CN107335449B - Composite component methanation catalyst and preparation method thereof - Google Patents
Composite component methanation catalyst and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a composite component methanation catalyst and a preparation method thereof. The compound component methanation catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the active component comprises nickel oxide and ruthenium dioxide, the active auxiliary agent is lanthanum oxide, and the carrier is a composite oxide of aluminum oxide, titanium dioxide and magnesium oxide; the sum of the total mass percentage of the catalyst is 100%, and the content of each component is NiO: 3% -10%, RuO2：0.2％～1％，TiO2：18％～30％，Al2O3：40％～55％，MgO：10％～25％，La2O3: 0.5 to 5 percent. The preparation method comprises the following steps: preparing a carrier precursor; preparing a carrier; soaking the carrier in soaking liquid by an isometric soaking method; drying and roasting to obtain the catalyst. The composite methanation catalyst has low activation temperature, high methanation activity and selectivity, low price and easy obtainment. The preparation method has the advantages of simple process, simple and convenient operation and low production cost.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a composite component methanation catalyst and a preparation method thereof.
Background
China is the largest energy consuming country in the world, and the largest energy resource in China is characterized by rich coal, poor oil and less gas. The method for producing the clean energy natural gas which is in short supply in China by taking coke oven gas, coal and the like as raw materials has great market prospect.
The methanation catalyst is the core of the technology for synthesizing natural gas. CO and CO2Methanation of (A) CO and CO in the presence of a methanation catalyst2Hydrogenation toMethane, the main reactions occurring during methanation are:
CO+3H2→CH4+H2O △H＝－2.06×105J (1)
CO2+4H2→CH4+2H2O △H＝－1.65×105J (2)
therefore, the methanation reaction is a strong exothermic reaction, and the low temperature is favorable for the reaction. The activation temperature of the Ni-based catalyst widely adopted in the existing industrial device is higher, so that the raw material gas in the methanation device can be subjected to methanation reaction only by being preheated to reach higher temperature, and the reaction is not facilitated. In addition, in order to cope with the high load of the methanation process, the catalyst needs to load higher Ni, so that the cost of the catalyst is higher. Ruthenium has excellent low-temperature methanation activity, but due to the property of noble metals, the high ruthenium loading is not favorable for industrial application.
Therefore, the methanation catalyst provided has the advantages of low activation temperature, high methanation activity and selectivity, low price and easy obtainment, and becomes a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The compound component methanation catalyst provided by the invention has the advantages of low activation temperature, very high methanation activity and selectivity, low price and easy obtainment.
The invention also provides a preparation method of the compound component methanation catalyst.
The technical scheme adopted by the invention is as follows:
the composite component methanation catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the active component comprises nickel oxide and ruthenium dioxide, the active auxiliary agent is lanthanum oxide, and the carrier is a composite oxide of aluminum oxide, titanium dioxide and magnesium oxide;
the total mass percentage of the catalyst is 100%, and the content of each component is as follows:
NiO：3％～10％，
RuO2：0.2％～1％，
TiO2：18％～30％，
Al2O3：40％～55％，
MgO：10％～25％，
La2O3：0.5％～5％。
preferably, the Al2O3Is gamma-Al2O3。
Preferably, the titanium dioxide is anatase titanium dioxide.
The preparation method of the composite component methanation catalyst comprises the following steps:
step 1: preparing a carrier precursor: preparing a magnesium nitrate aqueous solution, and uniformly mixing the aluminum oxide, the titanium dioxide and the magnesium nitrate solution to obtain a suspension A; preparation K2CO3Obtaining an aqueous solution B; adding the alkali liquor B into the turbid liquid A under the stirring action until the pH value of the mixed liquid is 8-9, filtering, and washing filter residues until NO NO exists3 -Residual, drying, calcining and sieving to obtain a carrier precursor C;
step 2: preparing a carrier: adding water and graphite into the carrier precursor C, uniformly mixing, pressing, molding and roasting to obtain a carrier D;
and step 3: dipping: preparing Ni (NO)3)2、La(NO3)3Taking the mixed solution of the ruthenium-containing compound as an impregnation solution, and putting the carrier D into the impregnation solution for impregnation by adopting an isometric impregnation method;
and 4, step 4: drying and roasting: and taking out the impregnated carrier D, drying and roasting to obtain the catalyst.
Further, the concentration of the magnesium nitrate aqueous solution in the step 1 is 3-20 wt.%, and K is2CO3The concentration of the aqueous solution is 3 wt.% to 15 wt.%; the drying temperature is 90-150 ℃, and the drying time is 1-5 hours; the calcining temperature is 300-600 ℃, and the calcining time is 2-6 hours; the sieve mesh is 20 meshes.
Further, in the step 2, the amount of water added to the carrier precursor C is 5 to 15% of the mass of the carrier precursor C, and the amount of graphite added is 3 to 5% of the mass of the carrier precursor C.
Further, in the step 3, Ni (NO) in the impregnation liquid3)2Is in a concentration of 3 wt.% to 20 wt.%, La (NO)3)3The concentration of the ruthenium-containing compound is 0.3-15 wt.%, the concentration of the ruthenium-containing compound is 0.1-10 wt.%, the dipping temperature is 50-90 ℃, and the dipping time is 1-5 hours.
Further, in the step 3, the ruthenium-containing compound is ruthenium chloride or ruthenium nitrate.
Further, in the step 4, the drying temperature is 90-150 ℃, and the drying time is 1-5 hours; the roasting temperature is 600-1100 ℃, and the roasting time is 1-10 hours.
Compared with the prior art, the invention has the following beneficial effects:
the composite methanation catalyst has low activation temperature, high methanation activity and selectivity, low price and easy obtainment. The preparation method has the advantages of simple process, simple and convenient operation and low production cost.
The catalyst provided by the invention uses nickel and ruthenium as composite active components, and the synergistic effect of the two active components enables the catalyst to have the characteristics of low activation temperature, high methanation activity, high thermal stability, good carbon deposition resistance and the like, can meet the requirement of low-temperature activation of a first reactor in a methanation process, and can be applied to low-temperature methanation for CO2And is beneficial for reducing the consumption of thermal energy in industrial plants.
The catalyst has lower nickel and ruthenium carrying capacity, and the cost of the catalyst is reduced; the catalyst of the invention uses lanthanum as an active auxiliary agent, which is beneficial to the dispersion of active components and improves the thermal stability of the catalyst.
Detailed Description
The present invention will be described in detail with reference to specific examples. These examples are given for the purpose of better illustrating the invention and the scope of the invention is not limited by these examples.
Example 1
Preparing the composite component methanation catalyst.
The preparation method comprises the following steps:
step 1: preparation of Carrier precursor
256g Mg (NO)3)2·6H2Adding 3000mL of deionized water for dissolving O, and adding 204g of gamma-Al into the solution2O3And 80g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Solution until the mixed solution pH was 9. Filtering the mixed solution, and washing the filter cake until NO3-a residue. And drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by using a 20-mesh sieve to obtain the carrier precursor.
Step 2: preparation of the support
Adding water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 700 ℃ for 6 hours to obtain the carrier.
And step 3: impregnation
1.52g of RuCl was taken3、88.00g Ni(NO3)2·6H2O、0.86gLa(NO3)3·6H2And O, preparing an aqueous solution, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method.
And 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the composite component methanation catalyst.
Example 2
Preparing the composite component methanation catalyst.
The preparation method comprises the following steps:
step 1: preparation of Carrier precursor
256g Mg (NO)3)2·6H2Adding 3000mL of deionized water for dissolving O, and adding 153g of gamma-Al into the solution2O3And 40g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Solution until the mixed solution pH was 9. Filtering the mixed solution, and washing the filter cake until NO3-a residue. And drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by using a 20-mesh sieve to obtain the carrier precursor.
Step 2: preparation of the support
Adding the carrier precursor into water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 800 ℃ for 6 hours to obtain the carrier.
And step 3: impregnation
1.82g of RuCl was taken3、90.40g Ni(NO3)2·6H2O、0.93gLa(NO3)3·6H2And O, preparing an aqueous solution, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method.
And 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the composite component methanation catalyst.
Example 3
Preparing the composite component methanation catalyst.
The preparation method comprises the following steps:
step 1: preparation of Carrier precursor
256Mg (NO)3)2·6H2Adding 3000mL of deionized water for dissolving, and adding 102g of gamma-Al into the solution2O3And 53.33g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Solution until the mixed solution pH was 9. Filtering the mixed solution, and washing the filter cake until NO3-a residue. And drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by using a 20-mesh sieve to obtain the carrier precursor.
Step 2: preparation of the support
Adding the carrier precursor into water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 700 ℃ for 6 hours to obtain the catalyst carrier.
And step 3: impregnation
3.05g of RuCl was taken3、37.89g Ni(NO3)2·6H2O、1.30gLa(NO3)3·6H2And O, preparing an aqueous solution, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method.
And 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the composite component methanation catalyst.
Example 4
This example is a comparative example.
Preparing a single Ni component methanation catalyst.
The preparation method comprises the following steps:
step 1: preparation of Carrier precursor
256Mg (NO)3)26H2O dissolved in 3000mL of deionized water and 102g of gamma-Al added to the solution2O3And 53.33g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Solution until the mixed solution pH was 9. Filtering the mixed solution, and washing the filter cake until NO3-a residue. And drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by using a 20-mesh sieve to obtain the carrier precursor.
Step 2: preparation of the support
Adding the carrier precursor into water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 700 ℃ for 6 hours to obtain the catalyst carrier.
And step 3: impregnation
37.89g of Ni (NO) was sampled3)2·6H2And O, preparing an aqueous solution, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method.
And 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the single Ni component methanation catalyst.
Example 5
This example is a comparative example.
This example added Ni (NO) compared to example 33)2·6H2Amount of O used, whichThe rest is the same as the example 3, and the specific preparation method comprises the following steps:
step 1: preparation of Carrier precursor
256Mg (NO)3)2·6H2Adding 3000mL of deionized water to dissolve O, and adding 102g of gamma-Al into the solution2O3And 53.33g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Solution until the mixed solution pH was 9. Filtering the mixed solution, and washing the filter cake until NO3-a residue. And drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by using a 20-mesh sieve to obtain the carrier precursor.
Step 2: preparation of the support
Adding the carrier precursor into water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 700 ℃ for 6 hours to obtain the catalyst carrier.
And step 3: impregnation
3.05g of RuCl was taken3、75.78g Ni(NO3)2·6H2O、1.30gLa(NO3)3·6H2And O, preparing an aqueous solution, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method.
And 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the composite component methanation catalyst.
Example 6
And (4) measuring the activity of the catalyst.
The catalysts prepared in examples 1 to 5 were loaded in a fixed bed reactor of a catalyst evaluation apparatus and tested under the following conditions:
TABLE 1 feed gas composition for methanation synthesis of natural gas
| Components | CO | CO2 | H2 | N2 | CH4 | C2H6 |
| V/％ | 8.50 | 3.59 | 57.99 | 3.56 | 23.87 | 2.40 |
Filling conditions are as follows: the dosage of the catalyst is as follows: 10mL, and the filling particle size is 3.2-4.0 mm.
Reduction conditions of the methanation catalyst: temperature: 500 ℃; the pressure is 0.5 MPa; the space velocity is 2500h-1(ii) a Reducing medium: high-purity hydrogen; reduction time: for 2 hours.
Test condition 1: steam-gas ratio: 0.25; the pressure is 1.50 MPa; space velocity: 6000h-1(ii) a The outlet temperature is increased slowly according to the speed of 10 ℃/h from 100 ℃, and the CO of the tail gas is recorded2The temperature at which the concentration begins to change is recorded as the activation temperature of the methanation reaction;
test condition 2: the outlet temperature is 300 ℃; steam-gas ratio: 0.25; the pressure is 1.50 MPa; space velocity: 6000h-1Recording the tail gas CO at the time of stable reaction2Concentration;
an Agilent 7820A gas chromatography instrument with a flame particle detector was selectedAnd a thermal conductivity detector, which is filled with a capillary column and takes argon as carrier gas to mainly analyze CO and CO in the gas2、CH4、H2(ii) a Selecting QGS-08B of Beijing Branch Mikazak analytical instrument Limited company to analyze CO in outlet tail gas2And (4) concentration.
TABLE 2 results of methanation reaction of composite component methanation catalyst
From the experimental data of the above examples, it can be seen that the composite component methanation catalyst of the present invention has low activation temperature, and CO in the tail gas at the reaction outlet2The volume concentration reaches 10-6Magnitude. Compared with the catalyst with a single Ni component, the catalyst of example 4 has lower activation temperature and CO2The conversion rate is also higher; the activity of the invention is also higher and the activation temperature is lower than in example 5, which has a higher Ni content than in example 5. The catalyst has optimal active composition, excellent low-temperature methanation activity and methanation selectivity, and is beneficial to reducing the preheating temperature of raw material gas and saving energy consumption in industrial application.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (1)
1. The application of the composite component methanation catalyst in the methanation of synthetic natural gas is characterized in that the preparation method of the composite component methanation catalyst comprises the following steps:
step 1: preparation of Carrier precursor
256Mg (NO)3)2·6H2Adding 3000mL of deionized water for dissolving, and adding 102g of gamma-Al into the solution2O3And 53.33g of anatase TiO2After fully stirring and infiltrating, slowly adding 5% K2CO3Dissolving until the pH value of the mixed solution is 9; filtering the mixed solution, and washing the filter cake until NO3-a residue; drying the filter cake at 105 ℃ for 4 hours, calcining at 400 ℃ for 5 hours, and sieving by a 20-mesh sieve to obtain a carrier precursor;
step 2: preparation of the support
Adding a carrier precursor into water accounting for 15% of the mass of the carrier precursor and graphite accounting for 3% of the mass of the carrier precursor, uniformly mixing, pressing and molding, and roasting at 700 ℃ for 6 hours to obtain a catalyst carrier;
and step 3: impregnation
3.05g of RuCl was taken3、37.89g Ni(NO3)2·6H2O、1.30gLa(NO3)3·6H2Preparing an aqueous solution from O, and soaking the carrier in the solution at 80 ℃ for 2 hours by using an isometric method;
and 4, step 4: drying and roasting
And taking out the impregnated carrier, drying at 105 ℃ for 6 hours, and roasting at 400 ℃ for 3 hours to obtain the composite component methanation catalyst.
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| CN103933994B (en) * | 2014-04-18 | 2015-12-02 | 昌邑凯特新材料有限公司 | A kind of for CO and CO 2the preparation method of the high-temperature methanation catalyst of methane is produced with hydrogen reaction |
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