CN114939433A - Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof - Google Patents
Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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Abstract
The invention relates to a composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, and preparation and application thereof, wherein the composite catalyst is formed by compounding a silanization modified HZSM-5 molecular sieve doped with metal and an iron-based catalyst according to a mass ratio of 1 (0.25-4); wherein the mass ratio of the HZSM-5 molecular sieve, the metal oxide and the silicon dioxide in the metal-doped silanization modified HZSM-5 molecular sieve is 100 (0.1-0.5) to 5-30; the iron-based catalyst takes alumina as a carrier, iron element as an active component and transition metal and alkali metal as auxiliary active components. The composite catalyst obtained by the preparation method of the inventionThe catalyst has good performance and is used for catalyzing carbon dioxide hydrogenation to directly prepare aromatic hydrocarbon. CO in the reaction 2 The conversion rate of the catalyst can reach 42 percent, and CH 4 The selectivity is reduced to about 8 percent, the selectivity of aromatic hydrocarbon reaches 63 percent, wherein the selectivity of BTX accounts for over 75 percent of the total aromatic hydrocarbon.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, and preparation and application thereof.
Background
In the past two centuries, with the development of economic society and the wide use of fossil fuels such as coal, petroleum and natural gas, huge economic benefits are created for the development of human society, but a large amount of carbon dioxide is discharged at the same time, so that a series of ecological environmental problems such as global warming, glacier melting, ocean acidification and the like are caused. Therefore, CO was investigated 2 Capture and catalytic conversion of CO 2 Resource utilization is an effective way for solving the greenhouse effect, replacing fossil fuels and generating chemicals with higher economic value, and has important significance for the sustainable development of world energy and ecological environment. CO 2 2 The chemical conversion of (A) with the aim of obtaining energy or chemicals of economic value is to achieve CO 2 One of the ideal ways to recycle resources. Aromatic hydrocarbons are used as important basic chemical raw materials, and with the continuous development of petrochemical industry, the demand thereof is increasing on a global scale, so that CO is recycled 2 The process of synthesizing aromatic hydrocarbon by hydrogenation is receiving wide attention, and the research and development of the catalyst are the key to realize the synthesis of aromatic hydrocarbon by hydrogenation of carbon dioxide.
At present, CO 2 The hydrogenation for preparing aromatic hydrocarbon can be realized by a two-step method and a direct one-step method, wherein the main process of the two-step method is CO 2 Hydrogenation to methanol on a copper-based catalyst, and then methanol through an MTA process to produce aromatics on a molecular sieve catalyst. The process for preparing aromatic hydrocarbon from methanol is developed successively by Qinghua university, Shanxi coal chemical institute of Chinese academy, Dajun chemical institute of Chinese academy, and U.S. Mobil corporation abroad at home. However, the MTA process suffers from a short catalyst life. CO 2 2 The reports of preparing aromatic hydrocarbon by direct hydrogenation are less, and the research work is mainly based on CO 2 FTS process of (A) to produce hydrocarbons and CO 2 In the process of preparing hydrocarbon by preparing methanol and methanol through hydrogenation, the catalyst is mainly concentrated on a metal oxide catalyst and a Fe-based catalyst composite molecular sieve catalyst.
The patent CN109942359A uses a composite double-bed packed catalyst, the catalyst in the first bed is loaded with iron and potassium by three-dimensional honeycomb graphene as a carrierThe catalyst in the second bed layer is an acidic molecular sieve which is used for aromatizing the low-carbon olefin into aromatic hydrocarbon, and the selectivity of the aromatic hydrocarbon can be more than 68 percent. Patent CN110743606A adopts methanol intermediate route to compound oxide catalyst with molecular sieve for directly catalyzing CO 2 Preparation of aromatic hydrocarbon, CO by hydrogenation 2 The conversion rate is 14%, and the selectivity of aromatic hydrocarbon (carbon-based selectivity) in the hydrocarbon product is 80%. Patent CN107840778A uses a composite catalyst of iron-based catalyst and molecular sieve catalyst, and can obtain 33% CO 2 Conversion and aromatics selectivity (of the hydrocarbons) of 41%. Literature (Industrial)&Engineering Chemistry Research,2020,59,19194- 2 Preparation of aromatic hydrocarbon, CO by hydrogenation 2 The conversion rate reaches 36.4%, the selectivity of aromatic hydrocarbon is 35.5%, and the selectivity of byproduct CO is 10.2%. In such catalyst systems, CO 2 CO predominantly on Fe-based catalysts 2 And (3) FTS reaction, generating low-carbon olefin in the product, and aromatizing the low-carbon olefin on a molecular sieve to finally obtain the aromatic hydrocarbon.
In general, CO is currently available 2 The research report of directly preparing aromatic hydrocarbon by hydrogenation reports that the selectivity of aromatic hydrocarbon is still low. Stability of the catalyst and process is another technical challenge for future industrialization, as the main products are unstable unsaturated hydrocarbons, especially carbon dioxide hydro-synthesized aromatics. Obviously, the path for industrialization of these processes will be lengthy and continuous. Thus, CO is realized 2 The research and development of the catalyst for preparing aromatic hydrocarbon by direct hydrogenation with high selectivity is to realize CO 2 The key point of the hydrogenation synthesis of aromatic hydrocarbon industrialization.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composite catalyst for directly preparing light aromatic hydrocarbons by carbon dioxide hydrogenation, and also aims to provide a preparation method of the catalyst and an application of the catalyst in directly preparing the light aromatic hydrocarbons by carbon dioxide hydrogenation.
The technical scheme of the invention is as follows: CO 2 2 Synthetic procedure for FTS route aromatics: first, CO 2 In Fe 3 O 4 Bit reduced to CO by RWGS and then chi-Fe 5 C 2 In-situ hydrogenation to C 2 -C 5 An olefin. The olefin intermediates formed on the Fe-based component then diffuse into the pores of the zeolite and oligomerize to C on BAS 6+ An olefin. Then, C is subjected to multi-step hydrogen transfer and cyclization reactions 6+ Olefins are converted to naphthenes, which in turn produce aromatics. In addition, the aromatic hydrocarbons initially obtained undergo a series of conversions, such as alkylation, isomerization, etc., which broaden the final distribution of the aromatic products. Even small amounts of aromatics may produce polycyclic aromatics and eventually graphitized coke, resulting in catalyst deactivation. BAS plays a decisive role in the multi-step reaction process of zeolite olefin aromatization. In addition, normal and isoparaffins are produced simultaneously with the formation of aromatics, since the hydrogen transfer mechanism balances the hydrogen deficient hydrocarbons with the formation of paraffins.
In order to solve the problem of preparing CO by carbon dioxide hydrogenation 2 The method for preparing the composite catalyst for directly preparing the aromatic hydrocarbon by carbon dioxide hydrogenation is provided according to the formation principle of the aromatic hydrocarbon. The composite catalyst prepared by the preparation method has good performance, and is characterized in that (1) metal doping plays a role in dehydrogenation of generated intermediate product alkane, and is beneficial to generation of intermediate product alkene; (2) the silanization modification passivates the surface acidity of the molecular sieve, and byproducts such as alkane and the like generated by the hydrogenation of intermediate product olefin are inhibited, so that the selectivity of aromatic hydrocarbon is improved. The method (1) and the method (2) are combined to be beneficial to the generation of aromatic hydrocarbon. The invention designs a method for preparing aromatic hydrocarbon directly by using a metal-doped silanization modified HZSM-5 molecular sieve composite metal oxide catalyst for carbon dioxide hydrogenation. The method not only overcomes the problems of low selectivity of light aromatic hydrocarbon, high selectivity of byproducts and the like and the defect of difficult implementation, but also can passivate the external acid sites of zeolite and inhibit aromatic hydrocarbon isomerization and alkylation by surface silanization modification of the molecular sieve, and is beneficial to the production of the light aromatic hydrocarbon.
The specific technical scheme of the invention is as follows: a composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation is characterized in that the composite catalyst is formed by compounding a silanization modified HZSM-5 molecular sieve doped with metal and an iron-based catalyst according to a mass ratio of 1 (0.25-4); wherein the mass ratio of the HZSM-5 molecular sieve, the doping amount of the metal oxide and the loading amount of the silicon dioxide in the metal-doped silanization modified HZSM-5 molecular sieve is 100 (0.1-0.5) to 5-30; the iron-based catalyst takes alumina as a carrier, an iron element as an active component, and a transition metal and an alkali metal as auxiliary active components, wherein the mass ratio of the alumina to the iron oxide to the transition metal oxide to the alkali metal oxide is 1 (4-8) to (0.4-5) to (0.02-0.1).
Preferably, the metal oxide in the metal-doped silanization modified HZSM-5 molecular sieve is one of Rh, Pd, Fe or Zn. The preferred silicon-aluminum ratio of the HZSM-5 molecular sieve is 10-100.
Preferably, the transition metal of the iron-based catalyst is any one of Cu, Zn, Mn or Ni; the alkali metal is Na or K.
The invention also provides a method for preparing the composite catalyst, which comprises the following steps:
1) dissolving metal nitrate and tetraethyl orthosilicate in absolute ethyl alcohol, and preparing a solution;
2) weighing an HZSM-5 molecular sieve, adding the HZSM-5 molecular sieve into the solution prepared in the step 1), and stirring and ultrasonically dipping for 0.5-2 h; and (3) drying: roasting: obtaining a metal-doped silanization modified HZSM-5 molecular sieve;
3) preparing an iron-based catalyst by adopting a method combining a coprecipitation method and an isometric impregnation method;
4) respectively tabletting the metal-doped silanization modified HZSM-5 molecular sieve and the iron-based catalyst, granulating by 20-60 meshes, and physically mixing to obtain the composite catalyst.
Preferably, the drying temperature in the step 2) is 50-110 ℃, and the drying time is 5-24 h; the roasting temperature is 400-600 ℃, and the roasting time is 3-10 h.
The invention also provides the application of the composite catalyst in the direct preparation of light aromatic hydrocarbon by carbon dioxide hydrogenation. The method comprises the following specific steps:
1) firstly, filling the composite catalyst in a fixed bed reactor, introducing hydrogen with the flow rate of 50-150mL/min, reducing at normal pressure at the reduction temperature of 350-450 ℃ for 4-8 h;
2) after reduction, according to H 2 /CO 2 The molar ratio is 1-4, the space velocity of the raw material is 200- cat H) (preferably 1000 + 10000 mL/(g) cat H)), slowly increasing the pressure of the reaction system to reach the reaction pressure of 1.0-6.0MPa, and raising the temperature to 400 ℃ to start the reaction to obtain the product light aromatic hydrocarbon. Measuring reaction tail gas every 4h, and analyzing the composition of a gas product by using a gas chromatograph; after reacting for 48h, analyzing the composition of the liquid phase product by an Agilent gas chromatograph, and finally calculating to obtain CO 2 Conversion rate and light aromatic selectivity.
Has the beneficial effects that:
(1) the key point of the invention is the selection of the catalyst, and other process conditions such as reaction temperature, reaction pressure, raw material proportion, space velocity and the like can be reasonably determined. By way of example, the reaction temperature may be 250-450 ℃; the reaction pressure can be 1.0-6.0 MPa; the volume ratio of hydrogen to carbon dioxide hydrogenation can be 1-4; the space velocity can be 1000-10000 mL/(g) cat ·h)。
(2) The composite catalyst used in the invention, HZSM-5 molecular sieve is modified by silanization through metal doping, promotes the generation of intermediate product olefin, inhibits the product hydroconversion and can improve the selectivity of light aromatic hydrocarbon.
(3) When the catalyst is used for preparing aromatic hydrocarbon by carbon dioxide hydrogenation, the conversion rate of carbon dioxide can reach 42 percent, wherein CH 4 The selectivity of the aromatic hydrocarbon can be reduced to about 8 percent, and the selectivity of the aromatic hydrocarbon in the total hydrocarbon can reach 63 percent. Wherein the selectivity of BTX accounts for more than 80 percent of the total aromatic hydrocarbon.
Detailed Description
The present invention is illustrated in detail by the following specific examples, which are to be construed as merely illustrative and explanatory of the present invention and not limitative of the scope thereof.
[ example 1 ]
(1) Preparation of metal-doped silanization modified HZSM-5 molecular sieve
Weigh 10.10g Fe (NO) 3 ) 3 ·9H 2 Dissolving O and 5.2g TEOS (tetraethoxysilane) in 10mL of absolute ethyl alcohol, and stirring to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 And (25) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 2h, and drying (at the temperature of 110 ℃ for 12h), wherein the roasting temperature is 550 ℃ and the roasting time is 5h to obtain the metal-doped silanized modified HZSM-5 molecular sieve (the mass ratio of the doping amount of the HZSM-5 molecular sieve to the doping amount of the metal oxide to the loading amount of the silicon dioxide is 100:0.5: 30).
(2) Preparation of iron-based catalyst
20.2g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、0.73gZn(NO 3 ) 2 ·6H 2 O and 2.25gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 10.6g of anhydrous Na was weighed 2 CO 3 The solid is added with 100mL of deionized water to prepare Na with the concentration of 1.0mol/L 2 CO 3 D is added into the prepared Na dropwise under the condition of 80 ℃ water bath 2 CO 3 In the solution, titration was carried out while stirring, and the titration end point was pH 7. Then, after aging, washing, drying (110 ℃), and roasting (400 ℃), the roasting time is 4h, and the Fe-Zn-Al catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide is 1:4:5) is obtained.
The Fe-Zn-Al-Na catalyst is prepared by an impregnation method. Mixing 8.48g of Na 2 CO 3 Adding into deionized water to prepare 0.25mol/LNa 2 CO 3 The solution is immersed on an Fe-Zn-Al catalyst, and the Fe-Zn-Al catalyst is dried (110 ℃) and roasted (400 ℃) for 4 hours to obtain the iron-based catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide to the alkali metal oxide is 1:4:5: 0.02).
(3) The silanization modified HZSM-5 molecular sieve doped with metal and the iron-based catalyst are respectively tableted and granulated to obtain particles of 40-60 meshes, and 1.0g of the modified HZSM-5 molecular sieve catalyst and 1.0g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 350 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 1, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and raising the temperature to 320 ℃ to start the reaction.
The catalyst reaction results are shown in table 1.
[ example 2 ]
(1) Preparation of metal-doped silanization modified HZSM-5 molecular sieve
Weigh 0.024gRh (NO) 3 ) 3 And 0.71g TEOS (tetraethyl orthosilicate) are dissolved in 10mL of absolute ethyl alcohol and stirred to form a solution C with a certain concentration; in addition, 5gHZSM-5 (SiO) was weighed 2 /Al 2 O 3 100) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 0.5h, drying (the temperature is 50 ℃ and the time is 24h), and roasting (the temperature is 600 ℃ and the roasting time is 3h) to obtain the metal-doped silanized modified HZSM-5 molecular sieve (the mass ratio of the doping amount of the HZSM-5 molecular sieve and the metal oxide to the loading amount of the silicon dioxide is 100:0.1: 5).
(2) Preparation of iron-based catalyst
Weighing 10.1g Fe (NO) 3 ) 3 ·9H 2 O、6.04gCu(NO 3 ) 2 ·3H 2 O and 1.125gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 13.8g of anhydrous K are weighed out 2 CO 3 Adding 100mL of deionized water into the solid to prepare the solid with the concentration of 1.0mol/LK 2 CO 3 Adding D dropwise into the prepared K under the condition of water bath at the temperature of 80 DEG C 2 CO 3 In the solution, titration was carried out with stirring, and the titration end point was pH 10. Then aging and washingWashing, drying (50 ℃), and roasting (600 ℃) for 5 hours to obtain the Fe-Cu-Al catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide is 1:8: 0.4).
The Fe-Cu-Al-K catalyst is prepared by adopting an impregnation method. 0.138gK 2 CO 3 Adding into deionized water to prepare 0.25mol/LK 2 CO 3 The solution is immersed on a Fe-Cu-Al catalyst, and the Fe-Cu-Al catalyst is dried (50 ℃) and roasted (600 ℃) for 5 hours to obtain the iron-based catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide to the alkali metal oxide is 1:8:0.4: 0.04).
(3) The silanization modified HZSM-5 molecular sieve doped with metal and the iron-based catalyst are respectively tableted and granulated to obtain particles of 40-60 meshes, and 1.0g of the modified HZSM-5 molecular sieve catalyst and 1.0g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 350 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 3, and the space velocity of the raw material is 1000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and raising the temperature to 320 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
[ example 3 ] A method for producing a polycarbonate
(1) Preparation of metal-doped silanization modified HZSM-5 molecular sieve
Weigh 0.28gZn (NO) 3 ) 2 ·6H 2 Dissolving O and 0.71g TEOS (tetraethyl orthosilicate) in 10mL of absolute ethyl alcohol, and stirring to form a solution C with a certain concentration; in addition, 5gHZSM-5 (SiO) was weighed 2 /Al 2 O 3 100) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 1H, drying (the temperature is 50 ℃ for 24H), and roasting (the temperature is 600 ℃ for 3H) to obtain the metal-doped silanization modified HZSM-5 molecular sieve (the mass ratio of HZSM-5 molecular sieve, metal oxide doping amount and silica loading amount is 100:0.2: 10).
(2) Iron-based catalyst prepared according to example 2
(3) The silanization modified HZSM-5 molecular sieve doped with metal and the iron-based catalyst are respectively tableted and granulated to obtain particles of 20-40 meshes, and 0.4g of the modified HZSM-5 molecular sieve catalyst and 0.4g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 450 ℃, the flow rate is 50mL/min, and the reduction time is 4 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 1, and the space velocity of the raw material is 10000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 1.0MPa, and raising the temperature to 400 ℃ to start the reaction.
The catalyst reaction results are shown in table 1.
[ example 4 ]
(1) Preparation of metal-doped silanization modified HZSM-5 molecular sieve
Weigh 0.54gPd (NO) 3 ) 2 And 0.71g TEOS (tetraethyl orthosilicate) are dissolved in 10mL of absolute ethyl alcohol and are stirred and dissolved to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 100) slowly adding the molecular sieve into the solution C, uniformly stirring, standing, soaking for 2h, drying (the temperature is 80 ℃ and the time is 12h), and roasting (the temperature is 550 ℃ and the roasting time is 5h) to obtain the metal-doped silanized modified HZSM-5 molecular sieve (the mass ratio of the doping amount of the HZSM-5 molecular sieve to the doping amount of the metal oxide to the loading amount of the silicon dioxide is 100:0.3: 5).
(2) Preparation of iron-based catalyst
Weighing 20.2g Fe (NO) 3 ) 3 ·9H 2 O、1.82gNi(NO 3 ) 2 ·6H 2 O and 2.25gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 10.6g of anhydrous Na was weighed 2 CO 3 The solid is added into 100mL of deionized water to be prepared into the solution with the concentration of 1.0mol/LNa 2 Adding D dropwise into the prepared Na solution in a water bath at the temperature of 80 DEG C 2 CO 3 In the solution, titration was carried out while stirring, and the titration end point was pH 7. Then, the Fe-Ni-Al catalyst (the mass ratio of alumina to ferric oxide to transition metal oxide is 1:6:1) is obtained after aging, washing, drying (80 ℃) and roasting (550 ℃) for 6 hours.
The Fe-Ni-Al-K catalyst is prepared by an impregnation method. Mixing 0.52gNa 2 CO 3 Adding into deionized water to prepare 0.25mol/LNa 2 CO 3 The solution is dipped on a Fe-Ni-Al catalyst, and the catalyst is dried (80 ℃) and roasted (550 ℃) for 6 hours to obtain the catalyst base (the mass ratio of the alumina, the ferric oxide, the transition metal oxide and the alkali metal oxide is 1:6:1: 0.06).
(3) The silanization modified HZSM-5 molecular sieve doped with metal and the iron-based catalyst are respectively tableted and granulated to obtain particles of 20-40 meshes, and 1.6g of the modified HZSM-5 molecular sieve catalyst and 1.6g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 400 ℃, the flow rate is 150mL/min, and the reduction time is 8 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 4, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 6.0MPa, and increasing the temperature to 250 ℃ to start reaction.
The results of the catalyst reaction are shown in table 1.
[ example 5 ]
(1) Preparation of metal-doped silanization modified HZSM-5 molecular sieve
Weigh 0.024gRh (NO) 3 ) 3 And 0.71g TEOS (tetraethyl orthosilicate) are dissolved in 10mL of absolute ethyl alcohol and stirred to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 And (25) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 1h, drying (the temperature is 110 ℃ and the time is 12h), and roasting (the temperature is 550 ℃ and the roasting time is 5h) to obtain the catalyst A (the mass ratio of the HZSM-5 molecular sieve, the doping amount of the metal oxide and the loading amount of the silicon dioxide is 100:0.1: 10).
(2) Iron-based catalyst prepared according to example 2
(3) The silanization modified HZSM-5 molecular sieve doped with metal and the iron-based catalyst are respectively tableted and granulated to obtain particles of 20-40 meshes, and 0.4g of the modified HZSM-5 molecular sieve catalyst and 0.4g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 300 ℃, the flow rate is 150mL/min, and the reduction time is 4 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 4, and the space velocity of the raw material is 10000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 1.0MPa, and raising the temperature to 400 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
Comparative example 6
(2) Preparation of metal doped HZSM-5 molecular sieve
Weigh 10.10g Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 10mL of absolute ethyl alcohol, and stirring to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 Slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 2h, drying (the temperature is 110 ℃ for 5h), and roasting (the temperature is 400 ℃ for 10h) to obtain the metal-doped HZSM-5 molecular sieve (the HZSM-5 molecular sieve and the metal oxide are doped with the metal oxide), wherein the metal-doped HZSM-5 molecular sieve is prepared by the steps ofThe mass ratio of the amounts is 100: 0.1).
(1) Preparation of iron-based catalyst
Weighing 20.2g Fe (NO) 3 ) 3 ·9H 2 O、0.73gZn(NO 3 ) 2 ·6H 2 O and 2.25gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 10.6g of anhydrous K was weighed 2 CO 3 The solid is added with 100mL of deionized water to be prepared into the solution with the concentration of 1.0mol/L K 2 CO 3 Under the condition of water bath at the temperature of 80 ℃, D is dropwise added into the prepared K 2 CO 3 In the solution, titration was carried out with stirring, and the titration end point was pH 7. Then, after aging, washing, drying (110 ℃), and roasting (400 ℃), the roasting time is 4h, and the Fe-Zn-Al catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide is 1:4:2) is obtained.
The Fe-Zn-Al-K catalyst is prepared by adopting an impregnation method. Mixing 8.48gK 2 CO 3 Adding into deionized water to prepare 0.25mol/LNa 2 CO 3 The solution is immersed on an Fe-Zn-Al catalyst, and the Fe-Zn-Al catalyst is dried (110 ℃) and roasted (400 ℃) for 4 hours to obtain the iron-based catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide to the alkali metal oxide is 1:4:2: 0.1).
(3) The metal-doped HZSM-5 molecular sieve and the iron-based catalyst are respectively tableted and granulated to obtain particles of 20-40 meshes, and 0.4g of the HZSM-5 molecular sieve catalyst and 0.4g of the iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 350 ℃, the flow rate is 50mL/min, and the reduction time is 4 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 1, and the space velocity of the raw material is 1000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 1.0MPa, and raising the temperature to 450 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
Comparative example 7
(1) Preparation of metal doped HZSM-5 molecular sieve
Weigh 0.28gZn (NO) 3 ) 2 ·6H 2 Dissolving O in 10mL of absolute ethyl alcohol, and stirring to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 And (25) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 3h, drying (at the temperature of 80 ℃ for 12h), and roasting (at the temperature of 550 ℃ for 5h) to obtain the metal-doped HZSM-5 molecular sieve (the mass ratio of the doping amount of the HZSM-5 molecular sieve to the doping amount of the metal oxide is 100: 0.2).
(2) Preparation of iron-based catalyst
Weighing 15.6g Fe (NO) 3 ) 3 ·9H 2 O、0.82gMn(NO 3 ) 2 ·4H 2 O and 1.65gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 13.8g of anhydrous K was weighed 2 CO 3 The solid is added into 100mL deionized water to prepare the solution with the concentration of 1.0mol/LK 2 CO 3 Under the condition of water bath at the temperature of 80 ℃, D is dropwise added into the prepared K 2 CO 3 In the solution, titration was carried out with stirring, and the titration end point was pH 8. Then, after aging, washing, drying (110 ℃), and roasting (500 ℃), the roasting time is 5h, and the Fe-Mn-Al catalyst is obtained (the mass ratio of the alumina to the ferric oxide to the transition metal oxide is 1:8: 0.5).
The Fe-Mn-Al-K catalyst is prepared by adopting an impregnation method. 0.82gK 2 CO 3 Adding into deionized water to prepare 0.25mol/LK 2 CO 3 The solution is immersed on a Fe-Mn-Al catalyst, and the Fe-Mn-Al catalyst is dried (110 ℃) and roasted (500 ℃) for 5 hours to obtain the iron-based catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide to the alkali metal oxide is 1:8:0.5: 0.02).
(3) The metal-doped HZSM-5 molecular sieve and the iron-based catalyst are respectively tableted and granulated to obtain particles of 40-60 meshes, and 1.0g of the HZSM-5 molecular sieve catalyst and 1.0g of the iron-based catalyst B are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 400 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 1, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and raising the temperature to 320 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
Comparative example 8
(1) Preparation of silanization modified HZSM-5 molecular sieve
Weighing 3.8g TEOS (tetraethyl orthosilicate) and dissolving in 10mL absolute ethyl alcohol, and stirring to form a solution C with a certain concentration; in addition, 5g of HZSM-5 (SiO) was weighed 2 /Al 2 O 3 And (25) slowly adding the molecular sieve into the solution C, uniformly stirring, ultrasonically soaking for 0.5h, drying (at the temperature of 110 ℃ for 12h), and roasting (at the temperature of 550 ℃ for 5h) to obtain the silanized modified HZSM-5 molecular sieve (the mass ratio of the HZSM-5 molecular sieve to the silica loading is 100: 10).
(2) The iron-based catalyst prepared in example 2 was selected.
(3) The silanization modified HZSM-5 molecular sieve and the iron-based catalyst are respectively tableted and granulated to obtain particles of 40-60 meshes, and 1.0g of HZSM-5 molecular sieve catalyst and 1.0g of iron-based catalyst are respectively physically mixed to obtain the composite catalyst.
(4) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 450 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 1, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and raising the temperature to 320 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
Comparative example 9
(1) Preparation of iron-based catalyst
Weighing 20.2g Fe (NO) 3 ) 3 ·9H 2 O、0.56gCu(NO 3 ) 2 ·3H 2 O and 2.25gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 400mL of deionized water and stirred at room temperature to give a solution D. In addition, 13.8g of anhydrous K was weighed 2 CO 3 The solid is added with a certain amount of deionized water to prepare the solution with the concentration of 1.0mol/LK 2 CO 3 Under the condition of water bath at the temperature of 80 ℃, D is dropwise added into the prepared K 2 CO 3 In the solution, titration was carried out while stirring at a titration rate of 1mL/min and at a titration end point of pH 7. Then, after aging (80 ℃), washing, drying and roasting (600 ℃), the Fe-Cu-Al catalyst is obtained (the mass ratio of alumina to ferric oxide to transition metal oxide is 1:6: 2).
The Fe-Cu-Al-K catalyst is prepared by adopting an impregnation method. 0.625gK 2 CO 3 Adding into deionized water to prepare 0.25mol/LK 2 CO 3 The solution is immersed on a Fe-Cu-Al catalyst, and the Fe-Cu-Al catalyst is dried (50 ℃) and roasted (600 ℃) for 5 hours to obtain the iron-based catalyst (the mass ratio of the alumina to the ferric oxide to the transition metal oxide to the alkali metal oxide is 1:6:2: 0.1).
(2) The iron-based catalyst is tableted and granulated to obtain the 40-60 mesh iron-based catalyst. 1.0g of iron-based catalyst was taken.
(3) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by iron-based catalyst
Filling an iron-based catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40-mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the iron-based catalyst under the following conditions: the temperature is 400 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 3, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and raising the temperature to 320 ℃ to start the reaction.
The catalyst reaction results are shown in table 1.
Comparative example 10
(1) Selecting iron-based catalyst prepared in practical comparative example 9
(2) Tabletting and granulating the HZSM-5 molecular sieve and the iron-based catalyst respectively to obtain particles of 40-60 meshes, and physically mixing 1.0g of the HZSM-5 molecular sieve catalyst and 1.0g of the iron-based catalyst respectively to obtain the composite catalyst.
(3) Evaluation of reaction for preparing aromatic hydrocarbon by carbon dioxide hydrogenation catalyzed by composite catalyst
Filling the composite catalyst in a constant temperature area in the middle of a reaction tube, and filling 50g of 20-40 mesh quartz sand in the upper part and the lower part of the reaction tube respectively; reducing the composite catalyst under the following conditions: the temperature is 350 ℃, the flow rate is 80mL/min, and the reduction time is 5 h; after the reduction is finished, according to H 2 /CO 2 The molar ratio is 3, and the space velocity of the raw material is 5000 mL/(g) cat H) feeding, slowly increasing the pressure of the reaction system to 3.0MPa, and increasing the temperature to 320 ℃ to start the reaction.
The results of the catalyst reaction are shown in table 1.
TABLE 1 reaction results of different catalysts for direct production of light aromatics by carbon dioxide hydrogenation
In table 1: c 2 -C 4 Hydrocarbon products with carbon chains from 2 to 4; non-aromatic C 5+ Is products of alkane and alkene with carbon chain more than or equal to 5; aromatic is an aromatic product; BTX/A is the ratio of light aromatics to total aromatics.
Claims (8)
1. A composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation is characterized in that the composite catalyst is formed by compounding a silanization modified HZSM-5 molecular sieve doped with metal and an iron-based catalyst according to a mass ratio of 1 (0.25-4); wherein the mass ratio of the HZSM-5 molecular sieve, the metal oxide and the silicon dioxide in the metal-doped silanization modified HZSM-5 molecular sieve is 100 (0.1-0.5) to 5-30; the iron-based catalyst takes alumina as a carrier, an iron element as an active component, and a transition metal and an alkali metal as auxiliary active components, wherein the mass ratio of the alumina to the iron oxide to the transition metal oxide to the alkali metal oxide is 1 (4-8) to (0.4-5) to (0.02-0.1).
2. The composite catalyst of claim 1, wherein the metal oxide in the metal-doped silanized modified HZSM-5 molecular sieve is one of Rh, Pd, Fe, or Zn.
3. The composite catalyst of claim 1, wherein the HZSM-5 molecular sieve has a silica-alumina ratio of 10 to 100.
4. The composite catalyst according to claim 1, characterized in that the transition metal of the iron-based catalyst is any one of Cu, Zn, Mn or Ni; the alkali metal is Na or K.
5. A method for preparing the composite catalyst of claim 1, which comprises the following specific steps:
1) dissolving metal nitrate and tetraethyl orthosilicate in absolute ethyl alcohol, and preparing a solution;
2) weighing an HZSM-5 molecular sieve, adding the HZSM-5 molecular sieve into the solution prepared in the step 1), and stirring and ultrasonically dipping for 0.5-2 h; and (3) drying: roasting: obtaining a metal-doped silanization modified HZSM-5 molecular sieve;
3) preparing an iron-based catalyst by adopting a method combining a coprecipitation method and an isometric impregnation method;
4) respectively tabletting the metal-doped silanization modified HZSM-5 molecular sieve and the iron-based catalyst, granulating by 20-60 meshes, and physically mixing to obtain the composite catalyst.
6. The method according to claim 5, wherein the drying temperature in step 2) is 50-110 ℃ and the drying time is 5-24 h; the roasting temperature is 400-600 ℃, and the roasting time is 3-10 h.
7. The use of the composite catalyst of claim 1 in the direct production of light aromatics by hydrogenation of carbon dioxide.
8. The application of claim 7, which comprises the following specific steps:
1) firstly, filling the composite catalyst in a fixed bed reactor, introducing hydrogen with the flow rate of 50-150mL/min, reducing at normal pressure, wherein the reduction temperature is 350-450 ℃, and the reduction time is 4-8 h;
2) after reduction, according to H 2 /CO 2 The molar ratio is 1-4, the space velocity of the raw material is 200- cat H) feeding, boosting the pressure of a reaction system to achieve the reaction pressure of 1.0-6.0MPa, and raising the temperature to 250-400 ℃ to start reaction to obtain the product light aromatic hydrocarbon.
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| CN115845859A (en) * | 2022-11-25 | 2023-03-28 | 金宏气体股份有限公司 | Modified iron-based catalyst for synthesizing alpha-olefin by carbon dioxide hydrogenation and preparation method thereof |
| CN116510770A (en) * | 2023-01-18 | 2023-08-01 | 华东理工大学 | Composite catalyst and preparation method and application thereof |
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