CN112569942B - Preparation method of methane synthesis catalyst - Google Patents

Preparation method of methane synthesis catalyst Download PDF

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CN112569942B
CN112569942B CN201910931473.6A CN201910931473A CN112569942B CN 112569942 B CN112569942 B CN 112569942B CN 201910931473 A CN201910931473 A CN 201910931473A CN 112569942 B CN112569942 B CN 112569942B
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catalyst
alloy powder
washing
nickel
methane synthesis
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CN112569942A (en
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吴学其
黄先亮
徐本刚
蔡进
王金利
张�杰
朱艳芳
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a preparation method of a methane synthesis catalyst, which comprises the steps of mixing metal nickel, metal aluminum and porous silicon according to a certain proportion, and preparing the methane synthesis catalyst after the processes of melting, atomizing, drying, screening, activating, washing and the like. The methane synthesis catalyst prepared by the method is a catalyst with a nickel-silicon composite framework, improves the melting point of the catalyst, has larger pore diameter, can improve the activity of the catalyst, and avoids the phenomenon of catalyst inactivation caused by the blockage of pore channels of the catalyst due to coking.

Description

Preparation method of methane synthesis catalyst
Technical Field
The invention belongs to the field of coal chemical industry, and particularly relates to a preparation method of a methane synthesis catalyst.
Background
Methane is widely used in civilian and industrial applications. As fuels, such as natural gas and coal gas; as chemical raw materials, the catalyst can be used for producing acetylene, nitrochloromethane, carbon disulfide, methane chloride, dichloromethane, trichloromethane, carbon tetrachloride, hydrocyanic acid and the like.
The energy resource of China is characterized by less oil, poor gas and rich coal. The coal resources are relatively rich and sufficientThe method for producing methane by using cheap coal resources has high energy utilization rate and low unit calorific value water consumption, and is an important way for solving the contradiction between supply and demand of natural gas in China. The methane synthesis technology mainly comprises the technology of directly synthesizing methane from coal, the technology of preparing methane from the coal through synthesis gas, the technology of biologically synthesizing methane, and CO 2 The technique for synthesizing methane by methanation, the technique for synthesizing methane by coke oven gas and the like. Wherein the research of the technology for preparing methane by coal through synthesis gas is the most extensive.
The technology for preparing methane from coal through synthesis gas is also called a steam oxidation gasification method, and the main reaction comprises two steps:
the method comprises the steps of preparing synthetic gas through coal gasification: c + O 2 →CO 2 ，C+H 2 O→CO+H 2 ，C+CO 2 →2CO；
The method comprises the following steps of: CO +3H 2 →CH 4 +H 2 O。
The technology for preparing methane from coal through synthesis gas is also called two-step method technology for preparing methane from coal, the catalyst selected is a nickel-based catalyst, the activity is high, the selectivity is good, the price is low, a fixed bed reactor and a fluidized bed reactor are commonly used as a methanation reactor, and the technology is commercially applied at present.
Methanation catalysts are generally based on Al 2 O 3 As a carrier, methanation catalyst as disclosed in patent US 3933833 for high purity gamma-Al 2 O 3 Is used as a carrier and loaded with active components of nickel oxide and cobalt oxide.
The patent CN 1043639A discloses a methanation catalyst and Al 2 O 3 Is used as carrier, ni is used as active component, and rare-earth metal or alkaline-earth metal is used as cocatalyst.
In the methanation catalyst disclosed in patent CN 1043449A, nickel is used as an active component, rare earth metal and magnesium are used as promoters, and the balance is alumina.
The methanation catalysts take alumina as a carrier, are used in the methanation reaction of trace COx, have low reaction temperature, low water vapor partial pressure in reaction gas and good stability.
However, these catalysts have poor support hydrothermal stability and also suffer from carbon deposition in methanation reactions.
Because the methanation reaction is a strong exothermic reaction, the temperature of most of the reaction reaches over 600 ℃, so that the catalyst is required to have good thermal stability.
The methanation catalyst disclosed in patent CN 1033635A takes magnesium aluminate spinel as a carrier and nickel as an active component, and the catalyst has good activity and stability when reacting at a temperature of over 600 ℃.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a coal-to-methane synthesis catalyst with porous silicon as a framework and nickel as an active unit, which solves the problem that the activity of the catalyst is reduced due to coking of the existing methane synthesis catalyst.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a methane synthesis catalyst, which comprises the following steps:
melting: adding metal nickel, metal aluminum and porous silicon into a smelting furnace according to a proportion for melting;
secondly, atomization: carrying out high-pressure water atomization on the molten material;
drying: drying the atomized alloy powder;
screening: screening the dried alloy powder;
activation: activating the screened alloy powder with caustic alkali solution;
sixthly, washing with water: and washing the activated alloy powder with deionized water, and removing excessive alkali and generated salt to obtain the methane synthesis catalyst.
Preferably, the mass ratio of the metallic nickel to the metallic aluminum in the step of making is 0.6-1.5.
Preferably, the porous silicon described in the first step has a particle diameter of 100 to 1000nm and a pore diameter of 20 to 100nm.
Preferably, the mass ratio of the added amount of the porous silicon to the added amount of the metallic nickel is 0.1-0.3.
Preferably, the melting temperature in the step of the process is 1200-1650 ℃.
Preferably, the atomization temperature in the step two is 1200-1550 ℃.
Preferably, the alloy particles with the particle size of 0.3-0.9mm are selected by the middle screen;
preferably, the caustic alkali solution used for activation in the step fifthly is one or two of sodium hydroxide and potassium hydroxide, and the total mass concentration of the solution is 5% -30%.
Preferably, the aluminum mass content in the activated alloy powder is 5-20%.
Preferably, the washing is carried out by the water in the step sixteenth, and the pH value of the washing liquid is 8-10.
The invention has the beneficial effects that:
(1) According to the invention, porous silicon is added into the methane synthesis catalyst to serve as a framework, and nickel and the porous silicon are stably combined to form a composite framework, so that the melting point of the nickel-aluminum alloy is improved, the condition that nickel crystal grains are enlarged due to melting is effectively inhibited, and the service life of the catalyst is prolonged;
(2) Compared with supported nickel, the catalyst prepared by the invention has larger pore diameter, the reaction is carried out on the inner surface of the catalyst more, the activity of the catalyst can be improved, and the phenomenon of catalyst deactivation caused by the blockage of pore channels of the catalyst by coking is avoided.
Drawings
FIG. 1 is a schematic flow diagram of the preparation of a catalyst in an example of the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to specific examples and drawings, but the scope of the present invention is not limited to the examples. The reagents used in the examples of the present invention are all commercially available.
The preparation of the catalyst in the following examples is illustrated with reference to FIG. 1.
Example 1
Adding 10 parts of metallic nickel, 10 parts of metallic aluminum and 2 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for smelting, controlling the temperature to 1350 ℃, atomizing the fused alloy by using high-pressure water, controlling the atomizing temperature to 1300 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into a 20% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 10%, stopping activation, washing with deionized water until the pH value of washing filtrate is 10, and obtaining the methane synthesis catalyst C1.
Example 2
10 parts of metallic nickel, 15 parts of metallic aluminum and 1.8 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm are added into a smelting furnace for melting, the temperature is controlled to be 1600 ℃, the melted alloy is atomized by high-pressure water, the atomization temperature is 1500 ℃, the atomized alloy powder is dried and then screened, the alloy powder with the particle size of 0.3-0.9mm is selected and added into 30 percent of sodium hydroxide aqueous solution, the aluminum content in the alloy powder is controlled to be 20 percent, the activation is stopped, and the alloy powder is washed by deionized water until the pH value of washing filtrate is 10, so that the methane synthesis catalyst C2 is obtained.
Example 3
Taking 12 parts of metallic nickel, 8 parts of metallic aluminum and 1.5 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm, adding the metallic nickel, 8 parts of metallic aluminum and 1.5 parts of porous silicon into a smelting furnace for smelting, controlling the temperature at 1450 ℃, atomizing the molten alloy by using high-pressure water, controlling the atomizing temperature at 1300 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into a 20% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 6%, stopping activation, washing by using deionized water until the pH value of washing filtrate is 10, and obtaining the methane synthesis catalyst C3.
Example 4
Adding 10 parts of metallic nickel, 10 parts of metallic aluminum and 3 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for smelting, controlling the temperature to 1350 ℃, atomizing the fused alloy by using high-pressure water, controlling the atomizing temperature to 1300 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into a 10% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 15%, stopping activation, washing with deionized water until the pH value of washing filtrate is 9, and obtaining the methane synthesis catalyst C4.
Example 5
Adding 13.5 parts of metallic nickel, 9 parts of metallic aluminum and 4 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for melting, controlling the temperature at 1250 ℃, atomizing the melted alloy by using high-pressure water, controlling the atomizing temperature at 1200 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into a 5% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 10%, stopping activation, washing with deionized water until the pH value of washing filtrate is 10, and obtaining the methane synthesis catalyst C5.
Example 6
Adding 10 parts of metallic nickel, 12 parts of metallic aluminum and 1 part of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for melting, controlling the temperature at 1400 ℃, atomizing the melted alloy by using high-pressure water, controlling the atomizing temperature at 1300 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into 18% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 12%, stopping activation, washing with deionized water until the pH value of washing filtrate is 8.5, and obtaining the methane synthesis catalyst C6.
Example 7
Adding 9.5 parts of metallic nickel, 14 parts of metallic aluminum and 2 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for smelting, controlling the temperature at 1550 ℃, atomizing the fused alloy by using high-pressure water, controlling the atomizing temperature at 1400 ℃, drying and screening the atomized alloy powder, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into a 15% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 17%, stopping activation, washing with deionized water until the pH value of washing filtrate is 9.5, and obtaining the methane synthesis catalyst C7.
Example 8
Adding 13 parts of metallic nickel, 9.5 parts of metallic aluminum and 1.4 parts of porous silicon with the particle size of 100-1000nm and the pore diameter of 20-100nm into a smelting furnace for melting, controlling the temperature to 1350 ℃, atomizing the melted alloy by high-pressure water, controlling the atomizing temperature to 1300 ℃, drying the atomized alloy powder, screening, selecting alloy powder with the particle size of 0.3-0.9mm, adding the alloy powder into 30% sodium hydroxide aqueous solution, controlling the aluminum content in the alloy powder to be 10%, stopping activation, washing by deionized water until the pH value of washing filtrate is 8, and obtaining the methane synthesis catalyst C8.
Comparative example 1
Reference is made to patent CN102319574a, example 1.
1g of polyoxyethylene-polyoxypropylene-polyoxyethylene is dissolved in ethanol, after the polyoxyethylene-polyoxypropylene-polyoxyethylene is fully dissolved, 3g of aluminum propoxide is added, the mixture is stirred for 4 hours at 40 ℃, the mixture is placed in a drying box at 60 ℃ to be dried for 48 hours, and the mesoporous alumina is obtained after the mixture is roasted at 400 ℃. Respectively preparing 2.48g of nickel nitrate and 0.95g of cerium nitrate into solutions, firstly soaking the prepared 2.5g of mesoporous alumina carrier into the cerium nitrate solution, drying the soaked carrier at 120 ℃ for 2h, roasting at 450 ℃, then soaking into the nickel nitrate solution, drying at 120 ℃ for 2h, then roasting for 4h to obtain a nickel-loaded catalyst, then soaking into a solution prepared from 0.4g of magnesium nitrate, drying at 120 ℃ for 2h after soaking, and tabletting and forming after roasting at 500 ℃ for 4h to obtain the comparative example 1.
Catalyst performance test conditions:
fixed bed reactor, catalyst loading 40ml, feed gas composition (v/v%): CO 4% -8%, CO 2 4%-6%、H 2 35%-70%、CH 4 5 to 20 percent, the reaction pressure is 3.0MPa, and the space velocity is 2000h -1 And the inlet temperature is 260-280 ℃. Before the catalyst is used, reduction is needed, and the activation conditions are as follows: reducing atmosphere H 2 (ii) a Reduction pressure: normal pressure; reduction space velocity of 1000h -1 (ii) a The temperature programming is slowly increased to 450 ℃ and stays for 4.0h (the temperature rising rate is 1 ℃/1 min).
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Claims (6)

1. A method for preparing a methane synthesis catalyst, wherein the catalyst is prepared by the steps of:
melting: melting metallic nickel, metallic aluminum and porous silicon according to a proportion, wherein the melting temperature is 1200-1650 ℃; the particle size of the porous silicon is 100-1000nm, the pore diameter is 20-100nm, and the mass ratio of the added amount of the porous silicon to the added amount of the metal nickel is 0.1-0.3;
and (2) atomization: carrying out high-pressure water atomization on the molten material at the atomization temperature of 1200-1550 ℃;
drying: drying the atomized alloy powder;
screening: screening the dried alloy powder;
activation: activating the screened alloy powder with caustic solution;
sixthly, washing with water: and washing the activated alloy powder with deionized water, and removing excessive alkali and generated salt to obtain the methane synthesis catalyst.
2. The method of claim 1, wherein the mass ratio of metallic nickel to metallic aluminum in step (i) is 0.6-1.5.
3. The method according to claim 1, wherein the alloy particles with the particle size of 0.3-0.9mm are selected by a sieve in step four.
4. The method according to claim 1, characterized in that the caustic alkali solution used for activation in step fifthly is one or two of sodium hydroxide solution and potassium hydroxide solution, and the total mass concentration of the solution is 5% -30%.
5. A method according to claim 1 or 4, characterized in that the aluminium content by mass of the activated alloy powder is 5-20%.
6. The method as claimed in claim 1, wherein the step sixteenth is carried out by washing with water, and the pH value of the washing liquid is 8-10.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979332A (en) * 1975-02-03 1976-09-07 Shell Oil Company High temperature methanation with molten salt-based catalyst systems
CN1765731A (en) * 2004-10-28 2006-05-03 中国石油化工股份有限公司 Method for removing CO from hydrogen rich gas
CN104069872A (en) * 2014-07-08 2014-10-01 赛鼎工程有限公司 Preparation method and application of catalyst applicable to methanation of slurry reactor
CN104084220A (en) * 2014-07-08 2014-10-08 赛鼎工程有限公司 Preparation method and application of sulfur-tolerant methanation raney nickel catalyst for fixed bed
CN105817219A (en) * 2015-01-04 2016-08-03 神华集团有限责任公司 Methanation catalyst and preparation method and application thereof
CN106914243A (en) * 2015-12-28 2017-07-04 中国科学院大连化学物理研究所 A kind of preparation method of metallic element impurity Si sill catalyst and the method for methane anaerobic ethene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3582088B2 (en) * 1993-09-08 2004-10-27 東ソー株式会社 Hydrogenation method of carbon dioxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979332A (en) * 1975-02-03 1976-09-07 Shell Oil Company High temperature methanation with molten salt-based catalyst systems
CN1765731A (en) * 2004-10-28 2006-05-03 中国石油化工股份有限公司 Method for removing CO from hydrogen rich gas
CN104069872A (en) * 2014-07-08 2014-10-01 赛鼎工程有限公司 Preparation method and application of catalyst applicable to methanation of slurry reactor
CN104084220A (en) * 2014-07-08 2014-10-08 赛鼎工程有限公司 Preparation method and application of sulfur-tolerant methanation raney nickel catalyst for fixed bed
CN105817219A (en) * 2015-01-04 2016-08-03 神华集团有限责任公司 Methanation catalyst and preparation method and application thereof
CN106914243A (en) * 2015-12-28 2017-07-04 中国科学院大连化学物理研究所 A kind of preparation method of metallic element impurity Si sill catalyst and the method for methane anaerobic ethene

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