CN107552056B - Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof - Google Patents
Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing carbon monoxide by hydrogenation of carbon dioxide and a preparation method thereof, and mainly solves the technical problem that in the prior art, a large amount of by-product methane exists. The invention adopts a catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, which comprises the following components in parts by mole: a) 0.9-10 parts of metal Zr element or Ti element; b) 1-10 parts of alkaline earth metal elements; c) 0.1-5 parts of metal Mn element or Fe element, thereby better solving the problem and being applicable to the industrial production of synthesis gas by carbon dioxide hydrogenation.
Description
Technical Field
The invention belongs to the field of carbon dioxide hydrogenation utilization, and mainly relates to a catalyst for preparing carbon monoxide through carbon dioxide hydrogenation, a preparation method and application thereof.
Background
Carbon dioxide is a main greenhouse gas, is the main cause of global warming, is a very abundant carbon resource which can be utilized, and has the current utilization rate of only about 1 percent. 2011, global CO2The total emission is 310 hundred million tons, wherein CO in China2The total emission amount reaches 82 hundred million tons, and the emission amount is the first in the world. Development of CO2Technologies such as capture, storage, conversion utilization, etc. will be a common pursuit of goals for the global chemist. With CO2The greenhouse effect caused by large amount of emission is increasingly serious, and CO2Is being actively studied, wherein the reverse water gas shift reaction (CO) is used2+H2＝CO+H2O, RWGS for short) is considered to be one of the most promising reactions.
The reverse water gas shift Reaction (RWGS) can convert a large amount of greenhouse gases into synthesis gas, and then the synthesis gas is used for preparing a series of downstream chemical products with high added values. In addition, in addition to producing synthesis gas from natural gas, coal, heavy oil, slag oil, and the like, RWGS is a novel, environmentally friendly route to produce synthesis gas. Therefore, from the viewpoint of global carbon cycle and carbon resource utilization, the most stable state CO of carbon element2The carbon resources which can be utilized by human beings, such as methanol, methane and the like, can be finally converted through the RWGS process and the catalyst technology.
The reverse water gas shift reaction is an endothermic reaction, and the high temperature is favorable for generating CO, but the overhigh reaction temperature not only causes high energy consumption, but also has higher requirements on reaction materials. Typically in the range of 400 ℃ to 600 ℃. When the temperature is higher than 600 ℃, the energy consumption is very high, and the reaction economy is poor. The reverse water gas shift reaction is an isometric reaction, so the pressure has little influence on the reaction, but in order to increase the reaction rate, a certain pressure is increased appropriately.
In order to improve the CO selectivity, the side reactions are suppressed as much as possible. The main side reaction of the reverse water gas shift reaction is the methanation of CO (CO + 3H)2＝CH4+H2O). The suppression of the methanation side reaction is mainly started from the following aspects: a) temperature, which is a strongly exothermic reaction, increases the temperature, moving the equilibrium to the left, high temperature being beneficial for CO suppression2Methanation; b) pressure, which is a volume reduction reaction, increasing pressure, balancing to the right, high pressure will promote CO2Carrying out methanation side reaction; (c) the hydrogen-carbon ratio is reduced, the methane selectivity is reduced, and the inhibition of CO is facilitated2And (4) carrying out methanation reaction. These are all the reasons that the suppression of methanation reaction is performed under the process conditions, and the avoidance of methanation center is the fundamental point from the perspective of catalyst design.
At present, the reaction mechanism of the reverse water gas shift is still controversial, and three possible mechanisms mainly exist. One is the redox mechanism:
CO2+2Cu→Cu2O+CO (1)
H2+Cu2O→2Cu+H2O (2)
the reaction (1) is an oxidation step and has low speed; the reaction (2) is a reduction step and is rapid, so the reaction (1) is a rate control step, and Cu is CO2An active center. The second mechanism is the formate decomposition mechanism:
H2→2H·
CO2+H·→COOH·
COOH·→CO+OH·
OH·+H·→H2O
the third mechanism is an oxygen vacancy mechanism:
the mechanism is characterized by deactivating CO by oxygen vacancies2The oxygen vacancy concentration and oxygen transfer capacity of the catalyst are closely related to the catalytic activity.
The catalyst for reverse water gas shift mainly includes copper-base catalyst, nickel-base catalyst, noble metal catalyst, other new catalytic material, etc. Copper-based catalysts are not suitable for high temperature reactions because of their poor thermal stability, tendency to sinter and oxidize [ see appl. Catal. A: Gen.2004,257,97-106]. Since the Ni-based catalyst is usually used as a methanation catalyst, CH as a by-product is easily produced when it is used as a reverse water gas shift catalyst4The use of Ni, a metal element, should be avoided. Noble metal catalysts are expensive and tend to be deactivated by sintering at high temperatures.
By converting water gas into CO2Conversion to CO is a CO with great potential for use2And (5) a conversion and utilization process. Early research reports that Fe-Cr oxide catalyst is used for the reaction, but the disadvantages are that the methanation side reaction is serious, and in addition, the addition of Cr element has negative influence on the environment. WO9606064A1 adopts Zn-Cr/Al2O3Both the catalyst and EP2175986a2, which employ chromium-alumina catalysts, suffer from the disadvantages described above.
Ja Hun KWak et Al reported monodisperse Pd/Al2O3Reverse water gas shift catalyst, indicating that the function of Pd is to activate dissociation H2While the carrier alumina is used for activating and adsorbing CO2The addition of L a can also promote the activation of CO2But the cost is higher because noble metal is adopted as an active component [ see ACS Catal.2013,3,2094-]。
Chinese patent CN101624186B proposes a two-stage reverse water gas shift reaction process, which adopts a catalyst loaded with at least two elements of Co, Ni, W, Mo, the reaction temperature is higher than 580 ℃, and no Co selectivity is given, and the energy consumption is large due to the higher reaction operation temperature.
Wang et al [ see Journal of Rare Earth, 2008,26(1): 66-70; Chemistry L ets, 2013,42:682-]1 wt% K modified Co-CeO2Catalyst promotes CO2Adsorbing and poisoning methanation active site, CH4The selectivity dropped to 1% but no stability results were given. Since the oxidation state Co is easily reduced to metallic Co at high temperature, the generation of methane is inevitable.
Abolfazl et al [ see Chinese Journal of Chemical Engineering,2013,21(9): 1007-1014; journal of Nanoscience and Nanotechnology,2014,14(9): 6841-6847; the Chemical Biochemical Engineering Quartz, 2013,27(3):275-278] researches Fe-Mo, Ni-Mo and Co-Mo systems for RWGS reaction respectively, and as a result, the NiMoO4 and Fe2(MoO4)3 phase structures which are difficult to reduce are formed, which is beneficial to improving the stability of the catalyst, but for the Co-Mo/Al2O3 system, the CO selectivity is reduced to 87% after 1 h.
Grabowski et al [ see ACS catalysis,2011,1:266-]The Ag/ZrO2 catalyst is prepared by adopting a coprecipitation method, and the finding that the tetragonal phase carrier loads Ag+The catalyst forms formate intermediate species, while the dispersed Ag0 active phase dissociates the adsorbed CO2Producing surface CO and O species. Wangluhui et al (see CN 103183346A)]Use of a nickel cerium catalyst for RWGS reaction, CO thereof2The conversion was only 25%.
European patents EP742172 and EP737647 propose a process for the preparation of a catalyst containing CO and CO by steam reforming of methane2And H2In the process of the synthesis gas, water generated by the reverse water gas shift reaction is removed by adopting an adsorbent, and the process method needs stages of adsorption, pressure reduction, regeneration and the like, and has more complex steps.
Lumay, germany, developed the camele process, i.e., the generation of methanol from carbon dioxide using the water-gas shift reverse reaction. However, the conversion of methanol by direct hydrogenation of carbon dioxide is very low, and it should be mentionedHigh methanol yields necessitate an increase in the circulating gas flow. The CAMERE process is mainly characterized in that a reverse water gas shift reactor and a methanol synthesis tower are combined together, so that the problem of low-temperature CO is solved2Low conversion rate, greatly reduced raw gas circulation.
A new process for camre methanol synthesis was also developed by korean national institute of science and technology catalyst laboratory. In the process, an inversion reactor and a methanol synthesis tower are arranged in series, and CO is2/H2Firstly, the inverse transformation reaction of water gas is carried out in an inverse transformation reactor to generate CO and H2O, the reaction condition is normal pressure, 600-700 ℃, and the adopted catalyst is ZnAl2O4. The generated gas product is dehydrated and then enters a methanol synthesis reactor to generate.
At present, the research work on the water gas reverse shift reaction and the catalyst is rarely reported at home, and the above-mentioned korean institute of science and technology, test laboratory, lurgi company and the like have been developed and researched abroad, and the batch test of 5kg/d scale has been completed at present.
According to the reported results in the prior literature, CO is generated at a relatively high temperature (600-800 ℃), and2the conversion rate can reach about 40 percent, which also proves the reason that RWGS is an endothermic reaction and is beneficial to balance and move rightwards at high temperature. The patent or literature reports show that the methane is produced in large amount.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, which has the advantages of high CO selectivity and less byproduct methane when used for preparing carbon monoxide by carbon dioxide hydrogenation.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for preparing carbon monoxide by hydrogenating carbon dioxide comprises the following components in parts by mole: a) 0.9-10 parts of metal Zr element and/or Ti element; b) 1-10 parts of alkaline earth metal elements; c) 0.1-5 parts of metal Mn element and/or Fe element.
In the technical scheme, the content of metal Zr and/or Ti is preferably 1-5 parts by mole.
In the above-mentioned embodiment, the molar ratio of Zr to Ti (10: 1) to (1: 5) is preferable, and the molar ratio of Zr to Ti (5: 1) to (1: 2) is more preferable.
In the technical scheme, the content of the alkaline earth metal is preferably 1-5 parts by mole.
In the technical scheme, the content of the metal Fe or Mn is preferably 0.1-1 part by mole.
In the above-described embodiment, the element selected from the alkaline earth metals is preferably at least one of Mg, Ca, and Ba.
In order to solve the second technical problem, the invention adopts the following technical scheme that the preparation method of the catalyst comprises the following steps:
(1) preparing a precursor salt aqueous solution A of Zr element and/or Ti element, wherein the precursor salt of the Zr element and/or Ti element is preferably at least one of acetate, nitrate and sulfate;
(2) preparing a precursor salt aqueous solution B of at least one element selected from alkaline earth metals;
(3) preparing a precursor salt solution C of Mn element and/or Fe element, wherein the precursor salt of Mn element and/or Fe element is preferably at least one of acetate and nitrate;
(3) a, B, C is mixed and evenly stirred, and the mixture is evenly dripped into a container in parallel flow with a precipitator and quickly stirred, the temperature of a water bath is 60-80 ℃, and the pH value is controlled at 8-9;
(4) separating out mother liquor, carrying out hydrothermal treatment on the precipitate, drying and roasting to obtain a finished product.
For the purpose of the invention, the drying mode is not particularly required, but vacuum drying is preferably adopted, the drying temperature is preferably 90-120 ℃, and the drying time is preferably 12-48 hours. The high-temperature roasting temperature is preferably 650-1000 ℃, and the roasting time is preferably 5-15 hours.
The use method of the catalyst for preparing carbon monoxide by hydrogenation of carbon dioxide comprises the following steps:
carbon dioxide and hydrogen are used as raw material gases, the reaction temperature is 550-600 ℃, the reaction pressure is normal pressure-1 MPa, and H is2/CO2The volume ratio of (1:1) - (3:1) and the volume space velocity of 6000-15000 h-1Under the condition, the raw material gas contacts and reacts with the catalyst to obtain carbon monoxide and water vapor. And (3) passing the generated carbon monoxide, steam and unreacted feed gas through a cooler and a gas-liquid separator, and separating out water to obtain a gas mixture rich in carbon monoxide, carbon dioxide and hydrogen.
In the technical scheme, the preferable range of the reaction pressure is normal pressure to 0.5MPa, and the preferable volume space velocity of the feed gas is 8000-12000 h-1。
The catalyst can be used for the reaction of preparing carbon monoxide by hydrogenating carbon dioxide, and the specific reaction equation is as follows:
CO2+H2→CO+H2O
CO2conversion (X)CO2) And CO (S)CO) The selectivity calculation formula is as follows:
the catalyst and the preparation method thereof can fully convert greenhouse gas carbon dioxide into synthesis gas rich in carbon monoxide and hydrogen, and are used for synthesizing downstream chemical products with high added values. In addition, the catalyst and the use method thereof have the advantages of low reaction temperature below 600 ℃, high conversion rate and good stability. In order to improve the conversion rate, the invention optimizes and matches the acid-base center (carbon dioxide adsorption activation work) on the surfaceCan) with a metal center (H)2Dissociation activation function) to make it at higher H2On the premise of activation capacity, the catalyst has higher carbon dioxide adsorption and activation capacity, thereby realizing higher CO2Conversion rate; in order to improve the stability of the catalyst, the invention forms a spinel active phase through high-temperature treatment, improves the reduction resistance of the catalyst, and enables the catalyst to endure the high-temperature strong-reducing hydrothermal condition of the reverse water gas shift reaction.
The catalyst prepared by the technical scheme has the reaction temperature of 550-600 ℃, the reaction pressure of normal pressure of 0.5Mpa and H2/CO2The volume ratio of (1:1) - (3:1) and the space velocity of 6000-15000 h-1Under the condition of CO2The conversion rate is 43-53%, the CO selectivity is higher than 95%, and the catalyst is not inactivated after continuously and stably running for 1000 hours. CO compared with the prior art2The conversion rate and the stability of the catalyst are both obviously improved, and a good technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1]
[ catalyst preparation ]: weighing 429.3 g of zirconium nitrate, 148 g of magnesium nitrate and 4.1 g of ferric nitrate, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed at 600 deg.C and 0.5Mpa, after reaction, cooling and separatingAnd (6) discharging water. The evaluation results are shown in Table 1.
[ example 2]
[ catalyst preparation ]: weighing 402 g of titanium sulfate, 164 g of calcium nitrate and 201.9 g of ferric nitrate, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 200 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the water bath temperature to be 80 ℃, adjusting the pH value to be 9, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 36 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
[ example 3]
[ catalyst preparation ]: weighing 42.9 g of zirconium nitrate, 26.1 g of barium nitrate and 3.6 g of 50% manganese nitrate solution, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed at 600 deg.CAnd 0.5MPa, after the reaction, water is separated out by cooling. The evaluation results are shown in Table 1.
[ example 4]
[ catalyst preparation ]: 386.1 g of zirconium nitrate, 40.2 g of titanium sulfate, 148 g of magnesium nitrate and 4.1 g of ferric nitrate are weighed and respectively dissolved in deionized water, and then uniformly mixed to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
[ example 5]
[ catalyst preparation ]: weighing 85.8 g of zirconium nitrate, 321.6 g of titanium sulfate, 234.9 g of barium nitrate and 4.1 g of ferric nitrate, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation ]: the catalyst is loaded into a fixed bed reactor, the composition of the gas mixture is CO 2-333 ml/min, the H2-667 ml/min catalyst bed is operated at 600 ℃ and 0.5Mpa, after the reaction, the water is separated out by cooling. The evaluation results are shown in Table 1.
[ example 6]
[ catalyst preparation ]: weighing 214.6 g of zirconium nitrate, 130.5 g of barium nitrate, 41 g of ferric nitrate and 3.6 g of 50% manganese nitrate solution, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
[ example 7]
[ catalyst preparation ]: weighing 214.6 g of zirconium nitrate, 130.5 g of barium nitrate, 20.5 g of ferric nitrate and 18 g of 50% manganese nitrate solution, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
[ example 8]
[ catalyst preparation ]: weighing 40.2 g of titanium sulfate, 26.1 g of barium nitrate, 20.5 g of ferric nitrate and 18 g of 50% manganese nitrate solution, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight.
[ catalyst activation ]: and filtering and washing the solution after standing overnight, and then placing the filter cake into a hydrothermal kettle for hydrothermal treatment at the temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
TABLE 1
Catalyst composition in the table is in mole fraction.
Comparative example 1
Preparation of the carrier: a, taking 200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose; b, taking 40 g of water, adding 26 g of zinc nitrate, then adding 10.0 g of aqueous solution containing 30% of nitric acid in percentage by weight, and mixing and dissolving uniformly. Slowly adding the B into the A, uniformly stirring, kneading for 40 minutes, extruding and molding, drying for 18 hours at 100 ℃, and roasting for 5 hours at 800 ℃ to obtain the molded composite carrier.
Pretreatment of a carrier: drying and activating the carrier at 170 ℃ for 4 hours for later use.
Preparing an impregnation liquid: zirconium nitrate 42.9 g, barium nitrate 26.1 g, and 50% manganese nitrate solution 3.6 g were weighed. Adding 7.6 g of citric acid, adding water, heating for dissolving, stirring until the citric acid is completely dissolved, weighing 100.0 g of composite carrier, uniformly spraying the impregnation liquid on the carrier, drying and roasting to obtain the catalyst.
The catalyst was charged to a fixed bed reactor and the gas mixture had a composition of CO2 ═ 333ml/min, H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 2.
Comparative example 2
Preparation of the carrier: a, taking 200.0 g of pseudo-boehmite and 3.0 g of pore-forming agent methyl cellulose; b, taking 40 g of water, adding 26 g of zinc nitrate, then adding 10.0 g of aqueous solution containing 30% of nitric acid in percentage by weight, and mixing and dissolving uniformly. Slowly adding the B into the A, uniformly stirring, kneading for 40 minutes, extruding and molding, drying for 18 hours at 100 ℃, and roasting for 5 hours at 800 ℃ to obtain the molded composite carrier.
Pretreatment of a carrier: drying and activating the carrier at 170 ℃ for 4 hours for later use.
Preparing an impregnation liquid: weighing 40.2 g of titanium sulfate, 26.1 g of barium nitrate, 20.5 g of ferric nitrate and 18 g of 50% manganese nitrate solution, adding water, heating to dissolve, stirring until the solution is completely dissolved, weighing 100.0 g of composite carrier, uniformly spraying impregnation liquid on the carrier, drying and roasting to obtain the catalyst.
Loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 2.
TABLE 2@
@In the table, the composition data of the catalyst are mole parts, and the carrier is mass percent.
[ examples 9 to 14]
The catalyst prepared in example 5 was selected and evaluated under different process conditions, and the evaluation results are shown in table 3.
TABLE 3
Claims (9)
1. The catalyst for preparing carbon monoxide by hydrogenating carbon dioxide comprises the following components in parts by mole:
a) 0.9-10 parts of metal Zr element and Ti element;
b) 1-10 parts of alkaline earth metal elements;
c) 0.1-5 parts of metal Fe element and/or Mn element;
the molar ratio of Zr to Ti (10: 1) to (1: 5).
2. The catalyst for preparing carbon monoxide by hydrogenation of carbon dioxide according to claim 1, wherein the content of Zr and Ti is 1-5 parts by mole.
3. The catalyst for producing carbon monoxide by hydrogenation of carbon dioxide according to claim 1, wherein the molar ratio of Zr to Ti is (5: 1) - (1: 2).
4. The catalyst for preparing carbon monoxide by hydrogenation of carbon dioxide according to claim 1, wherein the content of alkaline earth metal is 1 to 5 parts by mole.
5. The catalyst for preparing carbon monoxide through hydrogenation of carbon dioxide according to claim 1, wherein the content of metal Fe and/or Mn is 0.1-1 part by mole.
6. The catalyst for hydrogenation of carbon dioxide to carbon monoxide according to claim 1, wherein the element selected from the group consisting of alkaline earth metals is at least one of Mg, Ca and Ba.
7. The method for preparing the catalyst for preparing carbon monoxide by hydrogenating carbon dioxide according to any one of claims 1 to 6, comprising the steps of:
(i) preparing a precursor salt solution A of Zr element and Ti element;
(ii) preparing a precursor salt solution B selected from an alkaline earth metal element;
(iii) preparing a precursor salt solution C of Fe element and/or Mn element;
(iv) a, B, C is mixed, evenly stirred, and dripped into a container in parallel with a precipitator and quickly stirred, the temperature of a water bath is controlled to be 60-80 ℃, and the pH value is controlled to be 8-9;
(v) separating out mother liquor, carrying out hydrothermal treatment on the precipitate, drying and roasting to obtain a finished product.
8. A method for preparing carbon monoxide by carbon dioxide hydrogenation takes carbon dioxide and hydrogen as raw material gases, and the reaction temperature is 550-600 ℃, the reaction pressure is normal pressure-1 MPa, and H is2/CO2The volume ratio of (1:1) - (3:1) and the volume space velocity of 6000-15000 h-1Under the condition, the raw material gas is in contact reaction with the catalyst of any one of claims 1 to 6 to obtain carbon monoxide and water vapor.
9. The method for preparing carbon monoxide by hydrogenation of carbon dioxide according to claim 8, wherein the generated carbon monoxide, steam and unreacted raw gas are passed through a cooler and a gas-liquid separator, and water is separated to obtain a gas mixture containing carbon monoxide, carbon dioxide and hydrogen.
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| CN114618509A (en) * | 2022-03-21 | 2022-06-14 | 上海尼普敦环境科技有限公司 | Carbon dioxide hydrogenation reduction catalyst and preparation method thereof |
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