Method for preparing hydrocarbon fuel through carbon dioxide hydrogenation on InOx-coated NPC / [Zn, Al] Beta molecular sieve bifunctional catalyst

Abstract

The invention relates to a method for preparing hydrocarbon fuel through carbon dioxide hydrogenation on an InOx (at) NPC / [Zn, Al] Beta molecular sieve bifunctional catalyst, and aims to solve the problems of weak carbon dioxide activation capability, low added value of products and the like when the existing bifunctional catalyst is used in a carbon dioxide hydrogenation conversion reaction process. The method for preparing the hydrocarbon fuel comprises the following steps: adsorbing In < 3 + > in a water solution by using pretreated phosphoramidate chelate resin, carbonizing to prepare N and P doped carbon-confined indium oxide, mixing with a Zn in-situ isomorphous replacement [Zn, Al] Beta molecular sieve to prepare a bifunctional catalyst, filling a fixed bed reactor with the bifunctional catalyst, activating, introducing CO2 and H2-Ar mixed gas, and carrying out in-situ isomorphous replacement to prepare the hydrocarbon fuel. The hydrocarbon fuel is obtained under certain reaction conditions. The bifunctional catalyst provided by the invention can realize concerted catalysis of a metal site and an acid site, not only significantly improves the CO2 conversion rate, but also improves the selectivity and yield of target products butane and aromatic hydrocarbon which can be used as fuels.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for preparing hydrocarbon fuel by carbon dioxide hydrogenation on an N, P-doped carbon-confined InOx@NPC and Zn isomorphous substitution modified Beta molecular sieve (InOx@NPC / [Zn, Al]Beta) bifunctional catalyst. BACKGROUND

[0002] With the rapid development of modern industry, the over-consumption of fossil fuels has led to a year-on-year increase in the concentration of carbon dioxide in the atmosphere, causing increasingly serious ecological and environmental problems. In order to achieve sustainable development of industry, methods for carbon dioxide capture and resource utilization have become a hot topic of widespread concern. Carbon dioxide can be used as a C1 resource. In recent years, significant progress has been made in the research of carbon dioxide hydrogenation into chemicals such as methanol, C2-C4 low-carbon olefins, butane and aromatic hydrocarbons. Butane in C4 hydrocarbons is widely used as a raw material for fuel, refrigerant and synthetic chemicals, while aromatic hydrocarbons, as a basic chemical raw material, can be widely used in the aerospace, textile and other industries, have high added value, and are also important blending components for improving the octane number of gasoline. However, due to the chemical inertness of carbon dioxide and its multi-path conversion characteristics, the catalytic conversion process of carbon dioxide will lead to high selectivity of carbon monoxide and low selectivity of hydrocarbon target products. Therefore, it is still a great challenge to convert carbon dioxide into butane and aromatic hydrocarbons and other fuel and chemical components with high selectivity, and the development of high-efficiency bifunctional catalysts is the key to the selective conversion of carbon dioxide into butane and aromatic hydrocarbons and other products.

[0003] Carbon dioxide hydrogenation conversion to hydrocarbon compounds usually uses a bifunctional catalyst with metal active sites and acid sites. The metal active sites of the bifunctional catalyst are usually provided by metal oxides, and the acid sites are mainly provided by zeolite molecular sieves. Carbon dioxide hydrogenation conversion can be achieved by the Fischer-Tropsch path and the methanol intermediate path. The Fischer-Tropsch path usually uses a catalyst composed of Fe-based oxides or carbides and molecular sieves, and the reaction products are limited by the ASF distribution, and the selectivity of hydrocarbon products as liquid fuels is low. When a bifunctional catalyst with ZnZrOx complex metal oxide as the metal site is used, carbon dioxide hydrogenation conversion follows the methanol intermediate path, and the products are not limited by the ASF distribution, and can be prepared with high selectivity.

[0004] The distribution and selectivity of hydrocarbon compounds produced by carbon dioxide hydrogenation are closely related to the type of metal oxide and the type of molecular sieve that provides acidic sites and its pore characteristics. The metal sites of bifunctional catalysts for carbon dioxide hydrogenation following the methanol intermediate pathway usually include ZnZrOx, ZnAlOx, and ZnCrOx, etc. Composite metal oxides prepared by co-precipitation, hydrothermal synthesis, and sol-gel methods have large crystal grain sizes, few exposed active sites, and low oxygen vacancy density that can activate carbon dioxide, thus limiting their ability to catalyze carbon dioxide conversion. In order to improve the conversion rate of carbon dioxide, the reaction needs to be carried out at a higher temperature, but high temperature will exacerbate the occurrence of reverse water gas shift reaction, resulting in an increase in the selectivity of by-products such as carbon monoxide, and a decrease in the selectivity of hydrocarbon target products to varying degrees. Therefore, it is crucial to develop new methods for preparing metal oxides to expose more active sites and build more oxygen vacancies to improve the activation ability of carbon dioxide, while inhibiting the reverse water gas shift side reaction, for the development of high-efficiency catalysts for the hydrogenation of carbon dioxide to produce hydrocarbon fuels. Indium (In), indium oxide (In2O3), and other metal composite or double metal oxide catalysts prepared therefrom have abundant oxygen vacancies and strong ability to activate carbon dioxide, making them suitable catalysts for the hydrogenation of carbon dioxide to methanol (CN120460007A and CN119076045A). However, nanometer metals may agglomerate during their preparation or application, resulting in a decrease in catalytic active sites.

[0005] In the reaction of carbon dioxide hydrogenation to produce C4 hydrocarbons and liquid hydrocarbons, methanol intermediates generated on the surface of metal oxides diffuse to the acid sites of molecular sieves to further undergo C-C coupling and further conversion into hydrocarbon products. The pore characteristics and acidity of molecular sieves are crucial to their catalytic activity and the distribution of hydrocarbon products. Compared with other zeolites, Beta zeolite molecular sieves with three-dimensional twelve-membered ring openings and helical channels help form hydrocarbon pool species (HCP) such as methylbenzene and methylnaphthalene, and further promote the conversion of methanol intermediates into butane. However, Beta silicoaluminate zeolite molecular sieves have strong acidity, which not only reduces the yield of hydrocarbon products, but also leads to the generation of polyaromatic hydrocarbons, thereby accelerating the deactivation of the catalyst due to carbon deposition. Modifying silicoaluminate molecular sieves to reduce their acid strength is expected to improve their catalytic stability and the selectivity of hydrocarbon products. The isomorphous substitution method introduces Ga, Zt, Zn, etc. heteroatoms into the zeolite framework by in-situ synthesis or post-synthesis, replaces all or part of the framework Al of the molecular sieve, and realizes fine adjustment of the acidity of the molecular sieve by changing the type and amount of introduced heteroatoms, thereby improving its catalytic performance in carbon dioxide hydrogenation and increasing the yield of hydrocarbon fuels in the products. SUMMARY

[0006] The purpose of the present application is to solve the problems of low active site density of metal oxides, large amount of use, weak ability of activating carbon dioxide, and high selectivity of carbon monoxide caused by intensified reverse water-gas shift reaction at high reaction temperature in the existing bifunctional catalyst used in the carbon dioxide hydrogenation reaction process, and to solve the problems of excessive acidity of the Beta silicoaluminate zeolite molecular sieve providing acid sites, the main carbon dioxide hydrogenation product being gaseous hydrocarbons such as butane, and low added value of the product, and to provide a method for preparing a hydrocarbon fuel mainly composed of butane and aromatic hydrocarbons by carbon dioxide hydrogenation through a bifunctional catalyst composed of N, P doped carbon limited indium oxide (InOx@NPC) and Zn in situ isomorphous substitution modified [Zn, Al] Beta molecular sieve.

[0007] The method for preparing a hydrocarbon fuel by carbon dioxide hydrogenation on the InOx@NPC / [Zn, Al] Beta molecular sieve bifunctional catalyst of the present application is realized according to the following steps:

[0008] I. The amino phosphoric acid chelating resin (D418) is mixed and stirred with deionized water, washed and dried to obtain pretreated D418 resin (PD418); then the pretreated D418 resin, deionized water and indium nitrate are mixed and stirred, (solid phase) and pyrolysis treatment is carried out under a nitrogen atmosphere at 600-800 o C to obtain N, P doped carbon limited indium oxide InOx@NPC;

[0009] II. The silica sol is used as a silicon source, the sodium aluminate is used as an aluminum source, the sodium hydroxide is used as an alkali source, the zinc oxide is used as a zinc source, and the tetraethylammonium hydroxide TEAOH is used as a template agent, the silicon source is calculated according to the amount of SiO2, the aluminum source is calculated according to the amount of Al2O3, and the uniform mixing is carried out according to the molar ratio of SiO2:ZnO:Al2O3:NaOH:TEAOH:H2O=100:(0.2-1.2):(0.8-1.8):(3.0-4.0):(15-25):(1500-2000) to prepare an initial gel, which is then transferred to a stainless steel crystallization kettle with a polytetrafluoroethylene liner, and hydrothermal crystallization reaction is carried out at 135-145 o C, and the solid product is obtained after washing, drying and calcination, then the solid product is mixed with 0.5-1 mol / L of an ammonium nitrate solution, and stirring treatment is carried out at 50-80 o C to carry out ion exchange, and then washing, drying and calcination are carried out to obtain the Zn in situ isomorphous substitution nano H type [Zn, Al] Beta molecular sieve;

[0010] III. The N, P doped carbon limited indium oxide InOx@NPC is mixed with the [Zn, Al] Beta molecular sieve, and the InOx@NPC / [Zn, Al] Beta bifunctional catalyst is obtained after tabletting, grinding and sieving;

[0011] Four, the InOx@NPC / [Zn, Al]Beta molecular sieve bifunctional catalyst is loaded into a constant temperature zone of a fixed bed reactor, activated at 300-340 DEG C under a nitrogen atmosphere, after the reaction temperature is reduced, carbon dioxide and H2-Ar mixed gas are introduced into the fixed bed reactor, under the conditions that the reaction temperature is 250-350 DEG C, the reaction pressure is 1-4 MPa, the volume ratio of carbon dioxide and H2-Ar mixed gas is 1:1-4, the volume space velocity of carbon dioxide and H2-Ar mixed gas is 3000-6000 mL·g cat -1 ·h -1 The hydrocarbon fuel mainly composed of butane and aromatic hydrocarbons is obtained.

[0012] The In 3+ After carbonization under a nitrogen atmosphere, N, P doped carbon confined indium oxide (InOx@NPC) is prepared, and the [Zn, Al]Beta molecular sieve is mixed with Zn in situ to prepare a 20-40 mesh bifunctional catalyst, which is loaded into a fixed bed reactor, activated under a nitrogen atmosphere, and then mixed with CO2 and H2-Ar mixed gas in a certain proportion, under the conditions that the reaction temperature is 250-350 DEG C, the reaction pressure is 1-4 MPa, the volume space velocity of carbon dioxide and H2-Ar mixed gas is 3000-6000 mL·g cat -1 ·h- 1 The hydrocarbon fuel mainly composed of butane and aromatic hydrocarbons is obtained. The amount of indium used in the bifunctional catalyst is greatly reduced, and the catalyst has abundant oxygen vacancies that can activate carbon dioxide. The [Zn, Al]Beta molecular sieve has mild Brønsted acid sites and stronger Lewis acid sites, which can improve the carbon dioxide conversion rate and the selectivity of butane and aromatic hydrocarbons as fuel components.

[0013] The method for preparing hydrocarbon fuel by carbon dioxide hydrogenation on the InOx@NPC / [Zn, Al]Beta molecular sieve bifunctional catalyst has the following beneficial effects:

[0014] 1、The pretreated amino phosphonic acid chelating resin (PD418) is used to adsorb In 3+ After pyrolysis under a nitrogen atmosphere, a series of carbon confined InOx@NPC with different In contents is prepared. Due to the abundant oxygen vacancies, InOx@NPC has strong ability to activate carbon dioxide and hydrogen, and the carbon confinement makes InOx have good stability.

[0015] 2、The Zn isomorphously substituted modified [Zn, Al]Beta molecular sieve prepared by the Zn in-situ synthesis method in the application has more moderate Brønsted acid sites, stronger Lewis acid sites with dehydrogenation activity, and the acid sites of the bifunctional catalyst can improve the aromatic selectivity of the further conversion process of methanol intermediates.

[0016] 3、The InOx@NPC / [Zn, Al]Beta bifunctional catalyst prepared by mixing InOx@NPC and [Zn, Al]Beta molecular sieve in a certain mass ratio in the application can realize the synergistic catalysis of metal sites and acid sites, not only significantly improving the CO2 conversion rate, but also improving the selectivity and yield of butane and aromatic hydrocarbons as fuel. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is the O1s XPS spectrum of 0.4InOx@NPC in catalyst A adopted in example 1;

[0018] Figure 2 is the CO2-TPD curve of 0.4InOx@NPC in catalyst A adopted in example 1;

[0019] Figure 3 is the O1s XPS spectrum of 0.2InOx@NPC in catalyst B adopted in example 2;

[0020] Figure 4 is the CO2-TPD curve of 0.2InOx@NPC in catalyst B adopted in example 2;

[0021] Figure 5 is the O1s XPS spectrum of 0.5InOx@NPC in catalyst C adopted in example 3;

[0022] Figure 6 is the CO2-TPD curve of 0.5InOx@NPC in catalyst C adopted in example 3;

[0023] Figure 7 is the XRD spectrum of [Zn, Al]Beta-SI1 in catalyst A adopted in example 1;

[0024] Figure 8 is the SEM photo of [Zn, Al]Beta-SI1 in catalyst A adopted in example 1;

[0025] Figure 9 is the FT-IR spectrum of [Zn, Al]Beta-SI1~[Zn, Al]Beta-SI4 in catalyst A, D, E, F adopted in example 1 and examples 4~6.

[0026] Figure 10 is a Py-IR spectrum of [Zn,Al]Beta-SI1 in catalyst A employed in Example 1;

[0027] Figure 11 is an XRD spectrum of [Zn,Al]Beta-SI2 in catalyst D employed in Example 4;

[0028] Figure 12 is a SEM photo of [Zn,Al]Beta-SI2 in catalyst D employed in Example 4;

[0029] Figure 13 is a Py-IR spectrum of [Zn,Al]Beta-SI2 in catalyst D employed in Example 4;

[0030] Figure 14 is an XRD spectrum of [Zn,Al]Beta-SI3 in catalyst E employed in Example 5;

[0031] Figure 15 is a SEM photo of [Zn,Al]Beta-SI3 in catalyst E employed in Example 5;

[0032] Figure 16 is a Py-IR spectrum of [Zn,Al]Beta-SI3 in catalyst E employed in Example 5;

[0033] Figure 17 is an XRD spectrum of [Zn,Al]Beta-SI4 in catalyst F employed in Example 6;

[0034] Figure 18 is a SEM photo of [Zn,Al]Beta-SI4 in catalyst F employed in Example 6;

[0035] Figure 19 is a Py-IR spectrum of [Zn,Al]Beta-SI4 in catalyst F employed in Example 6;

[0036] Figure 20 is a catalytic performance test chart of catalysts A, B and C employed in Examples 1-3 in carbon dioxide hydrogenation reaction;

[0037] Figure 21 is a catalytic performance test chart of catalysts D, E and F employed in Examples 4-6 in carbon dioxide hydrogenation reaction;

[0038] Figure 22 is a catalytic performance test chart of catalysts G, H and I employed in Examples 8-10 in carbon dioxide hydrogenation reaction. DETAILED DESCRIPTION

[0039] Specific implementation method one: the method for preparing hydrocarbon fuel by carbon dioxide hydrogenation on the InOx@NPC / [Zn,Al]Beta bifunctional catalyst in the embodiment is implemented according to the following steps:

[0040] I. The amino phosphoric acid chelating resin (D418) is mixed with deionized water and stirred, washed and dried to obtain pretreated D418 resin (PD418). Then the pretreated D418 resin, deionized water and indium nitrate are mixed and stirred, and the solid phase is pyrolyzed at 600-800 o C under a nitrogen atmosphere to obtain N, P doped carbon confined indium oxide InOx@NPC;

[0041] II. The silica sol is used as a silicon source, the sodium aluminate is used as an aluminum source, the sodium hydroxide is used as an alkali source, the zinc oxide is used as a zinc source, and the tetraethylammonium hydroxide (TEAOH) is used as a template agent. The silicon source is calculated according to the amount of SiO2, and the aluminum source is calculated according to the amount of Al2O3. The molar ratio of SiO2:ZnO:Al2O3:NaOH:TEAOH:H2O is 100:(0.2-1.2):(0.8-1.8):(3.0-4.0):(15-25):(1500-2000). The initial gel is uniformly mixed and transferred to a stainless steel crystallization kettle with a polytetrafluoroethylene liner. The hydrothermal crystallization reaction is carried out at 135-145 o C, and the solid product is obtained. Then the solid product is mixed with a 0.5-1 mol / L ammonium nitrate solution and stirred at 50-80 o C to carry out ion exchange. After washing, drying and calcination, the Zn in-situ isomorphously substituted nano H-type [Zn,Al]Beta molecular sieve is obtained.

[0042] III. The N, P doped carbon confined indium oxide InOx@NPC is mixed with the [Zn,Al]Beta molecular sieve, and after tabletting, grinding and sieving, the InOx@NPC / [Zn,Al]Beta bifunctional catalyst is obtained.

[0043] IV. The InOx@NPC / [Zn,Al]Beta bifunctional catalyst is loaded into the constant temperature zone of a fixed bed reactor, activated at 300-340 °C under a nitrogen atmosphere, and then carbon dioxide and H2-Ar mixed gas are introduced into the fixed bed reactor after the reaction temperature is lowered. The reaction temperature is 250-350 °C, the reaction pressure is 1-4 MPa, the volume ratio of carbon dioxide to H2-Ar mixed gas is 1:1-4, and the volume space velocity of carbon dioxide and H2-Ar mixed gas is 3000-6000 mL·g cat1 -1·h -1 The reaction is carried out under the condition of 700

[0044] The amino phosphoric acid chelating resin (D418) in the embodiment has abundant porosity, large specific surface area and strong ability of adsorbing metal ions, and can form carbon carriers with defect sites through the release of N and P heteroatoms during pyrolysis, thereby realizing the carbon thermal reduction, anchoring metal nanoclusters, realizing the high dispersion and inhibition of the agglomeration of the metal nanoclusters, and forming abundant oxygen vacancies for the activation of CO2, thereby significantly improving the adsorption and activation capacity of carbon dioxide.

[0045] The N and P doped carbon confined indium oxide (InOx@NPC) in the embodiment can form more active sites (oxygen vacancies) that can adsorb and activate carbon dioxide, and therefore has strong carbon dioxide conversion capacity in the process of carbon dioxide hydrocarbon conversion. Meanwhile, the molecular sieve [Zn, Al]Beta modified by Zn isomorphous substitution can effectively weaken the Bronsted acid strength and increase the density of Lewis acid sites, can provide more suitable active sites for the methanol intermediates generated on the InOx@NPC, and promote the dehydrogenation of the naphthenic intermediates, and therefore can improve the carbon dioxide conversion rate and the aromatic hydrocarbon selectivity, and solve the problems of the composite metal oxide prepared by the co-precipitation method, such as the low oxygen vacancy density, the strong Bronsted acid in the channel of the traditional silicate Beta molecular sieve, the main product of the carbon dioxide hydrogenation reaction being n-butane with low added value, and the low aromatic hydrocarbon selectivity.

[0046] The embodiment reduces the Brønsted acid strength of the Beta molecular sieve by Zn isomorphous substitution modification, and forms Lewis acid sites with stronger dehydrogenation activity; the amino phosphoric acid chelating resin (D418) is used to adsorb In 3+ The carbon confined indium oxide (InOx@NPC) prepared by carbonization under inert atmosphere is a metal site, and the bifunctional catalyst prepared by mixing the two powders is used for carbon dioxide hydrogenation reaction, and through the synergistic catalysis of the metal site and the acid site, the selectivity of butane and aromatic hydrocarbons in the reaction product and the catalytic stability can be improved, and the catalyst has broad application potential in the resource utilization of carbon dioxide, the production of various fine chemicals with high added value and the field of clean fuel production.

[0047] Specific embodiment two: different from the specific embodiment one, the step one is pyrolysis treatment at 700 o C for 3-5 h.

[0048] Embodiment three: different from the embodiment one or two, the mass percentage content of In in InOx@NPC in step one is 0.2-0.5%.

[0049] In the embodiment, 15 parts of deionized water and 0.001-0.02 parts of indium nitrate are added to 1 part of D418 chelating resin when preparing InOx@NPC. The content of In in InOx@NPC is determined by ICP method.

[0050] Embodiment four: different from one of the embodiments one to three, the initial gel is prepared by uniformly mixing SiO2, ZnO, Al2O3, NaOH, TEAOH and H2O in step two according to the molar ratio of SiO2:ZnO:Al2O3:NaOH:TEAOH:H2O=100:(0.4-1.0):(1.0-1.6):3.5:20:(1800-2000).

[0051] Embodiment five: different from one of the embodiments one to four, the hydrothermal crystallization reaction is carried out at 135-145 o C for 4-8 days.

[0052] Embodiment six: different from one of the embodiments one to five, the stirring treatment is carried out at 50-80 o C for 4-10 h.

[0053] Embodiment seven: different from one of the embodiments one to six, the mass percentage content of Zn in [Zn, Al]Beta molecular sieve is 0.18%-0.29% and the mass percentage content of Al is 0.50%-0.66% in step two.

[0054] Embodiment eight: different from one of the embodiments one to seven, the mass ratio of InOx@NPC to [Zn, Al]Beta molecular sieve is 3:1-1:3 in step three.

[0055] Embodiment nine: different from one of the embodiments one to eight, the activation is carried out at 320-340°C under nitrogen atmosphere for 1-3 h in step four.

[0056] Embodiment ten: different from one of the embodiments one to nine, the volume content of H2 in H2-Ar mixed gas is 95% and the volume content of Ar is 5% in step four.

[0057] Eleven, the difference between this embodiment and the first to tenth embodiments is that the reaction in step four is carried out under the conditions that the reaction temperature is 280-320 °C, the reaction pressure is 2-3 MPa, the volume ratio of carbon dioxide to H2-Ar mixed gas is 1:2-3, and the volume space velocity of carbon dioxide and H2-Ar mixed gas is 4000-5000 mL·g cat -1 ·h -1 .

[0058] Example 1: The method for preparing hydrocarbon fuel by carbon dioxide hydrogenation on the InOx@NPC / [Zn,Al]Beta bifunctional catalyst is carried out according to the following steps:

[0059] I. The preparation method of N, P doped carbon confined indium oxide (InOx@NPC) is as follows: 1 part of aminophosphonic acid chelating resin (D418) and 5 parts of deionized water are mixed and stirred for 24 h, and then centrifuged, washed and dried to obtain pretreated D418 resin (PD418); then 1 part of pretreated D418 resin, 10 parts of deionized water and 0.01 part of indium nitrate are mixed and stirred for 1 h, and then centrifuged, washed and dried, and then pyrolyzed at 700 o C for 3 h under nitrogen atmosphere to obtain N, P doped carbon confined indium oxide InOx@NPC, which is recorded as 0.4InOx@NPC, i.e. the mass percentage of In is 0.4%;

[0060] II. The synthesis method of Zn isomorphously substituted [Zn,Al]Beta zeolite is as follows:

[0061] According to the mass fraction, 0.16 parts of sodium hydroxide, 10 parts of deionized water and 0.065 parts of zinc oxide are mixed and digested in a stainless steel crystallization kettle with a polytetrafluoroethylene liner, and then cooled to room temperature. Then 0.53 parts of sodium metaaluminate, 9.314 parts of a mixed solution of tetraethylammonium hydroxide and 5 parts of water, and 18.67 parts of silica sol are added, and stirred uniformly to obtain an initial gel. In the preparation of the initial gel, the molar ratio of ZnO:Al2O3 is 0.6:1.4. The initial gel is transferred to a stainless steel crystallization kettle with a polytetrafluoroethylene liner, and crystallized at 145 o C for 5 days, and then centrifuged, washed, dried and calcined to obtain a sodium type nano-Beta zeolite; the sodium type nano-Beta zeolite is mixed with a 0.5 mol / L ammonium nitrate solution, and stirred at 70 o C for 5 h to carry out ion exchange twice, and then centrifuged, washed, dried and calcined to obtain an H type nano-Zn isomorphously substituted [Zn,Al]Beta zeolite, which is recorded as [Zn,Al]Beta-SI1;

[0062] Three, 0.4InOx@NPC and [Zn, Al]Beta-SI1 molecular sieve were mixed according to a mass ratio of 1:1, tabletting, grinding and sieving into 20-40 meshes to obtain 0.4InOx@NPC / [Zn, Al]Beta-SI1 bifunctional catalyst, which was recorded as catalyst A;

[0063] Four, the 0.4InOx@NPC / [Zn, Al]Beta-SI1 bifunctional catalyst was loaded into the constant temperature zone of a fixed bed reactor, activated under nitrogen atmosphere at 320°C for 2 h, and then carbon dioxide and H2-Ar mixed gas (H2 / CO2 volume ratio = 3:1) were introduced into the fixed bed reactor under the conditions of a reaction temperature of 300°C, a reaction pressure of 3 MPa, a volume space velocity of carbon dioxide and H2-Ar (95% H2, 5% Ar) mixed gas of 4000 mL·g-1·h-1, to carry out the reaction, and a butane and aromatic hydrocarbon-based hydrocarbon fuel was obtained. cat -1 ·h -1

[0064] The compositions of the two active components in the 0.4InOx@NPC / [Zn, Al]Beta-SI1 bifunctional catalyst A prepared in Example 1 are shown in Table 1, and the composition of the hydrocarbon fuel produced by the carbon dioxide hydrogenation reaction was analyzed by gas chromatography, as shown in Table 2. The carbon dioxide conversion rate was 18.9%, the carbon monoxide selectivity was 8.9%, the butane selectivity was 41.1%, and the aromatic hydrocarbon selectivity was 35.2%.

[0065] Example 2: The difference between this example and Example 1 is that 0.005 parts of indium nitrate were added when preparing the N, P-doped carbon-confined indium oxide, which was recorded as 0.2InOx@NPC (the mass percentage content of In was 0.2%), and it was mixed with [Zn, Al]Beta-SI1 prepared according to the method in Example 1 according to a mass ratio of 1:1, tabletted and sieved into 20-40 meshes to prepare a bifunctional catalyst, which was recorded as catalyst B. The reaction temperature in the fixed bed reactor was controlled at 300°C, and the other reaction conditions were the same as in Example 1. The composition of the carbon dioxide hydrogenation reaction product was analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion rate was 16.7%, the carbon monoxide selectivity was 8.2%, the butane selectivity was 43.6%, and the aromatic hydrocarbon selectivity was 27.9%. o

[0066] ​​Example 3: The difference between this example and Example 1 is that 0.02 parts of indium nitrate is added in the preparation of N, P-doped carbon-confined indium oxide, which is denoted as 0.5InOx@NPC (the mass percentage of In is 0.5%), and the N, P-doped carbon-confined indium oxide is mixed with the [Zn, Al]Beta-SI1 prepared according to the method in Example 1 at a mass ratio of 1:1, tabletted, and sieved into 20-40 meshes to prepare a bifunctional catalyst, which is denoted as catalyst C. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in Example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 17.8%, the carbon monoxide selectivity is 9.1%, the butane selectivity is 41.0%, and the aromatic hydrocarbon selectivity is 32.4%.

[0067] Example 4: The difference between this example and Example 1 is that the molar ratio of ZnO:Al2O3 in the initial gel for preparing the Zn isomorphously substituted Beta zeolite is 0.6:1.4, and the Zn isomorphously substituted Beta zeolite prepared is denoted as [Zn, Al]Beta-SI2. The [Zn, Al]Beta-SI2 is mixed with the N, P-doped carbon-confined indium oxide 0.4InOx@NPC prepared according to the method in Example 1 at a mass ratio of 1:1, tabletted, and sieved into 20-40 meshes to prepare a bifunctional catalyst, which is denoted as catalyst D. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in Example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 18.8%, the carbon monoxide selectivity is 9.2%, the butane selectivity is 42.2%, and the aromatic hydrocarbon selectivity is 37.6%.

[0068] Example 5: The difference between this example and Example 1 is that the molar ratio of ZnO:Al2O3 in the initial gel for preparing the Zn isomorphously substituted Beta zeolite is 0.8:1.2, and the Zn isomorphously substituted Beta zeolite prepared is denoted as [Zn, Al]Beta-SI3. The [Zn, Al]Beta-SI3 is mixed with the N, P-doped carbon-confined indium oxide 0.4InOx@NPC prepared according to the method in Example 1 at a mass ratio of 1:1, tabletted, and sieved into 20-40 meshes to prepare a bifunctional catalyst, which is denoted as catalyst E. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in Example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 18.9%, the carbon monoxide selectivity is 8.8%, the butane selectivity is 41.2%, and the aromatic hydrocarbon selectivity is 39.3%.

[0069] Example 6: This example is different from example 1 in that the molar ratio of ZnO:Al2O3 in the initial gel of the Zn isomorphously substituted modified Beta zeolite is 1:1. The Zn isomorphously substituted modified Beta zeolite prepared, denoted as [Zn,Al]Beta-SI4, is mixed with the N, P doped carbon confined indium oxide 0.4InOx@NPC prepared according to the method in example 1 in a mass ratio of 1:1, tabletted and sieved into 20-40 mesh to prepare a bifunctional catalyst, denoted as catalyst F. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 18.6%, the carbon monoxide selectivity is 8.6%, the butane selectivity is 41.3%, and the aromatic selectivity is 35.6%.

[0070] Example 7: This example is different from example 1 in that the N, P doped carbon confined oxide 0.4InOx@NPC prepared according to the method in example 1 is mixed with the Zn isomorphously substituted modified Beta zeolite [Zn,Al]Beta-SI3 prepared according to the method in example 5 in a mass ratio of 2:1, tabletted and sieved into 20-40 mesh to prepare a bifunctional catalyst, denoted as catalyst G. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 21.2%, the carbon monoxide selectivity is 9.7%, the butane selectivity is 34.6%, and the aromatic selectivity is 43.5%.

[0071] Example 8: This example is different from example 1 in that the N, P doped carbon confined indium oxide 0.4InOx@NPC prepared according to the method in example 1 is mixed with the [Zn,Al]Beta-SI3 prepared according to the method in example 5 in a mass ratio of 3:1, tabletted and sieved into 20-40 mesh to prepare a bifunctional catalyst, denoted as catalyst H. The reaction temperature in the fixed bed reactor is controlled at 300 o C, and other reaction conditions are the same as in example 1. The composition of the carbon dioxide hydrogenation reaction products is analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion is 23.2%, the carbon monoxide selectivity is 11.5%, the butane selectivity is 32.9%, and the aromatic selectivity is 23.8%.

[0072] Example 9: In this example, the N, P doped carbon confined indium oxide 0.4 InOx@NPC prepared in Example 1 was mixed with [Zn, Al] Beta-SI3 prepared in Example 5 in a mass ratio of 1:2, tabletted and sieved into 20-40 mesh to prepare a bifunctional catalyst, which is denoted as Catalyst I. The reaction temperature in the fixed bed reactor was controlled at 300 o C, and other reaction conditions were the same as in Example 1. The composition of the carbon dioxide hydrogenation reaction products was analyzed by gas chromatography, and the results are shown in Table 2. The carbon dioxide conversion was 17.6%, the carbon monoxide selectivity was 8.5%, the butane selectivity was 42.7%, and the aromatic hydrocarbon selectivity was 34.2%.

[0073] Table 1: Catalyst composition in each example

[0074]

[0075] Table 2: Results of carbon dioxide hydrogenation to produce hydrocarbon fuels in each example

[0076]

[0077] Reaction conditions: reaction pressure 3 MPa, H2 / CO2=3:1 (volume ratio), total volume space velocity 4000 h -1 ;

[0078] Butane selectivity refers to the mass percentage of C4 alkanes in all hydrocarbon products in the product;

[0079] # Aromatic hydrocarbon selectivity refers to the mass percentage of aromatic hydrocarbons in all hydrocarbon products in the product.

Claims

1. A method for the hydrogenation of carbon dioxide to hydrocarbon fuels on an InOx@NPC / [Zn, Al]Beta bifunctional catalyst, characterized in that The method for preparing hydrocarbon fuel by carbon dioxide hydrogenation on the InOx@NPC / [Zn, Al]Beta bifunctional catalyst is realized according to the following steps: I. The amino phosphoric acid chelating resin and deionized water are mixed and stirred, washed and dried to obtain pretreated D418 resin; then the pretreated D418 resin, deionized water and indium nitrate are mixed and stirred, and pyrolysis treatment is carried out under a nitrogen atmosphere at 600-800 o C to obtain N, P doped carbon confined indium oxide InOx@NPC; II. Silicon sol is used as silicon source, sodium aluminate is used as aluminum source, sodium hydroxide is used as alkali source, zinc oxide is used as zinc source, and tetraethylammonium hydroxide (TEAOH) is used as template agent. The silicon source is calculated according to the amount of SiO2, and the aluminum source is calculated according to the amount of Al2O3. The molar ratio of SiO2:ZnO:Al2O3:NaOH:TEAOH:H2O is 100:(0.2-1.2):(0.8-1.8):(3.0-4.0):(15-25):(1500-2000). The initial gel is prepared by uniform mixing, and then transferred to a stainless steel crystallization kettle with a polytetrafluoroethylene liner. The initial gel is crystallized at 135-145 o C under hydrothermal conditions. After washing, drying, and calcination, a solid product is obtained. Then the solid product is mixed with 0.5-1 mol / L ammonium nitrate solution, and stirred at 50-80 o C to perform ion exchange. After washing, drying, and calcination, a Zn in-situ isomorphously substituted nano H-type [Zn,Al]Beta molecular sieve is obtained. III. mixing the N, P doped carbon confined indium oxide InOx@NPC and the [Zn, Al]Beta molecular sieve, tabletting, grinding and sieving to obtain the InOx@NPC / [Zn, Al]Beta bifunctional catalyst; Four, the InOx@NPC / [Zn, Al]Beta molecular sieve bifunctional catalyst is loaded into a constant temperature zone of a fixed bed reactor, activated at 300-340°C under a nitrogen atmosphere, after being reduced to a reaction temperature, carbon dioxide and H2-Ar mixed gas are introduced into the fixed bed reactor, the reaction temperature is 250-350°C, the reaction pressure is 1-4 MPa, the volume ratio of carbon dioxide and H2-Ar mixed gas is 1:1-4, the volume space velocity of carbon dioxide and H2-Ar mixed gas is 3000-6000 mL·g cat -1 ·h -1 Under the conditions, a hydrocarbon fuel is obtained.

2. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that Step one in 700 o pyrolysis under C for 3-5 h.

3. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that The mass percentage content of In in the N, P doped carbon confined indium oxide InOx@NPC in step one is 0.2-0.5%.

4. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step two, the initial gel is prepared by uniformly mixing SiO2, ZnO, Al2O3, NaOH, TEAOH and H2O in a molar ratio of 100: (0.4-1.0): (1.0-1.6): 3.5: 20: (1800-2000).

5. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step two, the temperature is 135-145 o C and the hydrothermal crystallization reaction is carried out for 4-8 days.

6. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step two, the temperature is 50 to 80 o C for 4 to 10 h.

7. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step two, the mass percentage content of Zn in the [Zn, Al]Beta molecular sieve is 0.18%-0.29%, and the mass percentage content of Al is 0.50%-0.66%.

8. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step three, the mass ratio of InOx@NPC to [Zn, Al]Beta molecular sieve is 3:1-1:

3.

9. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that In step four, the volume content of H2 in the H2-Ar mixed gas is 95%, and the volume content of Ar is 5%.

10. The method for carbon dioxide hydrogenation to hydrocarbon fuel on the bifunctional InOx@NPC / [Zn, Al]Beta molecular sieve catalyst according to claim 1, characterized in that The reaction in step four is carried out at a reaction temperature of 280-320 °C, a reaction pressure of 2-3 MPa, a volume ratio of carbon dioxide to H2-Ar mixed gas of 1:2-3, and a volume space velocity of carbon dioxide and H2-Ar mixed gas of 4000-5000 mL·g cat -1 ·h -1 .

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