CN111266130A - Low-temperature sulfur-tolerant methanation catalyst with composite structure carrier and preparation method thereof - Google Patents

Low-temperature sulfur-tolerant methanation catalyst with composite structure carrier and preparation method thereof Download PDF

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CN111266130A
CN111266130A CN202010177162.8A CN202010177162A CN111266130A CN 111266130 A CN111266130 A CN 111266130A CN 202010177162 A CN202010177162 A CN 202010177162A CN 111266130 A CN111266130 A CN 111266130A
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composite structure
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mcm
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王晓龙
郜时旺
刘练波
许世森
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Huaneng Clean Energy Research Institute
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
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Abstract

The invention provides a low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier and a preparation method thereof, wherein the low-temperature sulfur-tolerant methanation catalyst comprises the following components in parts by weight: (5-30) parts of active component, (2-15) parts of assistant metal component, (40-82) parts of carrier and (5-45) parts of carrier improver, wherein the carrier improver is MCM-41; the composite structure carrier low-temperature sulfur-tolerant methanation catalyst 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 composite structure carrier low-temperature sulfur-tolerant methanation catalyst is particularly suitable for the multistage or multistage methanation reaction process, is used in the first 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.

Description

Low-temperature sulfur-tolerant methanation catalyst with composite structure 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 with a composite structure carrier and a preparation method thereof.
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 sulfur-resistant methanation catalysts are supported catalysts, Mo, W, Ni, Co and the like are used as active components of the catalysts, and Al is selected2O3、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, the La, the Cr, the Fe and the like is not high, the CO conversion rate is 50-90 percent generally, 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 andthe preparation method comprises the following steps of respectively preparing a mixture of oxide and sulfide of lanthanide series elements, a mixture of oxide and sulfide of Mo metal and an alumina or silica carrier, wherein the lanthanide series elements such as Ce and Mo metal have an atomic ratio of 9/1, and the weight of the alumina or silica carrier accounts for 1-10% of 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, comprising: 0-20 parts of catalyst promoter (M1) AOB; 5-90 parts of catalyst active component (M2) COD; 5-90 parts of support modifier (M3) EOF and 100 parts of porous support (M4) GOH, wherein M1 is Co, Ni, La 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 not the same as M4; the above-mentioned (M3) EOF and (M4) GOH may also be ZrO substituted by 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, along with the continuous progress of methanation reaction, in the final 1-2 stages/stages of methanation reaction, the reactantCH as product in the 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.
MCM-41 is a typical representation in M41S family, and has a hexagonal ordered mesoporous structure, and the pore size of the structure can be adjusted between 1.5 and 30nm according to different synthesis conditions. MCM-41 has uniform aperture, hole wall thickness of about 1nm, high specific surface area of more than 1200m2/g, large adsorption capacity (0.7mL/g) and high stability. CN104971767B reports that Ni-MCM-41 catalyst prepared by in-situ synthesis method shows good activity in sulfur-tolerant methanation reaction, but does not report that the catalyst has high CO content2Activity at contents was evaluated.
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.
Disclosure of Invention
The invention aims to provide a low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier, which solves the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier, which comprises the following components in parts by weight: the catalyst comprises (5-30) parts of active component, (2-15) parts of assistant metal component, (40-82) parts of carrier and (5-45) parts of carrier improver, wherein the carrier improver is MCM-41.
Preferably, the composition comprises the following components in parts by weight: active component (13-25), assistant metal component (2-5), carrier (43-76) and carrier improver (5-16).
Preferably, the composition comprises the following components in parts by weight: the catalyst comprises (14-16) parts of active component, (2-4) parts of auxiliary metal component, (52-72) parts of carrier and (8-12) parts of carrier improver.
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 La2O3Or K2O and Cr2O3The carrier improver is a mixture of MCM-41 and MCM-48, MCM-41 and MCM-22, MCM-41 and β zeolite or MCM-41 and UZM-9, and the active component is MoS2Or MoO3And MoS2A mixture of (a).
A preparation method of a composite structure carrier low-temperature sulfur-tolerant methanation catalyst is based on the composite structure carrier low-temperature sulfur-tolerant methanation catalyst and 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 (40-82)% of the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier; the content of the carrier accounts for 5-45% of the total mass of the low-temperature sulfur-tolerant methanation catalyst with the composite structure;
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 composite structure carrier low-temperature sulfur-tolerant methanation catalyst accounts for (5-30)% 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 (2-15)% of the total mass of the composite structure carrier 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: the calcination is carried out at the temperature of 400 ℃ and 800 ℃ for 2 to 10 hours.
Preferably, in step 4, precursor solutions of the active component and the auxiliary metal component are respectively loaded on the carrier/carrier improver composite structural carrier by using an impregnation method or a deposition precipitation method to obtain 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, in step 5, the roasting and drying process conditions are as follows: the calcination is carried out for 2 to 10 hours under the temperature condition of 400 ℃ and 800 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a composite structure carrier low-temperature sulfur-tolerant methanation catalyst and a preparation method thereof, wherein the catalyst is a four-component catalyst and can comprise a catalyst active component MO3Catalyst promoter K2O, carrier ZrO2And a carrier improver MCM-41, a catalyst promoter and a carrier improver for improving the performance of the catalyst, particularly the performance of catalytic activation temperature and high-temperature activity stabilityThe four components of the catalyst have synergistic effect, so that the catalytic performance, stable performance and sulfur resistance of the final catalyst are obviously improved.
In conclusion, the composite-structure carrier low-temperature sulfur-tolerant methanation catalyst has the characteristics of low activation temperature, high methanation reaction catalytic activity, high hydrothermal stability and long service life in a high hydrogen sulfide atmosphere, so that the composite-structure carrier low-temperature sulfur-tolerant methanation catalyst is particularly suitable for the multistage or multistage methanation reaction process, is used in the first 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.
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 with a composite structure carrier, which comprises the following components in parts by weight: active component (5-30), assistant metal component (2-15), carrier (40-82) and carrier improver (5-45).
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 MoS3A mixture of (a).
The metal promoter component is K2O; or may be K2O and MgO, K2O with CaO, K2O and La2O3Or K2O and Cr2O3A mixture of (a).
The carrier improver is MCM-41, or the mixture of MCM-41 and MCM-48, MCM-41 and MCM-22, MCM-41 and β zeolite or MCM-41 and UZM-9.
The MCM-41 is a modified molecular sieve with high hydrothermal stability.
The invention provides a low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier, which is prepared by mixing a catalyst material with a carrier according to the weightThe coating comprises the following components in parts by weight: (13-25) parts of MoO3And (2-5) parts of K2O, (43-76) parts of ZrO2And (5-16) MCM-41.
The invention provides a low-temperature sulfur-tolerant methanation catalyst with a composite structure 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 (8-12) parts MCM-41.
Before or when the catalyst is used, the active component is MoS2Or MoO3And MoS2A mixture of (a).
The composite structure carrier low-temperature sulfur-tolerant methanation catalyst can be used in the multistage or multistage methanation reaction process, is used in the final 1-2 stages/stage methanation reaction, and is suitable for different reactors such as adiabatic fixed bed methanation reactors, tubular isothermal bed methanation reactors and the like.
The invention provides a preparation method of a composite structure carrier low-temperature sulfur-tolerant methanation catalyst, which comprises the following steps:
step 1, preparing ZrO by precipitation method, precipitation method, or sol-gel method2The carrier or the selected commercial ZrO2A carrier;
step 2, loading the carrier modifier MCM-41 on the ZrO by an immersion method and 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 the temperature of more than or equal to 400-800 ℃ of the decomposition temperature of the precursor to obtain ZrO2a/MCM-41 composite structure carrier;
step 4, repeating the step 1 to the step 3 until ZrO2The content of the carrier improver in the MCM-41 composite structure carrier accounts for (40-82)% of the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier, and the content of the carrier accounts for (5-45)% of the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier;
step 5, the active component MoO of the catalyst is prepared by an impregnation method or a deposition precipitation method3And a promoter metal component K2O precursor solution supported on the above ZrO2/MCM-41 on a composite structural support;
step 6, adding more than or equal to MoO serving as an active component3And a promoter metal component K2Under the condition of precursor decomposition temperature of O, the active component MoO is impregnated3And a promoter metal component K2ZrO of O2The carrier with the/MCM-41 composite structure is roasted and dried to obtain the active component MoO of the supported catalyst3And a promoter metal component K2ZrO of O2A sulfur-tolerant methanation catalyst with a/MCM-41 composite structure carrier;
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 (5-30)% 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 (2-15)% of the total mass of the composite structure carrier low-temperature sulfur-tolerant methanation catalyst.
In the step 5, the precursor solution 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 an application of a composite structure carrier low-temperature sulfur-tolerant methanation catalyst, which is used for preparing methane and H containing sulfur (0.1-5% by volume) from synthesis gas2、CO、CO2、CH4、H2The application of the O mixed gas methanation.
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 of the present invention is a four component catalyst which may include a catalyst active component MO3Catalyst promoter K2O, carrier ZrO2And a carrier improver MCM-41, a catalyst promoter and a carrier improver for improving the performance of the catalyst, particularly the performance of catalytic activation temperature and high-temperature activity stability, and the catalystThe synergistic effect of the components obviously improves the catalytic performance, stable performance 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)4Or ZrO (NO)3)2Or ZrOCl2Solution A;
s2, immersing MCM-41 powder prepared by commercial or in-situ synthesis method in the solution A to obtain ZrO impregnated with MCM-41 precursor2A porous support;
s3 ZrO impregnating MCM-41 precursor2Putting the porous carrier into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried ZrO impregnated with MCM-41 precursor2A porous support;
s4, at a temperature equal to or higher than the decomposition temperature of the MCM-41 precursor, e.g. Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2Decomposition temperature of 400 ℃ and 800 ℃ of the dried ZrO impregnated with MCM-41 precursor2Roasting the porous carrier for 2-10 hours to obtain ZrO2a/MCM-41 composite structure carrier;
s5, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked in MoO3Precursor and promoter of (2)2O precursor solution, e.g. (NH)4)6Mo7O24、KNO3The solution of (1);
s6, soaking MoO in the solution3/K2ZrO of O precursor2Putting the/MCM-41 composite structure carrier into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2a/MCM-41 composite structure carrier;
s7, 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/MCM-41 composite structure carrier for 2-10 hours to obtain MoO3/K2O/ZrO2The load of the/MCM-41 composite structure;
s8, repeating the steps of dipping, drying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of/MCM-41, thus obtaining the 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)4Or ZrO (NO)3)2Or ZrOCl2Solution A;
s2, in the MCM-41 molecular sieve synthesis process, adding a silicon source TEOS dropwise and adding the prepared solution A dropwise, then stirring vigorously, transferring to a hydrothermal synthesis reaction kettle for crystallization at the crystallization temperature of 100 ℃ for 140 ℃ for 18-36 hours to obtain a crystallized stock solution;
s3, cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in a drying oven and roasting to obtain ZrO2a/MCM-41 composite structure carrier;
s4, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked in MoO3Precursor and promoter of (2)2In solution of O precursor, e.g. (NH)4)6Mo7O24、KNO3The solution of (1);
s5, soaking MoO in the solution3/K2ZrO of O precursor2Putting the/MCM-41 composite structure carrier into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2a/MCM-41 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 precursor2the/MCM-41 composite structure carrier is roasted for 2 to 10 hours to obtain MoO3/K2O/ZrO2The load of the/MCM-41 composite structure;
s6, repeating the steps of soaking and dryingDrying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of/MCM-41, thus obtaining the sulfur-tolerant methanation catalyst.
(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)4Or ZrO (NO)3)2Or ZrOCl2Mixing a certain amount of MCM-41 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 MCM-41 to obtain a coprecipitate;
s3, adding Zr (OH) into the solution4And MCM-41 coprecipitate, standing and aging for 2-20 hours, washing and filtering the formed precipitate or coprecipitate at least once, thereby obtaining Zr (OH) after impurity removal4And MCM-41;
s4, removing impurities from the Zr (OH)4Putting the coprecipitate of MCM-41 and MCM-41 into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried impurity-removed Zr (OH)4And MCM-41;
s5, in the case of more than or equal to Zr (OH)4Calcining the dried impurity-removed Zr (OH) at a decomposition temperature of, for example, 500-4And MCM-41 for 1 to 10 hours, thereby obtaining ZrO2a/MCM-41 composite structure carrier;
s6, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked in MoO3Precursor and promoter of (2)2In solution of O precursor, e.g. (NH)4)6Mo7O24、KNO3The solution of (1);
s7, soaking MoO in the solution3/K2ZrO of O precursor2Putting the/MCM-41 composite structure carrier into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried impregnated MoO3/K2ZrO of O precursor2/MA CM-41 composite structural support;
s8, at least one MoO3/K2At the decomposition temperature of the O precursor, e.g. (NH)4)6Mo7O24、KNO3At the decomposition temperature of 400 ℃ and 800 ℃, the dried impregnated MoO3/K2ZrO of O precursor2the/MCM-41 composite structure carrier is roasted for 2 to 10 hours to obtain MoO3/K2O/ZrO2a/MCM-41 composite structure carrier;
s9, repeating the steps of dipping, drying and roasting until MoO is reached3/K2O/ZrO2The required weight ratio of/MCM-41, thus obtaining the sulfur-tolerant methanation catalyst.
(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, immersing MCM-41 powder prepared by commercial or in-situ synthesis method in the solution A to obtain ZrO impregnated with MCM-41 precursor2A porous support;
s3, impregnating the ZrO of the MCM-41 precursor2Putting the porous carrier into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried ZrO impregnated with MCM-41 precursor2A porous support;
s4, at a temperature not lower than the decomposition temperature of the MCM-41 precursor, such as Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2At a decomposition temperature of 400 ℃ and 800 ℃, drying the ZrO impregnated with the MCM-41 precursor2Roasting the porous carrier for 2-10 hours to obtain ZrO2a/MCM-41 composite structure carrier;
s5, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked in MoO3And 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/MCM-41 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/MCM-41 composite structure carrier to obtain the sulfur-tolerant methanation catalyst.
(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 MCM-41 molecular sieve synthesis process, adding a silicon source TEOS dropwise and adding the prepared solution A dropwise, then stirring vigorously, transferring to a hydrothermal synthesis reaction kettle for crystallization at the crystallization temperature of 100 ℃ for 140 ℃ for 18-36 hours to obtain a crystallized stock solution;
s3, cooling the crystallized stock solution to normal temperature, filtering, washing with deionized water, drying in a drying oven and roasting to obtain ZrO2a/MCM-41 composite structure carrier;
s4, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked 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/MCM-41 composite structure carrier;
s6, at not less thanUnder the temperature conditions of decomposition 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/MCM-41 composite structure carrier to obtain the sulfur-tolerant methanation catalyst.
(VI) preparing composite structure carrier low-temperature sulfur-tolerant methanation catalyst by precipitation method
S1, preparation of Zr (NO)3)4Or ZrO (NO)3)2Or ZrOCl2Mixing a certain amount of MCM-41 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 MCM-41 to obtain a coprecipitate;
s3, adding Zr (OH) into the solution4And MCM-41 coprecipitate, standing and aging for 2-20 hours, washing and filtering the formed precipitate or coprecipitate at least once, thereby obtaining Zr (OH) after impurity removal4And MCM-41;
s4, removing impurities from the Zr (OH)4Putting the coprecipitate of MCM-41 and MCM-41 into a drying oven or a drying oven at 60-130 ℃, and drying for 2-24 hours to obtain dried impurity-removed Zr (OH)4And MCM-41;
s5, in the case of more than or equal to Zr (OH)4Removing Zr (OH) from the dried product at decomposition temperature, e.g. 500-4And MCM-41, and calcining for 1-10 hours, thereby obtaining ZrO2/MCM-41 composite structure carrier
S6, subjecting the ZrO to2the/MCM-41 composite structure carrier is soaked 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, preparing a mixture containing the coprecipitateAfter the solution is kept stand and aged for 2-24 hours, the coprecipitate is washed and filtered by deionized water at least once, and the coprecipitate is the MoO deposited and precipitated3、K2ZrO loaded with O precursor2a/MCM-41 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/MCM-41 composite structure carrier to obtain the sulfur-tolerant methanation catalyst.
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 20MoO by impregnation3-3K2O/52ZrO2-25MCM41 catalyst
74.5 g ZrO (NO)3)2·2H2O is dissolved in 60 g of deionized water and stirred to prepare a dipping solution. 34.5 g of a commercially available MCM-41 carrier (specific surface area 800m 2/g) was weighed, added to the dipping solution, vigorously stirred for 2 hours to form a uniform suspension, evaporated to dryness with a rotary evaporator, dried in a drying oven at 110 ℃ for 12 hours, and finally calcined in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/MCM-41 composite structure carrier. 24.5 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/MCM-41 composite structure carrier into the dipping solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying the suspension in a drying box at the temperature of 110 ℃ for 12 hours, and finally roasting the suspension in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain the carrier with the composition of 20MoO3-3K2O/52ZrO2-25MCM41 of the inventionAn oxidizing agent.
EXAMPLE two in situ Synthesis method + impregnation method for preparing 18MoO3-2K2O/65ZrO2-15MCM41 catalyst
Mixing 88.5 g ZrO (NO)3)2·2H2O is dissolved in 60 g of deionized water and stirred to prepare a dipping solution. Slowly dripping 22.4 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/MCM-41 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/MCM-41 composite structure carrier into the dipping solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying the suspension in a drying box at the temperature of 110 ℃ for 12 hours, and finally roasting the suspension in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain the carrier with the composition of 18MoO3-2K2O/65ZrO215MCM41 catalyst of the invention.
EXAMPLE III preparation of 25MoO by precipitation + impregnation3-5K2O/45ZrO2-25MCM41 catalyst
A commercially available 31.2 g MCM-41 and 45.5 g ZrO (NO) were weighed out separately3)2.2H2And O, dissolving the components in 400 g of deionized water, and 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 to generate coprecipitation, then refluxing the solution in parallel flow for 48 hours at 90 ℃, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying oven at 110 ℃ to dry for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/MCM-41 composite structure carrier. 27.5 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 7.2 g KNO3Dissolved in 60 g of deionized water, thenStirring to prepare the dipping solution. ZrO 2 is mixed with2Adding the/MCM-41 composite structure carrier into the dipping solution, violently stirring for 2 hours to form uniform suspension, evaporating the water by using a rotary evaporator, drying the suspension in a drying box at the temperature of 110 ℃ for 12 hours, and finally roasting the suspension in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain a suspension with the composition of 25MoO3-5K2O/45ZrO225MCM41 catalyst of the invention.
EXAMPLE four preparation of 12MoO by impregnation + precipitation3-5K2O/70ZrO2-13MCM41 catalyst
92.3 g ZrO (NO)3)2·2H2O is dissolved in 80 g of deionized water and stirred to prepare a dipping solution. Weighing 18.5 g of a commercially available MCM-41 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 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/MCM-41 composite structure carrier. 24.5 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.5 g KNO3And ZrO obtained as described above2the/MCM-41 composite structure carrier is dissolved in 400 g of deionized water and is stirred 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 to generate coprecipitation, refluxing the solution in parallel flow for 48 hours at 90 ℃, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying oven at 110 ℃ to dry for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the catalyst with the composition of 12MoO3-5K2O/70ZrO213MCM41 catalyst of the invention.
EXAMPLE V in situ Synthesis + precipitation method for 22MoO3-3K2O/65ZrO2-10MCM41 catalyst
89.8 g of ZrO (NO)3)2·2H2O is dissolved in 60 g of deionized water and stirred to prepare a dipping solution. Slowly dripping 23.2 g of silicon source TEOS into the prepared solution, then violently stirring, and transferring to a hydrothermal synthesis reactionCrystallizing in a kettle at 140 ℃ for 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/MCM-41 composite structure carrier. 22.5 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.3 g KNO3And ZrO obtained as described above2the/MCM-41 composite structure carrier is dissolved in 400 g of deionized water and is stirred 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 to generate coprecipitation, refluxing the solution in parallel flow for 48 hours at 90 ℃, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying oven at 110 ℃ to dry 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/45ZrO230MCM 41.
EXAMPLE sixthly preparation of 8MoO by precipitation3-4K2O/58ZrO2-30MCM41 catalyst
Commercially available MCM-41 (45.4 g) and ZrO (NO) (77.4 g) were weighed out separately3)2.2H2O, which were dissolved in 400 grams of deionized water and stirred 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 to generate coprecipitation, then refluxing the solution in parallel flow for 48 hours at 90 ℃, filtering and washing to obtain coprecipitate, putting the coprecipitate into a drying oven at 110 ℃ to dry for 12 hours, and finally roasting in a muffle furnace at 600 ℃ for 4 hours to obtain ZrO2the/MCM-41 composite structure carrier. 14.2 g of ammonium molybdate ((NH)4)6Mo7O24·4H2O), 4.3 g KNO3And ZrO obtained as described above2the/MCM-41 composite structure carrier is dissolved in 400 g of deionized water and is stirred to prepare a mixed solution. Weighing 600 g of 1M/L ammonia water solution, carrying out parallel flow on the two solutions to generate coprecipitation, then refluxing the solution in parallel flow for 48 hours at 90 ℃, filtering and washing to obtain coprecipitate, and drying the coprecipitate at 110 DEG COven drying for 12 hr, and roasting at 600 deg.C in muffle furnace for 4 hr to obtain 8MoO3-4K2O/58ZrO230MCM 41.
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 methanation catalyst was loaded into a stainless steel reaction tube and the catalyst was in 50mL/min of reducing gas (3% H) before 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 the composite structure carrier is characterized by comprising the following components in parts by weight: the catalyst comprises (5-30) parts of active component, (2-15) parts of assistant metal component, (40-82) parts of carrier and (5-45) parts of carrier improver, wherein the carrier improver is MCM-41.
2. The low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier as claimed in claim 1, which is characterized by comprising the following components in parts by weight: active component (13-25), assistant metal component (2-5), carrier (43-76) and carrier improver (5-16).
3. The low-temperature sulfur-tolerant methanation catalyst with a composite structure carrier as claimed in claim 1, which is characterized by comprising the following components in parts by weight: the catalyst comprises (14-16) parts of active component, (2-4) parts of auxiliary metal component, (52-72) parts of carrier and (8-12) parts of carrier improver.
4. The composite structure carrier low-temperature sulfur-tolerant methanation catalyst as claimed in claim 1, 2 or 3, wherein the carrier is monoclinic phase 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 composite structure carrier as claimed in claim 1, 2 or 3, wherein the carrier is ZrO 22With CeO or ZrO2With Al2O3A mixture of (a); the metal promoter component is K2O and MgO, K2O with CaO, K2O and La2O3Or K2O and Cr2O3The carrier improver is a mixture of MCM-41 and MCM-48, MCM-41 and MCM-22, MCM-41 and β zeolite or MCM-41 and UZM-9, and the active component is MoS2Or MoO3And MoS2A mixture of (a).
6. A preparation method of a composite structure carrier low-temperature sulfur-tolerant methanation catalyst is characterized in that the composite structure carrier low-temperature sulfur-tolerant methanation catalyst based on any one of claims 1-5 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 (40-82)% of the low-temperature sulfur-tolerant methanation catalyst of the composite structure carrier; the content of the carrier accounts for 5-45% of the total mass of the low-temperature sulfur-tolerant methanation catalyst with the composite structure;
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 composite structure carrier low-temperature sulfur-tolerant methanation catalyst accounts for (5-30)% 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 (2-15)% of the total mass of the composite structure carrier 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: the calcination is carried out at the temperature of 400 ℃ and 800 ℃ for 2 to 10 hours.
8. The method for preparing the low-temperature sulfur-tolerant methanation catalyst of the metal oxide and molecular sieve composite carrier according to claim 6, wherein in the step 4, precursor solutions of the active component and the auxiliary metal component are respectively loaded on the carrier/carrier improver composite structure carrier by using an impregnation method or a deposition precipitation method to obtain 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 as claimed in claim 6, wherein in the step 5, the roasting and drying process conditions are as follows: the calcination is carried out for 2 to 10 hours under the temperature condition of 400 ℃ and 800 ℃.
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