CN113058583B - GaZrO x Preparation method and application of bimetallic oxide solid solution catalyst - Google Patents
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Abstract
The invention provides a carbon dioxide (CO) 2 ) High-efficiency synthesis of methanol and dimethyl ether GaZrO by hydrogenation x (Y%) preparation method and application of bimetallic solid solution catalyst, Y represents n Ga /(n Ga +n Zr ) The numerical value of (c). The catalyst is prepared by a method of solvent volatilization induced self-assembly (EISA) by taking Ga and Zr as metal sources and taking a block copolymer as a template agent. Said GaZrO x The bimetallic oxide solid solution catalyst can be applied to CO 2 The reaction for preparing the methanol and the dimethyl ether by hydrogenation is carried out at 3MPa,603K, 24000ml/(g) cat H) under conditions of CO 2 The conversion per pass exceeds 9.0%, the selectivity of methanol and dimethyl ether reaches 72.7%, and the space-time yield of methanol and dimethyl ether is 0.61g (methanol+DME) /(g cat H). The catalyst prepared by the method has better activity than the catalyst prepared by the traditional coprecipitation method under the same condition. In addition, the catalyst also has the characteristics of sintering resistance, good stability and the like.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a method for preparing methanol and dimethyl ether GaZrO by carbon dioxide hydrogenation x A preparation method and application of a bimetallic oxide solid solution catalyst.
Background
Carbon dioxide (CO) 2 ) The dramatic increase in emission has had a serious impact on the human living environment and global climate, and in recent years CO has been a major concern 2 The emission reduction and the effective utilization of the carbon dioxide cause high attention of countries all over the world. At present, CO 2 This can be reduced in three ways: control of CO 2 Emission of CO 2 Capture and storage of CO 2 Chemical transformation and utilization of. Methanol and dimethyl ether are not only heavyThe desired platform molecules, which can be further converted into fuels and valuable chemicals, can also be used as hydrogen storage compounds. Thus, CO is converted 2 As a carbon source, the catalytic hydrogenation for preparing the methanol and the dimethyl ether can realize the sustainable utilization of resources.
From CO 2 And H 2 The synthesis of methanol mainly comprises the following reactions: (1) methanol synthesis:
(2) Reverse water gas shift Reaction (RWGS):
methanol synthesis is an exothermic reaction, while the side reaction RWGS is an endothermic reaction. With increasing temperature, there is a competing relationship between methanol synthesis and the RWGS reaction. At the same time, the water produced in the two reactions accelerates the sintering of the active sites in the catalyst, which leads to the deactivation of the catalyst. In addition, CO 2 Thermodynamic stability and kinetic inertness (Δ G) f = 394.4kJ mol-1) is also an obstacle to methanol synthesis. Therefore, the design can promote CO at low temperature 2 The activation of the molecule and the catalyst system capable of preventing the formation of by-products are important indexes of the high-efficiency methanol synthesis catalyst.
CO 2 Catalysts for the hydro-synthesis of methanol can be generally classified into three types: (1) A copper-based catalyst for preparing methanol from synthetic gas is prepared from ZnO and ZrO 2 、CeO 2 、Al 2 O 3 、SiO 2 Carbon nanofibers, graphene, MOFs, and the like. Copper-based catalysts are widely used in methanol production due to low cost, but the formation of water as a by-product promotes catalyst agglomeration and oxidation of active copper, resulting in severe deactivation of the catalyst (university of continental project patent CN 101513615A, shanxi coal chemical institute patent CN 103263926A, rake technology Limited patent CN 104383928A; shanghai Hua Yi patent CN 102580750A, rake technology Limited patent CN 102240553A, xiamen university patent CN 3232Patent CN 101786001A, shanghai high research institute patent CN 103272607A); (2) noble metal-based catalysts such as Pd, au, pt, ag, etc. Although noble metal-based catalysts exhibit high activity, the preparation cost is high; (3) Bimetallic catalysts mainly comprise alloys (such as Rh-W, pd-Ga, pt-Co, pd-Zn, etc.), intermetallic compounds (such as Pd-Ga, pd-Zn, pd-In, ni-Ga, etc.) and metal oxide catalysts (patent CN 109420484A of the institute of chemical and physical research). Based on the problems of the above copper-based catalyst and noble metal-based catalyst, for CO 2 The high activity bimetallic oxide catalyst for synthesizing methanol and dimethyl ether by hydrogenation is produced, but the current preparation method is mostly limited to coprecipitation method, and high activity CO is still lacked 2 A catalyst for preparing methanol and dimethyl ether by hydrogenation.
Disclosure of Invention
The invention provides GaZrO used for synthesizing methanol and dimethyl ether by carbon dioxide hydrogenation x The preparation method of the bimetallic solid solution catalyst has the advantages of high activity, good stability, difficult inactivation and the like.
The GaZrO used for synthesizing methanol and dimethyl ether by hydrogenating carbon dioxide x The preparation method of the bimetallic solid solution catalyst is characterized by comprising the following steps: respectively preparing Ga and Zr metal salt alcohol solutions, wherein the molar loading of metal Ga is more than or equal to 7 percent and less than or equal to 36 percent, and the total molar quantity of metal ions is 10-50mmol; preparing 1-5g of template alcohol solution, wherein the mass concentration of the template is 0.01-0.5g/g Alcohol(s) (ii) a The three are continuously stirred for 12 to 24 hours at the temperature of 293K to 313K; the mixing mode comprises that the template agent alcoholic solution is dripped into the metal salt alcoholic solution, the metal salt alcoholic solution is dripped into the template agent alcoholic solution or the two are mixed in a parallel flow way; continuously stirring for 2-24h at the temperature of 293K-313K after mixing; transferring the solution into a borosilicate culture dish, and placing the borosilicate culture dish in a fume hood to stand still for 2-7 days to evaporate the solvent; the obtained gel is calcined in flowing air at 673K-873K for 3-10h.
Further, the Ga salt is one or more than two of chloride, nitrate, acetate and sulfate; the Zr salt is chloride, nitrate, acetate, sulfate, zirconyl nitrate, oxychlorideOne or more of zirconium and zirconium isopropoxide; the template agent is one or more than two of P123, F127, P84, P104, F108 and P105 block copolymers; the alcoholic solution is C 1 -C 10 One or more than two kinds of alcohol.
Furthermore, the calcining atmosphere is one or more of air, oxygen, nitrogen and helium.
The resulting GaZrO x (7, 19, 25, 27, 36%) the catalyst was in a solid solution structure, exhibiting Ga doped ZrO into ZrO 2 The structural features of the crystal lattice of (1) are shown in figure 3.
Meanwhile, the invention also provides GaZrO prepared by the preparation method x Use of a bimetallic solid solution catalyst, gaZrO x The bimetallic solid solution catalyst can be applied to the synthesis of methanol and dimethyl ether by the hydrogenation of carbon dioxide, and the application steps are as follows:
the activity evaluation of the catalyst on the reaction of synthesizing methanol and dimethyl ether by hydrogenating carbon dioxide is carried out on a pressurized fixed bed continuous flow reactor-gas chromatography combined system. Before reaction, the catalyst is activated for 1-12h at 473K-673K by one or two of pure hydrogen, argon and nitrogen. The conditions for synthesizing the methanol and the dimethyl ether by hydrogenating the carbon dioxide are as follows: the pressure of the raw material gas is 1-20MPa, the reaction temperature is 513K-673K, and the airspeed is 6000-40000 ml/(g) cat ·h)，n(H 2 )：n(CO 2 ) And (1-30). The reaction products were separated and identified using an on-line gas chromatograph equipped with a Thermal Conductivity Detector (TCD) and a hydrogen Flame Ionization Detector (FID). Capillary chromatography columns (Agilent HP-Plot Q,30m x 0.53mm x 40 μm) attached to FID were used for analysis of hydrocarbons, alcohols and other carbonaceous products. A packed column (TDX-01, 2m X3 mm, torilong information technology Co., ltd., lanzhou) connected to the TCD was analyzed for other gas products (Ar, CO, CH) 4 And CO 2 ). The line between the reactor and the valve was heated to 373K-433K to prevent condensation of the product. CH (CH) 4 As a bridge between FID and TCD for quantitative analysis of the product.
The invention develops a GaZrO prepared by a solvent evaporation induction self-assembly method x Bimetallic oxide solid solution catalystPreparation method of, gaZrO prepared x The bimetallic oxide solid solution catalyst can be used for the reaction of preparing methanol and dimethyl ether by carbon dioxide hydrogenation. The catalyst prepared by the method has better activity than the catalyst prepared by the traditional coprecipitation method under the same condition. In addition, the catalyst prepared by the preparation method has the characteristics of sintering resistance, good stability and the like.
The catalyst prepared by the preparation method can effectively convert carbon dioxide into methanol and dimethyl ether, has the optimal reaction temperature of 603-623K, and is sintering-resistant and good in stability. At 3MPa,603K, 24000ml/(g) cat H) of CO 2 The conversion per pass exceeded 9.0%, the selectivity for methanol and dimethyl ether reached 72.7%, and the space-time yield of methanol and dimethyl ether was 0.61g (methanol+DME) /(g cat ·h)。
Drawings
FIG. 1: gaZrO x (27%) 100h long-range stability of the catalyst. T =603K, P =3.0MPa, H 2 /CO 2 ＝3/1，GHSV＝24,000ml/(g cat ·h)。
FIG. 2: preparation of GaZrO by EISA method and coprecipitation method x And (3) comparing the carbon dioxide hydrogenation catalytic performances of the catalysts. Reaction conditions are as follows: t =513-653K, P =3.0MPa, H 2 /CO 2 ＝3/1，GHSV＝24,000ml/(g cat ·h)。
FIG. 3: zrO (zirconium oxide) 2 ，GaZrO x (7, 19, 25, 27, 36%) and Ga 2 O 3 Powder X-ray diffraction pattern of the catalyst. Symbols (. Circle.) and (. Circle.) denote tetragonal phase and monoclinic phase ZrO, respectively 2 。
Detailed Description
Example 1
1g of triblock copolymer P-123, 10mmol of ZrCl 4 Dissolved in two beakers containing 10g of ethanol, respectively, and stirred at room temperature for 12h. The two solutions were mixed and stirring was continued at room temperature for 2h. The resulting solution was transferred to a borosilicate petri dish and placed in a fume hood for 3-5 days, and the solvent was evaporated. Calcining the dried gel in flowing air (10 ml/min) at a heating rate of 1K/min at 773K for 5h to obtain the catalystThe agent is described as: zrO (ZrO) 2 . Tabletting, crushing and screening 230-400 μm for catalytic evaluation.
0.3g of the sieved catalyst was diluted with 0.7g of quartz sand, placed in a reaction tube at constant temperature and fixed with glass wool. At 613K, flowing H 2 (30 std ml/min, atmospheric pressure) for 2 hours, followed by cooling to the desired reaction temperature. Mixing the gas mixture V (H) 2 )：V(CO 2 ): v (Ar) =72: and (3) introducing the mixture into a reaction tube through a mass flow meter, wherein the reaction conditions are as follows: 3MPa,513-653K, GHSV =24,000ml/(g) cat H). The catalyst evaluation results are shown in Table 1.
Example 2
The metal salt used for the preparation of the catalyst is 10mmol GaCl 3 The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: ga 2 O 3 . The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 3
The catalysts of example 1 and example 2 are used as per n Ga /(n Ga +n Zr ) Ratio of =0.27, the resulting catalyst is noted as: ga 2 O 3 +ZrO 2 . The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 4
1g of triblock copolymer P-123, 0.65mmol of GaCl 3 And 9.35mmol of ZrCl 4 Dissolved in three beakers containing 10g of ethanol, respectively, and stirred at room temperature for 12h. The three solutions were mixed and stirring was continued at room temperature for 2h. The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: gaZrO x (7%). The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 5
The metal salt used for the catalyst preparation was 1.89mmol GaCl 3 And 8.11mmol of ZrCl 4 The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: gaZrO x (19%). Catalyst evaluation procedure andthe reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 6
The metal salt used for the preparation of the catalyst was 2.50mmol of GaCl 3 And 7.50mmol of ZrCl 4 The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: gaZrO x (25%). The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 7
The metal salt used for the preparation of the catalyst was 2.70mmol of GaCl 3 And 7.30mmol of ZrCl 4 The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: gaZrO x (27%). The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1. Further, at T =603k, p =3.0mpa 2 /CO 2 ＝3/1，GHSV＝24,000ml/(g cat H) for 100 hours, the catalyst showed no deactivation and exhibited a certain stability. The results are shown in FIG. 1.
Example 8
The metal salt used for the catalyst preparation was 3.60mmol GaCl 3 And 6.40mmol of ZrCl 4 The other catalyst preparation steps were the same as in example 1, and the resulting catalyst was noted as: gaZrO x (36%). The catalyst evaluation procedure and reaction conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1.
Example 9
3mmol of Ga (NO) are weighed 3 ) 3 ·9H 2 O and 8mmol of Zr (NO) 3 ) 4 ·5H 2 O, dissolved in 100ml of deionized water. 31.22mmol (NH) were stirred vigorously at 343K 4 ) 2 CO 3 The aqueous solution was added dropwise to the above metal salt solution at a rate of 3 ml/min. The product was cooled to room temperature after aging for 2h at 343K. Suction filtration, washing with deionized water for 3-4 times, and drying at 383K for 4h. Finally calcined in flowing air (10 ml/min) at a heating rate of 1K/min for 3h at 773K, and the catalyst obtained is noted: gaZrO 2 x (27%) (coprecipitation method). Catalyst evaluation procedure and reactionThe conditions were the same as in example 1, and the catalyst evaluation results are shown in Table 1 and FIG. 2.
Example 10
The catalyst preparation procedure was the same as in example 7. The reaction conditions in the catalyst evaluation step were changed to: 2MPa,513-653K, GHSV =24, 000ml/(g) cat H). The catalyst evaluation results are shown in Table 1.
Example 11
The catalyst preparation procedure was the same as in example 7. The reaction conditions in the catalyst evaluation step were changed to: 4MPa,513-653K, GHSV =24,000ml/(g) cat H). The catalyst evaluation results are shown in Table 1.
Table 1: gaZrO of different metal ratios x Catalyst, different preparation methods and catalytic evaluation results under different reaction pressures. Reaction conditions are as follows: 603K, n (H) 2 )/n(CO 2 )＝3：1。
As can be seen from Table 1, pure Ga 2 O 3 Methanol synthesis activity ratio of catalyst pure ZrO 2 The catalyst was slightly higher. GaZrO 2 x (7, 19, 25, 27, 36%) bimetallic oxide solid solution catalyst for the synthesis of methanol and dimethyl ether with (Ga) 2 O 3 +ZrO 2 ) The physically mixed catalyst was more active than the other, indicating that there was a strong synergy between Zr and Ga. Wherein the GaZrO x (27%) catalyst in CO 2 The best performance is shown in the hydrogenation reaction: at 3MPa,603K,24000mL g cat -1 h -1 Under reaction conditions of (1), gaZrO x (27%) the catalyst had 9.02% CO 2 Conversion, methanol and dimethyl ether selectivity of 72.73%, and 0.61g (methanol+DME) /(g cat H) space-time yields of methanol and dimethyl ether. Furthermore, as the pressure increased from 2MPa to 4MPa 2 The conversion rate is increased sharply, the selectivity of the methanol and the dimethyl ether is increased slightly, and the space-time yield can reach 0.76g (methanol+DME) /(g cat H). In addition, in the same reaction stripIn contrast to the coprecipitation method, gaZrO prepared by the EISA method x (27%) the catalyst exhibited better CO 2 Activity of hydrogenation to prepare methanol and dimethyl ether (figure 2).
Claims (4)
1.GaZrO x The application of the bimetallic oxide solid solution catalyst in the synthesis of methanol and dimethyl ether by carbon dioxide hydrogenation is characterized in that the GaZrO x The method for inducing self-assembly of the bimetallic oxide catalyst by solvent volatilization comprises the following steps:
respectively preparing Ga and Zr metal salt alcohol solutions, wherein the molar loading amount of metal Ga is more than or equal to 25 percent and less than or equal to 27 percent of Ga/(Ga + Zr), and the total molar amount of metal ions is 10-50mmol; preparing 1-5g of template alcohol solution, wherein the mass concentration of the template is 0.01-0.5g/g Alcohol(s) (ii) a The three are continuously stirred for 12 to 24 hours at the temperature of 293K to 313K; the mixing mode comprises that the template agent alcoholic solution is dripped into the metal salt alcoholic solution, the metal salt alcoholic solution is dripped into the template agent alcoholic solution or the two are mixed in a parallel flow way; continuously stirring for 2-24h at the temperature of 293K-313K after mixing; transferring the solution into a borosilicate culture dish, and placing the borosilicate culture dish in a fume hood to stand still for 2-7 days to evaporate the solvent; calcining the obtained gel in flowing air at 673K-873K for 3-10h;
the Ga metal salt is one or more than two of chloride, nitrate, acetate and sulfate;
the Zr metal salt is one or more than two of chloride, nitrate, acetate, sulfate, zirconyl nitrate, zirconium oxychloride and zirconium isopropoxide;
the template agent is one or more than two of P123, F127, P84, P104, F108 and P105 block copolymers;
the alcoholic solution is C 1 -C 10 One or more of alcohols;
the reaction for synthesizing the methanol and the dimethyl ether by the hydrogenation of the carbon dioxide is carried out on a pressurized fixed bed continuous flow reactor, and the reaction conditions are as follows: the pressure of the raw material gas is 2-4MPa, the reaction temperature is 603K, and the space velocity is 24000 ml/(g) cat ·h)，n(H 2 ):n(CO 2 )＝3:1；
The catalyst is activated before being applied, and the activation conditions are as follows: activating at 473K-673K with one or two of pure hydrogen, argon, nitrogen and helium for 1-12h.
2. The use of claim 1, wherein: the calcining atmosphere is one or more of air, oxygen and nitrogen.
3. Use according to claim 1, characterized in that: the reaction pressure is 3-4MPa.
4. Use according to claim 1, characterized in that: the resulting catalyst was tabletted, crushed, and screened 180-800 μm for evaluation.
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| WO2005026093A1 (en) * | 2003-09-17 | 2005-03-24 | Korea Institute Of Science And Technology | Method for the production of dimethyl ether |
| CN103263926A (en) * | 2013-05-14 | 2013-08-28 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methanol through carbon dioxide hydrogenation as well as preparation method and application thereof |
| CN109420486A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application |
| CN109420485A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | CdO-TiO for hydrogenation of carbon dioxide methanol2Catalyst and preparation and application |
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| WO2005026093A1 (en) * | 2003-09-17 | 2005-03-24 | Korea Institute Of Science And Technology | Method for the production of dimethyl ether |
| CN103263926A (en) * | 2013-05-14 | 2013-08-28 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methanol through carbon dioxide hydrogenation as well as preparation method and application thereof |
| CN109420486A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application |
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| High-Performance MaZrOx(Ma=Cd, Ga) Solid-Solution Catalysts for CO2 Hydrogenation to Methanol;Jijie Wang et al.;《ACS Catal.》;20191004;第9卷;Supporting Information第3-4页，第10254页左栏第1段 * |
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