CN108479843B - Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst - Google Patents
Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst Download PDFInfo
- Publication number
- CN108479843B CN108479843B CN201810325038.4A CN201810325038A CN108479843B CN 108479843 B CN108479843 B CN 108479843B CN 201810325038 A CN201810325038 A CN 201810325038A CN 108479843 B CN108479843 B CN 108479843B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sulfur
- catalyst
- composite molecular
- microporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst, and relates to the technical field of methanation catalysts. The microporous-mesoporous composite molecular sieve is characterized in that a microporous-mesoporous composite molecular sieve ZSM-5/MCM-41 is used as a support body, a metal M is used as an active component, the active component is embedded into a framework structure of the microporous-mesoporous composite molecular sieve, the mass percent of the active component M is 1-20 wt%, the balance is the microporous-mesoporous composite molecular sieve ZSM-5/MCM-41, and the mass ratio of the microporous molecular sieve ZSM-5 to the mesoporous molecular sieve MCM-41 is 1: 1-1: 5. the catalyst prepared by the invention has a micropore and mesopore structure, the methane selectivity is higher, the CO conversion rate of the catalyst is 100% under the optimal condition, the methane selectivity reaches more than 90%, and the catalyst has the advantages of low active component loading capacity, high activity, good high temperature resistance, good hydrothermal stability and long service life of the catalyst, and has great industrial application prospects.
Description
Technical Field
The invention relates to the technical field of methanation catalysts, in particular to preparation and application of an embedded microporous-mesoporous composite molecular sieve sulfur-resistant methanation catalyst, and more particularly relates to a methanation catalyst containing sulfur-containing substances (3000-8000 p) such as hydrogen sulfidepm) of CO, H2A preparation method of a sulfur-tolerant methanation catalyst for converting mixed gas into methane and application of the catalyst in SNG preparation.
Background
In recent years, with the increasing exhaustion of petrochemical energy and the increasing demand of natural gas, the problems of ecology, environment and the like caused by the combustion of the petrochemical energy are increasingly serious, and people tend to use clean and efficient natural gas more and more. The energy structure of China is characterized by rich coal, poor oil and little gas, the rich coal resource of China is utilized, the Substitute Natural Gas (SNG) is prepared by adopting the coal-to-natural gas technology, the structure of a coal deep-processing product can be optimized, the method is environment-friendly, and the method is favorable for relieving the problem of shortage of natural gas supply in China.
The key technology of the coal-to-natural gas technology is the design of a methanation reactor and the development of a methanation catalyst. In the existing industrial methanation catalyst, the effect is better that of a load type Ni-based catalyst, but the Ni-based catalyst is very sensitive to sulfur species and is very easy to generate sulfur poisoning, so that the catalyst is inactivated. Therefore, when a Ni-based catalyst is used, it is necessary to remove H from the raw material gas2S and other sulfur-containing substances, the content of which is lower than 1ppm, which undoubtedly increases the equipment investment of coal-based natural gas. Therefore, the development of the sulfur-tolerant methanation catalyst is particularly important for the maturity and development of the coal-to-natural gas process technology.
At present, most of sulfur-resistant methanation catalysts are supported catalysts, Mo, W, Ni, Co and the like are used as active components, and Al2O is selected3、CeO2、ZrO2、SiO2And TiO2The like is used as a carrier, K, La, Cr, Fe and the like are used as auxiliary agents, but the methanation catalytic activity of the K, La, Cr and Fe is generally not high, the CO conversion rate is generally 50-90%, and CH is4The selectivity is only 60% -70%, and most catalysts are not subjected to a catalyst life test or have short lives, and most catalysts are not high-temperature-resistant and easy to sinter and deactivate, so that the development of a sulfur-resistant methanation process is greatly limited.
The mesoporous molecular sieve MCM-41 has the characteristics of hexagonal ordered arrangement of pore channels, uniform size, continuously adjustable pore diameter within the range of 2-10nm, large specific surface area and the like, and synthesizes a frameworkMCM-41 with heteroatoms incorporated in the structure, non-tetracoordinated ions in the framework such as: al (Al)3+、Cu2+、Fe3+、Zn2+Etc., can be counterbalanced by protons or other transition metal ions to form catalytically active centers. Ni-MCM-41 catalyst prepared by in-situ synthesis method in CO2Reforming CH4The reaction shows good thermal stability. The Chinese patent application No. 201410148170.4 discloses an embedded sulfur-tolerant methanation catalyst and a preparation method thereof, wherein mesoporous molecular sieve MCM-41 is used as a carrier, metal Ni, Mo and W are used as main active components to be synthesized into an MCM-41 framework structure and used for methanation reaction, and compared with a supported catalyst, the catalyst shows good high temperature resistance, but the catalytic activity, especially the low-temperature catalytic activity, is still to be improved, and the hydrothermal stability is not high.
ZSM-5 zeolite having ten-membered rings and a basic structural unit consisting of eight pentatomic rings has a very stable crystal structure, and ZSM-5 has been one of the highest thermal properties of the known zeolites so far, so that it is particularly suitable for use in high-temperature processes. ZSM-5 has high silicon-aluminum ratio, small surface charge density, good hydrophobicity, difficult carbon deposition and good hydrothermal stability, and is widely used as a catalyst of FCC. Meanwhile, ZSM-5 has strong acidity and adjustable acidity, and is widely applied to the field of acid catalysis; in addition, ZSM-5 has a unique pore structure, so that the catalyst becomes a good shape-selective catalyst. The novel catalytic material microporous-mesoporous ZSM-5/MCM-41 composite molecular sieve has the advantages of both ZSM-5 and MCM-41. Based on the above, the preparation and the application of the embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst are especially necessary.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an embedded micropore-mesopore composite molecular sieve sulfur-resistant methanation catalyst, which takes a composite molecular sieve ZSM-5/MCM-41 as a carrier, adopts an in-situ synthesis method to embed active components into a composite molecular sieve skeleton structure, has fine metal active component particles and good high temperature resistance, overcomes the defect that the existing catalyst needs to remove sulfur to be below 0.1ppm in the process of preparing natural gas from coal, can directly methanize raw material coal gas without deep desulfurization and purification, and has good catalytic activity, high temperature resistance and hydrothermal stability.
In order to achieve the purpose, the invention is realized by the following technical scheme: an embedded micropore-mesopore composite molecular sieve sulfur-tolerant methanation catalyst takes micropore-mesopore composite molecular sieve ZSM-5/MCM-41 as a support body and metal M as an active component, and the active component is embedded into a micropore-mesopore composite molecular sieve framework structure, wherein the content of the active component M is 1-20 parts by mass and the balance is micropore-mesopore composite molecular sieve ZSM-5/MCM-41 based on 100 parts by mass of the catalyst and calculated by metal elements, the mass ratio of micropore molecular sieve ZSM-5 to mesopore molecular sieve MCM-41 is 1: 1-1: 5;
the active component M is M or MxNyWherein M is Ni, Mo, Mn, etc., N is O or S, x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 0 and less than or equal to 7.
Preferably, the microporous molecular sieve ZSM-5 is a microporous molecular sieve carrier ZSM-5 with high specific surface area, and the specific surface area of the microporous molecular sieve carrier ZSM-5 is 300-500 m2/g，SiO2/Al2O3The molar ratio is 30-400; the mesoporous molecular sieve MCM-41 is a mesoporous molecular sieve MCM-41 with high specific surface area, and the specific surface area is 600-1500 m2The pore diameter is 3-10 nm.
The preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps:
(1) preparing a salt solution of M;
(2) dispersing a ZSM-5 microporous molecular sieve in a NaOH solution, adding a template CTAB, stirring vigorously, adding a prepared M salt solution dropwise while adding a silicon source TEOS dropwise, stirring vigorously for a certain time, and transferring to a hydrothermal reaction kettle for crystallization;
(3) cooling the crystallized stock solution to room temperature, performing suction filtration, washing to be neutral, drying in vacuum, and roasting to obtain a catalyst, wherein the M load in the catalyst is 1-20 wt%;
the M salt is nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, ammonium molybdate, sodium molybdate, potassium molybdate, manganese sulfate, manganese nitrate and manganese carbonate;
the temperature of the hydrothermal reaction kettle is 80-150 ℃; the crystallization time is 2-168 h; the room temperature is 15-30 ℃; the drying temperature is 50-100 ℃, and the drying time is 2-10 h; the roasting temperature is 400-700 ℃, and the roasting time is 2-10 h.
Preferably, the temperature of the hydrothermal reaction kettle is 100-120 ℃; the crystallization time is 12-24 h; the room temperature is 20-25 ℃.
The solvent adopted by the M salt solution is deionized water, ethanol and acetone.
The embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst is applied to preparation of SNG (single crystal glass) containing sulfur in feed gas, and the catalyst is in the atmosphere of sulfur-containing H2The space velocity of the-CO mixed gas is 3000-60000 h-1The pressure is 0.1-5.0 MPa, the reaction temperature is 200-700 ℃, and the molar ratio of H2/CO in the mixed gas is 1-4.
Preferably, said sulfur-containing H2CO gas mixture, the sulphur component being H2S, thiophenes or R-SH, the sulfur content is 3000-8000 ppm.
The invention has the beneficial effects that: the composite molecular sieve ZSM-5/MCM-41 is used as a carrier, an in-situ synthesis method is adopted to embed active components into a composite molecular sieve skeleton structure to prepare the sulfur-resistant methanation catalyst, and the prepared catalyst has fine metal active component particles and good high-temperature resistance; compared with a single molecular sieve methanation catalyst, the ZSM-5/MCM-41 composite molecular sieve sulfur-tolerant catalyst has excellent catalytic activity, high temperature resistance and hydrothermal stability in the application of SNG methanation reaction.
(1) The catalyst takes mesoporous molecular sieve MCM-41 with stable chemical properties and good thermal conductivity and a composite molecular sieve consisting of microporous molecular sieve ZSM-5 with high silica-alumina ratio, small surface charge density, good hydrophobicity, carbon deposition resistance and good hydrothermal stability as a carrier, and active components are embedded into a framework structure of the composite molecular sieve, so that the catalyst has good high temperature resistance, hydrothermal stability and catalytic life, the catalyst structure is not damaged when being calcined for 50 hours in a nitrogen atmosphere at the high temperature of 800 ℃, the catalytic activity is not obviously reduced, the catalyst structure is not obviously damaged when being subjected to hydrothermal treatment for 10 hours at the temperature of 780 ℃, and the catalytic activity is not reduced.
(2) The catalyst shows excellent reaction activity and methane activity in the SNG reaction for preparing the natural gas from the coal, and shows good catalytic activity in the temperature range of 250-450 ℃, wherein the CO conversion rate reaches 100% and the methane selectivity reaches more than 90% in the temperature range of 300-400 ℃.
(3) The catalyst does not contain noble metal active components, the preparation method is simple and easy to implement, and the catalyst also has better catalytic activity at lower temperature, high cost performance and great industrial application prospect.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The specific implementation mode adopts the following technical scheme: an embedded micropore-mesopore composite molecular sieve sulfur-tolerant methanation catalyst takes micropore-mesopore composite molecular sieve ZSM-5/MCM-41 as a support body and metal M as an active component, and the active component is embedded into a micropore-mesopore composite molecular sieve framework structure, wherein the content of the active component M is 1-20 parts by mass and the balance is micropore-mesopore composite molecular sieve ZSM-5/MCM-41 based on 100 parts by mass of the catalyst and calculated by metal elements, the mass ratio of micropore molecular sieve ZSM-5 to mesopore molecular sieve MCM-41 is 1: 1-1: 5.
it is worth noting that the microporous molecular sieve ZSM-5 is a microporous molecular sieve carrier ZSM-5 with a high specific surface area, and the specific surface area is 300-500 m2/g，SiO2/Al2O3The molar ratio is 30-400; the mesoporous molecular sieve MCM-41 is a mesoporous molecular sieve MCM-41 with high specific surface area, and the specific surface area is 600-1500 m2(ii)/g, the pore diameter is 3-10 nm; the active component M is M or MxNyWherein M is Ni, Mo, Mn, etc., N is O or S, x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 0 and less than or equal to 7.
The preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps:
(1) preparing a salt solution of M;
(2) dispersing a ZSM-5 microporous molecular sieve in a NaOH solution, adding a template CTAB, stirring vigorously, adding a prepared M salt solution dropwise while adding a silicon source TEOS dropwise, stirring vigorously for a certain time, and transferring to a hydrothermal reaction kettle for crystallization;
(3) and cooling the crystallized stock solution to room temperature, performing suction filtration, washing to be neutral, drying in vacuum, and roasting to obtain the catalyst, wherein the M load in the catalyst is 1-20 wt%.
Notably, the M salt is nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, ammonium molybdate, sodium molybdate, potassium molybdate, manganese sulfate, manganese nitrate and manganese carbonate; the solvent adopted by the M salt solution is deionized water, ethanol and acetone. The temperature of the hydrothermal reaction kettle is 80-150 ℃, and preferably 100-120 ℃; the crystallization time is 2-168 hours, preferably 12-24 hours; the room temperature is 15-30 ℃, and preferably 20-25 ℃; the drying temperature is 50-100 ℃, and the drying time is 2-10 h; the roasting temperature is 400-700 ℃, and the roasting time is 2-10 h.
The embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst is applied to preparation of SNG (single crystal glass) containing sulfur in feed gas, and the catalyst is in the atmosphere of sulfur-containing H2The space velocity of the-CO mixed gas is 3000-60000 h-1The pressure is 0.1-5.0 MPa, the reaction temperature is 200-700 ℃, and the molar ratio of H2/CO in the mixed gas is 1-4.
Notably, the sulfur-containing H2CO gas mixture, the sulphur component being H2S, thiophenes or R-SH, the sulfur content is 3000-8000 ppm.
The specific implementation mode changes the situation that the traditional methanation catalyst takes alumina as a carrier, but takes a composite molecular sieve which is composed of a mesoporous molecular sieve MCM-41 with stable chemical properties and good heat conductivity and a microporous molecular sieve ZSM-5 with high silica-alumina ratio, small surface charge density, good hydrophobicity, difficult carbon deposition and good hydrothermal stability as a carrier, and adopts an in-situ synthesis method to embed active components into the composite molecular sieveIn the framework structure of the synthetic molecular sieve, the microporous-mesoporous ZSM-5/MCM-41 composite sulfur-resistant molecular sieve methanation catalyst is prepared, the preparation method is simple, and the prepared catalyst has the advantages of good catalytic activity, high temperature resistance, hydrothermal stability, catalytic life and the like. The catalyst is at normal pressure, H2In the synthesis gas with S content of 3000-8000ppm, at 400 ℃ and at a space velocity of 12000h at 300--1Under the optimal condition, the CO conversion rate reaches 100 percent, the methane selectivity reaches 95 percent, and the method has great industrial prospect.
Example 1: the preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps: 3.2g of nickel nitrate hexahydrate is weighed and dissolved in 20ml of deionized water to prepare an aqueous nickel nitrate solution. Dispersing 3.3g of ZSM-5 molecular sieve in NaOH solution, heating the solution to 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding a nickel nitrate aqueous solution and a silicon source (tetraethoxysilane) into the solution, adjusting the pH value of the solution to 11, wherein the molar ratio of each substance in the solution is as follows: 1.0 ZSM-5: 0.12 Ni: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. And violently stirring and aging the mixed solution for 2 hours, then transferring the mixed solution into a hydrothermal reaction kettle, crystallizing the mixed solution for 72 hours at 100 ℃, rapidly cooling the mixed solution to room temperature, filtering and washing the mixed solution to be neutral, drying the mixed solution overnight at 100 ℃, calcining the dried mixed solution for 6 hours at 550 ℃, and removing a template agent to obtain the 10 wt% Ni-ZSM-5/MCM-41 composite molecular sieve sulfur-resistant methanation catalyst which is marked as catalyst A.
Example 2: the preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps: 1.3g of ammonium molybdate was weighed and dissolved in 20ml of deionized water to prepare an aqueous ammonium molybdate solution. Dispersing 3.3g of ZSM-5 molecular sieve in NaOH solution, heating the solution to 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding an ammonium molybdate aqueous solution and a silicon source (tetraethoxysilane) into the solution, adjusting the pH value of the solution to 11, wherein the molar ratio of each substance in the solution is as follows: 1.0 ZSM-5: 0.07 Mo: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. The mixed solution is stirred vigorously and aged for 2 hours, then transferred into a hydrothermal reaction kettle, crystallized for 72 hours at 100 ℃, quenched to room temperature, filtered, washed to be neutral, dried at 100 ℃ overnight, and finally dried 5Calcining for 6 hours at 50 ℃, and removing the template agent to obtain the 10 wt% Mo-ZSM-5/MCM-41 composite molecular sieve sulfur-tolerant methanation catalyst which is marked as catalyst B.
Example 3: the preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps: 3.2g of nickel nitrate hexahydrate is weighed and dissolved in 10ml of deionized water to prepare an aqueous nickel nitrate solution. 1.3g of ammonium molybdate was weighed and dissolved in 10ml of deionized water to prepare an aqueous ammonium molybdate solution. Dispersing 3.3g of ZSM-5 molecular sieve in NaOH solution, heating the solution to 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding nickel nitrate aqueous solution, ammonium molybdate aqueous solution and silicon source (tetraethoxysilane) into the solution, adjusting the pH value of the solution to 11, wherein the molar ratio of each substance in the solution is as follows: 1.0 ZSM-5: 0.12 Ni: 0.07 Mo: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. The mixed solution is stirred vigorously and aged for 2 hours, then transferred into a hydrothermal reaction kettle, crystallized for 72 hours at 100 ℃, quenched to room temperature, filtered, washed to be neutral, dried overnight at 100 ℃, calcined for 6 hours at 550 ℃, and the template agent is removed to obtain the 10 wt% Ni-10 wt% Mo-ZSM-5/MCM-41 composite molecular sieve sulfur-resistant methanation catalyst which is marked as catalyst C.
Example 4: the preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst comprises the following steps: 3.2g of nickel nitrate hexahydrate is weighed and dissolved in 10ml of deionized water to prepare an aqueous nickel nitrate solution. 0.65g of ammonium molybdate was weighed and dissolved in 10ml of deionized water to prepare an aqueous ammonium molybdate solution. Dispersing 3.3g of ZSM-5 molecular sieve in NaOH solution, heating the solution to 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding nickel nitrate aqueous solution, ammonium molybdate aqueous solution and silicon source (tetraethoxysilane) into the solution, adjusting the pH value of the solution to 11, wherein the molar ratio of each substance in the solution is as follows: 1.0 ZSM-5: 0.12 Ni: 0.07 Mo: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. The mixed solution is stirred vigorously and aged for 2 hours, then transferred into a hydrothermal reaction kettle, crystallized for 72 hours at 100 ℃, quenched to room temperature, filtered, washed to be neutral, dried overnight at 100 ℃, calcined for 6 hours at 550 ℃, and the template agent is removed to obtain the sulfur-resistant armor of the 10 wt% Ni-5 wt% Mo-ZSM-5/MCM-41 composite molecular sieveAlkylation catalyst, designated catalyst D.
Comparative example 1: 1.3g of ammonium molybdate was weighed and dissolved in 20ml of deionized water to prepare an aqueous ammonium molybdate solution. Dissolving a certain amount of NaOH and a template agent in deionized water at 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding an ammonium molybdate aqueous solution and a silicon source (tetraethoxysilane) into the NaOH solution, adjusting the pH value of the solution to 11, and adjusting the molar ratio of substances in the solution to be 0.07 Mo: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. And violently stirring and aging the mixed solution for 2 hours, then transferring the mixed solution into a hydrothermal reaction kettle, crystallizing the mixed solution for 72 hours at 100 ℃, rapidly cooling the mixed solution to room temperature, filtering and washing the mixed solution to be neutral, drying the mixed solution overnight at 100 ℃, calcining the dried mixed solution for 6 hours at 550 ℃, and removing a template agent to obtain a 10 wt% Mo-MCM-41 monomolecular sieve methanation catalyst which is marked as catalyst a.
Comparative example 2: 3.2g of nickel nitrate hexahydrate is weighed and dissolved in 10ml of deionized water to prepare an aqueous nickel nitrate solution. 1.3g of ammonium molybdate was weighed and dissolved in 10ml of deionized water to prepare an aqueous ammonium molybdate solution. Dissolving a certain amount of NaOH and a template agent in deionized water at 40 ℃, adding a certain amount of template agent (hexadecyl trimethyl ammonium bromide) under vigorous stirring, slowly dropwise adding a nickel sulfate aqueous solution, an ammonium molybdate aqueous solution and a silicon source (tetraethoxysilane) into the NaOH solution, adjusting the pH value of the solution to 11, wherein the molar ratio of each substance in the solution is as follows: 0.12 Ni: 0.07 Mo: 0.12 CTAB: 1.0 TEOS: 0.2 NaOH: 100H2And O. And violently stirring and aging the mixed solution for 2 hours, then transferring the mixed solution into a hydrothermal reaction kettle, crystallizing the mixed solution for 72 hours at 100 ℃, rapidly cooling the mixed solution to room temperature, filtering and washing the mixed solution to be neutral, drying the mixed solution overnight at 100 ℃, calcining the dried mixed solution for 6 hours at 550 ℃, and removing a template agent to obtain the 10 wt% Ni-10 wt% Mo-MCM-41 monomolecular sieve methanation catalyst which is marked as catalyst b.
Comparative example 3: 3.2g of nickel nitrate hexahydrate and 1.3g of ammonium molybdate were weighed and dissolved in 25ml of deionized water to prepare an aqueous solution of nickel nitrate-ammonium molybdate. Then 6.6g of microporous-mesoporous composite molecular sieve ZSM-5/MCM-41 is weighed and dipped in nickel nitrate-ammonium molybdate aqueous solution by adopting an isometric dipping method at normal temperature. And standing at room temperature for 8h after stirring, drying at 100 ℃ for 6h, and roasting at 550 ℃ for 6h to obtain the supported sulfur-tolerant methanation catalyst with 10 wt% of nickel and molybdenum loads, namely 10 wt% of Ni-10 wt% of Mo/MCM-41, which is marked as catalyst c.
Example 5: this example illustrates the application of the sulfur-tolerant methanation catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 in the preparation of SNG by a high-concentration CO sulfur-containing methanation reaction.
The catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 were packed in a fixed bed microreactor having an inner diameter of 8mm, and N was used before the reaction2Purging the reaction system to remove air, reducing the reaction system with high-purity hydrogen for 2h at 600 ℃, then reducing the temperature to 300 ℃ under the protection of nitrogen, testing the catalytic activity of the catalyst in the reaction atmosphere, then calcining the catalyst at 800 ℃ for 10h under the atmosphere of nitrogen, reducing the reaction temperature to 300 ℃, and inspecting the catalytic activity again. Gas products obtained by the reaction are analyzed on line by gas chromatography, and the raw material gas composition and the catalytic reaction conditions are as follows:
the raw material gas composition is as follows: CO: 30% of H2：90％，H2S: 3000ppm, the balance being N2；
Catalyst loading: 0.1 g;
reaction temperature: 300 ℃;
reaction pressure: 2 MPa;
the reaction space velocity: 12000h-1；
The composition of raw material gas and catalytic reaction conditions applicable to the catalyst of the invention can also be as follows: the volume space velocity of the synthesis gas is 3000-60000 h-1The pressure is 0.1-5.0 Mpa, the temperature is 200-700 ℃, and H2The mole ratio of/CO is 1-4, H2The S content is 3000-8000 ppm.
CO conversion and CH were determined and calculated as follows4The selectivity, results are listed in table 1:
conversion rate of CO: cCO(1-amount of CO contained in product/amount of CO contained in raw material gas). times.100%
CH4And (3) selectivity: sCH4Is converted to CH4CO amount of (2)/amount of CO conversion) × 100%
Example 6: this example illustrates the hydrothermal stability of the sulfur-tolerant methanation catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 in the preparation of SNG by the sulfur-containing methanation reaction of high-concentration CO.
The catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 were packed in a fixed bed microreactor having an inner diameter of 8mm, and N was used before the reaction2Purging the reaction system to remove air, reducing with high-purity hydrogen at 600 deg.C for 2h, reducing to 300 deg.C under nitrogen protection, testing its catalytic activity in the reaction atmosphere, and introducing water vapor with partial pressure of 4.5 x 104Pa, nitrogen flow 30 ml/min, temperature rising to 780 ℃ hydrothermal aging for 10h, switching to reaction atmosphere, cooling to 300 ℃, and investigating the catalytic activity again. The gas product obtained by the reaction was analyzed on-line by gas chromatography, and the feed gas composition and the catalytic reaction conditions were the same as in example 5, and the results are shown in table 1.
TABLE 1 CO conversion and CH for each catalyst4Selective comparison table
As can be seen from the comparison of the catalyst A, B, C, D in Table 1, the embedded composite molecular sieve sulfur-tolerant methanation catalyst shows good high-temperature resistance and hydrothermal stability, and the catalytic activity is not reduced through high-temperature calcination and hydrothermal aging tests. The combination of the active components Ni and Mo can obviously improve the catalytic activity of the catalyst, but the Mo content is too high, which can cause the reduction of the catalytic activity of the catalyst. By comparing the catalyst B with the catalyst a and the catalyst D with the catalyst B, the hydrothermal stability and the catalytic activity of the embedded composite molecular sieve sulfur-tolerant methanation catalyst are obviously improved compared with those of the embedded single molecular sieve sulfur-tolerant methanation catalyst. By comparing the catalyst D with the catalyst c, the sulfur-tolerant methanation catalyst with the embedded composite single molecular sieve is obviously improved in catalytic activity, high temperature resistance and hydrothermal stability compared with the supported composite molecular sieve methanation catalyst.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The embedded micropore-mesopore composite molecular sieve sulfur-tolerant methanation catalyst is characterized in that a micropore-mesopore composite molecular sieve ZSM-5/MCM-41 is used as a support body, a metal M is used as an active component, and the active component is embedded into a micropore-mesopore composite molecular sieve framework structure, wherein the content of the active component M is 1-20 parts by mass and the balance is the micropore-mesopore composite molecular sieve ZSM-5/MCM-41 based on 100 parts by mass of the catalyst and calculated by metal elements, and the mass ratio of the micropore molecular sieve ZSM-5 to the mesopore molecular sieve MCM-41 is 1: 1-1: 5;
the active component M is M or MxNyWherein M is Ni, Mo, Mn, N is O or S, x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 0 and less than or equal to 7.
2. The embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst according to claim 1, wherein the microporous molecular sieve ZSM-5 is a microporous molecular sieve carrier ZSM-5 with a high specific surface area, and the specific surface area is 300-500 m2/g，SiO2/Al2O3The molar ratio is 30-400.
3. The embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst according to claim 1, wherein the mesoporous molecular sieve MCM-41 is a mesoporous molecular sieve MCM-41 with a high specific surface area, and the specific surface area is 600-1500 m2The pore diameter is 3-10 nm.
4. The preparation method of the embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst is characterized by comprising the following steps:
(1) preparing a salt solution of M;
(2) dispersing a ZSM-5 microporous molecular sieve in a NaOH solution, adding a template CTAB, stirring vigorously, adding a prepared M salt solution dropwise while adding a silicon source TEOS dropwise, stirring vigorously for a certain time, and transferring to a hydrothermal reaction kettle for crystallization;
(3) cooling the crystallized stock solution to room temperature, performing suction filtration, washing to be neutral, drying in vacuum, and roasting to obtain a catalyst, wherein the M load in the catalyst is 1-20 wt%;
the M salt is nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, ammonium molybdate, sodium molybdate, potassium molybdate, manganese sulfate, manganese nitrate and manganese carbonate;
the temperature of the hydrothermal reaction kettle is 80-150 ℃; the crystallization time is 2-168 h; the room temperature is 15-30 ℃; the drying temperature is 50-100 ℃, and the drying time is 2-10 h; the roasting temperature is 400-700 ℃, and the roasting time is 2-10 h.
5. The preparation method of the embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst according to claim 4, characterized in that the temperature of the hydrothermal reaction kettle is 100-120 ℃; the crystallization time is 12-24 h; the room temperature is 20-25 ℃.
6. The method for preparing the embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst according to claim 4, wherein a solvent used by the M salt solution is deionized water, ethanol or acetone.
7. The embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst is applied to preparation of SNG (single crystal glass) containing sulfur in raw material gas, and is characterized in that the catalyst is in the atmosphere of H containing sulfur2A mixed gas of-CO with an airspeed of 3000-60000 h-1The pressure is 0.1 MPa-5.0 MPa, the reaction temperature is 200-700 ℃,the molar ratio of H2/CO in the mixed gas is 1-4.
8. The application of the embedded microporous-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst of claim 7 to preparation of SNG (single sulfur glass) containing sulfur in raw material gas, wherein the SNG is characterized in that the SNG contains sulfur H2CO gas mixture, the sulphur component being H2S, thiophenes or R-SH, the sulfur content is 3000-8000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810325038.4A CN108479843B (en) | 2018-04-12 | 2018-04-12 | Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810325038.4A CN108479843B (en) | 2018-04-12 | 2018-04-12 | Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108479843A CN108479843A (en) | 2018-09-04 |
| CN108479843B true CN108479843B (en) | 2021-02-09 |
Family
ID=63315838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810325038.4A Active CN108479843B (en) | 2018-04-12 | 2018-04-12 | Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108479843B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| CN104549408A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | MCM-22/ZSM-5 in-situ intergrowth methanol aromatization catalyst and preparation method of catalyst |
| CN104549476A (en) * | 2015-01-12 | 2015-04-29 | 天津大学 | Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor |
| CN104711022A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Two-stage catalytic gasoline upgrading method for increasing gasoline yield and producing ultra-low sulfur gasoline |
| CN104971767A (en) * | 2014-04-14 | 2015-10-14 | 华东理工大学 | Embedded-type sulfur tolerant methanation catalyst, preparation method and application thereof |
| CN105728027A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method thereof |
-
2018
- 2018-04-12 CN CN201810325038.4A patent/CN108479843B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| CN104549408A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | MCM-22/ZSM-5 in-situ intergrowth methanol aromatization catalyst and preparation method of catalyst |
| CN104711022A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Two-stage catalytic gasoline upgrading method for increasing gasoline yield and producing ultra-low sulfur gasoline |
| CN104971767A (en) * | 2014-04-14 | 2015-10-14 | 华东理工大学 | Embedded-type sulfur tolerant methanation catalyst, preparation method and application thereof |
| CN105728027A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method thereof |
| CN104549476A (en) * | 2015-01-12 | 2015-04-29 | 天津大学 | Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor |
Non-Patent Citations (3)
| Title |
|---|
| 中孔MCM-41分子筛在微孔沸石ZSM-5上附晶生长的研究;李福祥;《燃料化学学报》;19980415;第102-107页 * |
| 复合分子筛催化热解生物质制生物油的研究;刘小娟;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120615(第6期);第12、13、19、20页 * |
| 微介孔复合分子筛的合成及其在芳烃加氢反应中的催化性能研究;于家琳;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150515;第22-23、28-31、35-36页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108479843A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7169354B2 (en) | Modified Y-type molecular sieve and production method, hydrocracking catalyst and production method, and hydrocracking method for hydrocarbon oil | |
| CN108529642B (en) | Preparation method of Cu-SSZ-13 molecular sieve | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN111437870A (en) | Metal @ MFI multi-level pore structure encapsulated catalyst and encapsulation method and application thereof | |
| CN110639466A (en) | Dearsenic adsorbent and preparation method thereof | |
| CN109251764A (en) | A kind of Hydrodearsenic Catalyst and its preparation method and application | |
| CN104971767B (en) | A kind of embedded catalyst for methanation in presence of sulfur and preparation method and application | |
| CN107970933B (en) | Carbon-three selective hydrogenation catalyst, preparation method and hydrogenation method | |
| CN107303508B (en) | Modified alumina carrier and preparation method thereof, dehydrogenation catalyst and application thereof | |
| CN106607087B (en) | Catalyst for catalytic conversion of nitrogen-containing compounds by carbon monoxide | |
| CN109289847B (en) | Catalyst for catalyzing propane dehydrogenation reaction, preparation method thereof and method for preparing propylene by propane dehydrogenation | |
| CN111250096A (en) | Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof | |
| CN111135857B (en) | Preparation method and application of reduction catalyst | |
| CN108479843B (en) | Preparation of embedded micropore-mesoporous composite molecular sieve sulfur-tolerant methanation catalyst | |
| CN110329992B (en) | Catalyst for preparing hydrogen by reforming methanol with low temperature water vapor and preparation method thereof | |
| CN108262063A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN111229302A (en) | Cobalt-based catalyst and application thereof | |
| CN108003920B (en) | Fuel oxidation desulfurization method using supported metal oxide bifunctional catalytic adsorption desulfurizer | |
| CN107597183B (en) | Preparation method of denitration catalyst | |
| CN108568310B (en) | Embedded microporous-mesoporous composite molecular sieve methanation catalyst and application thereof | |
| CN112604709B (en) | Hydrogenation catalyst for sulfur-containing waste gas treatment and application thereof | |
| CN103769227A (en) | Modified silica gel carrier, and preparation method and applications thereof | |
| KR20180116000A (en) | Catalysts for methanation of carbon dioxide and the manufacturing method of the same | |
| KR20170027674A (en) | High Efficiency Ni-based Catalyst for Steam Methane Reforming and use thereof | |
| CN109745978B (en) | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Jiaying Inventor after: Hao Zhuoli Inventor after: Geng Haibo Inventor after: Chen Li Inventor after: Zheng Hui Inventor before: Zhang Jiaying Inventor before: Hao Zhuoli Inventor before: Geng Haibo |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210926 Address after: 050006 room 2102, block C, Vientiane Tiancheng Business Plaza, No. 15, Yuhua West Road, Qiaoxi District, Shijiazhuang City, Hebei Province Patentee after: Hebei Landrace cellulose Technology Co.,Ltd. Address before: 050081 No.12 Changxing street, Qiaoxi District, Shijiazhuang City, Hebei Province Patentee before: SHIJIAZHUANG University OF APPLIED TECHNOLOGY (SHIJIAZHUANG RADIO AND TELEVISION University) |
|
| TR01 | Transfer of patent right |