CN111408399A - Low-temperature sulfur-tolerant methanation catalyst with metal oxide and molecular sieve composite carrier and preparation method thereof - Google Patents

Low-temperature sulfur-tolerant methanation catalyst with metal oxide and molecular sieve composite carrier and preparation method thereof Download PDF

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CN111408399A
CN111408399A CN202010177863.1A CN202010177863A CN111408399A CN 111408399 A CN111408399 A CN 111408399A CN 202010177863 A CN202010177863 A CN 202010177863A CN 111408399 A CN111408399 A CN 111408399A
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solution
low
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composite structure
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王晓龙
郜时旺
许世森
刘练波
王绍民
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Huaneng Clean Energy Research Institute
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    • 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
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

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Abstract

The low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier and the preparation method thereof are four-component catalysts which can comprise a catalyst active component MO3Catalyst promoter K2O, carrier ZrO2And a carrier improver SBA-15; the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier has the characteristics of low activation temperature, high methanation reaction catalytic activity, high hydrothermal stability and long service life in high hydrogen sulfide atmosphere, so that the low-temperature sulfur-tolerant methanation catalyst is particularly characterized byThe method is suitable for the multistage or multistage methanation reaction process, is used in the methanation reaction of the first 1-2 stages/stages, and is suitable for different reactors such as an adiabatic fixed bed methanation reactor, a tubular isothermal bed methanation reactor and the like.

Description

Low-temperature sulfur-tolerant methanation catalyst with metal oxide and molecular sieve composite carrier and preparation method thereof
Technical Field
The invention belongs to the technical field of natural gas preparation from coal-based synthesis gas, and particularly relates to a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier and a preparation method thereof.
In particular to an effective component of CO and H of synthetic gas containing acid gas such as hydrogen sulfide2Conversion to CH4The high-stability sulfur-tolerant catalyst of the composite structure, wherein the catalyst is formed by a catalyst promoter K2O, catalyst active component MoO3And ZrO2the/SBA-15 composite structure carrier. Meanwhile, the invention also relates to a preparation method of the catalyst.
Background
The natural gas is used as an efficient, safe and clean fossil energy, and the proportion of the natural gas in global energy consumption is increased year by year; along with the enhancement of environmental awareness and the improvement of life quality of people, especially the aggravation of haze weather in China, the demand of natural gas is increased year by year. However, the energy structure of China is 'rich coal, lack of oil and little gas', the development of coal-based natural gas by utilizing relatively rich coal resources can not only make up the situation of insufficient natural gas resources of China and reduce the gaps of supply and demand of natural gas of China, but also has important strategic significance for realizing diversification of oil and gas resources, energy safety, energy conservation, emission reduction and the like.
In the existing industrial methanation catalyst, the effect is better to be a supported Ni-based catalyst, however, the Ni-based catalyst is very sensitive to carbon deposition from the surface and sulfur species, thereby leading to the inactivation and the poisoning of the catalyst, and when the Ni-based catalyst is used, H contained in the feed gas must be removed2S and other acidic gases to make the content of the acidic gases lower than 1ppm, and carrying out water-gas shift modulation H on the gasified crude gas2the/CO ratio, which undoubtedly greatly increases the equipment investment for coal-to-natural gas. Therefore, it is particularly important to develop sulfur tolerant catalysts and study their application in sulfur containing methanation.
At present, most of the sulfur-tolerant methanation catalysts are supported catalysts, and Mo, W, Ni and Mo are adoptedCo and the like are used as active components of the catalyst, and Al is selected2O3、CeO2、ZrO2、SiO2And TiO2K, L a, Cr, Fe and the like are used as carriers and are used as auxiliary agents, but the methanation catalytic activity of the carriers is not high, the CO conversion rate is generally 50-90 percent, and the CH4The selectivity is only 60-70%, and the activation temperature is higher, generally more than 450 ℃. Most catalysts are not subjected to a catalyst life test or have short life, and most catalysts are not high-temperature resistant, so that the progress of the sulfur-resistant methanation process is greatly limited. And high CO in the raw material gas2At a content, the CO conversion rate is reduced to 20-50 percent, and CH4The selectivity is only 30% -50%.
US4260553 discloses a three component catalyst and a process for its preparation, wherein the three components are a mixture of an oxide and a sulphide of a lanthanide, for example Ce, with the Mo metal in an atomic ratio of 9/1, a mixture of an oxide and a sulphide of Mo metal, and an alumina or silica support, respectively, the alumina or silica support being present in an amount of 1 to 10% by weight based on the total weight of the catalyst; the catalyst is prepared by adding lanthanide and nitrate of other components and ammonium molybdate into the same container, and adding Al2O3The support, heated, dried and calcined to obtain the final catalyst, the results show that: the catalyst has certain improvement in the aspects of carbon monoxide conversion rate and methane selectivity, and has certain sulfur resistance.
CN103157485A discloses a supported sulfur-tolerant methanation catalyst, which comprises 0-20 parts by weight of catalyst auxiliary agent (M1) AOB, 5-90 parts by weight of catalyst active component (M2) COD, 5-90 parts by weight of carrier modifier (M3) EOF and 100 parts by weight of porous carrier (M4) GOH, wherein M1 is Co, Ni, L a and/or K, M2 is Mo, W and/or V, M3 is Ce, Zr, Ti, Mg and/or Si, M4 is Ce or Al, and M3 is different from M4, the (M3) EOF and (M4) GOH can also be ZrO2、TiO2MgO and/or SiO2And (4) substituting. The catalyst has high catalytic activity of methanation reaction.
All of the above references are incorporated herein by reference in their entirety.
From the viewpoint of selecting an industrial catalyst, factors in terms of catalyst reaction stability, catalyst production cost, product yield, etc. are also considered in addition to the catalytic activity and product selectivity of the catalyst, so that the catalyst is commercially competitive in industrial production. Although the catalysts disclosed in the above patent documents have some improvements in the conversion of carbon monoxide and the selectivity of methane over conventional catalysts, they have a disadvantage in the reaction stability, and the catalytic activity of the catalysts is significantly reduced with the use at high temperatures for a long period of time, which results in a shortened catalyst life.
Meanwhile, in the process of multi-stage or multi-stage methanation reaction, as the methanation reaction continues to proceed, in the final 1-2 stages/stage methanation reaction, CH as a product in the reaction system4And CO2The content is high, which can inhibit methanation reaction to a certain extent, and simultaneously, side reactions such as inverse water-vapor transformation and the like can occur, thereby limiting H2And further conversion of CO to CH4And CO2In this case, the catalyst used in the last 1-2 stages/stages of methanation reaction described above is required to have high methanation reaction catalytic activity, low reverse steam shift reaction activity and high catalytic activity stability. However, most of the existing methanation catalysts do not meet the above requirements.
SBA-15 is a pure silicon mesoporous structure molecular sieve with hexagonal morphology, high degree of order, thick wall, large aperture and controllable number of mesopores. The SBA-15 mesoporous material has relatively large aperture, regular pore channel, good mechanical and hydrothermal stability, stable skeleton structure, easily modified inner surface, amorphous skeleton with certain wall thickness and easy doping, and thus has attracted people's interest in chemical industry, environmental energy, biotechnology, adsorption separation, catalysis, light, electricity, magnetism and other fields.
In view of the foregoing, there is still a need for developing a sulfur-tolerant methanation catalyst capable of exhibiting a low activation temperature, high methanation catalytic activity, low reverse water-vapor shift reaction activity and high catalytic activity stability, and particularly, a catalyst suitable for low-temperature methanation of the last 1-2 stages/stage of a multistage or multistage methanation process.
The object of the present invention is to develop a high-stability low-temperature sulfur-tolerant methanation catalyst meeting the above requirements and a process for the preparation of such a catalyst.
Disclosure of Invention
The invention aims to provide a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier and a preparation method thereof, which solve the defect of insufficient catalyst stability in the conventional multistage or multistage methanation reaction process.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier, which comprises the following components in parts by weight: the catalyst comprises (5-25) parts of active component, (2-13) parts of auxiliary metal component, (35-75) parts of carrier and (8-55) parts of carrier improver, wherein the carrier improver is SBA-15.
Preferably, the composition comprises the following components in parts by weight: active component (13-25), assistant metal component (2-8), carrier (43-76) and carrier improver (22-38).
Preferably, the composition comprises the following components in parts by weight: active component (14-16), assistant metal component (2-4), carrier (52-72) and carrier improver (28-36).
Preferably, the support is monoclinic phase ZrO2(ii) a The active component is MoO3(ii) a The metal promoter component is K2O。
Preferably, the support is ZrO2With CeO or ZrO2With Al2O3A mixture of (a); the metal promoter component is K2O and MgO, K2O with CaO, K2O and L a2O3Or K2O and Cr2O3A mixture of (a); the active component is MoS2Or MoO3And MoS2A mixture of (a).
A preparation method of a low-temperature sulfur-tolerant methanation catalyst based on a metal oxide and molecular sieve composite carrier comprises the following steps:
step 1, loading a carrier improver on a carrier to form a carrier precursor with a composite structure;
step 2, roasting and drying the composite structure carrier precursor obtained in the step 1 to obtain a carrier/carrier improver composite structure carrier;
step 3, repeating the step 1 to the step 2 until the content of the carrier improver in the carrier/carrier improver composite structure carrier accounts for (8-55)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst, and the content of the carrier accounts for (35-75)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst;
step 4, loading the active component and the auxiliary metal component on a carrier/carrier improver composite structure carrier to obtain a composite structure carrier;
step 5, roasting and drying the composite structure carrier obtained in the step 4 to obtain a low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier;
and 6, repeating the steps 4 to 5 until the content of the active component in the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier accounts for (5-25)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst, and the content of the auxiliary metal component accounts for (2-13)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst.
Preferably, in step 1, the carrier modifying agent is loaded on the carrier by using an impregnation method or an in-situ synthesis method to form a composite structure carrier precursor; in the step 2, the roasting and drying process conditions are as follows: roasting and drying for 2-10 hours at the temperature of 400-800 ℃.
Preferably, in step 4, precursor solutions of the catalyst active component and the promoter metal component are respectively loaded on the carrier/carrier improver composite structural carrier by using an impregnation method or a precipitation deposition method to form the composite structural carrier.
Preferably, the precursor solution of the active component is a nitrate solution, a chloride solution, an oxalate solution, a formate solution, an acetate solution, a sulfate solution, an oxychloride solution, an oxynitrate solution, or an ammonium salt solution containing Mo; the precursor solution of the auxiliary metal component is a nitrate solution, a chloride solution, an oxalate solution, a formate solution, an acetate solution, a sulfate solution, an oxychloride solution, an oxynitrate solution or an ammonium salt solution containing K.
Preferably, the roasting and drying are carried out under the following process conditions: roasting and drying for 2-10 hours at the temperature of 400-800 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier and the preparation method thereof are four-component catalysts which can comprise a catalyst active component MO3Catalyst promoter K2O, carrier ZrO2And a carrier improver SBA-15, a catalyst promoter and a carrier improver are used for improving the performance of the catalyst, particularly the performance of catalytic activation temperature and high-temperature activity stability, and the four components of the catalyst cooperate to obviously improve the catalytic performance, performance stability and sulfur resistance of the final catalyst.
In conclusion, the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier has the characteristics of low activation temperature, high methanation reaction catalytic activity, high hydrothermal stability and long service life in high hydrogen sulfide atmosphere, so that the low-temperature sulfur-tolerant methanation catalyst is particularly suitable for the first 1-2 stages/stage methanation reaction in the multistage or multistage methanation reaction process, and is suitable for different reactors such as an adiabatic fixed bed and a tubular isothermal bed methanation reactor.
Drawings
FIG. 1 is a tabulated graph of 100 hour activity data for each example.
Detailed Description
The present invention is described in further detail below.
The invention provides a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier, which comprises the following components in parts by weight: active component (5-25), assistant metal component (2-13), carrier (35-75) and carrier improver (8-55).
Wherein the support is monoclinic phase ZrO2(ii) a Or may be ZrO2With CeO or ZrO2With Al2O3A mixture of (a).
The active component is MoO3、MoS2Or MoO3And MoS2A mixture of (a).
The metal promoter component is K2O; or may be K2O and MgO, K2O with CaO, K2O and L a2O3Or K2O and Cr2O3A mixture of (a).
The carrier improver is SBA-15.
The invention provides a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier, which comprises the following components in parts by weight: (13-25) parts of MoO3And (2-8) parts of K2O, (43-75) parts of ZrO2And (22-38) SBA-15.
The invention provides a low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier, which comprises the following components in parts by weight: (14-16) parts of MoO3And (2-4) parts of K2O and (52-72) parts of ZrO2And (28-36) parts of SBA-15.
Before or during use of the catalyst, MoO3At least partially or wholly MoS2And (4) substituting.
The sulfur-tolerant methanation catalyst can be used in multistage or multistage methanation reaction processes, is used in the final 1-2 stages/stages of methanation reaction, and is suitable for different reactors such as adiabatic fixed beds, tubular isothermal bed methanation reactors and the like.
The invention provides a preparation method of a low-temperature sulfur-tolerant methanation catalyst with a metal oxide and molecular sieve composite carrier, which comprises the following steps:
step 1, preparing ZrO by precipitation, precipitation or sol-gel method2The carrier or the selected commercial ZrO2A carrier;
step 2, loading a carrier improver SBA-15 on the ZrO by an impregnation method or an in-situ synthesis method2Forming a composite structure support precursor on the support;
step 3, roasting and drying the precursor of the composite structure carrier at a temperature of more than or equal to 800 ℃ under the condition that the precursor is an industrial raw material containing Zr, such as zirconium nitrate, zirconium oxychloride and the like, and the decomposition temperature is 400-2a/SBA-15 composite structure carrier;
step 4, repeating the step 1 to the step 3 until ZrO2The content of the carrier improver in the SBA-15 composite structure carrier accounts for (8-55)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst, and the content of the carrier accounts for (35-75)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst;
step 5, the active component MoO of the catalyst is prepared by an impregnation method or a deposition precipitation method3And a promoter metal component K2The precursor solution of O is loaded on the composite structure carrier;
step 6, at least the active component MoO of the catalyst3And a promoter metal component K2The precursor of O is roasted and dried at the decomposition temperature of 400-800 ℃ to obtain the active component MoO of the supported catalyst3And a promoter metal component K2ZrO of O2the/SBA-15 composite structure carrier low-temperature sulfur-tolerant methanation catalyst;
and 7, repeating the steps 5 to 6 until the content of the active component in the composite structure carrier low-temperature sulfur-tolerant methanation catalyst accounts for (5-25)% of the total mass of the composite structure carrier low-temperature sulfur-tolerant methanation catalyst, and the content of the auxiliary metal component accounts for (2-13)% of the total mass of the composite structure carrier low-temperature sulfur-tolerant methanation catalyst.
Wherein, in the step 5, the active component MoO of the catalyst3And a promoter metal component K2The precursor solution of O is a nitrate solution, a chloride solution, an oxalate solution, a formate solution, an acetate solution, a sulfate solution, an oxychloride solution, an oxynitrate solution or an ammonium salt solution containing Mo and K.
The invention provides a low temperature of a metal oxide and molecular sieve composite carrierApplication of sulfur-tolerant methanation catalyst in preparation of methane and H containing sulfur (0.1-5 vol.%) by using synthesis gas2、CO、CO2、CH4Or H2The methanation of coke oven gas and pyrolysis gas of O.
The volume space velocity of the synthesis gas treated by the catalyst is 3000-60000H < -1 >, the pressure is normal pressure-8.0 MPa, the temperature is 250-700 ℃, and the H in the synthesis gas is2The mol ratio of/CO is 0.5-4, and CO2Volume content is 50% and CH4Volume content of-30% and H2The O volume content is 30 percent.
The sulfur-tolerant methanation catalyst prepared by the invention is a four-component catalyst, and comprises a catalyst active component MO3Catalyst promoter K2O, carrier ZrO2And a carrier improver SBA-15, wherein the catalyst promoter metal and the carrier improver are used for improving the performance of the catalyst, particularly the performance of catalytic activation temperature and high-temperature activity stability, and the four components of the catalyst cooperate to obviously improve the catalytic performance, performance stability and sulfur resistance of the final catalyst.
(I) preparation of composite structure carrier low-temperature sulfur-tolerant methanation catalyst by impregnation method
S1, preparation of Zr (NO)3)4、ZrO(NO3)2Or ZrOCl2Solution A;
s2, soaking SBA-15 powder prepared by a commercial or in-situ synthesis method in the solution A to obtain ZrO impregnated with the SBA-15 precursor2A porous support;
s3 preparation of ZrO impregnated with SBA-15 precursor obtained as described above2Putting the porous carrier into a drying box or a drying box at 60-130 ℃, and drying for 2-24 hours to obtain dried ZrO impregnated with SBA-15 precursor2A porous support;
s4, at a temperature not lower than the decomposition temperature of the SBA-15 precursor, e.g. Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2Decomposition temperature of 400 ℃ and 800 ℃ of the ZrO to be impregnated with the SBA-15 precursor2Roasting the porous carrier for 2-10 hours to obtain ZrO2a/SBA-15 composite structure carrier;
s5, subjecting the ZrO to2the/SBA-15 composite structure carrier is impregnated in MoO3Precursor and promoter of (2)2O precursor solution, e.g., (NH)4)6Mo7O24Solution, KNO3A solution;
s6, soaking MoO in the solution3/K2ZrO of O precursor2Putting the/SBA-15 composite structure carrier into a drying box or a drying box at the temperature of 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2a/SBA-15 composite structure carrier;
s7, at least one MoO3/K2At the decomposition temperature of the O precursor, e.g. (NH)4)6Mo7O24、KNO3At a decomposition temperature of, for example, 400-800 ℃ for 2-10 hours to obtain MoO3/K2O/ZrO2the/SBA-15 composite structure loads;
s8, repeating the steps of dipping, drying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of/SBA-15, thereby obtaining MoO3/K2O/ZrO2the/SBA-15 composite structure low-temperature sulfur-tolerant methanation catalyst.
(II) preparing composite structure carrier low-temperature sulfur-tolerant methanation catalyst by in-situ synthesis method and impregnation method
S1, preparation of Zr (NO)3)4、ZrO(NO3)2Or ZrOCl2Solution A;
s2, in the SBA-15 molecular sieve synthesis process, adding a silicon source TEOS dropwise and adding a prepared solution A dropwise, then stirring vigorously, transferring to a hydrothermal synthesis reaction kettle for crystallization, wherein the crystallization temperature is 100-;
s3, cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in an oven and roasting to obtain ZrO2a/SBA-15 composite structure carrier;
s4, subjecting the ZrO to2/SBA-15 composite structure carrierThe body is impregnated in MoO3Precursor and promoter of (2)2O precursors, e.g. (NH)4)6Mo7O24、KNO3In the solution of (1);
s5, soaking MoO3/K2ZrO of O precursor2Putting the/SBA-15 composite structure carrier into a drying box or a drying box at the temperature of 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2a/SBA-15 composite structure carrier;
s6, at least one MoO3/K2At the decomposition temperature of the O precursor, e.g. (NH)4)6Mo7O24、KNO3The decomposition temperature of 400 ℃ and 800 ℃, and soaking the dried MoO3/K2ZrO of O precursor2Roasting the/SBA-15 composite structure carrier for 2-10 hours to obtain MoO3/K2O/ZrO2the/SBA-15 composite structure loads;
s8, repeating the steps of dipping, drying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of SBA-15, thereby obtaining the low-temperature sulfur-tolerant methanation catalyst of the carrier with the composite structure.
(III) preparing the composite structure carrier low-temperature sulfur-tolerant methanation catalyst by a precipitation method and an impregnation method
S1, preparation of Zr (NO)3)4、ZrO(NO3)2Or ZrOCl2Mixing a certain amount of SBA-15 with the solution A in proportion to form a mixed solution B;
s2, slowly and dropwise adding ammonia water into the solution B until the precipitation is complete, or adding the solution B and the ammonia water into the precipitation kettle in parallel flow, and keeping the pH value between 3 and 10, thereby forming Zr (OH)4And SBA-15;
s3, adding Zr (OH) into the solution4Standing and aging the mixed solution of the coprecipitate and SBA-15 for 2-20 hours, washing and filtering the formed precipitate or coprecipitate at least once, thereby obtaining Zr (OH) after impurity removal4And SBA-15;
s4, removing impurities from the mixtureZr (OH)4Putting the coprecipitate of SBA-15 and the raw materials into a drying oven or a drying oven at the temperature of 60-130 ℃ for drying for 2-24 hours;
s5, in the case of more than or equal to Zr (OH)4Calcining the dried Zr (OH) at a decomposition temperature of, for example, 500-4And SBA-15 for 1 to 10 hours, thereby obtaining ZrO2a/SBA-15 composite structure carrier;
s6, subjecting the ZrO to2the/SBA-15 composite structure carrier is impregnated in MoO3Precursor and promoter of (2)2In a solution of a precursor of O, e.g. (NH)4)6Mo7O24Solution, KNO3A solution;
s7, soaking MoO in the solution3/K2ZrO of O precursor2Putting the/SBA-15 composite structure carrier into a drying box or a drying box at the temperature of 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2a/SBA-15 composite structure carrier;
s8, at MoO or higher3/K2At the decomposition temperature of the O precursor, e.g. (NH)4)6Mo7O24、KNO3At the decomposition temperature of 400 ℃ and 800 ℃, the impregnated MoO is3/K2ZrO of O precursor2Roasting the/SBA-15 composite structure carrier for 2-10 hours to obtain MoO3/K2O/ZrO2a/SBA-15 composite structure carrier;
s9, repeating the steps of dipping, drying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of SBA-15, thereby obtaining the low-temperature sulfur-tolerant methanation catalyst of the carrier with the composite structure.
(IV) impregnation method and precipitation method for preparing composite structure carrier low-temperature sulfur-tolerant methanation catalyst
S1, preparation of Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2Solution A;
s2, soaking SBA-15 powder prepared by a commercial or in-situ synthesis method in the solution A to obtain ZrO impregnated with the SBA-15 precursor2A porous support;
s3 ZrO impregnated with the above SBA-15 precursor2Putting the porous carrier into a drying box or a drying box at 60-130 ℃, and drying for 2-24 hours to obtain dried ZrO impregnated with SBA-15 precursor2A porous support;
s4, impregnating ZrO of the SBA-15 precursor under the condition of the decomposition temperature of the SBA-15 precursor being not lower than2Porous supports, e.g. Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2At a decomposition temperature of, for example, 400-800 ℃ for 2 to 10 hours to obtain ZrO2a/SBA-15 composite structure carrier;
s5, subjecting the ZrO to2the/SBA-15 composite structure carrier is impregnated in MoO3、K2In a solution of a precursor of O, e.g. (NH)4)6Mo7O24、KNO3Then, adjusting the pH value of the solution by adding nitric acid or ammonia water until a coprecipitate is formed;
s6, standing and aging the solution containing the coprecipitate for 2-24 hours, washing and filtering the coprecipitate at least once by deionized water, wherein the coprecipitate is the MoO deposited and precipitated3、K2ZrO loaded with O precursor2a/SBA-15 composite structure carrier;
s7 at a temperature not lower than the decomposition temperature of the MoO3 precursor, e.g., (NH)4)6Mo7O24、KNO3At a decomposition temperature of 400 ℃ and 800 ℃, the impregnated MoO is treated3、K2ZrO supported by O precursor2And roasting and drying the/SBA-15 composite structure carrier to obtain the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier.
(V) preparing composite structure carrier low-temperature sulfur-tolerant methanation catalyst by in-situ synthesis method and precipitation method
S1, preparation of Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2Solution A;
s2, in the SBA-15 molecular sieve synthesis process, adding a silicon source TEOS dropwise and adding a prepared solution A dropwise, then stirring vigorously, transferring to a hydrothermal synthesis reaction kettle for crystallization, wherein the crystallization temperature is 100-;
s3, cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in a drying oven and roasting to obtain ZrO2a/SBA-15 composite structure carrier;
s4, subjecting the ZrO to2the/SBA-15 composite structure carrier is impregnated in MoO3、K2In a solution of a precursor of O, e.g. (NH)4)6Mo7O24、KNO3Then, adjusting the pH value of the solution by adding nitric acid or ammonia water until a coprecipitate is formed;
s5, standing and aging the solution containing the coprecipitate for 2-24 hours, washing and filtering the coprecipitate at least once by deionized water, wherein the coprecipitate is the MoO deposited and precipitated3、K2ZrO loaded with O precursor2a/SBA-15 composite structure carrier;
s6, at a temperature not lower than the decomposition temperature of the MoO3 precursor, e.g. (NH)4)6Mo7O24、KNO3At a decomposition temperature of, for example, 400 ℃ and 800 ℃ to dry the above-mentioned impregnated MoO3、K2ZrO supported by O precursor2the/SBA-15 composite structure carrier is adopted, so that the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier is obtained.
(VI) preparing composite structure carrier low-temperature sulfur-tolerant methanation catalyst by precipitation method
S1，Zr(NO3)4Or ZrO (NO)3)2Or ZrOCl2Solution A, or mixing a certain amount of SBA-15 with the solution A in proportion to form mixed solution B;
s2, slowly and dropwise adding ammonia water into the solution B until the precipitation is complete, or adding the solution B and the ammonia water into the precipitation kettle in parallel flow, and keeping the pH value between 3 and 10, thereby forming Zr (OH)4And SBA-15 to obtain a coprecipitate;
s3, adding Zr (OH) into the solution4Standing and aging the mixed solution of the coprecipitate and SBA-15 for 2-20 hours, and washing and filtering the formed precipitate or coprecipitate at least once to obtainTo Zr (OH) after impurity removal4And SBA-15;
s4, removing impurities from the Zr (OH)4Putting the coprecipitate of SBA-15 and the raw materials into a drying oven or a drying oven at the temperature of 60-130 ℃ for drying for 2-24 hours;
s5, in the case of more than or equal to Zr (OH)4Calcining the dried Zr (OH) at a decomposition temperature of, for example, 500-4And SBA-15 for 1 to 10 hours, thereby obtaining ZrO2/SBA-15 composite structure carrier
S6, subjecting the ZrO to2the/SBA-15 composite structure carrier is impregnated in MoO3、K2In a solution of a precursor of O, e.g. (NH)4)6Mo7O24、KNO3Then, adjusting the pH value of the solution by adding nitric acid or ammonia water until a coprecipitate is formed;
s7, standing and aging the solution containing the coprecipitate for 2-24 hours, washing and filtering the coprecipitate at least once by deionized water, wherein the coprecipitate is the MoO deposited and precipitated3、K2ZrO loaded with O precursor2a/SBA-15 composite structure carrier;
s8, at a temperature not lower than the decomposition temperature of the MoO3 precursor, e.g. (NH)4)6Mo7O24、KNO3At a decomposition temperature of 400 ℃ and 800 ℃, the impregnated MoO is treated3、K2ZrO supported by O precursor2And roasting and drying the/SBA-15 composite structure carrier to obtain the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier.
The present invention will be described in detail with reference to specific examples. In the present invention, ZrO2The support is preferably a monoclinic phase of ZrO2ZrO other than the tetragonal phase2. The following examples are not specifically described, and the respective proportions or parts of the materials are proportions or parts by weight.
Example one preparation of 21MoO by impregnation3-3K2O/55ZrO2-21SBA15 catalyst
81.5 g ZrO (NO)3)2·2H2O dissolved in 60 g to removeThe seed water is stirred to prepare a dipping solution. Weighing 32.5 g of a commercially available SBA-15 carrier (specific surface area of 800m 2/g), adding the carrier into the impregnation solution, vigorously stirring for 2 hours to form a uniform suspension, evaporating the water content by using a rotary evaporator, drying the suspension in a drying oven at 110 ℃ for 12 hours, and finally, roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/SBA-15 composite structure carrier. 22.1 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 4.5 g KNO3Dissolved in 60 g of deionized water, and stirred to prepare a dipping solution. ZrO 2 is mixed with2Adding the/SBA-15 composite structure carrier into the impregnation solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying in a drying box at 110 ℃ for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the catalyst with the composition of 20MoO3-3K2O/52ZrO225SBA 15.
EXAMPLE two in situ Synthesis method + impregnation method for preparing 18MoO3-2K2O/64ZrO2-16SBA15 catalyst
86.1 g of ZrO (NO)3)2·2H2O is dissolved in 60 g of deionized water and stirred to prepare a dipping solution. Slowly dripping 22.9 g of silicon source TEOS into the prepared solution, then violently stirring, transferring into a hydrothermal synthesis reaction kettle for crystallization, wherein the crystallization temperature is 140 ℃, and the crystallization time is 36 hours; cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in a drying oven at 110 deg.C for 12 hr, and calcining in a muffle furnace at 600 deg.C for 4 hr to obtain ZrO2the/SBA-15 composite structure carrier. 19.5 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 3.4 g KNO3Dissolved in 60 g of deionized water, and stirred to prepare a dipping solution. ZrO 2 is mixed with2Adding the/SBA-15 composite structure carrier into the impregnation solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying in a drying box at 110 ℃ for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the catalyst with the composition of 18MoO3-2K2O/65ZrO215SBA 15.
EXAMPLE III precipitation + impregnation method for preparation of 24MoO3-5K2O/48ZrO2-23SBA15 catalyst
Separately, 29.8 g of SBA-15 and 44.5 g of ZrO (NO) were weighed out3)2.2H2Dissolving the raw materials in 400 g of deionized water, stirring to prepare a mixed solution, weighing 600 g of ammonia water solution with the concentration of 1M/L, carrying out parallel flow on the two solutions, carrying out coprecipitation, refluxing the solution in parallel flow at 90 ℃ for 48 hours, filtering and washing to obtain a coprecipitate, putting the coprecipitate into a drying box at 110 ℃ for drying for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/SBA-15 composite structure carrier. 26.5 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 7.2 g KNO3Dissolved in 60 g of deionized water, and stirred to prepare a dipping solution. ZrO 2 is mixed with2Adding the/SBA-15 composite structure carrier into the impregnation solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying in a drying box at 110 ℃ for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the catalyst with the composition of 25MoO3-5K2O/45ZrO225SBA 15.
EXAMPLE four preparation of 15MoO by impregnation + precipitation3-5K2O/66ZrO2-14SBA15 catalyst
87.3 g of ZrO (NO)3)2·2H2O is dissolved in 80 g of deionized water and stirred to prepare a dipping solution. Weighing 19.3 g of a commercially available SBA-15 carrier (specific surface area of 800m 2/g), adding the carrier into the impregnation solution, vigorously stirring for 2 hours to form a uniform suspension, evaporating the water content by using a rotary evaporator, drying the suspension in a drying oven at 110 ℃ for 12 hours, and finally, roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/SBA-15 composite structure carrier. 26.1 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.5 g KNO3And ZrO obtained as described above2Weighing 600 g of ammonia water solution with the concentration of 1M/L, carrying out parallel flow on the two solutions to ensure that the two solutions generate coprecipitation, then refluxing the solution in parallel flow at 90 ℃ for 48 hours, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying box at 110 ℃ for drying for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the carrier with the composition of 12MoO3-5K2O/70ZrO213SBA 15.
EXAMPLE V in situ Synthesis + precipitation method for preparation of 25MoO3-2K2O/65ZrO2-8SBA15 catalyst
90.5 g ZrO (NO)3)2·2H2O is dissolved in 60 g of deionized water and stirred to prepare a dipping solution. Slowly dripping 19.8 g of silicon source TEOS into the prepared solution, then violently stirring, transferring into a hydrothermal synthesis reaction kettle for crystallization, wherein the crystallization temperature is 140 ℃, and the crystallization time is 36 hours; cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in a drying oven at 110 deg.C for 12 hr, and calcining in a muffle furnace at 600 deg.C for 4 hr to obtain ZrO2the/SBA-15 composite structure carrier. 24.8 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.3 g KNO3And ZrO obtained as described above2Weighing 600 g of ammonia water solution with the concentration of 1M/L, carrying out parallel flow on the two solutions to ensure that the two solutions generate coprecipitation, then refluxing the solution in parallel flow at 90 ℃ for 48 hours, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying box at 110 ℃ for drying for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the catalyst with the composition of 22MoO3-3K2O/45ZrO230SBA 15.
EXAMPLE six preparation of 18MoO by precipitation3-5K2O/52ZrO2-25SBA15 catalyst
Commercially available 38.4 g SBA-15 and 75.1 g ZrO (NO) were weighed out separately3)2.2H2Dissolving the raw materials in 400 g of deionized water, stirring to prepare a mixed solution, weighing 600 g of ammonia water solution with the concentration of 1M/L, carrying out parallel flow on the two solutions, carrying out coprecipitation, refluxing the solution in parallel flow at 90 ℃ for 48 hours, filtering and washing to obtain a coprecipitate, putting the coprecipitate into a drying box at 110 ℃ for drying for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/SBA-15 composite structure carrier. 14.2 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.3 g KNO3And ZrO obtained as described above2Weighing 600 g of ammonia water solution with the concentration of 1M/L, carrying out parallel flow on the two solutions to ensure that the two solutions generate coprecipitation, then refluxing the solution in parallel flow at 90 ℃ for 48 hours, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying box at 110 ℃ for drying for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the carrier with the composition of 8MoO3-4K2O/58ZrO230SBA 15.
The activity of the methanation catalysts prepared in the above six examples was measured on an adiabatic fixed bed, as shown in FIG. 1, 3g of the methanation catalyst was charged into a stainless steel reaction tube and the catalyst was subjected to a reducing gas (3% H) of 50m L/min before the reaction2S/H2) Activating at 300 deg.C for 4 h. The composition of the reaction raw material gas is H2/CO/N22/2/1 (vol/vol), H in gas2The volume fraction of S is 0.6 percent, and the volume space velocity of the reaction mixed gas is 6000h–1The reaction temperature was set at 350 ℃, 450 ℃, 550 ℃, 650 ℃ and the reaction pressure was set at 3 MPa. And (3) enabling reaction products to enter an Agilent 7890A type gas chromatograph for online detection after desulfurization and condensation dewatering, and analyzing experimental data by adopting an internal standard method.
The terms and expressions which have been employed in the specification are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof.
While several embodiments of the present invention have been shown and described, the present invention is not limited to the described embodiments. On the contrary, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The low-temperature sulfur-tolerant methanation catalyst with a metal oxide and molecular sieve composite carrier is characterized by comprising the following components in parts by weight: the catalyst comprises (5-25) parts of active component, (2-13) parts of auxiliary metal component, (35-75) parts of carrier and (8-55) parts of carrier improver, wherein the carrier improver is SBA-15.
2. The low-temperature sulfur-tolerant methanation catalyst with the metal oxide and molecular sieve composite carrier as the claim 1, which is characterized by comprising the following components in parts by weight: active component (13-25), assistant metal component (2-8), carrier (43-75) and carrier improver (22-38).
3. The low-temperature sulfur-tolerant methanation catalyst with the metal oxide and molecular sieve composite carrier as the claim 1, which is characterized by comprising the following components in parts by weight: active component (14-16), assistant metal component (2-4), carrier (52-72) and carrier improver (28-36).
4. The low temperature sulfur tolerant methanation catalyst of a metal oxide and molecular sieve composite support of claim 1, 2 or 3, wherein the support is a monoclinic phase of ZrO2(ii) a The active component is MoO3(ii) a The metal promoter component is K2O。
5. The low-temperature sulfur-tolerant methanation catalyst of a metal oxide and molecular sieve composite carrier according to claim 1, 2 or 3,characterized in that the carrier is ZrO2With CeO or ZrO2With Al2O3A mixture of (a); the metal promoter component is K2O and MgO, K2O with CaO, K2O and L a2O3Or K2O and Cr2O3A mixture of (a); the active component is MoS2Or MoO3And MoS2A mixture of (a).
6. A preparation method of a low-temperature sulfur-tolerant methanation catalyst based on a metal oxide and molecular sieve composite carrier is characterized by comprising the following steps of:
step 1, loading a carrier improver on a carrier to form a carrier precursor with a composite structure;
step 2, roasting and drying the composite structure carrier precursor obtained in the step 1 to obtain a carrier/carrier improver composite structure carrier;
step 3, repeating the step 1 to the step 2 until the content of the carrier improver in the carrier/carrier improver composite structure carrier accounts for (8-55)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst, and the content of the carrier accounts for (35-75)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst;
step 4, loading the active component and the auxiliary metal component on a carrier/carrier improver composite structure carrier to obtain a composite structure carrier;
step 5, roasting and drying the composite structure carrier obtained in the step 4 to obtain a low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier;
and 6, repeating the steps 4 to 5 until the content of the active component in the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier accounts for (5-25)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst, and the content of the auxiliary metal component accounts for (2-13)% of the total mass of the low-temperature sulfur-tolerant methanation catalyst.
7. The preparation method of the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier is characterized in that in the step 1, a carrier improver is loaded on the carrier by using an impregnation method or an in-situ synthesis method to form a composite structure carrier precursor; in the step 2, the roasting and drying process conditions are as follows: roasting and drying for 2-10 hours at the temperature of 400-800 ℃.
8. The method for preparing the low-temperature sulfur-tolerant methanation catalyst as claimed in claim 6, wherein in step 4, precursor solutions of the catalyst active component and the promoter metal component are loaded on the carrier/carrier improver composite structure carrier by an impregnation method or a deposition precipitation method respectively to form the composite structure carrier.
9. The method for preparing the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier according to claim 8, wherein the precursor solution of the active component is a nitrate solution, a chloride solution, an oxalate solution, a formate solution, an acetate solution, a sulfate solution, an oxychloride solution, an oxynitrate solution or an ammonium salt solution containing Mo; the precursor solution of the auxiliary metal component is a nitrate solution, a chloride solution, an oxalate solution, a formate solution, an acetate solution, a sulfate solution, an oxychloride solution, an oxynitrate solution or an ammonium salt solution containing K.
10. The preparation method of the low-temperature sulfur-tolerant methanation catalyst with the metal oxide and molecular sieve composite carrier, which is characterized in that the roasting and drying process conditions are as follows: roasting and drying for 2-10 hours at the temperature of 400-800 ℃.
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