Integrated hydro-conversion catalyst for organic sulfur and organic chlorine in feed gas and preparation method thereof

Abstract

The invention belongs to the technical field of catalyst preparation, and particularly relates to an integrated hydro-conversion catalyst for organic sulfur and organic chlorine in feed gas and a preparation method of the integrated hydro-conversion catalyst. The catalyst comprises 65 to 83% of a carrier, 8 to 20% of an active component I, 0.05 to 0.25% of an active component II, 0.5 to 1.5% of an active auxiliary agent, 1.2 to 5.5% of an auxiliary agent, 1.6 to 2.8% of a release agent and 1.5 to 4.0% of a pore forming agent. The prepared catalyst has relatively high low-temperature activity, high mechanical strength, high sulfur resistance, high chlorine resistance and high hydro-conversion precision, can operate in a scene containing trace organic sulfur and organic chlorine, and ensures that the hydrogenation conversion rate of the organic sulfur is greater than or equal to 97.8% and the hydrogenation conversion rate of the organic chlorine is greater than or equal to 98.2%.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and specifically relates to an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas and a preparation method thereof. Background Art

[0002] Coke oven gas is the main by-product of the coal coking process. Because it contains a large amount of high-value-added gases such as hydrogen, COx, alkanes, and olefins, it is often used in gas fuels, heat and power generation, metal smelting, or natural gas / synthesis gas production. However, since sulfur-containing and chlorine-containing pollutants are inevitably produced during the coal coking process, if they are not removed, the application scenarios of coke oven gas will be greatly limited. Usually, sulfur-containing and chlorine-containing pollutants include inorganic sulfur and inorganic chlorine such as hydrogen sulfide and hydrogen chloride, which are relatively easy to absorb / adsorb and remove, as well as some organic sulfur and organic chlorine such as thiophene, dimethyl disulfide, monochloromethane, and monochloroethane, which are difficult to remove directly. These harmful components will affect the coking operation and technical and economic indicators, and will also lead to catalyst poisoning in the subsequent natural gas / synthesis gas production stage. They may also corrode process equipment and pipelines, causing safety risks.

[0003] Chinese patent CN 118006371 A discloses a dechlorination and desulfurization agent and its preparation method, which can effectively remove hydrogen chloride and hydrogen sulfide in blast furnace gas. Chinese patent CN115466638A discloses a blast furnace gas integrated purifier and its preparation method, and obtains a purifier that integrates hydrogen chloride removal, carbonyl sulfide hydrolysis and hydrogen sulfide removal. Chinese patent CN116159563B discloses a desulfurization and dechlorination agent and its preparation method and application, which can effectively remove H 2 S and HCl, but the above patents only achieve the removal of inorganic chlorine, inorganic sulfur and part of organic sulfur, and fail to achieve the simultaneous hydrogenation conversion of organic sulfur and organic chlorine.

[0004] Chinese patent CN106008819A discloses a production device and production method of low-color carbon nine hydrogenated petroleum resin, wherein the first stage of hydrogenation uses a nickel catalyst, and utilizes its low-temperature desulfurization, denitrification, and dechlorination functions to convert sulfur-containing and chlorine-containing substances in the petroleum resin into inorganic sulfur and inorganic chlorine, but the patent does not clearly indicate whether the nickel catalyst achieves complete conversion of sulfur-containing and chlorine-containing substances after hydrogenation, nor does it involve specific indicators of the nickel catalyst's ability to hydrogenate organic sulfur and organic chlorine. Chinese patent CN 110302843 B discloses a five-coordinated aluminum oxide-rich and its synthesis method and application, and a high-loaded single-atom catalyst is prepared by mixing and dissolving a metal aluminum salt and a complexing agent and heating and activating it, which has a certain hydrogenation function for unsaturated hydrocarbons and chlorofluoroalkanes, but the patent does not mention the hydrogenation function for organic sulfur, nor does it evaluate the activity change of the catalyst after long-term operation.

[0005] Therefore, in view of the toxic substances such as organic sulfur and organic chlorine commonly contained in coke oven gas, it is urgently necessary to develop a catalyst with rich application scenarios, high selective activation of both C-Cl bonds and CS bonds and strong hydrogenation ability, so as to realize the integrated hydrogenation conversion of organic sulfur and organic chlorine, and at the same time have relatively high low-temperature activity and strong anchoring effect between carrier and active component, so as to avoid problems such as decreased hydrogenation conversion activity, carbon deposition, coking, sintering of active components, etc. caused by long-term use. Summary of the invention

[0006] The purpose of the present invention is to provide an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas and a preparation method thereof in view of the problem that the current hydrogenation conversion catalyst has limited application scenarios. The integrated hydrogenation conversion catalyst prepared by the present method has the advantages of rich application scenarios, high selective activation and strong hydrogenation ability for both C-Cl bonds and CS bonds, high conversion efficiency, low side reactions, strong resistance to carbon deposition, and long service life, and can better solve the problems existing in the existing catalysts in the background technology.

[0007] In order to achieve the above invention object, the specific technical solution of the present invention is:

[0008] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas comprises, based on 100% by mass, 65-83% of a carrier, 8-20% of an active component one, 0.05-0.25% of an active component two, 0.5-1.5% of an active aid, 1.2-5.5% of an auxiliary agent, 1.6-2.8% of a release agent, and 1.5-4.0% of a pore-forming agent.

[0009] As a preferred embodiment of the present application, the carrier is a silicon-doped alumina material.

[0010] As a better implementation in the present application, the active component one is one or a combination of cobalt, molybdenum, and tungsten.

[0011] As a better implementation in the present application, the second active component is platinum, palladium, or a combination of both.

[0012] As a better implementation in the present application, the active auxiliary agent is any one of ferrous sulfate and ferrous chloride or a combination of several thereof.

[0013] As a better implementation in the present application, the auxiliary agent is any one of tannic acid, formic acid, and ethylenediaminetetraacetic acid, or a combination of several of them.

[0014] As a better implementation in the present application, the release agent is any one or a combination of graphite, magnesium stearate, and calcium stearate.

[0015] As a better implementation in the present application, the pore-forming agent is any one of carboxymethyl cellulose, sesbania powder, and polyvinyl alcohol, or a combination of several of them.

[0016] As a preferred embodiment of the present application, the method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in a raw gas comprises the following steps:

[0017] (1) Weigh a certain amount of organosilicon alkoxide, organic solvent, and acidic reaction aid, add an appropriate amount of deionized water, and stir to dissolve in a 50° C. water bath to obtain a precursor A;

[0018] (2) Weigh a certain amount of inorganic aluminum salt, organic epoxide additive, and complexing agent, add an appropriate amount of deionized water, stir and dissolve in a water bath at 25° C. to obtain precursor B;

[0019] (3) Precursor A is added dropwise to precursor B in a 50° C. water bath, and the mixture is continuously stirred to obtain a silica-alumina sol composite. The mixture is then stirred and a coagulant is added dropwise to gel the silica-alumina sol composite. The gel is then aged and soaked in ethanol for 24-36 hours, and then vacuum dried. The dried sample is calcined at 300-380° C. for 2-4 hours to obtain a precursor C.

[0020] (4) Weigh a certain amount of the precursor C and add it to an appropriate amount of deionized water, stir vigorously to keep the liquid in a slurry state, then weigh a certain amount of the active component, a soluble salt, and add it to an appropriate amount of deionized water. After stirring and dissolving, use a pump to pump it into the slurry liquid to obtain a slurry precursor D;

[0021] (5) Weigh a certain amount of precipitant and add it to an appropriate amount of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D, measure the liquid pH to 10.4±0.2, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 110-130° C. to dry, and then calcine in an air atmosphere at 320-380° C. for 3 h to obtain a precursor E;

[0022] (6) Precursor E is transferred to a three-necked flask, an appropriate amount of deionized water is added and stirred to a slurry state, and then an active auxiliary agent, a soluble salt of the active component 2 and an auxiliary agent are added. Next, a sodium borohydride aqueous solution (20-120 mg / mL, preferably 80 mg / mL) with a molar number of 1.0-5.0 times that of the metal to be reduced is added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction is carried out for 40-120 min, preferably 60 min, and then filtered, the filter cake is washed until the pH of the filtrate is close to neutral, and the filter cake is dried in a nitrogen atmosphere at 110-130°C to obtain a precursor F;

[0023] (7) Weighing a certain amount of a release agent and a pore-forming agent, uniformly mixing them with the precursor F, and then pressing and molding them using a tablet press to obtain a precursor G;

[0024] (8) Precursor G is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 180-280°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450-480°C at a rate of 20°C / min, and maintained for 6-12 hours. During the whole process, the internal pressure of the quartz tube is maintained at 10-100 Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining a finished catalyst.

[0025] As a better embodiment of the present application, the organosilicon salt in step (1) is any one of methyl orthosilicate and ethyl orthosilicate, more preferably ethyl orthosilicate; the organic solvent is any one of methanol, ethanol, and acetone or a combination of several, more preferably ethanol; the acidic reaction auxiliary agent is any one of nitric acid, sulfuric acid, and acetic acid or a combination of several; the molar ratio of the organosilicon salt, organic solvent, deionized water, and acidic reaction auxiliary agent is 1: (4-7.5): (3.8-6.1): (0.01-0.045).

[0026] As a better implementation mode in the present application, the inorganic aluminum salt in step (2) is any one of aluminum nitrate and aluminum chloride, more preferably aluminum nitrate; the organic epoxide auxiliary agent is propylene oxide; the complexing agent is any one of glucose, sodium gluconate, oxalic acid or a combination of several thereof; the ratio of the amount of the inorganic aluminum salt, deionized water, organic epoxide auxiliary agent and complexing agent is 1:(25-95):(2.2-2.9):(1.7-5.4).

[0027] As a better implementation in the present application, in the process of adding the precursor A to the precursor B in step (3), the silicon-aluminum atomic ratio is controlled to be 1:(3.5-6.2); the coagulant is any one of ammonia water and ammonium carbonate or a combination of two thereof.

[0028] As a better implementation method in the present application, the mass ratio of precursor C to deionized water in step (4) is 1:(3.6-5.2); the active component-soluble salt is any one or a combination of cobalt nitrate, sodium molybdate, potassium molybdate, sodium tungstate, and ammonium metatungstate.

[0029] As a better implementation in the present application, the precipitant in step (5) is any one or a combination of ammonia water, sodium carbonate, potassium carbonate, and triethylamine.

[0030] As a better implementation mode of the present application, the soluble salt of the active component II in step (6) is any one or a combination of chloroplatinic acid, potassium chloroplatinate, palladium chloride, and palladium nitrate; the active auxiliary agent is any one or a combination of ferrous sulfate and ferrous chloride; the auxiliary agent is any one or a combination of tannic acid, formic acid, and ethylenediaminetetraacetic acid, more preferably tannic acid.

[0031] As a better implementation mode of the present application, the release agent in step (7) is any one or a combination of graphite, magnesium stearate, and calcium stearate; the pore-forming agent is any one or a combination of carboxymethyl cellulose, sesbania powder, and polyvinyl alcohol.

[0032] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas prepared by any of the above methods or a combination of method steps, wherein the shape of the obtained catalyst product is a four-leaf clover, a cylinder or a Raschig ring; the radial dimension of the catalyst is 4.0 mm, the axial dimension is 4.0 mm, and the radial strength is ≥80 N / cm.

[0033] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas prepared by any of the above methods or a combination of method steps, wherein the use conditions of the obtained catalyst product are a temperature of 125-280°C and a raw gas space velocity of 500-5000h -1 , the total organic sulfur content in the raw gas is ≤300ppm, the total organic chlorine content is ≤100ppm, and the pressure is 0.5-8MPa.

[0034] The present invention provides an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas. The integrated hydrogenation conversion catalyst has great advantages in selective hydrogenation of organic sulfur, selective hydrogenation of organic chlorine, and resistance to carbon deposition.

[0035] The present invention also provides a method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in a raw gas, which can accurately and effectively prepare the integrated hydrogenation conversion catalyst.

[0036] Compared with the prior art, the positive effects of the present invention are embodied in:

[0037] (1) The organic sulfur and organic chlorine integrated hydrogenation catalyst prepared by the present invention can ensure that the organic sulfur hydrogenation conversion rate is ≥97.8% and the organic chlorine hydrogenation conversion rate is ≥98.2% when the organic sulfur is ≤300 ppm and the organic chlorine is ≤100 ppm continuously introduced into the inlet and the reaction temperature is 125-280°C, thereby effectively solving the problem of excessive organic sulfur and organic chlorine content in the raw gas and avoiding affecting the use of the catalyst in the subsequent process.

[0038] (2) In the present invention, the added complexing agent has a suitable aluminum ion coordination ability, and relatively mild calcination conditions are subsequently adopted. The combination of the two can obtain a carrier containing relatively rich five-coordinated unsaturated aluminum to provide more binding sites, which is beneficial to anchoring active metals, effectively improving the stability of active components, avoiding decomposition, sintering or agglomeration during use, extending the catalyst replacement cycle and service life, and reducing the catalyst use cost. In addition, the silicon-doped alumina carrier prepared by the sol-gel method has a large specific surface area, excellent texture properties and a fine and uniform grain size, which can improve the dispersion of active metals and increase the utilization rate of metal centers.

[0039] (3) In the present invention, the dispersion of active metals on the carrier is improved by first precipitating and then reducing, ensuring the uniformity and effectiveness of the dispersion. The addition of a low-temperature water bath and auxiliary agents can eliminate the passivation layer on the surface of the active metal particles during the precipitation process, while making the metal particles obtained by reduction small in size and narrow in particle size distribution, thereby improving the low-temperature activity of the catalyst.

[0040] (4) In the present invention, the active metal is transformed from a single substance state to a sulfided state by chemical vapor deposition, thereby improving the purity of the sulfided metal after sulfidation and enhancing the sulfur resistance of the catalyst; at the same time, by introducing an active additive, the electron cloud density around the metal with catalytic activity is increased, thereby improving the selective activation ability of the active metal for C-Cl bonds and C-S bonds.

[0041] (5) In the present invention, the organic sulfur and organic chlorine integrated hydrogenation catalyst obtained by the preparation method has relatively high low-temperature activity, high mechanical strength, and high sulfur resistance and chlorine resistance, and can avoid the problems of decreased hydrogenation conversion activity, carbon deposition, coking, sintering of active components, poisoning, and catalyst pulverization after long-term use. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 For the carrier in Example 1 and Comparative Example 1 27 Al NMR spectrum. The peak areas of IV, V, and VI are positively correlated with the amount of tetra-coordinated, penta-coordinated, and hexa-coordinated unsaturated aluminum in the carrier, respectively.

[0043] Figure 2The organic sulfur hydrogenation conversion rate of the finished catalysts prepared in Example 1 and Comparative Example 5, i.e., H1 and H13, after continuous operation for 400 hours.

[0044] Figure 3 The organic chlorine hydrogenation conversion rate of the finished catalysts prepared in Example 1 and Comparative Example 5, i.e., H1 and H13, after continuous operation for 400 hours. DETAILED DESCRIPTION

[0045] All features disclosed in this specification, or steps in all methods or processes disclosed, except mutually exclusive features and / or steps, can be combined in any manner.

[0046] Any feature disclosed in this specification (including claims and abstract), unless otherwise stated, may be replaced by other equivalent or alternative features having similar purposes. That is, unless otherwise stated, each feature is only an example of a series of equivalent or similar features.

[0047] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0048] In the present application, unmarked % indicates mass percentage.

[0049] In the present invention, some conventional operating equipment, devices and components are omitted or only briefly described.

[0050] Embodiment 1:

[0051] A catalyst for the integrated hydrogenation conversion of organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 81.50%, the active component one accounts for 13%, the active component two accounts for 0.1%, the active additive accounts for 0.7%, the auxiliary agent accounts for 1.3%, the release agent accounts for 1.8%, and the pore-forming agent accounts for 1.6%.

[0052] The specific preparation steps are:

[0053] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and nitric acid were weighed respectively and prepared into a sol in a molar ratio of 1:5:4:0.03 to obtain a precursor A1.

[0054] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, sodium gluconate and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.5:1.9:50 to obtain a precursor B1.

[0055] (3) In a 50°C water bath, precursor A1 was added dropwise into precursor B1 at a silicon-aluminum atomic ratio of 1:4.5, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% volume concentration of ammonia aqueous solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 30 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 320°C for 3 hours to obtain precursor C1.

[0056] (4) Weigh 81.50 g of precursor C1, 24.68 g of cobalt nitrate hexahydrate and 20.20 g of sodium molybdate dihydrate, add them to 380 g of deionized water, and stir vigorously to obtain a slurry precursor D1.

[0057] (5) Weigh 100 g of concentrated aqueous ammonia and add it to 250 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D1 until the liquid pH is measured to be 10.5, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 115° C. to dry, and then calcine in an air atmosphere at 370° C. for 3 h to obtain precursor E1.

[0058] (6) The precursor E1 was transferred to a three-necked flask, 300 g of deionized water was added and stirred until a slurry state, and then 3.47 g of ferrous sulfate heptahydrate, 0.210 g of chloroplatinic acid and 1.3 g of tannic acid were added, and 100 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 115°C to obtain the precursor F1.

[0059] (7) 1.1 g of graphite, 0.7 g of calcium stearate, 0.8 g of polyvinyl alcohol and 0.8 g of sesbania powder were weighed and uniformly mixed with the precursor F1, and then compressed using a tablet press to obtain the precursor G1.

[0060] (8) Precursor G1 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450°C at a rate of 20°C / min and maintained for 8 hours. During the whole process, the internal pressure of the quartz tube is maintained at 10Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H1.

[0061] Embodiment 2:

[0062] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 78.80%, the active component one accounts for 15%, the active component two accounts for 0.1%, the active additive accounts for 0.8%, the auxiliary agent accounts for 1.5%, the release agent accounts for 1.9%, and the pore-forming agent accounts for 1.9%. The specific preparation steps are:

[0063] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and sulfuric acid were weighed respectively and prepared into a sol in a molar ratio of 1:5.2:4.3:0.025 to obtain a precursor A2.

[0064] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, folic acid and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.5:2.0:55 to obtain a precursor B2.

[0065] (3) In a 50°C water bath, precursor A2 was added dropwise into precursor B2 at a silicon-aluminum atomic ratio of 1:5.0, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% volume concentration of ammonia aqueous solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 36 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 350°C for 2.5 hours to obtain precursor C2.

[0066] (4) Weigh 78.80 g of precursor C2, 44.40 g of cobalt nitrate hexahydrate, 10.10 g of sodium molybdate dihydrate and 3.61 g of sodium tungstate, add to 330 g of deionized water, and stir vigorously to obtain a slurry precursor D2.

[0067] (5) Weigh 120 g of concentrated aqueous ammonia and add it to 300 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D2 until the liquid pH is measured to be 10.4, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 120° C. to dry, and then calcine in an air atmosphere at 360° C. for 3 h to obtain precursor E2.

[0068] (6) The precursor E2 was transferred to a three-necked flask, 320 g of deionized water was added and stirred to a slurry state, and then 3.97 g of ferrous sulfate heptahydrate, 0.249 g of palladium nitrate dihydrate and 1.5 g of tannic acid were added, and 120 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 minutes, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 110°C to obtain a precursor F2.

[0069] (7) 1.1 g of graphite, 0.8 g of calcium stearate, 1.2 g of polyvinyl alcohol and 0.7 g of sesbania powder were weighed and uniformly mixed with the precursor F2, and then pressed into a tablet using a tablet press to obtain the precursor G2.

[0070] (8) Precursor G2 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450°C at a rate of 20°C / min, and maintained for 8 hours. During the whole process, the internal pressure of the quartz tube is maintained at 20Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H2.

[0071] Embodiment 3:

[0072] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 76.58%, the active component one accounts for 16%, the active component two accounts for 0.12%, the active additive accounts for 0.9%, the auxiliary agent accounts for 2.2%, the release agent accounts for 2.0%, and the pore-forming agent accounts for 2.2%. The specific preparation steps are:

[0073] (1) Appropriate amounts of methyl orthosilicate, ethanol, deionized water and nitric acid were weighed respectively and prepared into a sol in a molar ratio of 1:5.5:4.8:0.03 to obtain a precursor A3.

[0074] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, sodium alginate and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.5:2.0:60 to obtain a precursor B3.

[0075] (3) In a 50°C water bath, precursor A3 was added dropwise into precursor B3 at a silicon-aluminum atomic ratio of 1:5.4, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% volume concentration of ammonia aqueous solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 30 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 330°C for 3 hours to obtain precursor C3.

[0076] (4) Weigh 76.58 g of precursor C3, 19.73 g of cobalt nitrate hexahydrate and 29.76 g of potassium molybdate, add to 370 g of deionized water, and stir vigorously to obtain a slurry precursor D3.

[0077] (5) Weigh 100 g of concentrated ammonia water and 25 g of ammonium carbonate, add them to 300 g of deionized water, and use a pump to pump them into the slurry precursor D3 after they are completely dissolved until the liquid pH reaches 10.3. Then filter and wash the filter cake until the pH of the filtrate is close to neutral. Then, dry the filter cake in an air atmosphere at 120° C., and then calcine it in an air atmosphere at 370° C. for 3 h to obtain the precursor E3.

[0078] (6) The precursor E3 was transferred to a three-necked flask, 350 g of deionized water was added and stirred to a slurry state, and then 2.33 g of ferrous chloride tetrahydrate, 0.299 g of potassium chloroplatinate, 1.5 g of tannic acid and 0.7 g of formic acid were added, and 130 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 115°C to obtain a precursor F3.

[0079] (7) 1.3 g of graphite, 0.7 g of magnesium stearate, 1.0 g of carboxymethyl cellulose and 1.2 g of sesbania powder were weighed and uniformly mixed with the precursor F3, and then compressed using a tablet press to obtain the precursor G3.

[0080] (8) Precursor G3 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 460°C at a rate of 20°C / min, and maintained for 6 hours. During the whole process, the internal pressure of the quartz tube is maintained at 20Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H3.

[0081] Embodiment 4:

[0082] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 72.95%, the active component one accounts for 18%, the active component two accounts for 0.15%, the active additive accounts for 1.1%, the auxiliary agent accounts for 2.9%, the release agent accounts for 2.2%, and the pore-forming agent accounts for 2.7%. The specific preparation steps are:

[0083] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and acetic acid were weighed respectively and prepared into a sol in a molar ratio of 1:5.8:5.2:0.03 to obtain a precursor A4.

[0084] (2) Appropriate amounts of aluminum chloride, propylene oxide, glucose and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.6:1.7:65 to obtain precursor B4.

[0085] (3) In a 50°C water bath, precursor A4 was added dropwise into precursor B4 at a silicon-aluminum atomic ratio of 1:5.7, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% by volume ammonia solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 28 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 360°C for 3 hours to obtain precursor C4.

[0086] (4) Weigh 73.95 g of precursor C4, 29.60 g of cobalt nitrate hexahydrate and 29.76 g of potassium molybdate, add them to 400 g of deionized water, and stir vigorously to obtain a slurry precursor D4.

[0087] (5) Weigh 150 g of concentrated aqueous ammonia and add it to 400 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D4 until the liquid pH is measured to be 10.5, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 120° C. to dry, and then calcine in an air atmosphere at 380° C. for 3 h to obtain precursor E4.

[0088] (6) The precursor E4 was transferred to a three-necked flask, 350 g of deionized water was added and stirred until a slurry state, and then 5.46 g of ferrous sulfate heptahydrate, 0.374 g of potassium chloroplatinate, 2.2 g of tannic acid and 0.7 g of ethylenediaminetetraacetic acid were added, and 150 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 120°C to obtain a precursor F4.

[0089] (7) 1.4 g of graphite, 0.8 g of calcium stearate, 1.8 g of carboxymethyl cellulose and 0.9 g of polyvinyl alcohol were weighed and uniformly mixed with the precursor F4, and then compressed using a tablet press to obtain the precursor G4.

[0090] (8) Precursor G4 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 470°C at a rate of 20°C / min, and maintained for 7 hours. During the whole process, the internal pressure of the quartz tube is maintained at 20Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H4.

[0091] Embodiment 5:

[0092] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 70.75%, the active component one accounts for 20%, the active component two accounts for 0.2%, the active additive accounts for 1.25%, the auxiliary agent accounts for 2.9%, the release agent accounts for 2.1%, and the pore-forming agent accounts for 2.8%. The specific preparation steps are:

[0093] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and nitric acid were weighed respectively and prepared into a sol in a molar ratio of 1:6.0:5.0:0.028 to obtain a precursor A5.

[0094] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, folic acid and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.4:2.2:60 to obtain a precursor B5.

[0095] (3) In a 50°C water bath, precursor A5 was added dropwise into precursor B5 at a silicon-aluminum atomic ratio of 1:5.7, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% by volume ammonia solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 24 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 350°C for 3.0 hours to obtain precursor C5.

[0096] (4) Weigh 70.75 g of precursor C5, 29.60 g of cobalt nitrate hexahydrate, 29.76 g of potassium molybdate and 5.05 g of sodium molybdate dihydrate, add to 360 g of deionized water, and stir vigorously to obtain a slurry precursor D5.

[0097] (5) Weigh 165 g of concentrated aqueous ammonia and add it to 400 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D5 until the liquid pH is measured to be 10.6, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 120° C. to dry, and then calcine in an air atmosphere at 380° C. for 3 h to obtain precursor E5.

[0098] (6) The precursor E5 was transferred to a three-necked flask, 350 g of deionized water was added and stirred until a slurry state, and then 6.20 g of ferrous sulfate heptahydrate, 0.421 g of chloroplatinic acid, 2.2 g of tannic acid and 0.7 g of ethylenediaminetetraacetic acid were added, and 180 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under nitrogen atmosphere, ultrasonic action, 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and then the filter cake was dried in a nitrogen atmosphere at 120°C to obtain the precursor F5.

[0099] (7) 1.4 g of graphite, 0.7 g of calcium stearate, 1.8 g of carboxymethyl cellulose and 1.0 g of sesbania powder were weighed and uniformly mixed with the precursor F5, and then compressed using a tablet press to obtain the precursor G5.

[0100] (8) Precursor G5 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. Argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450°C at a rate of 20°C / min and maintained for 8 hours. During the whole process, the internal pressure of the quartz tube is maintained at 25 Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H5.

[0101] Embodiment 6:

[0102] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 70.20%, the active component one accounts for 20%, the active component two accounts for 0.2%, the active additive accounts for 1.4%, the auxiliary agent accounts for 2.9%, the release agent accounts for 2.1%, and the pore-forming agent accounts for 3.2%. The specific preparation steps are:

[0103] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and nitric acid were weighed respectively and prepared into a sol in a molar ratio of 1:6.3:4.8:0.03 to obtain a precursor A6.

[0104] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, glucose and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.6:2.2:70 to obtain precursor B6.

[0105] (3) In a 50°C water bath, precursor A6 was added dropwise into precursor B6 at a silicon-aluminum atomic ratio of 1:5.9, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% volume concentration of ammonia aqueous solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 28 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 350°C for 3.5 hours to obtain precursor C6.

[0106] (4) Weigh 70.20 g of precursor C6, 19.73 g of cobalt nitrate hexahydrate, 37.20 g of potassium molybdate and 1.79 g of sodium tungstate dihydrate, add to 340 g of deionized water, and stir vigorously to obtain a slurry precursor D6.

[0107] (5) Weigh 155 g of concentrated aqueous ammonia and add it to 380 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D6 until the liquid pH is measured to be 10.5, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 115°C for drying. Next, calcine it in an air atmosphere at 370°C for 3 hours to obtain the precursor E6.

[0108] (6) The precursor E6 was transferred to a three-necked flask, 350 g of deionized water was added and stirred to a slurry state, and then 6.95 g of ferrous sulfate heptahydrate, 0.420 g of chloroplatinic acid, 2.1 g of tannic acid, 0.3 g of ethylenediaminetetraacetic acid and 0.5 g of formic acid were added, and 195 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 110°C to obtain a precursor F6.

[0109] (7) 1.4 g of graphite, 0.7 g of magnesium stearate, 2.2 g of carboxymethyl cellulose and 1.0 g of polyvinyl alcohol were weighed and uniformly mixed with the precursor F6, and then compressed using a tablet press to obtain the precursor G6.

[0110] (8) The precursor G6 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. At 100°C, argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 210°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450°C at a rate of 20°C / min and maintained for 9 hours. During the whole process, the internal pressure of the quartz tube is maintained at 30 Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H6.

[0111] Embodiment 7:

[0112] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 71.94%, the active component one accounts for 19%, the active component two accounts for 0.16%, the active additive accounts for 1.3%, the auxiliary agent accounts for 2.7%, the release agent accounts for 1.9%, and the pore-forming agent accounts for 3.0%. The specific preparation steps are:

[0113] (1) Appropriate amounts of methyl orthosilicate, methanol, deionized water and nitric acid were weighed respectively and prepared into a sol in a molar ratio of 1:6.0:5.1:0.025 to obtain a precursor A7.

[0114] (2) Appropriate amounts of aluminum chloride, propylene oxide, sodium gluconate and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.5:1.9:58 to obtain a precursor B7.

[0115] (3) In a 50°C water bath, precursor A7 was added dropwise into precursor B7 at a silicon-aluminum atomic ratio of 1:5.6, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% by volume ammonia solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 30 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 370°C for 3 hours to obtain precursor C7.

[0116] (4) Weigh 71.94 g of precursor C7, 37.20 g of potassium molybdate and 7.18 g of sodium tungstate dihydrate, add to 330 g of deionized water, and stir vigorously to obtain a slurry precursor D7.

[0117] (5) Weigh 140 g of concentrated aqueous ammonia and add it to 330 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D7 until the liquid pH is measured to be 10.5, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 115°C for drying. Next, calcine it in an air atmosphere at 380°C for 2.5 hours to obtain the precursor E7.

[0118] (6) The precursor E7 was transferred to a three-necked flask, 350 g of deionized water was added and stirred to a slurry state, and then 3.36 g of ferrous chloride, 0.252 g of chloroplatinic acid, 0.10 g of palladium nitrate dihydrate, 1.5 g of tannic acid, and 1.2 g of formic acid were added. 188 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under a nitrogen atmosphere, ultrasonic action, a 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and the filter cake was dried in a nitrogen atmosphere at 110°C to obtain a precursor F7.

[0119] (7) Weigh 0.8 g of graphite, 1.1 g of calcium stearate, 0.5 g of carboxymethyl cellulose and 2.5 g of polyvinyl alcohol, mix them evenly with the precursor F7, and then press them into a tablet using a tablet press to obtain the precursor G7.

[0120] (8) The precursor G7 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. At 100°C, argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 450°C at a rate of 20°C / min and maintained for 8 hours. During the whole process, the internal pressure of the quartz tube is maintained at 20Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H7.

[0121] Embodiment 8:

[0122] An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, in which the carrier accounts for 75.635%, the active component one accounts for 16%, the active component two accounts for 0.15%, the active additive accounts for 1.315%, the auxiliary agent accounts for 2.2%, the release agent accounts for 1.9%, and the pore-forming agent accounts for 2.8%. The specific preparation steps are:

[0123] (1) Appropriate amounts of ethyl orthosilicate, ethanol, deionized water and acetic acid were weighed respectively and prepared into a sol in a molar ratio of 1:5.8:5.2:0.035 to obtain a precursor A8.

[0124] (2) Appropriate amounts of aluminum nitrate nonahydrate, propylene oxide, sodium alginate and deionized water were weighed respectively and prepared into a sol in a molar ratio of 1:2.4:1.9:60 to obtain a precursor B8.

[0125] (3) In a 50°C water bath, precursor A8 was added dropwise into precursor B8 at a silicon-aluminum atomic ratio of 1:5.8, and stirring was continued to obtain a silica-aluminum sol complex. Then, while maintaining the stirring state, a 15% volume concentration of ammonia aqueous solution was added dropwise to gel the silica-aluminum sol complex. The gel was then immersed in ethanol for 24 hours. After vacuum drying, the sample was placed in a muffle furnace and calcined at 340°C for 3 hours to obtain precursor C8.

[0126] (4) Weigh 75.64 g of precursor C8, 9.87 g of cobalt nitrate hexahydrate, 27.73 g of sodium molybdate dihydrate and 4.02 g of ammonium metatungstate, add to 375 g of deionized water, and stir vigorously to obtain a slurry precursor D8.

[0127] (5) Weigh 150 g of concentrated aqueous ammonia and add it to 300 g of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D8 until the liquid pH is measured to be 10.5, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 110° C. to dry, and then calcine in an air atmosphere at 370° C. for 2.5 hours to obtain precursor E8.

[0128] (6) The precursor E8 was transferred to a three-necked flask, 365 g of deionized water was added and stirred to a slurry state, and then 6.53 g of ferrous sulfate heptahydrate, 0.374 g of potassium chloroplatinate, 1.5 g of tannic acid, 0.3 g of ethylenediaminetetraacetic acid and 0.4 g of formic acid were added, and 172 mL of sodium borohydride aqueous solution (80 mg / mL) was added dropwise under nitrogen atmosphere, ultrasonic action, 35°C water bath and continuous stirring. The reaction was carried out for 60 min, and then filtered. The filter cake was washed until the pH of the filtrate was close to neutral, and then the filter cake was dried in a nitrogen atmosphere at 110°C to obtain the precursor F8.

[0129] (7) 1.2 g of graphite, 0.7 g of calcium stearate, 1.5 g of carboxymethyl cellulose and 1.3 g of polyvinyl alcohol were weighed and uniformly mixed with the precursor F8, and then compressed using a tablet press to obtain the precursor G8.

[0130] (8) The precursor G8 is placed in the middle of a clean quartz tube, and an appropriate amount of sulfur powder is placed at the entrance of the quartz tube. The quartz tube is then placed in a multi-temperature zone tubular furnace. At 100°C, argon is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes. The tubular furnace is then adjusted to raise the temperature at the entrance of the quartz tube to 200°C, and the argon flow rate is reduced to 80 sccm. At the same time, the temperature zone in the middle of the tubular furnace is adjusted to raise the temperature in the middle of the quartz tube from room temperature to 465°C at a rate of 20°C / min, and maintained for 9 hours. During the whole process, the internal pressure of the quartz tube is maintained at 30 Pa. The tube is then cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, thereby obtaining the finished catalyst H8.

[0131] Comparative Example 1:

[0132] In this comparative example, no complexing agent was added when preparing the aluminum sol in step 2, and the remaining steps were the same as those in Example 1 to obtain the finished catalyst product H9.

[0133] Comparative Example 2:

[0134] In this comparative example, the complexing agent added in the preparation of aluminum sol in step 2 was changed from sodium gluconate to disodium ethylenediaminetetraacetate, and the remaining steps were the same as those in Example 1 to obtain a finished catalyst product H10.

[0135] Comparative Example 3:

[0136] In this comparative example, the complexing agent added in the preparation of aluminum sol in step 2 was changed from sodium gluconate to organic polyacid HEDP, and the remaining steps were the same as those in Example 1 to obtain the finished catalyst H11.

[0137] Comparative Example 4:

[0138] In this comparative example, the active metal loading in step 4-5 is changed from "precipitation followed by reduction" to "impregnation followed by direct reduction", that is, step 4-5 is changed to the following operation:

[0139] (4) Weigh 81.50 g of precursor C12, 24.68 g of cobalt nitrate hexahydrate, 20.20 g of sodium molybdate dihydrate, 3.47 g of ferrous sulfate heptahydrate, 0.210 g of chloroplatinic acid and 1.3 g of tannic acid, add them into 77.5 g of deionized water, stir vigorously and dry to obtain precursor D12.

[0140] The remaining steps are the same as those in Example 1 to obtain the finished catalyst H12.

[0141] Comparative Example 5:

[0142] In this comparative example, the preparation method described in Example 7 of Chinese Patent CN 110302843 B was adopted, and the specific preparation steps were:

[0143] (1) 34 g of aluminum sulfate (Al 2 (SO 4 ) 3 ) and 25g glycine (C 2 H 5 NO 2 ) was dissolved in 200 ml of deionized water to form a clear solution, which was stirred and evaporated in a water bath at 75°C for 4 h until it became viscous to obtain a jelly.

[0144] (2) The obtained colloid was placed in a round porcelain dish and placed in a microwave oven for 5 min at 900 W. The microwave was then turned off to cool it down. After it cooled naturally to room temperature, the microwave-heated product was placed in a tube furnace and heated from room temperature to 400°C at a rate of 3°C / min in an air atmosphere (air flow rate 100 mL / min) and calcined at 400°C for 4 h. After it cooled naturally to room temperature, the calcined product in the tube furnace was taken out. The obtained alumina powder was SDC-Al 2 O 3 carrier.

[0145] (3) SDC-Al 2 O 3 The support was dried at 120 °C for 6 h, and then SDC-Al 2 O 3 The support was immersed in an equal volume of HAuCl 4 The solid was then placed in an aqueous solution and aged at room temperature for 12 hours, followed by drying at 120°C for 24 hours (to evaporate the water in the impregnation solution). The dried solid was then placed in a tube furnace for a two-step calcination process. The first step of the calcination process was: in an air atmosphere (air flow rate 50 mL / min), the temperature was raised from room temperature to 400°C at a rate of 3°C / min and calcined at 400°C for 4 hours, followed by natural cooling to room temperature. The second step of the calcination process was: the gas in the tube furnace was switched to H 2 (H 2 The flow rate was 70 mL / min), the temperature was raised from room temperature to 200°C at a rate of 2°C / min and reduced at 200°C for 2 h, and then naturally cooled to room temperature. The finished catalyst H13 was obtained.

[0146] Comparative Example 6:

[0147] In this comparative example, the aluminum source used in the preparation of aluminum sol in step 2 was changed from aluminum nitrate nonahydrate to aluminum isopropoxide, and the remaining steps were the same as those in Example 1 to obtain the finished catalyst H14.

[0148] Comparative Example 7:

[0149] In this comparative example, the cobalt nitrate and sodium molybdate used in step 4 were replaced by nickel nitrate and copper nitrate, and the remaining steps were the same as those in Example 1 to obtain the finished catalyst H15.

[0150] Catalyst activity evaluation

[0151] 1. Raw gas composition

[0152] (1) Thiophene 300 ppm, methyl chloride 100 ppm, other components: carbon monoxide 10%, carbon dioxide 5%, methane 12%, ethane 3%, ethylene 2%, nitrogen 5%, the rest is hydrogen.

[0153] (2) Dimethyl disulfide 300 ppm, ethyl chloride 100 ppm, other components: carbon monoxide 10%, carbon dioxide 5%, methane 12%, ethane 3%, ethylene 2%, nitrogen 5%, and the rest is hydrogen.

[0154] 2. Test conditions

[0155] Temperature 240℃, raw gas space velocity 5000h -1 , pressure 1.0MPa.

[0156] 3. Test results

[0157] The test results of the organic sulfur and organic chlorine hydrogenation conversion rates after each catalyst in the examples and comparative examples was continuously operated for 400 hours are shown in Table 1.

[0158] Table 1 Test results of organic sulfur and organic chlorine hydrogenation conversion rate

[0159]

[0160] The best embodiment in the present invention is Embodiment 6. Compared with other embodiments, the catalyst H6 prepared in Embodiment 6 has a higher hydrogenation conversion rate for organic sulfur and organic chlorine such as thiophene, dimethyl disulfide, monochloromethane and monochloroethane, and the radial compressive strength is greater than 100N / cm. After continuous operation for 400 hours, it still has a high hydrogenation conversion rate, which can ensure the stability during continuous operation in industrial equipment.

[0161] By comparing Example 1 with Comparative Example 1, it can be seen that the addition of a complexing agent during the preparation of aluminum sol will have a significant impact on the hydrogenation conversion efficiency of organic sulfur and organic chlorine; by comparing Example 1 with Comparative Examples 2-3, it can be seen that the type of complexing agent added will have a significant impact on the hydrogenation conversion efficiency of organic sulfur and organic chlorine. Figure 1 It can be seen that selecting and adding a suitable chelating agent can produce a carrier containing relatively rich five-coordinated unsaturated aluminum to provide more binding sites, which is beneficial to anchoring active metals, avoiding sintering and agglomeration of active components, and extending the service life of the catalyst.

[0162] By comparing Example 1 and Comparative Example 4, it can be seen that the metal loaded by the "precipitation followed by reduction" method has a higher efficiency in hydrogenation conversion of organic sulfur and organic chlorine than the catalyst prepared by "impregnation followed by direct reduction". This may be because compared with the impregnation method, the metal loaded by the precipitation method is more evenly dispersed, the interaction between the metal and the carrier is stronger, and the microscopic pore structure can be regulated during the preparation process, ultimately showing a higher hydrogenation conversion efficiency.

[0163] Depend on Figure 2 and Figure 3It can be seen that the hydrogenation conversion rate and stability of the catalyst prepared in Comparative Example 5 are lower than those in Example 1. This may be because the silicon-doped alumina carrier has a larger specific surface area, better texture properties and a fine and uniform grain size, which can improve the dispersion of active metals, increase the utilization of metal centers, and improve operating stability.

[0164] By comparing Example 1 and Comparative Example 6, it can be seen that according to the preparation method of the present invention, the preferred aluminum source for synthesizing aluminum sol is an inorganic aluminum source, because the hydrolysis of organic aluminum sources such as aluminum isopropoxide is not well controlled, and the prepared gel may have low purity and uneven porosity, resulting in reduced chemical activity, which is not conducive to the production of catalysts. By comparing Example 1 and Comparative Example 7, it can be seen that nickel-based and copper-based materials commonly used in the field of desulfurization or hydrogenation catalysts are not suitable for the application scenarios of this method. This is because some "boron-rich" nickel-containing compounds will be generated in the subsequent reduction process, which greatly reduces the catalytic activity of nickel and copper as active components.

[0165] The above-mentioned embodiments only express the specific implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the protection scope of the present application. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the technical solution concept of the present application, and these all belong to the protection scope of the present application.

[0166] This background section is provided to generally present the context of the invention, and the work of the presently named inventors, the work to the extent described in this background section, and aspects of this section that did not constitute prior art at the time of application are neither explicitly nor implicitly admitted to be prior art to the present invention.

Claims

1. An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas, characterized by: Based on the mass percentage of 100, the catalyst includes 65-83% of a carrier, 8-20% of an active component one, 0.05-0.25% of an active component two, 0.5-1.5% of an active aid, 1.2-5.5% of an auxiliary agent, 1.6-2.8% of a release agent, and 1.5-4.0% of a pore-forming agent; the carrier is a silicon dioxide-doped alumina material; the active component one is one or a combination of cobalt, molybdenum, and tungsten; the active component two is one or a combination of two of platinum and palladium.

2. The integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 1, characterized in that: The active auxiliary agent is any one of ferrous sulfate and ferrous chloride or a combination of several thereof; the auxiliary agent is any one of tannic acid, formic acid and ethylenediaminetetraacetic acid or a combination of several thereof; the release agent is any one of graphite, magnesium stearate and calcium stearate or a combination of several thereof; the pore-forming agent is any one of carboxymethyl cellulose, sesbania powder and polyvinyl alcohol or a combination of several thereof.

3. The method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 1 or 2, characterized in that The steps include: (1) Weigh a certain amount of organosilicon alkoxide, organic solvent, and acidic reaction aid, add an appropriate amount of deionized water, and stir to dissolve in a water bath to obtain a precursor A; (2) Weigh a certain amount of inorganic aluminum salt, organic epoxide auxiliary agent and complexing agent, add an appropriate amount of deionized water, stir and dissolve in a water bath to obtain precursor B; (3) Precursor A is added dropwise to precursor B in a water bath, and stirring is continued to obtain a silica-alumina sol composite, and then a coagulant is added dropwise while maintaining stirring to gel the silica-alumina sol composite, and then the gel is aged and soaked in ethanol for 24-36 hours, and then vacuum dried, and the dried sample is calcined at 300-380° C. for 2-4 hours to obtain a precursor C; (4) Weigh a certain amount of the precursor C and add it to an appropriate amount of deionized water, stir vigorously to keep the liquid in a slurry state, then weigh a certain amount of the active component, a soluble salt, and add it to an appropriate amount of deionized water. After stirring and dissolving, use a pump to pump it into the slurry liquid to obtain a slurry precursor D; (5) Weigh a certain amount of precipitant and add it to an appropriate amount of deionized water. After it is completely dissolved, use a pump to pump it into the slurry precursor D, measure the liquid pH to 10.4±0.2, then filter, wash the filter cake until the pH of the filtrate is close to neutral, and then place the filter cake in an air atmosphere at 110-130° C. to dry, and then calcine in an air atmosphere at 320-380° C. for 2-4 hours to obtain a precursor E; (6) Precursor E is transferred to a three-necked flask, an appropriate amount of deionized water is added and stirred to a slurry state, and then an active agent, a soluble salt of the active component 2 and an auxiliary agent are added. Next, a sodium borohydride aqueous solution with a molar number of 1.0-5.0 times that of the metal to be reduced is added dropwise under a nitrogen atmosphere, ultrasonic action, a water bath and continuous stirring. The mixture is reacted for a period of time, and then filtered. The filter cake is washed until the pH of the filtrate is close to neutral, and then the filter cake is dried under a nitrogen atmosphere at 110-130° C. to obtain a precursor F; (7) Weighing a certain amount of a release agent and a pore-forming agent, uniformly mixing them with the precursor F, and then pressing and molding them using a tablet press to obtain a precursor G; (8) Precursor G is placed in the middle of a clean quartz tube, an appropriate amount of sulfur powder is placed at the entrance of the quartz tube, and then the quartz tube is placed in a multi-temperature zone tubular furnace. Under certain temperature conditions, argon gas is introduced into the tubular furnace at a certain flow rate, and then the tubular furnace is adjusted to increase the temperature at the entrance of the quartz tube and reduce the argon flow rate; at the same time, the temperature zone in the middle of the tubular furnace is adjusted to increase the temperature in the middle of the quartz tube from room temperature to 450-480°C at a certain rate and maintained for 6-12 hours. During the whole process, the internal pressure of the quartz tube is maintained at 10-100Pa; then it is cooled to room temperature under an argon atmosphere, and oxygen in nitrogen is introduced for passivation until there is no obvious self-heating phenomenon in the material in the quartz tube, and the finished catalyst is obtained.

4. The method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 3, characterized in that: In step (1), the organosilicon alkoxide is any one of methyl orthosilicate and ethyl orthosilicate; the organic solvent is any one of methanol, ethanol and acetone or a combination of several thereof; the acidic reaction auxiliary agent is any one of nitric acid, sulfuric acid and acetic acid or a combination of several thereof; the molar ratio of the organosilicon alkoxide, the organic solvent, deionized water and the acidic reaction auxiliary agent is 1:4-7.5:3.8-6.1:0.01-0.045; and the dissolving temperature under water bath stirring is 50°C.

5. The method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 3, characterized in that: The inorganic aluminum salt in step (2) is any one of aluminum nitrate and aluminum chloride; the organic epoxide auxiliary agent is propylene oxide; the complexing agent is any one of sodium alginate, glucose, sodium gluconate, and oxalic acid or a combination thereof; the ratio of the amount of the inorganic aluminum salt, deionized water, organic epoxide auxiliary agent, and complexing agent is 1:25-95:2.2-2.9:1.7-5.4; and the dissolution temperature under water bath stirring is 25°C.

6. The method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 3, characterized in that: In the process of adding the precursor A to the precursor B in step (3), the silicon-aluminum atomic ratio is controlled to be 1:3.5-6.2; the coagulant is any one of ammonia water and ammonium carbonate or a combination of two, and the water bath temperature is 50°C; the mass ratio of the precursor C to deionized water in step (4) is 1:3.6-5.2; the active component-soluble salt is any one of cobalt nitrate, sodium molybdate, potassium molybdate, sodium tungstate, and ammonium metatungstate or a combination of several thereof.

7. The method for preparing an integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas according to claim 3, characterized in that: The precipitant in step (5) is any one or a combination of ammonia water, sodium carbonate, potassium carbonate, and triethylamine; the soluble salt of the active component II in step (6) is any one or a combination of chloroplatinic acid, potassium chloroplatinate, palladium chloride, and palladium nitrate; the water bath temperature is 35° C.; the concentration of the sodium borohydride aqueous solution is 20-120 mg / mL, and the reaction time is 40-120 min; The release agent in step (7) is any one or a combination of graphite, magnesium stearate, and calcium stearate; the pore-forming agent is any one or a combination of carboxymethyl cellulose, sesbania powder, and polyvinyl alcohol; In step (8), the quartz tube is placed in a multi-temperature zone tubular furnace, and argon gas is introduced into the tubular furnace at a flow rate of 350 sccm for 30 minutes at 100°C. The tubular furnace is then adjusted so that the temperature at the inlet of the quartz tube is raised to 180-280°C, and the argon flow rate is reduced to 80 sccm; at the same time, the temperature zone in the middle of the tubular furnace is adjusted so that the middle of the quartz tube is heated from room temperature at a rate of 20°C / min.

8. An integrated hydrogenation conversion catalyst for organic sulfur and organic chlorine in raw gas prepared by the method according to any one of claims 3 to 7, characterized in that: The shape of the obtained catalyst product is a four-leaf clover, a cylinder or a Raschig ring; the radial dimension of the catalyst is 4.0 mm, the axial dimension is 4.0 mm, and the radial strength is ≥80 N / cm.

9. Use of the catalyst according to claim 8 in a hydrogenation conversion reaction of organic sulfur and organic chlorine contained in a raw gas.

10. The use according to claim 9, characterized in that The catalyst is used at a temperature of 125-280°C and a feed gas space velocity of 500-5000 h -1 , the total organic sulfur content in the raw gas is ≤300ppm, the total organic chlorine content is ≤100ppm, and the pressure is 0.5-8MPa.

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