CN108499568B - Nickel-based catalyst for reforming methane by pressurizing carbon dioxide - Google Patents

Nickel-based catalyst for reforming methane by pressurizing carbon dioxide Download PDF

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CN108499568B
CN108499568B CN201810410946.3A CN201810410946A CN108499568B CN 108499568 B CN108499568 B CN 108499568B CN 201810410946 A CN201810410946 A CN 201810410946A CN 108499568 B CN108499568 B CN 108499568B
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nitrate
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刘忠文
肖勇山
李婷
石先莹
宋永红
刘昭铁
杨策敬
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Shaanxi Normal University
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Abstract

The invention discloses a nickel-based catalyst for reforming methane by 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、ZrO2Or CexZr1‑xO2Wherein the value of x is 0.3-0.7; 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 2% -9%, and the balance is the carrier; the catalyst is prepared by taking glycine, alanine, threonine, citric acid, oxalic acid and the like as a coordination agent and a combustion improver 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

Nickel-based catalyst for reforming methane by pressurizing carbon dioxide
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for reforming methane by using carbon dioxide under a pressurized condition.
Background
In recent years, as people have been increasingly aware of the greenhouse effect, CO, which is one of the strongest greenhouse gases2Capture 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 by carbon dioxide needs to be carried out at high temperature, so that the carrier selected by the nickel-based catalyst has to haveHaving good thermal stability, e.g. Al2O3、SiO2、MgO、MgO-Al2O3、CeO2-ZrO2And mesoporous molecular sieves, ceramic foams, and the like. There are reports (Applied Catalysis A: General,2016,520, 140-150), Ce0.5Zr0.5-SiO2Ni-Supported catalysts for the carbon dioxide reforming methane reaction, although the sol-gel method for preparing Ce0.5Zr0.5-SiO2The mesoporous pore canal of the carrier has a certain confinement effect on nickel particles, but the catalyst is obviously inactivated after reacting for 45 hours at 700 ℃ under the normal pressure condition due to the small specific surface area of the mesoporous pore canal. In addition, most of the currently developed nickel-based catalysts take a methane reforming reaction of carbon dioxide under normal pressure as a probe reaction, storage and transportation of natural gas are under high pressure, and a conversion technology (such as a fischer-tropsch synthesis reaction and methanol synthesis) taking synthesis gas as a source is also realized under higher pressure, so that the methane reforming process under a pressurized condition is more reasonable and efficient from the perspective of overall energy efficiency. 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 carbon dioxide reforming methane nickel-based catalyst which has high activity and good stability under the pressurizing condition.
The carrier of the catalyst used for solving the technical problems is SiO2、Al2O3、TiO2At least one of Ni, Ni-Fe or Ni-Co as active component and CeO as assistant2、ZrO2Or CexZr1-xO2Wherein the value of x is 0.3-0.7; 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 2% -8%, 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 precursor and a carrier precursor are dissolved in ethanol, then an aqueous solution of a coordination-combustion improver is added, the mixture is stirred for 2 to 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 to 6 hours in an air atmosphere at 500 to 750 ℃, and the mixture is naturally cooled to room temperature, tableted, granulated and sieved by a 40 to 60-mesh sieve to obtain the catalyst.
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 0.5-2 times, preferably 1-1.5 times of the total molar amount of the metal elements in the active component precursor, the metal elements in the auxiliary agent precursor and the metal elements or/and metalloid elements in the carrier precursor.
Of the above catalysts, the catalyst is preferably used in an amount of 100% by massSelecting 10% of active component and 4% -7% of auxiliary agent; further preferred auxiliary agent is CexZr1-xO2。
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 above-mentioned adjuvant is CeO2When the precursor of the auxiliary agent is cerium nitrate or ammonium ceric nitrate; the auxiliary agent is ZrO2When the precursor of the auxiliary agent is zirconium nitrate or zirconyl nitrate; the auxiliary agent is CexZr1-xO2When the precursor of the auxiliary agent is a mixture of any one of cerium nitrate and ammonium ceric nitrate and any one of zirconium nitrate and zirconyl nitrate.
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 invention has the following beneficial effects:
1. the coordination-decomposition method is adopted, in the preparation process of the catalyst, the coordination-combustion improver can coordinate with metal cations in an active component precursor and an auxiliary agent precursor to form a complex, and the high dispersion of the metal cations can be ensured in the evaporation and rapid combustion processes of a solvent to form a strong interaction between the metal and a carrier; CeO generated by the reaction of the precursor of the auxiliary agent2、ZrO2、CexZr1-xO2Has low-temperature reducibility and alkaline sites, and is favorable for adsorbing and activating CO in high-temperature reaction2Thereby increasing the catalytic activity, and at the same time, CeO2、ZrO2、CexZr1-xO2Can strongly interact with NiThe active metal is not easy to migrate and aggregate in the high-temperature reaction, and small metal particles are kept. In addition, CeO2、ZrO2、CexZr1-xO2Also has good oxygen storage capacity, oxygen flow property and high-temperature thermal stability, and is helpful for activating CO2Eliminating carbon deposition produced in pressurized methane dry reforming.
2. The specific surface area of the nickel-based catalyst is 500-650 m2A pore volume of 0.30-0.55 cm/g3The catalyst has the advantages of high activity, high stability and extremely high anti-carbon deposition and anti-sintering capabilities, wherein the pore size distribution is 0.6-1.0 nm, the particle size of the active component is about 4.0-9 nm, the particle size distribution is narrow, the generation of carbon deposition on the surface of the nickel-based catalyst is favorably inhibited, the catalyst has high methane and carbon dioxide conversion rate for reforming methane by carbon dioxide under the pressurizing condition.
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 the catalyst composition, 10 percent of Ni to 5 percent of CeO2-SiO20.4150g (0.956mmol) of cerium nitrate hexahydrate and 1.63g (5.605mmol) of nickel nitrate hexahydrate and 9.6963g (46.543mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 6.6948g (53.104mmol) 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, 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, raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, keeping the constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 575m2Per g, pore volume 0.38cm3(ii)/g, pore size distribution 0.81 nm.
Example 2
According to the catalyst composition, 10% Ni-5% ZrO2-SiO20.3567g (1.335mmol) of zirconyl nitrate dihydrate and 1.63g (5.605mmol) of hexakisNickel nitrate hydrate and 9.6963g (46.543mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 5.6194g (53.48mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 569m2Per g, pore volume 0.35cm3(ii)/g, pore size distribution 0.78 nm.
Example 3
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 4.5 percent of Ce0.5Zr0.5O2-SiO20.1340g (0.501mmol) of zirconyl nitrate dihydrate, 0.2177g (0.501mmol) of cerium nitrate hexahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate and 9.7534g (46.817mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 6.0158g (53.424mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 614m2Per g, pore volume 0.39cm3(ii)/g, pore size distribution 0.77 nm.
Example 4
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 9 percent of Ce0.5Zr0.5O2-SiO20.2678g (1.003mmol) of zirconyl nitrate dihydrate, 0.4353g (1.003mmol) of cerium nitrate hexahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate and 9.2400g (44.3534mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 2.3147g (51.9627mmol) of alanine 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, and evaporating the solvent by using a rotary evaporator to obtainTransferring the viscous liquid to an electric heating furnace for combustion, placing 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 constant temperature, naturally cooling to room temperature, taking out, tabletting, granulating, sieving with a 40-60-mesh sieve to prepare the catalyst, wherein the specific surface area of the catalyst is 540m2Per g, pore volume 0.37cm3(ii)/g, pore size distribution 0.80 nm.
Example 5
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 5 percent of Ce0.7Zr0.3O2-SiO20.0837g (0.313mmol) of zirconyl nitrate dihydrate, 0.3175g (0.731mmol) of cerium nitrate hexahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate and 9.6963g (46.543mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 6.3368g (53.190mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 581m2Per g, pore volume 0.40cm3(ii)/g, pore size distribution 0.83 nm.
Example 6
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 5 percent of Ce0.6Zr0.4O2-SiO20.1152g (0.431mmol) of zirconyl nitrate dihydrate, 0.2809g (0.6471mmol) of cerium nitrate hexahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate and 9.6963g (46.543mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 3.9955g (53.223mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalytic catalystAn agent having a specific surface area of 579m2Per g, pore volume 0.38cm3(ii)/g, pore size distribution 0.78 nm.
Example 7
According to the catalyst composition, the catalyst comprises 5 percent of Ni and 5 percent of Ce0.5Zr0.5O2-SiO20.4837g (1.114mmol) of cerium nitrate hexahydrate, 0.4782g (1.114mmol) of zirconium nitrate pentahydrate, 1.226g (5.605mmol) of nickel oxalate and 20.5333g (98.563mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give solution A. 7.9871g (106.396mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 615m2Per g, pore volume 0.43cm3(ii)/g, pore size distribution 0.77 nm.
Example 8
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 5 percent of Ce0.5Zr0.5O2-TiO2-SiO20.3054g (0.557mmol) of cerium ammonium nitrate, 0.2391g (0.557mmol) of zirconium nitrate pentahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate, 8.5557g (41.068mmol) of ethyl orthosilicate, and 1.4018g (4.1200mmol) of tetrabutyl titanate were dissolved in 40g of ethanol to give a solution A. 3.8967g (51.907mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 561m2Per g, pore volume 0.38cm3(ii)/g, pore size distribution 0.92 nm.
Example 9
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 5 percent of Ce0.5Zr0.5O2-Al2O3-SiO20.3054g (0.557mmol) of cerium ammonium nitrate, 0.2391g (0.557mmol) of zirconium nitrate pentahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate, 1.3175g (6.450mmol) of aluminum isopropoxide and 8.5562g (41.070mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 4.0717g (54.239mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 588m2Per g, pore volume 0.45cm3(ii)/g, pore size distribution 0.91 nm.
Example 10
According to the catalyst composition, the catalyst comprises 10 percent of Ni and 5 percent of Ce0.5Zr0.5O2-TiO2-Al2O3-SiO20.3054g (0.557mmol) of cerium ammonium nitrate, 0.2391g (0.557mmol) of zirconium nitrate pentahydrate, 1.63g (5.605mmol) of nickel nitrate hexahydrate, 0.7007g (2.0589mmol) of tetrabutyl titanate, 0.6588g (3.2258mmol) of aluminum isopropoxide and 8.5562g (41.070mmol) of ethyl orthosilicate were dissolved in 40g of ethanol to give a solution A. 3.9842g (53.0737mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 578m2Per g, pore volume 0.44cm3(ii)/g, pore size distribution 0.88 nm.
Example 11
According to the catalyst composition, the catalyst comprises 8 percent of Ni, 2 percent of Fe and 5 percent of Ce0.5Zr0.5O2-Al2O3-SiO2Will be0.1862g (0.6962mmol) zirconyl nitrate dihydrate, 0.3022g (0.6962mmol) cerium nitrate hexahydrate, 1.63g (5.605mmol) nickel nitrate hexahydrate, 0.5948g (1.4724mmol) iron nitrate nonahydrate, 1.6468g (8.0633mmol) aluminum isopropoxide and 10.6946g (51.335mmol) ethyl orthosilicate were dissolved in 40g ethanol to give solution A. 6.0464g (67.8681mmol) of alanine 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 582m2Per g, pore volume 0.44cm3(ii)/g, pore size distribution 0.89 nm.
Example 12
According to the catalyst composition, 9 percent of Ni, 1 percent of Co and 5 percent of Ce0.5Zr0.5O2-TiO2-SiO20.1653g (0.6188mmol) zirconyl nitrate dihydrate, 0.2687g (0.6188mmol) cerium nitrate hexahydrate, 0.1805g (0.6198mmol) cobalt nitrate hexahydrate, 1.63g (5.605mmol) nickel nitrate hexahydrate, 9.5063g (45.6311mmol) ethyl orthosilicate, and 1.5575g (4.5766mmol) tetrabutyl titanate were dissolved in 40g ethanol to give solution A. 4.3293g (57.67mmol) 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 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 constant temperature for 4 hours, naturally cooling to room temperature, taking out, tabletting, granulating, sieving by using a 40-60-mesh sieve, and preparing the catalyst, wherein the specific surface area of the catalyst is 575m2Per g, pore volume 0.45cm3(ii)/g, pore size distribution 0.91 nm.
In order to prove the beneficial effects of the invention, the inventor uses the catalysts prepared in examples 1-12 in the reaction of catalyzing carbon dioxide to reform methane, and the specific test method is as follows:
0.15g of the catalyst was placed in a fixed bed reactorIn the reactor, H is introduced2And 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
Example 7
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 metal Ni or Ni-Fe or Ni-Co in the catalyst is 10%, the initial conversion rate of methane can reach more than 48%, the initial conversion rate of carbon dioxide can reach more than 68%, the service life of the catalyst is long, the stability is high, and the activity is basically stable and unchanged after the continuous reaction for 100 hours.

Claims (7)

1. A nickel-based catalyst for pressurized carbon dioxide reforming of methane, characterized by: 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、ZrO2Or CexZr1-xO2Wherein the value of x is 0.3-0.7; 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 4% -7%, and the balance is the carrier; the catalyst is prepared by the following method:
dissolving an active component precursor, an auxiliary agent precursor and a carrier precursor in ethanol according to the composition of the catalyst, then adding a water solution of a coordination-combustion improver, stirring for 2-4 hours at room temperature, evaporating 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 1-1.5 times of the total molar amount of metal elements in the active component precursor, metal elements in the auxiliary agent precursor and metal elements or/and metalloid elements in the carrier precursor.
2. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to claim 1, characterized in that: 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 4% -7%.
3. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to claim 2, characterized in that: the auxiliary agent is CexZr1-xO2。
4. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to any one of claims 1 to 3, characterized in that: the coordination-combustion improver is any one of glycine, alanine and threonine.
5. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to claim 1, characterized in that: 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.
6. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to claim 1, characterized in that: the auxiliary agent is CeO2When the precursor of the auxiliary agent is cerium nitrate or ammonium ceric nitrate; the auxiliary agent is ZrO2When the precursor of the auxiliary agent is zirconium nitrate or zirconyl nitrate; the auxiliary agent is CexZr1-xO2When the precursor of the auxiliary agent is a mixture of any one of cerium nitrate and ammonium ceric nitrate and any one of zirconium nitrate and zirconyl nitrate.
7. The nickel-based catalyst for pressurized carbon dioxide reforming of methane according to claim 1, characterized in that: 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.
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