CN112439451B - Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof - Google Patents

Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof Download PDF

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CN112439451B
CN112439451B CN201910823789.3A CN201910823789A CN112439451B CN 112439451 B CN112439451 B CN 112439451B CN 201910823789 A CN201910823789 A CN 201910823789A CN 112439451 B CN112439451 B CN 112439451B
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catalyst
titanium
low
molecular sieve
shift catalyst
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CN112439451A (en
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白志敏
王昊
李文柱
余汉涛
田兆明
赵庆鲁
姜建波
薛红霞
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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Qilu Petrochemical Co of Sinopec
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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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a low-temperature sulfur-tolerant shift catalyst and a preparation method and application thereof.A titanium-silicon molecular sieve and alumina are used as carriers to load catalytic active components, the catalytic active components are cobalt-molybdenum composite metal oxides, and the titanium-silicon molecular sieve is combined with an alkali metal compound; wherein the specific surface area of the catalyst is 200m 2 /g～250m 2 The distribution of pores with the pore diameter of 5 to 50nm in the catalyst accounts for more than 85 percent of the total pore volume. The preparation method comprises the following steps: the method comprises the steps of taking a titanium source, alkali silicate and aluminum salt as raw materials, carrying out coprecipitation and calcination to obtain a titanium-silicon molecular sieve combined with an alkali metal compound, mixing the titanium-silicon molecular sieve with alumina to form a carrier, adding molybdenum salt and cobalt salt into the carrier, carrying out reaction to enable the cobalt-molybdenum composite metal oxide to be loaded on the carrier to obtain the low-temperature sulfur-tolerant shift catalyst, carrying out coprecipitation in the coprecipitation method, and washing the precipitate until the pH value is 7.5-8.5. The catalyst provided by the disclosure has higher structural stability and catalytic activity.

Description

Low-temperature sulfur-tolerant shift catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of sulfur-tolerant shift for preparing synthesis gas by using heavy raw materials such as residual oil, heavy oil, petroleum coke, coal and the like, and relates to a low-temperature sulfur-tolerant shift catalyst, a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The Co-Mo sulfur-tolerant wide-temp. shift catalyst is mainly used for preparing raw material gas from heavy raw materials of heavy oil, residual oil and coal, and features lower activating temp. than Fe-series high-temp. shift catalyst, equivalent to Cu-series low-temp. shift catalyst, not lower heat resistance than Fe-Cr-series high-temp. shift catalyst, wide active temp. range, and almost covering the whole active temp. range of Fe-series high-temp. shift catalyst and Cu-series low-temp. shift catalyst. In addition, the most outstanding advantages are high sulfur and toxicity resistance, high strength, long service life and the like. The research on the carrier and the auxiliary agent of the sulfur-resistant shift catalyst is many, and the commonly used carrier components mainly comprise one or more of Mg, al, ti, si, ca, zr and the like. The commonly used auxiliary agents mainly comprise alkali metals, alkaline earth metals, mn, cu, rare earth and the like. Under the condition of low-temperature shift, the sulfur-tolerant shift catalyst needs to have good hydration resistance and structural stability, and the active auxiliary agents of the sulfur-tolerant shift catalyst are mostly alkali metal compounds, however, the inventor of the disclosure finds that the alkali metal compounds have the problem of loss under the condition of relatively high water-gas ratio, so that the activity and the service life are reduced, especially the capability of resisting working condition fluctuation is poor, and the alkali metal is easy to precipitate, lose or harden, and the like, so that the structural stability and the catalytic activity of the catalyst are influenced.
Disclosure of Invention
In order to solve the defects of the prior art, the purpose of the present disclosure is to provide a low-temperature sulfur-tolerant shift catalyst, a preparation method and an application thereof, wherein the catalyst has high structural stability and catalytic activity.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
in the first aspect, a low-temperature sulfur-tolerant shift catalyst takes a titanium silicalite and alumina as carriers to load catalytic active components, wherein the catalytic active components are cobalt-molybdenum composite metal oxides, and the titanium silicalite is combined with alkali metal compounds;
wherein the specific surface area of the catalyst is 200m 2 /g～250m 2 The distribution of pores with the pore diameter of 5 to 50nm in the catalyst accounts for more than 85 percent of the total pore volume.
The titanium-silicon molecular sieve is formed by partially replacing aluminum atoms in a silicon-aluminum molecular sieve by Ti atoms, has an MFI topological structure, is formed by connecting primary structural units such as a silicon-oxygen tetrahedron and a titanium-oxygen tetrahedron through an oxygen bridge to form a secondary structural unit of a multi-membered ring, further forms a three-dimensional microporous framework, and has excellent catalytic performance. According to the preparation method, a titanium silicalite molecular sieve is used for replacing part of alumina, so that the titanium silicalite molecular sieve is used for modifying an alumina carrier, and an alkali metal compound is directly combined with the titanium silicalite molecular sieve, so that the hydrothermal stability is excellent, the alkali metal can be prevented from being precipitated, lost or hardened, and the like, and the preparation method is suitable for being applied under the conditions of low temperature and high water-gas ratio. According to researches, when a titanium silicalite molecular sieve is used for replacing part of alumina, the strength and the low-temperature transformation rate of the catalyst are difficult to coordinate at the same time, and experiments show that when the pore distribution of the pore diameter of 5 to 50nm in the catalyst accounts for more than 85% of the total pore volume, the carrier has good hydrothermal stability and relatively concentrated pore size distribution, the retention time of reactants in a pore channel of the molecular sieve can be shortened, the diffusion resistance is reduced, and the titanium silicalite molecular sieve can be ensured to replace part of the alumina-loaded catalyst and has higher structural stability and catalytic activity.
Based on the weight percentage of the catalyst, the content is as follows:
aluminum, with Al 2 O 3 In 40 to 70 wt.%,
titanium, in TiO 2 0.5 to 4.0wt.%,
silicon, in SiO 2 In terms of 15 to 40 wt.%,
molybdenum in MoO 3 4-10 wt.%,
cobalt, in terms of CoO, in an amount of 2.0 to 4.0wt.%,
alkali metal, with M 2 Calculated by O, 1.0 to 4.0wt.%, and M is alkali metal.
The pore volume of the catalyst is not less than 0.5mL/g.
The shape of the catalyst is strip, clover or spherical.
On the other hand, a preparation method of the low-temperature sulfur-tolerant shift catalyst is characterized by taking a titanium source, an alkali metal silicate salt and an aluminum salt as raw materials, carrying out coprecipitation method and calcination to obtain a titanium-silicon molecular sieve combined with an alkali metal compound, mixing the titanium-silicon molecular sieve and alumina to form a carrier, adding molybdenum salt and cobalt salt into the carrier, carrying out reaction to load a cobalt-molybdenum composite metal oxide on the carrier, and obtaining the low-temperature sulfur-tolerant shift catalyst, wherein after coprecipitation in the coprecipitation method, the precipitate is washed until the pH value is 7.5 to 8.5.
In the method, alkali metal silicate is used as a silicon source, a molecular sieve structure is partially generated in the processes of coprecipitation, aging and crystallization, the structure of an original alumina carrier is modulated and modified, the pore distribution of the carrier is mainly concentrated between 5 and 50nm and accounts for more than 85 percent of the total pore volume, the hydrothermal stability of the carrier is good, the pore size distribution is relatively concentrated, the retention time of reactants in a pore channel of the molecular sieve can be shortened, and the diffusion resistance is reduced. Co metal and Mo metal are used as active components, more lattice defects and vacancies can be formed in the carrier in the processes of molecular sieve preparation and coprecipitation, more active centers can be formed or the effect of promoting the formation of the active centers is achieved, and meanwhile, the acid-base amphoteric active centers enable the active components to be better dispersed, the structure to be more stable, and the low-temperature activity and the activity stability to be more excellent. In addition, experiments show that the pH value for washing the precipitate after coprecipitation has great influence on the catalytic activity and strength of the catalyst, and when the pH value is higher than the range, the loss rate of alkali metal compounds in the catalyst is increased, so that the catalyst is difficult to form, and the strength is reduced; when the pH is lower than this range, the low-temperature shift activity of the catalyst is greatly affected, and the difficulty in washing increases, resulting in a large amount of waste liquid.
The steps for preparing the titanium-silicon molecular sieve are as follows: mixing a titanium source and alkali silicate, adjusting the pH value to be alkaline to obtain a solution A, uniformly mixing an aluminum salt solution and the solution A under a heating condition, washing the mixture with water after reaction until the pH value is 7.5-8.5, and calcining the mixture to obtain the titanium-silicon molecular sieve.
The mixing method of the titanium silicalite molecular sieve and the alumina is ball milling mixing.
The calcining temperature of the titanium silicalite molecular sieve is 500 to 650 ℃.
The method of supporting the cobalt-molybdenum composite metal oxide on the carrier is a sol-gel kneading method.
In a third aspect, the application of the low-temperature sulfur-tolerant shift catalyst in preparing synthesis gas by catalyzing low-temperature shift is provided.
The beneficial effect of this disclosure does:
the catalyst disclosed by the invention takes alumina and titanium silicalite molecular sieves as carriers, the pore distribution of the carriers is mainly concentrated between 5 and 50nm and accounts for more than 85% of the total pore volume, the carriers have good hydrothermal stability and relatively concentrated pore size distribution, the retention time of reactants in the pore channels of the molecular sieves can be shortened, the diffusion resistance can be reduced, meanwhile, more lattice defects and vacancies can be formed in the carriers, and more active centers can be formed or the formation of the active centers can be promoted. The original alumina carrier is modified, the acid-base amphoteric active center of the alumina carrier is increased, so that the active components are better dispersed, the structure is more stable, the low-temperature activity and the activity stability are more excellent, and meanwhile, after the alumina carrier is modified by the titanium-silicon molecular sieve, the catalyst carrier is excellent in hydrothermal stability, is suitable for being applied under the condition of high water-gas ratio at low temperature, and has good economic benefit and environmental protection benefit. The sulfur-tolerant shift catalyst has higher strength, good stability of structure and activity, low loss rate of active components, longer service life and the like, is suitable for the conditions of medium and low temperature, high airspeed and higher water-gas ratio, and can meet the requirements of industrial shift devices on the catalyst with the conditions of low temperature and higher water-gas ratio.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The problem that an alkali metal compound runs off under the condition that the water-gas ratio of the existing catalyst is relatively high is solved, and the low-temperature sulfur-tolerant shift catalyst, the preparation method and the application are provided.
In a typical embodiment of the present disclosure, a low-temperature sulfur-tolerant shift catalyst is provided, in which a titanium silicalite molecular sieve and alumina are used as carriers to load a catalytic active component, the catalytic active component is a cobalt-molybdenum composite metal oxide, and the titanium silicalite molecular sieve is combined with an alkali metal compound;
wherein the specific surface area of the catalyst is 200m 2 /g～250m 2 The pore distribution of the catalyst with the pore diameter of 5 to 50nm accounts for more than 85 percent of the total pore volume.
The titanium silicalite molecular sieve is used for modifying an alumina carrier, and is directly combined with an alkali metal compound, so that the hydrothermal stability is excellent, the alkali metal can be prevented from being separated out, lost or hardened, and the like, and the titanium silicalite molecular sieve is suitable for being applied under the conditions of low temperature and high water-gas ratio.
The purpose of limiting the pore distribution of 5 to 50nm in pore diameter to more than 85 percent of the total pore volume is to provide carrier hydrothermal stability and concentrate the relative distribution of the pore diameter, thereby shortening the retention time of reactants in a molecular sieve pore channel and reducing diffusion resistance.
In one or more examples of this embodiment, the catalyst is present in the following amounts, based on weight percent of the catalyst:
aluminum, with Al 2 O 3 In 40 to 70 wt.%,
titanium, with TiO 2 0.5 to 4.0wt.%,
silicon, in SiO 2 In terms of 15 to 40 wt.%,
molybdenum in MoO 3 In terms of 4-10 wt.%,
cobalt, in terms of CoO, in an amount of 2.0 to 4.0wt.%,
alkali metal, with M 2 1.0 to 4.0wt.% calculated by O, and M is alkali metal. When the components are in this range, the strength and activity of the catalyst are better.
In this series of examples, the alkali metal is sodium. Experiments show that when sodium is used as the active assistant, the effect is excellent.
In one or more embodiments of this embodiment, the catalyst has a pore volume of not less than 0.5mL/g. When the pore volume is 0.5 to 1.0 mL/g, the catalytic performance of the catalyst can be ensured, and the cost can be controlled.
In one or more embodiments of this embodiment, the morphology of the catalyst is a stripe, clover, sphere, or the like. The morphology of the catalyst influences the catalytic activity, and the catalyst with the morphology has good catalytic performance.
The other embodiment of the disclosure provides a preparation method of a low-temperature sulfur-tolerant shift catalyst, which comprises the steps of taking a titanium source, an alkali silicate salt and an aluminum salt as raw materials, carrying out coprecipitation and calcination to obtain a titanium-silicon molecular sieve combined with an alkali metal compound, mixing the titanium-silicon molecular sieve with alumina to form a carrier, adding molybdenum salt and cobalt salt into the carrier, carrying out reaction to enable cobalt-molybdenum composite metal oxide to be loaded on the carrier, and obtaining the low-temperature sulfur-tolerant shift catalyst, wherein after coprecipitation in the coprecipitation, the precipitate is washed until the pH is 7.5 to 8.5.
According to the method, alkali metal silicate is used as a silicon source, and a certain amount of alkali metal compound is reserved in the titanium-silicon molecular sieve by adjusting the pH value after precipitation and washing, so that the catalyst is ensured to have good low-temperature reaction activity.
The titanium source in the present disclosure is a compound containing titanium ions, such as tetraethyl titanate, tetraisopropyl titanate, n-butyl titanate, and the like.
The aluminum salt in the present disclosure means a compound capable of ionizing an aluminum ion in water, such as aluminum nitrate, aluminum chloride, aluminum sulfate, and the like.
The molybdenum salt in the present disclosure refers to a compound capable of ionizing molybdenum ions or molybdate ions dissolved in water, such as ammonium molybdate, molybdenum 2-ethylhexanoate, molybdenum nitrate, and the like.
The cobalt salt in the present disclosure refers to a compound capable of ionizing cobalt ions in water, such as cobalt nitrate, cobalt chloride, cobalt sulfate, and the like.
In one or more embodiments of this embodiment, the steps for preparing a titanium silicalite molecular sieve are: mixing a titanium source and alkali silicate, adjusting the pH value to be alkaline to obtain a solution A, uniformly mixing an aluminum salt solution and the solution A under a heating condition, washing the mixture with water after reaction until the pH value is 7.5-8.5, and calcining the mixture to obtain the titanium-silicon molecular sieve.
In this series of examples, the pH of solution A is not higher than 12. When the pH value of the solution A is 9.5 to 10.5, the pore size distribution of the obtained titanium silicalite molecular sieve is more concentrated.
In this series of examples, ammonia was used to adjust the pH. The introduction of other metal ions can be prevented.
In this series of examples, the heating conditions were 55 to 60 ℃. The dissolution speed can be accelerated.
In the series of examples, the reaction temperature is 75 to 85 ℃, and the reaction time is 3.5 to 4.5 hours.
In order to prevent evaporation of water during calcination from affecting the pore structure of the titanium silicalite, in this series of examples, drying is performed prior to calcination. When the titanium silicalite molecular sieve is dried at the temperature of 105 to 115 ℃, the water removal rate can be ensured, and the structure of the titanium silicalite molecular sieve is not influenced.
In one or more embodiments of this embodiment, the titanium silicalite molecular sieves are mixed with the alumina by ball milling. The uniformity of mixing the titanium-silicon molecular sieve and the alumina can be ensured, and the particle size of the carrier is controlled, so that the loading capacity of the catalytic active component is increased.
In one or more embodiments of this embodiment, the titanium silicalite molecular sieve is calcined at a temperature of from 500 ℃ to 650 ℃. The effect is better when the calcining temperature is 550 ℃.
The manner of supporting the cobalt molybdenum composite metal oxide on the carrier includes a coprecipitation method, a sol-gel method, a hydrothermal method, and the like, and in one or more examples of the embodiment, the manner of supporting the cobalt molybdenum composite metal oxide on the carrier is a method of kneading using a sol-gel.
In the series of embodiments, the steps are: mixing the carrier and the extrusion aid, adding molybdenum salt and cobalt salt, adding the binder, kneading, molding, and roasting to obtain the low-temperature sulfur-tolerant shift catalyst.
In the series of embodiments, the specific steps are as follows: mixing the carrier and the extrusion aid to obtain powder, adding the powder into a molybdenum salt solution, then adding cobalt salt and a binder to obtain a kneaded material, kneading the kneaded material into a shape, and roasting.
In the series of examples, the extrusion aid is sesbania powder and starch. When sesbania powder is adopted, the kneading effect is better. The content of the extrusion aid is 1-6% (m/m). When the content is 3 to 4 percent (m/m), the effect is better.
In this series of embodiments, the binder is one or more of citric acid, oxalic acid, nitric acid, and the like. When citric acid is used, the catalytic activity of the catalyst is better. The content of the binder is 1 to 6 percent (m/m). When the content is 2 to 4% (m/m), the catalytic activity of the catalyst is better.
In this series of examples, drying was performed prior to firing. Preventing water from affecting the pore volume. The drying is natural drying. Prevent the temperature from rising and the water evaporation rate from increasing to affect the pore volume.
In this series of examples, the calcination temperature is 350 to 550 ℃. When the roasting temperature is 450 ℃, the catalytic activity is better.
In a third embodiment of the present disclosure, there is provided a use of the above low-temperature sulfur-tolerant shift catalyst in preparing syngas by catalytic low-temperature shift.
The low temperature in the low-temperature sulfur-tolerant shift catalyst disclosed by the disclosure is a temperature in a range of 200 to 300 ℃.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
The concentrated aqueous ammonia used in the following examples is commercially available concentrated aqueous ammonia, and the concentration thereof is indicated to be 25% by mass.
Example 1
Dissolving 8.6g of tetraethyl titanate in 30mL of anhydrous alcohol, adding 165g of sodium silicate and 100mL of deionized water, heating and stirring, then adjusting the pH to 10 with concentrated ammonia water to obtain a solution A, dissolving 132g of aluminum nitrate in 250mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 4 hours, washing the material to pH 8.0 with deionized water, drying at 110 ℃, roasting at 600 ℃ for 3 hours, mixing with 30g of active alumina powder, ball-milling for 0.5 hour, adding 4g of sesbania powder and 2g of starch, and dry-mixing for 15 minutes; and adding 10.4g of ammonium molybdate into 30mL of deionized water for dissolving, adding the ammonium molybdate into the powder, dissolving 3g of citric acid, 3g of oxalic acid and 11.7g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material for kneading and forming, naturally drying, roasting at 480 ℃ for 4 hours, and naturally cooling to obtain the catalyst C1.
Example 2
Dissolving 2.9g of tetraethyl titanate in 20mL of anhydrous alcohol, adding 71g of sodium silicate and 70mL of deionized water, heating and stirring, then adjusting the pH to 10 with concentrated ammonia water to obtain a solution A, dissolving 147g of aluminum nitrate in 280mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 5 hours, washing the material to pH 8.0 with deionized water, drying the material at 120 ℃, roasting the material at 550 ℃ for 2 hours, mixing the material with 50g of activated alumina powder, carrying out ball milling for 1 hour, adding 3g of sesbania powder and 3g of starch, and carrying out dry mixing for 20 minutes; and adding 12.4g of ammonium molybdate into 40mL of deionized water to dissolve the ammonium molybdate, adding the ammonium molybdate into the powder, dissolving 3g of citric acid, 1mL of dilute nitric acid and 7.8g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material, kneading and forming, naturally drying, roasting at 400 ℃ for 5 hours, and naturally cooling to obtain the catalyst C2.
Wherein, the dilute nitric acid is obtained by mixing commercial concentrated nitric acid and deionized water according to the mass ratio of 1.
Example 3
Dissolving 11.4g of tetraethyl titanate in 45mL of anhydrous alcohol, adding 142g of sodium silicate and 90mL of deionized water, heating and stirring, then adjusting the pH to 10 with concentrated ammonia water to obtain a solution A, dissolving 110g of aluminum nitrate in 190mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 4 hours, washing the material to pH 8.0 with deionized water, drying the material at 110 ℃, roasting the material at 650 ℃ for 3 hours, mixing the material with 37g of activated alumina powder, carrying out ball milling for 0.5 hour, adding 2g of sesbania powder and 4g of starch, and carrying out dry mixing for 30 minutes; and adding 7.4g of ammonium molybdate into 20mL of deionized water to dissolve, adding the ammonium molybdate into the powder, dissolving 5g of citric acid and 15.5g of cobalt nitrate into 35mL of deionized water, adding the mixture into the kneaded material, kneading and forming, naturally drying, roasting at 450 ℃ for 3 hours, and naturally cooling to obtain the catalyst C3.
Example 4
Dissolving 5.7g of tetraethyl titanate in 25mL of anhydrous alcohol, adding 118.4g of sodium silicate and 80mL of deionized water, heating and stirring, then adjusting the pH to 10 with concentrated ammonia water to obtain a solution A, dissolving 147g of aluminum nitrate in 250mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 2 hours, washing the material to pH 8.0 with deionized water, drying at 110 ℃, roasting at 600 ℃ for 3 hours, mixing with 39g of active alumina powder, ball-milling for 3 hours, adding 6g of sesbania powder and 2g of starch, and dry-mixing for 25 minutes; adding 11.2g of ammonium molybdate into 40mL of deionized water for dissolving, adding the ammonium molybdate into the powder, dissolving 6g of citric acid and 13.6g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material for kneading and forming, naturally drying, roasting at 550 ℃ for 2 hours, and naturally cooling to obtain the catalyst C4.
Example 5
Dissolving 8.6g of tetraethyl titanate in 30mL of anhydrous alcohol, adding 165g of sodium silicate and 100mL of deionized water, heating and stirring, then adjusting the pH to 10 with strong ammonia water to obtain a solution A, dissolving 132g of aluminum nitrate in 250mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 4 hours, washing the material with deionized water to pH 7.0, drying at 110 ℃, roasting at 600 ℃ for 3 hours, mixing with 30g of active alumina powder, ball-milling for 0.5 hour, adding 4g of sesbania powder and 2g of starch, and dry-mixing for 15 minutes; and adding 10.4g of ammonium molybdate into 30mL of deionized water for dissolving, adding the ammonium molybdate into the powder, dissolving 3g of citric acid, 3g of oxalic acid and 11.7g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material for kneading and forming, naturally drying, roasting at 480 ℃ for 4 hours, and naturally cooling to obtain the catalyst D1.
Example 6
Dissolving 8.6g of tetraethyl titanate in 30mL of anhydrous alcohol, adding 165g of sodium silicate and 100mL of deionized water, heating and stirring, then adjusting the pH to 10 with concentrated ammonia water to obtain a solution A, dissolving 132g of aluminum nitrate in 250mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 4 hours, washing the material to pH 10.0 with deionized water, drying the material at 110 ℃, roasting the material at 600 ℃ for 3 hours, mixing the material with 30g of active alumina powder, carrying out ball milling for 0.5 hour, adding 4g of sesbania powder and 2g of starch, and carrying out dry mixing for 15 minutes; and adding 10.4g of ammonium molybdate into 30mL of deionized water for dissolving, adding the ammonium molybdate into the powder, dissolving 3g of citric acid, 3g of oxalic acid and 11.7g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material for kneading and forming, naturally drying, roasting at 480 ℃ for 4 hours, and naturally cooling to obtain the catalyst D2.
Example 7
Dissolving 8.6g of tetraethyl titanate in 30mL of anhydrous alcohol, adding 165g of sodium silicate and 100mL of deionized water, heating and stirring, then adjusting the pH to 12 with concentrated ammonia water to obtain a solution A, dissolving 162g of aluminum nitrate in 250mL of deionized water, heating to 60 ℃, adding the solution A while stirring, then heating the mixed solution to 80 ℃, maintaining the temperature for 4 hours, washing the material to pH 8.0 with deionized water, drying at 110 ℃, roasting at 600 ℃ for 3 hours, mixing with 26g of active alumina powder, ball-milling for 0.5 hour, adding 4g of sesbania powder and 2g of starch, and dry-mixing for 15 minutes; and adding 10.4g of ammonium molybdate into 30mL of deionized water to dissolve, adding the ammonium molybdate into the powder, dissolving 3g of citric acid, 3g of oxalic acid and 11.7g of cobalt nitrate into 30mL of deionized water, adding the mixture into the kneaded material, kneading and forming, naturally drying, roasting at 480 ℃ for 4 hours, and naturally cooling to obtain the catalyst D3.
The results of the physicochemical properties and the CO conversion at 230 ℃ of the catalyst in the examples of the present disclosure, which were measured by a pressure evaluation apparatus, are shown in Table 1. The pressurization evaluation device adopted by the present disclosure is shown in CN201510634166.3.
The detection conditions were as follows:
wherein the raw material gas comprises the following components: content of CO: 50.0 percent; CO 2 2 The content is as follows: 3.0 percent;
H 2 and (2) S content: more than 0.2 percent; and the balance: h 2 。
Catalyst loading: 50mL.
Vulcanization conditions are as follows:
temperature: 300 ℃; pressure: 2.0MPa; dry gas space velocity: 2000h -1 ；
H 2 And (2) S content: 0.3 percent; time: and (5) 20h.
Initial evaluation conditions for pressurization of sulfur-tolerant shift catalyst:
inlet temperature: 230 ℃; pressure: 4.0MPa; water/gas: 0.6;
dry gas space velocity: 3000h -1 ； H 2 And (2) S content: 0.2% -0.4%; time: and (4) 40h.
TABLE 1 catalyst Strength and pressure Activity
Figure 5734DEST_PATH_IMAGE001
As can be seen from Table 1, the overall physical and chemical properties and the CO conversion at 230 ℃ of the catalysts prepared in examples 1 to 4 are significantly better than those of the catalysts prepared in examples 5 to 7.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (9)

1. A low-temperature sulfur-tolerant shift catalyst is characterized in that a titanium silicalite molecular sieve and alumina are used as carriers to load catalytic active components, the catalytic active components are cobalt-molybdenum composite metal oxides, and the titanium silicalite molecular sieve is combined with alkali metal compounds;
wherein the specific surface area of the catalyst is 200m 2/g-250 m2/g, and the pore distribution of the catalyst with the pore diameter of 5-50nm accounts for more than 85% of the total pore volume;
the preparation method of the low-temperature sulfur-tolerant shift catalyst comprises the following steps:
the method comprises the steps of taking a titanium source, an alkali silicate metal salt and an aluminum salt as raw materials, utilizing a coprecipitation method and calcining to obtain a titanium-silicon molecular sieve combined with an alkali metal compound, mixing the titanium-silicon molecular sieve with alumina to form a carrier, adding molybdenum salt and cobalt salt into the carrier, reacting to load a cobalt-molybdenum composite metal oxide on the carrier, and obtaining the low-temperature sulfur-tolerant shift catalyst, wherein the precipitate is washed after coprecipitation in the coprecipitation method until the pH value is 7.5 to 8.5.
2. The low temperature sulfur tolerant shift catalyst of claim 1 comprising, based on weight percent of the catalyst:
aluminum, with Al 2 O 3 In 40 to 70 wt.%,
titanium, with TiO 2 0.5 to 4.0wt.%,
silicon, in SiO 2 In terms of 15 to 40 wt.%,
molybdenum in MoO 3 In terms of 4-10 wt.%,
cobalt, in terms of CoO, 2.0-4.0 wt.%,
alkali metal, with M 2 Calculated by O, 1.0 to 4.0wt.%, and M is alkali metal.
3. The low temperature sulfur tolerant shift catalyst of claim 1 wherein the catalyst has a pore volume of not less than 0.5mL/g.
4. The low temperature sulfur tolerant shift catalyst of claim 1 wherein the catalyst is in the form of a stripe, clover, tetrafoil or sphere.
5. The low temperature sulfur tolerant shift catalyst of claim 1 wherein the step of preparing the titanium silicalite is: mixing a titanium source and alkali silicate, adjusting the pH value to be alkaline to obtain a solution A, uniformly mixing an aluminum salt solution and the solution A under a heating condition, washing the mixture with water after reaction until the pH value is 7.5-8.5, and calcining the mixture to obtain the titanium-silicon molecular sieve.
6. The low temperature sulfur tolerant shift catalyst of claim 1 wherein the titanium silicalite molecular sieve and alumina are mixed by ball milling.
7. The low-temperature sulfur-tolerant shift catalyst according to claim 1, wherein the calcination temperature of the titanium silicalite is 500 to 650 ℃.
8. The low-temperature sulfur-tolerant shift catalyst according to claim 1, wherein the cobalt-molybdenum composite metal oxide is supported on the carrier by a sol-gel kneading method.
9. Use of the low-temperature sulfur-tolerant shift catalyst of any one of claims 1 to 8 in the preparation of syngas by catalytic low-temperature shift.
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CN87107892A (en) * 1987-11-14 1988-05-04 湖北省化学研究所 Sulfur-resistant CO conversion catalyst and preparation thereof
CN1778872A (en) * 2004-11-26 2006-05-31 中国石油天然气股份有限公司 Hydrogenation desulfurized catalyst containing molecular screen
CN102616805A (en) * 2011-01-28 2012-08-01 中国石油化工股份有限公司 Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10

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CN87107892A (en) * 1987-11-14 1988-05-04 湖北省化学研究所 Sulfur-resistant CO conversion catalyst and preparation thereof
CN1778872A (en) * 2004-11-26 2006-05-31 中国石油天然气股份有限公司 Hydrogenation desulfurized catalyst containing molecular screen
CN102616805A (en) * 2011-01-28 2012-08-01 中国石油化工股份有限公司 Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10

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