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CN112439450B - Modified sulfur-tolerant shift catalyst, preparation method and application - Google Patents

Modified sulfur-tolerant shift catalyst, preparation method and application Download PDF

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Publication number
CN112439450B
CN112439450B CN201910823787.4A CN201910823787A CN112439450B CN 112439450 B CN112439450 B CN 112439450B CN 201910823787 A CN201910823787 A CN 201910823787A CN 112439450 B CN112439450 B CN 112439450B
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catalyst
containing compound
molecular sieve
titanium
modified sulfur
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CN112439450A (en
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白志敏
余汉涛
田兆明
赵庆鲁
王昊
姜建波
薛红霞
李文柱
陈依屏
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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
    • 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
    • C01B2203/1082—Composition of support materials
    • 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 modified sulfur-tolerant shift catalyst and a preparation method and application thereof, and the catalyst comprises a carrier and a metal active component, wherein the carrier is a mixture of a titanium-silicon molecular sieve and alumina, the metal active component comprises a molybdenum-containing compound, a cobalt-containing compound and a potassium-containing compound, micropores are formed in the titanium-silicon molecular sieve, and the metal active component is loaded in the micropores in the titanium-silicon molecular sieve; 10-45 wt.% of titanium silicon molecular sieve, 40-75 wt.% of aluminum oxide, 5-12 wt.% of molybdenum oxide, 1.0-5.0 wt.% of cobalt oxide and 0.5-3.0 wt.% of potassium oxide. The preparation method comprises the following steps: uniformly mixing an aluminum-containing compound and a titanium-silicon molecular sieve, then bonding and calcining to obtain a catalyst carrier, mixing cobalt salt, molybdenum salt, potassium hydroxide and ethanolamine, adjusting the pH value to be alkaline to obtain a solution A, adding the catalyst carrier into the solution A, soaking, and then roasting to obtain the modified sulfur-resistant conversion catalyst.

Description

Modified 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 modified 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 cobalt-molybdenum catalyst has outstanding sulfur resistance and antitoxic performance, is suitable for the process of preparing synthesis gas by using residual oil, heavy oil, petroleum coke, coal and the like as raw materials, and simultaneously has excellent organic sulfur hydro-hydrolysis conversion function and good conversion function on inorganic sulfur and a few low-molecular sulfur-containing compounds such as sulfur, oxygen, carbon and the like. However, the inventors have found that the cobalt-molybdenum-based catalyst has a poor conversion rate to the hydrolysis reaction of sulfur-containing organic polymer compounds such as mercaptans, sulfides and benzothiophenes, and the reaction temperature is high. Along with the change of the coal types of raw materials, coal gasification processes are diversified, a small amount of mercaptan and thiophene byproducts can be brought into the raw material gas generated by some coal gasification processes, and the macromolecular sulfides can increase the burden of downstream product purification and bring great difficulty to industrial production.
Disclosure of Invention
In order to solve the defects of the prior art, the purpose of the present disclosure is to provide a modified sulfur-tolerant shift catalyst, a preparation method and an application thereof, wherein the catalyst can have a high conversion performance on a sulfur-containing high molecular compound under a low reaction temperature (250 to 350 ℃), and the shift reaction catalytic performance of the catalyst is not affected basically.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
in a first aspect, a modified sulfur-tolerant shift catalyst comprises a carrier and a metal active component, wherein the carrier is a mixture of a titanium silicalite and alumina, the metal active component comprises a molybdenum-containing compound, a cobalt-containing compound and a potassium-containing compound, micropores are formed in the titanium silicalite, and the metal active component is loaded in the micropores in the titanium silicalite;
wherein, the weight percentage of the titanium silicalite molecular sieve is 10 to 45 wt.% based on the weight percentage of the catalyst; 40 to 75 wt.% of alumina; 5 to 12 wt.% of molybdenum-containing compound calculated on molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; potassium-containing compound, 0.5 to 3.0 wt.% in terms of potassium oxide.
According to the method, the metal active components enter the micropores of the carrier, so that the dispersion is more uniform, the number of active sites is more, the activity stability of the catalyst is improved, the adsorption and hydrogenation reaction performance of the catalyst on sulfide is further enhanced, the catalyst has higher conversion performance on the sulfur-containing high molecular compound under the condition of lower reaction temperature, and the catalyst active components are dispersed in the inner holes of the titanium-silicon molecular sieve, so that the stability is higher.
In addition, experiments show that the adsorption and hydrogenation reaction performance of the titanium silicalite molecular sieve can be improved by utilizing the metal active component loaded on the internal micropores of the titanium silicalite molecular sieve, but the shift reaction catalytic performance of the catalyst can also be influenced, and when the catalyst contains the components, the catalyst not only has higher conversion performance on the sulfur-containing high molecular compound, but also has basically unaffected shift reaction catalytic performance.
The specific surface area of the catalyst was 220m 2 /g~280m 2 /g。
The pore volume of the catalyst is not less than 0.60mL/g, and the pore distribution with the pore diameter of 5nm to 50nm accounts for more than 70 percent of the total pore volume.
The shape of the catalyst is strip, clover or spherical.
The second aspect is a preparation method of a modified sulfur-tolerant shift catalyst, which comprises the steps of uniformly mixing an aluminum-containing compound with a titanium-silicon molecular sieve, then bonding the mixture through a binder, calcining the mixture to obtain a catalyst carrier, mixing cobalt salt, molybdenum salt, potassium hydroxide and ethanolamine, adjusting the pH value to be alkaline to obtain a solution A, adding the catalyst carrier into the solution A for soaking, and then calcining the soaked catalyst carrier to obtain the modified sulfur-tolerant shift catalyst;
in the obtained modified sulfur-resistant transformation catalyst, the titanium-silicon molecular sieve accounts for 10 to 45 wt.%, the aluminum oxide accounts for 40 to 75 wt.%, and the molybdenum compound accounts for 5 to 12 wt.% based on the molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; the potassium-containing compound is 0.5 to 3.0 wt.% in terms of potassium oxide.
According to the method, through modification of an alkaline solution, part of silicon of the titanium silicalite molecular sieve is removed, so that micropores are formed inside the titanium silicalite molecular sieve, and some micropores and cavities are formed inside the titanium silicalite molecular sieve, so that the framework of the molecular sieve can be effectively enlarged, the aperture is enlarged, the specific surface area of the molecular sieve is increased, the effective contact surface area of a catalyst and a reactant is increased, and the comprehensive activity of the catalyst is improved.
The catalyst active component is added during modification, so that the active component can more easily enter the micropores of the molecular sieve and is uniformly dispersed on the active sites of the micropores of the catalyst, the active sites are more, the catalytic activity is better, the adsorption and hydrogenation reaction performance of the catalyst on sulfur-containing high molecular compounds is enhanced, the catalyst has higher conversion performance on the sulfur-containing high molecular compounds under the condition of lower reaction temperature, the catalyst active component is dispersed in the inner holes of the molecular sieve, the stability is higher, and the conversion reaction performance of the catalyst is basically unaffected.
TiO of titanium silicalite molecular sieve 2 /SiO 2 The molar ratio is 0.1 to 0.5.
The preparation process of the catalyst carrier comprises the following steps: mixing an aluminum-containing compound and a titanium-silicon molecular sieve, dispersing in a solution, adding an extrusion aid and a binder, kneading, molding, and calcining to obtain the catalyst carrier.
Drying before calcining;
the calcination temperature is 500 to 700 ℃.
The pH value of the soaked materials is more than 11.
In a third aspect, the modified sulfur-tolerant shift catalyst is applied to the preparation of synthesis gas and/or the degradation of sulfur-containing high molecular compounds through CO shift.
The beneficial effect of this disclosure does:
the method adds titanium-silicon molecular sieve structure auxiliary agent into a sulfur-resistant conversion catalyst carrier, adopts alkali modification to improve the contents of mesopores and micropores of the conversion catalyst carrier, adds catalyst active components during modification, enables the active components to enter the micropores of the molecular sieve more easily and to be uniformly dispersed on the active sites of the micropores of the catalyst, so that the active sites are more and the catalytic activity is better, further enhances and improves the adsorption and hydrogenation reaction performance of the catalyst on sulfide, enables the catalyst to have higher conversion performance on sulfur-containing high molecular compounds under the condition of lower reaction temperature, and enables the catalyst active components to be dispersed in the inner holes of the molecular sieve, so that the stability is higher, and the conversion reaction performance is basically unaffected.
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.
In view of the defect that the existing cobalt-molybdenum catalyst has low degradation catalytic performance on high-molecular sulfides, the disclosure provides a modified sulfur-tolerant shift catalyst, and a preparation method and application thereof.
The modified sulfur-tolerant shift catalyst comprises a carrier and a metal active component, wherein the carrier is a mixture of a titanium silicalite and alumina, the metal active component comprises a molybdenum-containing compound, a cobalt-containing compound and a potassium-containing compound, micropores are formed in the titanium silicalite, and the metal active component is loaded in the micropores in the titanium silicalite;
wherein, the weight percentage of the titanium silicalite molecular sieve is 10 to 45 wt.% based on the weight percentage of the catalyst; 40 to 75 wt.% of alumina; 5 to 12 wt.% of molybdenum-containing compound calculated on molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; potassium-containing compound, 0.5 to 3.0 wt.% in terms of potassium oxide.
According to the method, the metal active components enter the micropores of the carrier, so that the dispersion is more uniform, the number of active sites is more, the activity stability of the catalyst is improved, the adsorption and hydrogenation reaction performance of the catalyst on sulfide is further enhanced, the catalyst has higher conversion performance on the sulfur-containing high molecular compound under the condition of lower reaction temperature, and the catalyst active components are dispersed in the inner holes of the titanium-silicon molecular sieve, so that the stability is higher. Meanwhile, when the catalyst is composed of the components, the catalyst not only has higher conversion performance on sulfur-containing high molecular compounds, but also has the conversion reaction catalytic performance which is basically not influenced.
In one or more embodiments of this embodiment, the catalyst has a specific surface area of 220m 2 /g~280m 2 (iv) g. The catalyst has stronger adsorption performance on sulfur-containing high molecular compounds, thereby enhancing the hydrogenation reaction performance and simultaneously ensuring the stable structure of the catalyst.
In one or more embodiments of the embodiment, the pore volume of the catalyst is not less than 0.60mL/g, and the pore distribution with pore diameters of 5nm to 50nm accounts for more than 70% of the total pore volume.
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 better catalytic performance.
The other embodiment of the disclosure provides a preparation method of a modified sulfur-tolerant shift catalyst, which comprises the steps of uniformly mixing an aluminum-containing compound with a titanium-silicon molecular sieve, then bonding the mixture through a binder, calcining the mixture to obtain a catalyst carrier, mixing cobalt salt, molybdenum salt, potassium hydroxide and ethanolamine, adjusting the pH value to be alkaline to obtain a solution A, adding the catalyst carrier into the solution A for soaking, and then calcining the soaked catalyst carrier to obtain the modified sulfur-tolerant shift catalyst;
in the obtained modified sulfur-tolerant shift catalyst, the weight of a titanium-silicon molecular sieve is 10 to 45 wt.%, the weight of aluminum oxide is 40 to 75 wt.%, and the weight of a molybdenum-containing compound is 5 to 12 wt.% calculated by molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; 0.5 to 3.0 wt.% of a potassium-containing compound in terms of potassium oxide.
The method modifies the titanium-silicon molecular sieve through the alkaline solution, removes part of silicon of the titanium-silicon molecular sieve, forms micropores in the titanium-silicon molecular sieve, enables active components to enter the micropores of the molecular sieve more easily, enables the active components to be dispersed in active sites of the micropores of the catalyst, increases the active sites, increases the catalytic performance of the catalyst, further improves the adsorption and hydrogenation reaction performance of the catalyst on sulfur-containing high molecular compounds, enables the catalyst to have higher conversion performance on the sulfur-containing high molecular compounds under the condition of lower reaction temperature, enables the active components of the catalyst to be dispersed in inner holes of the molecular sieve, and is higher in stability, and meanwhile, the conversion reaction performance of the catalyst is basically unaffected.
The purpose of ethanolamine addition in this disclosure is to coordinate with cobalt ions, preventing precipitation of cobalt ions under alkaline conditions, thereby affecting cobalt ions entering the internal micropores of the catalyst support.
The aluminum-containing compound in the present disclosure refers to a compound or mixture containing aluminum ions, such as alumina, pseudoboehmite, aluminum salt, and the like.
The cobalt salt in the present disclosure refers to a compound capable of ionizing cobalt ions in an ionized layer dissolved in water, such as cobalt nitrate, cobalt chloride, cobalt sulfate, and the like.
The molybdenum salt in the present disclosure means a compound capable of ionizing the molybdenum ion or molybdate ion dissolved in water, for example, ammonium molybdate, molybdenum 2-ethylhexanoate, molybdenum nitrate, etc.
In one or more embodiments of this embodiment, the TiO of the titanium silicalite molecular sieve 2 /SiO 2 The molar ratio is 0.1 to 0.5. More silicon can be provided and thus more micropores are formed.
The titanium silicalite molecular sieve comprises ETS-2, MCM-41, TS-1 and the like, and in one or more embodiments, the titanium silicalite molecular sieve is a TS-1 type titanium silicalite molecular sieve. When the TS-1 type titanium silicalite molecular sieve is adopted, the catalytic performance is better.
In one or more embodiments of this embodiment, the catalyst support is prepared by: mixing an aluminum-containing compound and a titanium-silicon molecular sieve, dispersing in a solution, adding an extrusion aid and a binder, kneading, molding, and calcining to obtain the catalyst carrier.
In the series of embodiments, the adhesive comprises water glass and an adhesive auxiliary agent, wherein the adhesive auxiliary agent is one or more of citric acid, oxalic acid, nitric acid and the like. When the binder is water glass and citric acid, the effect is better. When the water glass is added into the citric acid aqueous solution, sol can be formed, so that the bonding property is improved, and the aluminum-containing compound and the titanium silicalite molecular sieve are better combined together. The content of the binder is 1~6% (m/m), and when the content is 2~4% (m/m), the bonding effect is better.
In this series of examples, the specific preparation process of the catalyst support was: mixing an aluminum-containing compound with a titanium-silicon molecular sieve, adding an extrusion aid and an aqueous solution containing a bonding aid, adding water glass, kneading and molding, and calcining to obtain the catalyst carrier.
In this series of examples, the extrusion aid is sesbania powder or starch. When sesbania powder is adopted, the kneading effect is better. The content of the extrusion aid is 1~4% (m/m). When the content is 2~3% (m/m), the effect is better.
In one or more embodiments of this embodiment, the titanium silicalite is dried prior to calcination in order to prevent evaporation of water during calcination from affecting the pore structure of the titanium silicalite. The drying mode is natural drying.
In one or more embodiments of this embodiment, the calcination temperature is from 500 ℃ to 700 ℃. When the calcination temperature is 600 ℃, the morphology of the catalyst support is better.
In one or more embodiments of this embodiment, the aluminum-containing compound is alumina or pseudoboehmite. Can prevent partial aluminum loss caused by the dissolution of aluminum salt.
In one or more embodiments of this embodiment, the agent that adjusts the pH is ammonia. The composition of the catalyst is prevented from being influenced by the addition of metal ions.
In one or more embodiments of this embodiment, the temperature at which solution a is prepared is not less than 60 ℃. Ensuring the dissolution rate. When the temperature of the solution A is 70 to 80 ℃, the effect is better.
In one or more embodiments of this embodiment, the pH in solution a is greater than 11. When the pH value of the solution A is 11.5 to 12.0, the catalyst carrier is better modified, and the catalytic performance of the produced catalyst is higher.
In one or more embodiments of this embodiment, the pH of the soaked material is greater than 11. When the pH value of the soaked material is 11.5-12.0, the catalytic performance of the catalyst is better.
In one or more embodiments of this embodiment, the soaking time is 4 to 5 hours. Not only can ensure the complete modification of the catalyst carrier, but also can ensure that the active ingredients are immersed into the internal micropores.
In one or more embodiments of this embodiment, drying is performed prior to firing. The drying temperature is 60 to 100 ℃.
In one or more embodiments of this embodiment, the temperature of firing is 400 to 600 ℃. When the roasting temperature is 500 ℃, the effect is better.
In a third embodiment of the present disclosure, an application of the above modified sulfur-tolerant shift catalyst in preparation of syngas and/or degradation of sulfur-containing high molecular compounds by CO shift is provided.
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 ammonia used in the examples was commercially available concentrated ammonia, indicated as 25% strength by mass.
Example 1
15.5g of cobalt nitrate and 12.3g of ammonium molybdate were weighed, 2.7g of potassium hydroxide was added, 40mL of a mixed solution of ammonia water and 3mL of ethanolamine was added, and the mixture was heated to 70 ℃ to obtain a clear solution A having a pH of 12.3g of citric acid was added to 15mL of deionized water to give solution B.
Taking TiO 2 /SiO 2 28g of titanium silicalite molecular sieve with the molar ratio of 0.4 and 56g of activated alumina are mixed and ground for 0.5h, 4g of sesbania powder and 2g of starch are added and mixed uniformly, a solution B is added, 3mL of water glass (the modulus is 1.5, the same below) is added and kneaded uniformly, the mixture is molded and naturally dried, then the mixture is roasted at 600 ℃ for 3h to prepare a catalyst carrier, 84g of the catalyst carrier is weighed and poured into the solution A, the pH value is 11.5, the mixture is soaked for 2h, dried at 75 ℃, and roasted at 500 ℃ for 2h to obtain a finished product C1.
Example 2
13.6g of cobalt nitrate and 10.4g of ammonium molybdate were weighed, 4.0g of potassium hydroxide was added, 50mL of ammonia water and 2mL of ethanolamine were added, and the mixture was heated to 60 ℃ to obtain a clear solution A having a pH of 11.5. 3g of citric acid and 2mL of acetic acid were added to 20mL of deionized water, respectively, to obtain a solution B.
Taking TiO 2 /SiO 2 Mixing and grinding 16g of titanium silicalite molecular sieve with the molar ratio of 0.2 and 98g of pseudo-boehmite for 1.5h, adding 5g of sesbania powder, uniformly mixing, adding the solution B, uniformly kneading, molding, naturally drying, roasting at 550 ℃ for 3h to prepare a catalyst carrier, weighing 85g of the catalyst carrier, pouring the catalyst carrier into the solution A, measuring the pH value to be 11, soaking for 4h, drying at 100 ℃, and roasting at 450 ℃ for 3h to obtain a finished product C2.
Example 3
7.8g of cobalt nitrate and 9.8g of ammonium molybdate were weighed, 4.0g of potassium hydroxide was added, then 30mL of ammonia water and 1mL of ethanolamine were added, and heating was carried out to 50 ℃ to obtain a clear solution A having a pH of 13. 3g of oxalic acid and 2g of citric acid were added to 25mL of deionized water, respectively, to obtain a solution B.
Taking TiO 2 /SiO 2 Mixing and grinding 28g of titanium silicalite molecular sieve with the molar ratio of 0.5 and 59g of active alumina for 1 hour, adding 4g of sesbania powder and 4g of starch, uniformly mixing, adding the solution B, adding 2mL of water glass, uniformly kneading, molding, naturally drying, roasting at 450 ℃ for 3 hours to obtain a catalyst carrier, weighing 87g of the catalyst carrier, pouring the catalyst carrier into the solution A, measuring the pH value to be 12, soaking for 1h, drying at 80 ℃, and roasting at 500 ℃ for 3 hours to obtain a finished product C3.
Example 4
13.6g of cobalt nitrate and 3.7g of ammonium molybdate were weighed, 2.0g of potassium hydroxide was added, then 45mL of ammonia water and 1mL of ethanolamine were added, and heating was carried out to 80 ℃ to obtain a clear solution A having a pH of 12.3g of citric acid and 2mL of dilute nitric acid were added to 15mL of deionized water, respectively, to obtain a solution B. Wherein the dilute nitric acid is obtained by mixing commercially available concentrated nitric acid and deionized water according to the mass ratio of 1:5, and the concentration marked by the commercially available concentrated nitric acid is 68% (mass percentage).
Taking TiO 2 /SiO 2 Mixing and grinding 45g of titanium silicalite molecular sieve with the molar ratio of 0.1 and 40g of active alumina for 1 hour, adding 6g of sesbania powder, uniformly mixing, adding the solution B, kneading uniformly, molding, naturally drying, roasting at 600 ℃ for 3 hours to prepare a catalyst carrier, weighing 85g of the catalyst carrier, pouring the catalyst carrier into the solution A, measuring the pH value to be 11.5, soaking, and dryingThe product C4 is obtained after the product is dried at 2h and 60 ℃ and roasted at 450 ℃ for 3 h.
Example 5
12.5g of ammonium molybdate was weighed, 3g of potassium hydroxide was added and 30mL of deionized water was added to give a clear solution A. 15.5g of cobalt nitrate and 3g of citric acid were added to 15mL of deionized water to obtain solution B.
Taking TiO 2 /SiO 2 And (3) mixing and grinding 28g of titanium silicalite molecular sieve with the molar ratio of 0.4 and 56g of activated alumina for 0.5h, adding 4g of sesbania powder and 2g of starch, uniformly mixing, adding the solution B, adding 3mL of water glass, uniformly kneading, pouring the solution A, uniformly kneading, forming, naturally airing, and roasting at 600 ℃ for 3h to obtain a catalyst finished product D1.
Example 6
Weighing 15.5g of cobalt nitrate and 12.3g of ammonium molybdate, adding 2.7g of potassium hydroxide, adding a mixed solution of 30mL of ammonia water and 1mL of ethanolamine, heating to 70 ℃, and measuring the pH value to be 10 to obtain a transparent solution A. 3g of citric acid was added to 15mL of deionized water to obtain solution B.
Taking TiO 2 /SiO 2 28g of titanium silicalite molecular sieve with the molar ratio of 0.4 and 56g of activated alumina are mixed and ground for 0.5h, 4g of sesbania powder and 2g of starch are added and mixed uniformly, the solution B is added, 3mL of water glass is added and kneaded uniformly, the mixture is molded and naturally aired, then the mixture is baked for 3h at 600 ℃ to prepare a catalyst carrier, 84g of the catalyst carrier is weighed and poured into the solution A, the pH value is measured to be 9.5, the mixture is soaked for 2h, and after the mixture is dried at 75 ℃, the mixture is baked for 2h at 500 ℃ to obtain a finished product D2.
Example 7
15.5g of cobalt nitrate and 12.3g of ammonium molybdate were weighed, 2.7g of potassium hydroxide was added, 40mL of a mixed solution of ammonia water and 3mL of ethanolamine was added, and the mixture was heated to 70 ℃ to obtain a clear solution A having a pH of 12.3g of citric acid was added to 15mL of deionized water to obtain solution B.
Taking TiO 2 /SiO 2 Mixing and grinding 55g of titanium silicalite molecular sieve and 29g of activated alumina with the molar ratio of 0.4 for 0.5h, adding 4g of sesbania powder and 2g of starch, uniformly mixing, adding the solution B, adding 3mL of water glass, uniformly kneading, molding, naturally airing, roasting at 600 ℃ for 3h to obtain a catalyst carrier, weighing 84g of the catalyst carrierPouring the mixture into the solution A, measuring the pH value to be 11.5, soaking for 2h, drying at 75 ℃, and roasting for 2h at 500 ℃ to obtain a finished product D3.
The catalyst in the examples of the present invention was tested for pressurizing activity and organic sulfur conversion performance using a pressurizing evaluation apparatus, and the results are shown in Table 1. The pressurization evaluation device adopted in the disclosure is CN201510634166.3.
The detection conditions were as follows:
wherein the raw material gas composition is as follows: content of CO: 50.0 percent; CO 2 2 The content is as follows: 3.0 percent; organic sulfur content: 0.3 percent of
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: 320 ℃; pressure: 4.0MPa; water/gas: 1.0;
dry gas space velocity: 3000h -1 ；H 2 And (2) S content: 0.2% -0.4%; time: and (5) 20h.
TABLE 1 catalyst Activity under pressure and organic Sulfur conversion Performance
Figure 276680DEST_PATH_IMAGE001
As can be seen from Table 1, the catalyst prepared in example 1~7 has higher organic sulfur conversion compared to QCS-04. The catalyst prepared in example 1~4 has higher organic sulfur conversion and the shift catalytic activity is substantially unchanged.
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, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (8)

1. A modified sulfur-tolerant shift catalyst is characterized by comprising a carrier and a metal active component, wherein the carrier is a mixture of a titanium-silicon molecular sieve and alumina, the metal active component comprises a molybdenum-containing compound, a cobalt-containing compound and a potassium-containing compound, micropores are formed in the titanium-silicon molecular sieve, and the metal active component is loaded in the micropores in the titanium-silicon molecular sieve;
wherein, the weight percentage of the titanium silicalite molecular sieve is 10 to 45 wt.% based on the weight percentage of the catalyst; 40 to 75 wt.% of alumina; 5 to 12 wt.% of a molybdenum-containing compound based on molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; potassium-containing compound, 0.5 to 3.0 wt.% in terms of potassium oxide;
the preparation method of the modified sulfur-tolerant shift catalyst comprises the following steps:
uniformly mixing an aluminum-containing compound and a titanium-silicon molecular sieve, then carrying out binder and calcination to obtain a catalyst carrier, mixing cobalt salt, molybdenum salt, potassium hydroxide and ethanolamine, adjusting the pH value to be alkaline to obtain a solution A, adding the catalyst carrier into the solution A, and soaking, wherein the pH value of the soaked material is more than 11; then roasting the soaked catalyst carrier to obtain a modified sulfur-tolerant shift catalyst;
in the obtained modified sulfur-tolerant shift catalyst, the weight of a titanium-silicon molecular sieve is 10 to 45 wt.%, the weight of aluminum oxide is 40 to 75 wt.%, and the weight of a molybdenum-containing compound is 5 to 12 wt.% calculated by molybdenum oxide; 1.0 to 5.0 wt.% of a cobalt-containing compound as cobalt oxide; the potassium-containing compound is 0.5 to 3.0 wt.% in terms of potassium oxide.
2. The modified sulfur-tolerant shift catalyst of claim 1, wherein the catalyst has a specific surface area of 220m 2 /g~280m 2 /g。
3. The modified sulfur-tolerant shift catalyst according to claim 1, wherein the pore volume of the catalyst is not less than 0.60mL/g, and the pore distribution of 5nm to 50nm pores accounts for 70% or more of the total pore volume.
4. The modified sulfur tolerant shift catalyst of claim 1 wherein the catalyst has a shape of a bar, clover, tetrafoil or sphere.
5. The modified sulfur tolerant shift catalyst of claim 1 wherein the TiO of titanium silicalite is 2 /SiO 2 The molar ratio is 0.1 to 0.5.
6. The modified sulfur tolerant shift catalyst of claim 1 wherein the catalyst support is prepared by the process of: mixing an aluminum-containing compound and a titanium-silicon molecular sieve, dispersing in a solution, adding an extrusion aid and a binder, kneading, molding, and calcining to obtain the catalyst carrier.
7. The modified sulfur-tolerant shift catalyst of claim 1 which is dried prior to calcination;
the calcination temperature is 500 to 700 ℃.
8. Use of the modified sulfur tolerant shift catalyst of any one of claims 1~7 in the CO shift production of syngas and/or the degradation of sulfur containing high molecular compounds.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
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 Hydrodesulfurization catalyst containing molecular sieve
CN102923729A (en) * 2011-08-09 2013-02-13 中国石油天然气股份有限公司 Modification method of ETS-10 titanium silicalite molecular sieve

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US20060226049A1 (en) * 2005-04-08 2006-10-12 Nemeth Laszlo T Oxidative desulfurization of hydrocarbon fuels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 Hydrodesulfurization catalyst containing molecular sieve
CN102923729A (en) * 2011-08-09 2013-02-13 中国石油天然气股份有限公司 Modification method of ETS-10 titanium silicalite molecular sieve

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