CN108620079B - Nickel-based composite catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide - Google Patents
Nickel-based composite catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide Download PDFInfo
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Abstract
The invention discloses a nickel-based composite catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide, wherein the carrier of the catalyst is SiO2、Al2O3、TiO2At least one of Ni, Ni-Fe or Ni-Co as active component and CeO as assistant2‑La2O3、CeO2‑Sm2O3、CeO2‑Pr6O11、CeO2‑Nd2O3、CeO2‑Y2O3One of the composite oxides; based on the mass of the catalyst as 100 percent, the content of the active component is 5 to 15 percent, the total content of the auxiliary agent is 3 to 15 percent, and the balance is the carrier; the catalyst is prepared by taking glycine, alanine, threonine, citric acid, oxalic acid and the like as coordination-combustion promoters by adopting a coordination-decomposition method, and has the advantages of simple preparation process, low cost, economy and environmental protection. The catalyst has higher methane and carbon dioxide conversion rate for reforming methane by carbon dioxide under the pressurization condition, and shows high activity, high stability and extremely high anti-carbon deposition and anti-sintering capacity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a nickel-based composite catalyst for preparing synthesis gas by reforming methane with carbon dioxide under a pressurized condition.
Background
In recent years, with the growing awareness of the greenhouse effect, the greenhouse gas is the strongest greenhouse gasCO of one of2Capture and its use have attracted increasing attention. CO can be simultaneously utilized by reforming methane with carbon dioxide2And CH4Two kinds of greenhouse gases have great significance for reducing emission of greenhouse gases, and H of synthesis gas2the/CO is less than or equal to 1, and can be used as raw material gas for synthesizing carbonyl and organic oxygen-containing compounds. After the research on carbon dioxide reformed methane was reported by Ashcroft et al (nat. chem.,1991,352: 225-.
Catalyst systems for reforming methane with carbon dioxide are mainly divided into two types, one type is a catalyst taking precious metal (Pt, Rh, Ru, Pd and Ir) as an active component, and although the catalyst has high activity, selectivity and stability, the source of the catalyst is limited, the price is high, and the catalyst is difficult to realize commercial application. Another class is catalysts with non-noble group VIII metals (Fe, Ni, Co) as the active components, in the order of Ni > Co > Fe, where Ni-based catalysts are widely regarded for high catalytic activity and low cost. However, the Ni-based catalyst also has the disadvantages of easy carbon deposition and sintering, resulting in a decrease in catalytic activity. Therefore, the hot spot of reforming methane with carbon dioxide is mainly focused on how to improve the stability and the anti-carbon deposition performance of the Ni-based catalyst. Theoretical research shows that the nucleation and growth of fiber carbon can be inhibited only by smaller Ni particle size, thereby achieving the purpose of carbon deposition resistance. In practical application, the Ni-based catalyst is usually prepared by adopting an impregnation method, a precipitation method or a sol-gel method, the catalyst prepared by the methods can keep better catalytic activity and stability in a short period, but active components are easy to agglomerate and sinter and are easy to lose activity due to carbon deposition in the long-period carbon dioxide reforming methane reaction operation.
The reforming of methane with carbon dioxide requires high temperature reaction, so the carrier selected for the nickel-based catalyst must have good thermal stability, such as Al2O3、SiO2、MgO、MgO-Al2O3、CeO2-ZrO2And mesoporous molecular sieves, ceramic foams, and the like. In addition, most of the nickel-based catalysts developed at present use the reaction of reforming methane with carbon dioxide under normal pressure as a probe reaction, and the storage and transportation of natural gas are carried outThe high pressure conditions and the conversion techniques from synthesis gas (such as fischer-tropsch reactions and methanol synthesis) are also achieved at higher pressures, so the methane reforming process under pressurized conditions is more reasonable and efficient from an overall energy efficiency perspective. From the analysis of dynamics, the reaction rate is more favorable to be improved under the pressurizing condition, and the carbon deposition rate and the carbon elimination rate on the surface of the catalyst are also increased. When the rate of carbon deposition on the surface of the catalyst is greater than the rate of carbon deposition removal, the catalyst will accelerate carbon deposition deactivation and even plug the bed layer to terminate the reaction.
The research group (Ind. Eng. chem. Res.2014,53, 19077-19086; int. J. of hydrogen Energy 2014,39,11592-11605) of the inventor prepares Ni/SiO by using a combustion decomposition method with carboxylic acid or amino acid as a complexing agent2When the reaction pressure is increased from 1.0atm to 10atm, the carbon deposit amount of the catalyst is increased from 2.0 wt% to 80 wt% after 20h of reaction, although the catalyst has a certain carbon holding capacity, the carbon deposit amount gradually increases, once the carbon deposit amount exceeds the carbon holding capacity of the catalyst, the catalyst is rapidly deactivated, and the bed layer is blocked by the carbon deposit, so that the reaction has to be stopped.
It can be seen from the above that, the carbon deposition of the catalyst which can be developed under normal pressure and can stably operate in the reaction of reforming methane with carbon dioxide is particularly serious under the pressurized condition, so that the catalyst bed layer is blocked by the carbon deposition, and the reaction of reforming methane with carbon dioxide cannot be continued. Therefore, it is currently the focus of research to obtain a carbon dioxide reforming methane reaction catalyst having high activity and resistance to carbon deposition under pressurized conditions.
Disclosure of Invention
The invention aims to overcome the defect that the carbon dioxide reforming methane catalyst is easy to deposit carbon to cause inactivation under the pressurizing condition, and provides the rare earth modified nickel-based catalyst which has high activity and good stability under the pressurizing condition and is used for preparing the synthesis gas by reforming methane with carbon dioxide.
The carrier of the catalyst used for solving the technical problems is SiO2、Al2O3、TiO2At least one of (a) and (b) is activeThe component is Ni, Ni-Fe or Ni-Co, the auxiliary agent is CeO2-La2O3、CeO2-Sm2O3、CeO2-Pr6O11、CeO2-Nd2O3、CeO2-Y2O3Any one of the above composite oxides; based on the mass of the catalyst as 100%, the content of the active component is 5% -15%, the content of the auxiliary agent is 3% -15%, and the balance is the carrier; the catalyst is prepared by the following method:
according to the composition of the catalyst, an active component precursor, an auxiliary agent and a carrier precursor are dissolved in ethanol, then a coordination-combustion improver aqueous solution is added, the mixture is stirred for 2-4 hours at room temperature, a solvent is evaporated to obtain a viscous liquid, the liquid is heated and combusted, solid powder obtained by combustion is uniformly ground, the solid powder is roasted for 3-6 hours in an air atmosphere at 550-800 ℃, the mixture is naturally cooled to room temperature, and then is tableted and granulated, and the catalyst is obtained after passing through a 40-60-mesh sieve.
The coordination-combustion improver is any one of glycine, alanine, threonine, serine, ethylenediamine, citric acid, urea, trimesic acid, nicotinic acid and oxalic acid, preferably any one of glycine, alanine and threonine; the addition amount of the coordination-combustion improver is 0.5 to 2 times, preferably 1 to 1.5 times of the total molar amount of the metal elements in the active component precursor and the metal elements or/and metalloid elements (Si is a metalloid element) in the carrier precursor.
In the catalyst, the content of the active component is preferably 10% and the total content of the auxiliary agent is preferably 4% to 7% based on 100% by mass of the catalyst.
When the active component is Ni, the precursor of the active component is nickel nitrate or nickel oxalate; when the active component is Ni-Fe, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of ferric nitrate, ferric oxalate and ammonium ferric citrate; when the active component is Ni-Co, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of cobalt nitrate, cobalt acetylacetonate and cobalt oxalate.
The carrier precursor is at least one of methyl silicate, ethyl orthosilicate, propyl silicate, butyl silicate, aluminum isopropoxide, aluminum nitrate, pseudo-boehmite, tetrabutyl titanate and titanium isopropoxide.
In the above method for preparing the catalyst, it is further preferable to calcine the catalyst in an air atmosphere at 650 to 750 ℃ for 3 to 6 hours.
The auxiliary agent is preferably prepared by a sol-gel method, and the specific preparation method comprises the following steps: completely dissolving soluble salts of P123 and cerium and soluble salts of rare earth elements in absolute ethyl alcohol, then evaporating the solvent to dryness at 40-100 ℃, roasting the obtained dried gel at 400-600 ℃ for 3-5 hours in an air atmosphere, naturally cooling to room temperature, and grinding into powder to obtain an auxiliary agent; the soluble salt of the rare earth element is any one of La, Sm, Pr, Nd and Y.
In the preparation method of the auxiliary agent, the ratio of the molar weight of the P123 to the total molar weight of the metal elements in the soluble salt of cerium and the soluble salt of the rare earth elements is preferably 0.015-0.02: 1, wherein the soluble salt of cerium is any one of cerium nitrate, ammonium ceric nitrate, cerium acetate, cerium oxalate and cerium isopropoxide, and the soluble salt of the rare earth elements is nitrate or chloride of the rare earth elements.
The invention has the following beneficial effects:
1. the invention adopts a coordination-decomposition method, during the preparation process of the catalyst, the coordination-combustion improver can coordinate with metal cations in an active component precursor to form a complex, and the high dispersion of the metal cations can be ensured during the evaporation and rapid combustion processes of a solvent to form a strong interaction between the metal and a carrier; auxiliary agent CeO2-La2O3、CeO2-Sm2O3、CeO2-Pr6O11、CeO2-Nd2O3、CeO2-Y2O3The composite oxide has rich basic sites and oxygen vacancies, and can adsorb and activate CO in the reaction2The catalyst is favorable for eliminating carbon deposition on the surface of the catalyst in pressurized methane dry reforming, so that the catalytic activity and the stability are improved, and meanwhile, the rare earth oxide can have stronger interaction with active metal, so that the active metal can react at high temperatureThe catalyst is not easy to migrate and aggregate, the dispersion degree and the surface active metal content of active metal are improved, and smaller metal particles are kept, so that the high-temperature activity and the stability of the catalyst are improved.
2. In the catalyst, the active component has the particle size of about 4.0-10 nm, smaller particle size and narrower distribution, is beneficial to inhibiting the generation of carbon deposition on the surface of the catalyst, has higher methane and carbon dioxide conversion rate on the methane reformed by carbon dioxide under the pressurization condition, and shows high activity, high stability and extremely high carbon deposition resistance and sintering resistance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
According to CeO2-La2O3CeO in composite oxide2And La2O3The mass ratio of (3: 2) is that 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 2.5471g (5.867mmol) of cerous nitrate hexahydrate and 1.7894g (4.132mmol) of lanthanum nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the temperature is constant roasted for 4 hours, the xerogel is naturally cooled to the room temperature and is ground into powder to obtain the required CeO2-La2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-3 percent of CeO2-2％La2O3-SiO20.1645g of CeO2-La2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate and 9.6965g (46.5437mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 6.5739g (52.1491mmol) of oxalic acid dihydrate were dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, and evaporating the solvent by using a rotary evaporator to obtain viscous liquidAnd transferring the solid powder to an electric heating furnace for combustion, placing the solid powder obtained by combustion in a muffle furnace for roasting, heating to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4 hours at a constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving with a 40-60-mesh sieve to prepare the catalyst.
Example 2
According to CeO2-Sm2O3CeO in composite oxide2And Sm2O3The mass ratio of (A) to (B) is 4:3, 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 2.4946g (5.746mmol) of cerous nitrate hexahydrate and 1.8907g (4.254mmol) of samarium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the xerogel is roasted at constant temperature for 4 hours, the xerogel is naturally cooled to the room temperature and ground into powder to obtain Ce2-Sm2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-4 percent of CeO2-3％Sm2O3-SiO20.2303g of CeO2-Sm2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate and 9.4683g (45.4486mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 10.7285g (51.0540mmol) of citric acid monohydrate were dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 3
According to CeO2-Pr6O11CeO in composite oxide2And Pr6O11The mass ratio of (2: 1) to (0.986 g (0.17mmol)Adding P123 with the average molecular weight of 5800, 2.8836g (6.642mmol) of cerous nitrate hexahydrate and 1.4606g (3.3576mmol) of praseodymium nitrate hexahydrate into 20mL of absolute ethyl alcohol, stirring for 5 hours at room temperature to completely dissolve solids, transferring the obtained mixture into a culture dish, covering the culture dish by a porous PE film, transferring the culture dish into a blowing oven at 40 ℃ to evaporate the solvent for 48 hours, evaporating for 24 hours at 100 ℃, heating the obtained dried gel to 450 ℃ at the heating rate of 1 ℃/min in the air atmosphere flowing in a tubular furnace, roasting at constant temperature for 4 hours, naturally cooling to room temperature, grinding into powder to obtain CeO2-Pr6O11A composite oxide.
According to the catalyst composition, 10 percent of Ni-4 percent of CeO2-2％Pr6O11-SiO20.1974g of CeO2-Pr6O11The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate and 9.5824g (45.9962mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 5.8106g (51.6016mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 4
According to CeO2-Nd2O3CeO in composite oxide2And Nd2O3The mass ratio of (1) is 5:3, 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 2.6901g (6.197mmol) of cerous nitrate hexahydrate and 1.6676g (3.804mmol) of neodymium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the temperature is constant roasted for 4 hours, the xerogel is naturally cooled to the room temperature, and the xerogel is groundPowdering to obtain CeO2-Nd2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni to 5 percent of CeO2-3％Nd2O3-SiO20.2632g of CeO2-Nd2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate and 9.3542g (44.9010mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 6.0163g (50.5064mmol) of threonine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 5
According to CeO2-Y2O3CeO in composite oxide2And Y2O3The mass ratio of (A) to (B) is 3:4, 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 1.4316g (3.298mmol) of cerous nitrate hexahydrate and 2.5670g (6.702mmol) of yttrium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the xerogel is roasted at constant temperature for 4 hours, the xerogel is naturally cooled to the room temperature and ground into powder to obtain Ce2-Y2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-3 percent of CeO2-4％Y2O3-SiO20.2303g of CeO2-Y2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate and 9.4683g (45.4486mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 4.5484g (51.054mmol) of alanine were further dissolved in 40g of distilled water to obtain a solution B. Adding solution B into solution A, and placing the solution in a chamberStirring for 4 hours at a high temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing solid powder obtained by combustion into a muffle furnace for roasting, heating to 700 ℃ at a heating rate of 5 ℃/min, keeping the constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 6
According to CeO2-Y2O3CeO in composite oxide2And Y2O3The mass ratio of (1: 1) is that 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 1.7197g (3.961mmol) of cerous nitrate hexahydrate and 2.3129g (6.039mmol) of yttrium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the temperature is constant roasted for 4 hours, the xerogel is naturally cooled to the room temperature and ground into powder to obtain CeO2-Y2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-3 percent of CeO2-3％Y2O3-20％Al2O3-SiO20.1974g of CeO2-Y2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate, 2.6357g (12.9051mmol) of aluminum isopropoxide and 7.3009g (35.0447mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 6.3795g (53.5552mmol) of threonine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 7
According to CeO2-La2O3CeO in composite oxide2And La2O3The mass ratio of (A) to (B) is 3:4, 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 1.8023g (4.152mmol) of cerous nitrate hexahydrate and 2.1718g (5.848mmol) of lanthanum chloride heptahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the xerogel is roasted at constant temperature for 4 hours, the xerogel is naturally cooled to the room temperature and ground into powder to obtain Ce2-La2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-3 percent of CeO2-4％La2O3-20％TiO2-SiO20.2303g of CeO2-La2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate, 7.1868g (34.4971mmol) of ethyl orthosilicate and 2.8035g (8.2379mmol) of tetrabutyl titanate were dissolved in 40g of ethanol to give a solution A. 5.7583g (48.3404mmol) of threonine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 8
According to CeO2-Sm2O3CeO in composite oxide2And Sm2O3In a mass ratio of 2:1, 0.986g (0.17mmol) of P123 having a number average molecular weight of 5800, 2.2975g (6.696mmol) of cerium nitrate hexahydrate, 1.4688g (3.304mmol) of samarium nitrate hexahydrate were added to 20mL of anhydrous ethanol, stirred at room temperature for 5 hours to completely dissolve the solid, the resulting mixture was transferred to a petri dish, covered with a perforated PE membrane, then transferred to a 40 ℃ forced air oven to evaporate the solvent for 48 hours, and then at 100 ℃ CEvaporating for 24 hours, finally heating the obtained dry gel to 450 ℃ at the heating rate of 1 ℃/min in the air atmosphere flowing in the tubular furnace, roasting at constant temperature for 4 hours, naturally cooling to room temperature, grinding into powder to obtain CeO2-Sm2O3A composite oxide.
According to the catalyst composition, 10 percent of Ni-4 percent of CeO2-2％Sm2O3-10％Al2O3-10％TiO2-SiO20.1974g of CeO2-Sm2O3The complex oxide, 1.63g (5.6054mmol) of nickel nitrate hexahydrate, 1.4018g (4.1188mmol) of tetrabutyl titanate, 7.3009g (35.0447mmol) of ethyl orthosilicate and 1.3178g (6.4525mmol) of aluminum isopropoxide were dissolved in 40g of ethanol to give solution A. 3.8452g (51.2214mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 9
According to CeO2-Y2O3CeO in composite oxide2And Y2O3The mass ratio of (1: 1) is that 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 1.7195g (3.961mmol) of cerous nitrate hexahydrate and 2.3129g (6.039mmol) of yttrium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the temperature is constant roasted for 4 hours, the xerogel is naturally cooled to the room temperature and ground into powder to obtain CeO2-Y2O3A composite oxide.
According to the catalyst composition, 8 percent of Ni, 2 percent of Fe and 3 percent of CeO2-3％Y2O3-20％TiO2-SiO2Mixing 0.1974gCeO2-Y2O3The composite oxide, 0.4759g (1.1781mmol) of iron nitrate nonahydrate, 1.304g (4.4843mmol) of nickel nitrate hexahydrate, 2.8035g (8.2379mmol) of tetrabutyl titanate and 7.3009g (35.0447mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 5.5115g (48.9450mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solution A, stirring for 4 hours at room temperature, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing the solid powder obtained by combustion into a muffle furnace for roasting, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the temperature for 4 hours at constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
Example 10
According to CeO2-Nd2O3CeO in composite oxide2And Nd2O3The mass ratio of (1: 1) is that 0.986g (0.17mmol) of P123 with the number average molecular weight of 5800, 2.1458g (4.943mmol) of cerous nitrate hexahydrate and 2.1954g (5.057mmol) of neodymium nitrate hexahydrate are added into 20mL of absolute ethyl alcohol, the mixture is stirred for 5 hours at room temperature to completely dissolve the solid, the obtained mixture is transferred into a culture dish and covered by a PE film with holes, then the culture dish is transferred into a blast oven at 40 ℃ to evaporate the solvent for 48 hours, then the solvent is evaporated for 24 hours at 100 ℃, finally the obtained xerogel is heated to 450 ℃ at the heating rate of 1 ℃/min under the air atmosphere flowing in a tubular furnace, the temperature is constant roasted for 4 hours, the xerogel is naturally cooled to the room temperature and is ground into powder to obtain CeO2-Nd2O3A composite oxide.
According to the catalyst composition, 9 percent of Ni-1 percent of Co-3 percent of CeO2-3％Nd2O3-10％TiO2-SiO2Mixing 0.1974gCeO2-Nd2O3The complex oxide, 0.1625g (0.5882mmol) of cobalt nitrate hexahydrate, 1.467g (5.0449mmol) of nickel nitrate hexahydrate, 1.4018g (4.1190mmol) of tetrabutyl titanate and 8.4416g (40.5204mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 5.6609g (50.2725mmol) of glycine were further dissolved in 40g of distilled water to obtain a solution B. Adding the solution B into the solutionStirring the solution A at room temperature for 4 hours, evaporating the solvent by using a rotary evaporator to obtain a viscous liquid, transferring the viscous liquid onto an electric heating furnace for combustion, placing solid powder obtained by combustion into a muffle furnace for roasting, heating to 700 ℃ at the heating rate of 5 ℃/min, keeping the constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, and sieving by using a 40-60-mesh sieve to prepare the catalyst.
In order to prove the beneficial effects of the invention, the inventor uses the catalysts prepared in examples 1-10 in the reaction of catalyzing carbon dioxide to reform methane, and the specific test method is as follows:
0.15g of catalyst was placed in a fixed bed reactor and H was fed2And N2The volume ratio of the mixed gas to the mixed gas is 2:8, and the flow rate is 50 mL/min-1At 4 ℃ in min-1The temperature rising rate of (2) was increased from room temperature to 700 ℃ and reduced for 2.5 hours. Subsequently, H is turned off2Continuing to introduce N2At 2 ℃ min-1The temperature rises to 750 ℃ at a temperature rising rate, and after the temperature is stabilized, the reaction gas (CO) is switched to2And CH4Mixed gas of (1: 1) by volume), the total amount of the reaction gas is 130 mL. min-1CO at P ═ 1.0MPa and T ═ 750 deg.C2/CH41.0, 53200mL g-1·h-1The reaction was carried out under the conditions, and the gas after the reaction was detected and analyzed by chromatographs (5A and PQ columns) of a GC9560 model thermal conductivity cell detector of Shanghai, Hua-ai, and the experimental results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst of the present invention has high methane and carbon dioxide conversion rates under pressurized conditions for reforming methane with carbon dioxide, and CO is at 1.0MPa and 750 ℃ C2/CH41.0, 53200mL g-1·h-1Under the condition, when the content of Ni or Ni-Fe or Ni-Co in the catalyst is 10%, the initial conversion rate of methane can be up to above 48%, the initial conversion rate of carbon dioxide can be up to above 69%, the service life of said catalyst is long, stability is high, and after continuous reaction for 70h, its activity is basicallyIs stable and unchanged.
Claims (8)
1. A nickel-based composite catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide is characterized in that: the carrier of the catalyst is SiO2、Al2O3、TiO2At least one of Ni, Ni-Fe or Ni-Co as active component and CeO as assistant2-La2O3、CeO2-Sm2O3、CeO2-Pr6O11、CeO2-Nd2O3、CeO2-Y2O3Any one of the composite oxides; based on the mass of the catalyst as 100%, the content of the active component is 5% -15%, the content of the auxiliary agent is 5% -10%, and the balance is the carrier; the catalyst is prepared by the following method:
dissolving an active component precursor, an auxiliary agent and a carrier precursor in ethanol according to the composition of the catalyst, then adding a coordination-combustion improver aqueous solution, stirring for 2-4 hours at room temperature, evaporating to remove the solvent to obtain a viscous liquid, heating and burning the liquid, uniformly grinding solid powder obtained by burning, roasting for 3-6 hours at 650-750 ℃ in an air atmosphere, naturally cooling to room temperature, tabletting, granulating, and sieving by a 40-60-mesh sieve to obtain the catalyst;
the coordination-combustion improver is any one of glycine, alanine, threonine, citric acid and oxalic acid, and the addition amount of the coordination-combustion improver is 1.0-1.5 times of the total molar amount of metal elements in the active component precursor and metal elements or/and metalloid elements in the carrier precursor.
2. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: based on the mass of the catalyst as 100%, the content of the active component is 10%, and the content of the auxiliary agent is 5% -10%.
3. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1 or 2, wherein: the coordination-combustion improver is any one of glycine, alanine and threonine.
4. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: when the active component is Ni, the precursor of the active component is nickel nitrate or nickel oxalate; when the active component is Ni-Fe, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of ferric nitrate, ferric oxalate and ammonium ferric citrate; when the active component is Ni-Co, the precursor of the active component is a mixture of any one of nickel nitrate and nickel oxalate and any one of cobalt nitrate, cobalt acetylacetonate and cobalt oxalate.
5. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: the carrier precursor is at least one of methyl silicate, ethyl orthosilicate, propyl silicate, butyl silicate, aluminum isopropoxide, aluminum nitrate, pseudo-boehmite, tetrabutyl titanate and titanium isopropoxide.
6. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 1, wherein: the auxiliary agent is prepared by adopting a sol-gel method, and the specific preparation method comprises the following steps: completely dissolving soluble salts of P123 and cerium and soluble salts of rare earth elements in absolute ethyl alcohol, then evaporating the solvent to dryness at 40-100 ℃, roasting the obtained dried gel at 400-600 ℃ for 3-5 hours in an air atmosphere, naturally cooling to room temperature, and grinding into powder to obtain an auxiliary agent; the soluble salt of the rare earth element is any one of La, Sm, Pr, Nd and Y.
7. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 6, wherein: in the preparation method of the auxiliary agent, the ratio of the molar weight of P123 to the total molar weight of metal elements in the soluble salt of cerium and the soluble salt of rare earth elements is 0.015-0.02: 1.
8. The nickel-based composite catalyst for pressurized carbon dioxide reforming of methane to synthesis gas according to claim 6 or 7, wherein: the soluble salt of the cerium is any one of cerium nitrate, ammonium ceric nitrate, cerium acetate, cerium oxalate and cerium isopropoxide, and the soluble salt of the rare earth element is nitrate or chloride of the rare earth element.
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