to obtain the catalyst.

Synthesis of aromatic hydrocarbons

[ practical comparative example 42 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbonHydrocarbon synthesis reaction conditions: the reaction temperature is 480 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

As is clear from comparison with examples 5 to 8, the catalyst has excellent catalytic performance within the claimed reaction temperature range of 260 ℃ and 450 ℃, and the catalytic performance is greatly reduced when the temperature exceeds the temperature range. The reaction temperature is within 300-350 ℃, and the catalyst has better catalytic performance.

[ practical comparative example 43 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

As is clear from comparison with examples 5 to 8, the catalyst has excellent catalytic performance within the claimed reaction temperature range of 260 ℃ and 450 ℃, and the catalytic performance is greatly reduced below the temperature range. The reaction temperature is within 300-350 ℃, and the catalyst has better catalytic performance.

[ example 44 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

In a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:72:4, GHSV is 1200 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

As is clear from comparison with examples 13 to 16, the catalyst has excellent catalytic performance in the claimed reaction pressure range of 0.5 to 6MPa, and the catalytic performance is greatly lowered below the reaction pressure range. When the reaction pressure is 2-5MPa, the catalyst has better catalytic performance.

[ practical comparative example 45 ]

Catalyst preparation

Synthesis of aromatic hydrocarbons

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 330 ℃, and the reaction is carried outPressure 3MPa, carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:48:28, GHSV is 35000 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

As can be seen by comparison with examples 23-27, the space velocity of the claimed feed gas is 200-30000 mL/(g)_catH), the catalyst has good catalytic performance, and the space velocity of the raw material gas exceeds the pressure range, so that the catalytic performance is greatly reduced. When the space velocity is 900-10000 mL/(g)_catH), the catalyst has better catalytic performance.

[ practical comparative example 46 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 320 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 24:12:64, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

As is clear from comparison with examples 2, 5 and 7, the catalyst has a good catalytic performance in the claimed range of 1:1 to 1:5 in terms of the volume ratio of carbon dioxide to hydrogen, and beyond this range, the catalytic performance is greatly reduced. When the volume ratio of the carbon dioxide to the hydrogen is 1:2-1:4, the catalyst has better catalytic performance.

[ practical comparative example 47 ]

Catalyst preparation

And (3) synthesizing aromatic hydrocarbon.

The synthesis of aromatics is carried out in a fixed bed reactor. Aromatic hydrocarbon synthesis reaction conditions: the reaction temperature is 320 ℃, the reaction pressure is 4MPa, and the reaction pressure is carbon dioxide: hydrogen gas: the volume ratio of nitrogen is 12:84:4, GHSV is 1800 mL/(g)_catH). The catalyst was treated in an Ar atmosphere for 1 hour before the feed gas was introduced.

[ practical comparative example 48 ]

Catalyst preparation

Respectively taking M and H-ZMS-11(40) molecular sieves with the mass ratio of 7:1, uniformly grinding, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

By comparison with examples 28 to 31, the metal oxides claimed in the claims: the molecular sieve has a mass ratio of 1:5-5:1, the catalyst has good catalytic performance, and the catalytic performance is greatly reduced when the molecular sieve exceeds the range. When the metal oxide in the catalyst: when the mass ratio of the molecular sieve is 3:7-7:3, the catalyst has better catalytic performance.

[ practical comparative example 49 ]

Catalyst preparation

Respectively taking M and H-ZMS-11(40) molecular sieves with the mass ratio of 1:7, grinding uniformly, tabletting under 30MPa, crushing and sieving into particles of 40-60 meshes to obtain the catalyst.

Synthesis of aromatic hydrocarbons

From data analysis, the product of the bifunctional catalyst system formed by the catalyst for synthesizing methanol based on metal oxide and the molecular sieve mainly contains aromatic hydrocarbon; the metal oxide catalyst not only can realize CO₂The conversion to methanol and the effective inhibition of the reverse water gas reaction, and simultaneously has mild hydrogenation performance (different from CuZnAl and FeZn catalyst systems). The key point of improving the selectivity of the aromatic hydrocarbon is the construction of a dual-function catalyst system and the coordination between the metal oxide and the molecular sieve.

TABLE 1

In table 1: c₂-C₄Hydrocarbon products with carbon chains from 2 to 4; c₅₊Is products of alkane and alkene with carbon chain more than or equal to 5; a is an aromatic hydrocarbon product.

Claims

1. A catalyst for preparing aromatic hydrocarbon by directly hydrogenating carbon dioxide is characterized in that: the catalyst is formed by physically mixing a metal oxide catalyst M and a molecular sieve catalyst Z, and is expressed by M/Z;

the mass content of the oxide catalyst M in the catalyst is 20-80%, and the preferred mass content is 30-70%;

the metal oxide catalyst M is composed of metal oxide or metal oxide and a carrier; the metal oxide comprises one or more of oxides of group IIIA, IIB, IVB and VIB elements; the mass percentage of the oxide in M is 20-100%, preferably 60-100%;

the molecular sieve catalyst Z is one or more of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and MCM-22 molecular sieves, and preferably one or two of ZSM-5 and MCM-22; the silicon-aluminum ratio of the molecular sieve is 20-300, preferably 50-150.

2. The catalyst of claim 1, wherein the metal oxide is: ga. One or more oxides of In, Zn, Cd, Ti, Zr, Cr and Mo, preferably one or more oxides of Ga, In, Zn and Zr.

3. The catalyst of claim 1, wherein the support is: SiO 2₂、Al₂O₃One or two of them; the molecular sieve catalyst Z may use a modified molecular sieve or an unmodified molecular sieve.

4. A catalyst according to any one of claims 1 to 3, characterized in that the metal oxide catalyst M according to any one of claims 1 to 3 is prepared by a method which essentially comprises one or more of impregnation, coprecipitation, fractional precipitation, precipitation by deposition or mechanical mixing, comprising the steps of:

a. the dipping method comprises the following steps: preparing a soluble compound of one or more metal elements required by the metal oxide catalyst M into a solution, mixing the solution with one or more of the carrier or the metal oxide of any one of claims 1 to 3, and then evaporating to dryness;

a coprecipitation method: homogeneously precipitating a compound of one or more metal elements required for the metal oxide catalyst M with a precipitating agent, or onto a support, or onto one or more of the metal oxides according to any one of claims 1 to 3; the precipitant is an alkaline solution, preferably sodium carbonate, sodium hydroxide, ammonium nitrate or ammonium carbonate.

A fractional precipitation method: uniformly precipitating compounds of one or more metal elements in the metal oxide catalyst M with a precipitating agent in sequence, or uniformly precipitating the compounds on a carrier, or uniformly precipitating the compounds on one or more of the metal oxides according to any one of claims 1 to 3;

deposition and precipitation method: mixing a compound of one or more metal elements required for the metal oxide catalyst M with one or more of the support or the metal oxide of any one of claims 1 to 3 to form a suspension, and allowing the metal element compound to precipitate by controlling the pH;

mechanical mixing method: directly and mechanically mixing the oxides of a plurality of metal elements required by the metal oxide catalyst M according to a certain proportion (such as a ball milling mode);

b. aging: the aging temperature is 40-100 deg.C, preferably 80-100 deg.C; the aging time is 6 to 24 hours, preferably 15 to 20 hours;

c. drying at 80-110 deg.C, preferably 100 deg.C; the drying time is 10 to 20 hours, preferably 15 to 20 hours;

d. roasting: the roasting temperature is 300-800 ℃, preferably 400-600 ℃; the roasting time is 2 to 10 hours, preferably 4 to 8 hours;

during the catalyst precipitation in step a, the pH value of the system is controlled to be 6-10, preferably 6-8.

5. The catalyst according to any one of claims 1 to 3, characterized in that the molecular sieve Z is selected from modified molecular sieves and unmodified molecular sieves; the modification can be carried out by using one or more of Zn, Ga, Mo, Ag, Mn, P and Si elements; the modified element accounts for 0.1-20% of the mass of the modified molecular sieve, preferably 0.5-10%, more preferably 1-5%;

the modification method mainly adopts one or more of an impregnation method, an ion exchange method, a physical mixing method or a chemical liquid deposition method, and comprises the following steps:

a. the dipping method comprises the following steps: preparing a soluble compound containing one or more elements of Zn, Ga, Mo, Ag, Mn and P into a solution, mixing the solution with a molecular sieve, and directly loading a modified element on the molecular sieve by drying;

ion exchange method: preparing soluble compounds containing one or more elements of Zn, Ga, Mo, Ag, Mn and P into solution, mixing the solution with a molecular sieve, and exchanging modified element ions onto the molecular sieve;

physical mixing method: directly and mechanically mixing a compound containing one or more elements of Zn, Ga, Mo, Ag, Mn and P with a molecular sieve according to a certain proportion;

chemical liquid phase deposition method: mixing a compound containing a modifying element, a molecular sieve and an organic solvent (such as hexane but not limited to hexane), and loading the modifying element on the molecular sieve;

b. drying at 80-110 deg.C for 10-20 hr;

c. roasting: the roasting temperature is 300-800 ℃, preferably 400-600 ℃; the calcination time is 3 to 12 hours, preferably 5 to 10 hours.

6. A catalyst according to any one of claims 1 to 3, characterized in that the catalyst consists of a mixture of the oxidic catalyst and the molecular sieve catalyst, the mixing being carried out by means of a mechanical mixing process, preferably a ball milling process.

7. The catalyst according to claim 1 or 6, wherein the mixed catalyst M/Z is treated in argon and/or hydrogen for 0.5-4h, preferably 0.5-2h, before reaction; the treatment temperature is the subsequent reaction temperature, and the reaction temperature can be 260-450 ℃, preferably 300-350 ℃.

8. A method for synthesizing aromatic hydrocarbon, which is characterized in that the catalyst of any one of claims 1 to 7 is used for catalyzing the reaction of preparing the aromatic hydrocarbon by directly hydrogenating carbon dioxide.

9. A process for the synthesis of aromatic hydrocarbons as claimed in claim 8, characterized in that carbon dioxide and hydrogen are used as starting materials (the volume ratio of hydrogen to carbon dioxide may be H)₂:CO₂1-4) in the presence of a catalyst as defined in any one of claims 1-7 to produce an aromatic hydrocarbon; the reaction temperature can be 260-450 ℃, preferably 300-350 ℃; the reaction pressure may be from 0.5 to 6MPa, preferably from 2 to 5 MPa; the volume ratio of hydrogen to carbon dioxide can be H₂：CO₂1-5, preferably 2-4; the space velocity of the raw material can be 200-30000 mL/(g)_catH), preferably 900-_cat·h)。

10. A process for the synthesis of an aromatic hydrocarbon according to claim 8 or 9, wherein an inert diluent is optionally added to the reaction system; in order to make the hydrogenation reaction smooth and easy to control, or to improve the selectivity, an inert diluent can be added into the reaction system, wherein the inert diluent is one or two of nitrogen or argon, and the volume content of the inert diluent in the reaction system is 0-50%, preferably 0-20%.