CN115945227A - Activation method of carbonyl sulfide hydrolysis catalyst - Google Patents
Activation method of carbonyl sulfide hydrolysis catalyst Download PDFInfo
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- CN115945227A CN115945227A CN202211716750.XA CN202211716750A CN115945227A CN 115945227 A CN115945227 A CN 115945227A CN 202211716750 A CN202211716750 A CN 202211716750A CN 115945227 A CN115945227 A CN 115945227A
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- catalyst
- alumina
- carbonyl sulfide
- hydrolysis
- sulfide hydrolysis
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 40
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000004913 activation Effects 0.000 title abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an activation method of a carbonyl sulfide hydrolysis catalyst. The method comprises the following steps: (1) Putting carbonyl sulfide hydrolysis catalyst with alumina as carrier into deionized water or hydrogen peroxide solution and stirring; (2) Washing the stirred catalyst with deionized water to obtain a washed catalyst; (3) And drying the washed catalyst at 100-120 ℃ to obtain the activated carbonyl sulfide hydrolysis catalyst. The invention can enrich the surface hydroxyl of the alumina catalyst and greatly improve the activity of the catalyst by simply activating the alumina catalyst. The invention obtains the alumina catalyst with higher surface activity by controlling the temperature of the alumina hydrothermal treatment and the subsequent drying process, and the proper hydrothermal temperature can bring more favorable effect. Compared with other activation methods, the method adopted by the invention has the advantages of simple process and convenient operation, and the hydrolysis performance of the activated catalyst is obviously improved.
Description
Technical Field
The invention relates to an activation method of a carbonyl sulfide hydrolysis catalyst, in particular to a preparation method of a catalyst capable of improving the activity of the catalyst in a low-temperature carbonyl sulfide hydrolysis reaction, and belongs to the technical field of energy conservation and environmental protection.
Background
Carbonyl sulfide (COS) is one of organic sulfides, and widely exists in the process of preparing chemical raw material gas by taking coal, natural gas and petroleum as raw materials. Blast furnace gas is a byproduct combustible gas produced in the steel industry, and organic sulfur mainly comprising COS accounts for 60-80% of the total sulfur. In a conventional dry or wet desulfurization process, H 2 S、SO 2 Inorganic sulfur is easy to remove, but COS has stable chemical properties due to a special structure, and is difficult to effectively remove by using a common desulfurization method. At present, no mature technology and corresponding process equipment for removing carbonyl sulfide in blast furnace gas exist in the steel industry. The industrial removal method of COS mainly comprises hydrolysis conversion, hydrogenation conversion, organic amine solvent absorption and other methods. Wherein, the hydrolysis conversion method has the advantages of low reaction temperature, less side reaction and the like, and is widely applied. The hydrolysis conversion method needs a catalyst to catalyze the hydrolysis reaction to remove the COS, so that the stable and efficient catalyst is the key point for the research of the hydrolysis conversion method.
Alumina is widely used as a catalyst for hydrolyzing COS because of its characteristics of large specific surface area, surface alkalinity, good thermal stability and the like. Since the hydrolysis reaction is a base-catalyzed process, the preparation of conventional alumina-based catalysts generally enhances the surface basicity of the catalyst by supporting certain active components on the surface, such as alkali/alkaline earth metals, transition metals, and the like. Impregnation is a commonly used means for supporting metals, and the catalyst generally needs to be subjected to high-temperature roasting treatment after impregnation. And the high-temperature roasting process can dehydrate the surface of the catalyst, reduce the number of hydroxyl groups on the surface of the catalyst and reduce the number of surface alkaline sites, thereby reducing the hydrolytic activity of the catalyst.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for activating a carbonyl sulfide hydrolysis catalyst.
In order to achieve the above object, the method for activating a carbonyl sulfide hydrolysis catalyst according to the present invention comprises the steps of:
(1) Putting carbonyl sulfide hydrolysis catalyst with alumina as carrier into deionized water or hydrogen peroxide solution and stirring;
(2) Washing the stirred catalyst with deionized water to obtain a washed catalyst;
(3) And drying the washed catalyst at 100-120 ℃ to obtain the activated carbonyl sulfide hydrolysis catalyst.
Further, the carbonyl sulfide hydrolysis catalyst in the step (1) is blank alumina or metal-supported alumina.
Furthermore, the metal-loaded alumina has one or more of lanthanum, titanium, copper, nickel and cobalt as the loaded metal, and the metal loading is 0.5-5 wt%.
Further, the concentration of the hydrogen peroxide solution is 3-30 wt%.
Further, the stirring is performed for 1 to 2 hours at a temperature of between 30 and 80 ℃.
Further, the drying time is 3-4 hours.
Further, the cleaning is multiple cleaning.
The method can enrich the surface hydroxyl of the alumina catalyst and greatly improve the activity of the catalyst by simply activating the alumina catalyst. The invention obtains the alumina catalyst with higher surface activity by controlling the temperature of the alumina hydrothermal treatment and the subsequent drying process, and the proper hydrothermal temperature brings more favorable effect. Compared with other activation methods, the method provided by the invention has the advantages of simple process and convenience in operation, and the hydrolysis performance of the activated catalyst is obviously improved. The alumina catalyst prepared by the method has important significance for reducing the activation cost of the alumina catalyst and optimizing the carbonyl sulfide removal process of blast furnace gas.
Drawings
FIG. 1 is a schematic diagram showing the hydrolytic activity of the catalyst prepared in comparative example 1 of the present invention
FIG. 2 is a schematic view of the hydrolytic activity of the catalyst prepared in example 1 of the present invention
FIG. 3 is a schematic view showing the hydrolytic activity of the catalyst prepared in comparative example 2 of the present invention
FIG. 4 is a schematic diagram showing the hydrolytic activity of the catalyst prepared in example 2 of the present invention
FIG. 5 is a schematic diagram showing the hydrolytic activity of the catalyst prepared in comparative example 3 of the present invention
FIG. 6 is a schematic view of the hydrolytic activity of the catalyst prepared in example 3 of the present invention
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The catalysts used in the examples described below were either bare alumina or alumina-based carbonyl sulfide hydrolysis catalysts prepared by impregnation.
The blank alumina catalyst is calcined only in a muffle furnace in air atmosphere, and the calcination temperature is 350 ℃.
The preparation process of the alumina-based catalyst prepared by the impregnation method comprises the following steps:
(1) Adding the weighed absolute ethyl alcohol into a wide-mouth bottle, placing the wide-mouth bottle on a magnetic stirrer, adding the weighed metal salt under stirring, and stirring for 30min to obtain a solution A, wherein the speed of the magnetic stirrer is 360r/min.
(2) The solution A was dropped on an alumina catalyst, and the obtained sample was transferred to an oven at 50 ℃ for evaporation treatment for 6 hours.
(3) And (3) placing the sample obtained in the step (2) into a muffle furnace, and roasting for 3h at 350 ℃ in an air atmosphere to obtain the impregnated carbonyl sulfide hydrolysis catalyst.
Comparative example 1
5mL of the calcined blank alumina catalyst is loaded into a quartz tube fixed bed reactor with the inner diameter of 10mm, and the volume space velocity is 4000h -1 The COS hydrolysis performance test was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in FIG. 1, and the hydrolysis conversion rate is seen to be at 300minReduce to about 70%.
Comparative example 2
Taking 5mL of alumina catalyst loaded with metal lanthanum, loading the alumina catalyst into a quartz tube fixed bed reactor with the inner diameter of 10mm, and controlling the volume space velocity at 4000h -1 The COS hydrolysis performance test was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in figure 3, and the hydrolysis conversion rate is stabilized at about 78% after 500 min.
Comparative example 3
Taking 5mL of aluminum oxide catalyst loaded with metal copper, loading the aluminum oxide catalyst into a quartz tube fixed bed reactor with the inner diameter of 10mm, and controlling the volume space velocity at 4000h -1 The COS hydrolysis performance test was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in figure 5, the catalyst activity is reduced rapidly, and the hydrolysis conversion rate is reduced to about 20 percent in about 150 min.
Example 1
The blank alumina catalyst after roasting is put into deionized water, stirred for 1 to 2 hours at the temperature of between 50 and 70 ℃, washed by the deionized water and then dried for 3 to 4 hours at the temperature of between 100 and 120 ℃. Then 5mL of catalyst is taken and loaded into a quartz tube fixed bed reactor with the inner diameter of 10mm, and the volume space velocity is 4000h -1 The COS hydrolysis performance test was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in figure 2, and compared with comparative example 1, the hydrolysis conversion rate is obviously improved.
Example 2
The aluminum oxide catalyst loaded with metal lanthanum is placed in deionized water, stirred for 1 to 2 hours at the temperature of between 50 and 70 ℃, washed by the deionized water and then dried for 3 to 4 hours at the temperature of between 100 and 120 ℃. Then 5mL of catalyst is taken and loaded into a quartz tube fixed bed reactor with the inner diameter of 10mm, and the volume space velocity is 4000h -1 The hydrolysis performance test of COS was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in figure 4, compared with the comparative example 2, the hydrolysis conversion rate is also obviously improved, and the hydrolysis conversion rate is more than 98 percent after 500 min.
Example 3
The aluminum oxide catalyst loaded with the metallic copper is placed in deionized water, stirred for 1 to 2 hours at the temperature of between 50 and 70 ℃, washed by the deionized water and then dried for 3 to 4 hours at the temperature of between 100 and 120 ℃. Then 5mL of catalyst is taken and loaded into a quartz tube fixed bed reactor with the inner diameter of 10mm, and the volume space velocity is 4000h -1 The COS hydrolysis performance test was carried out under the conditions of a reaction pressure of 0.1MPa, a reaction temperature of 80 ℃ and a COS content of 300 ppm. The activity is shown in fig. 6, and compared with the comparative example 2, the catalyst is still in a deactivated state, but the deactivation time is obviously shifted backwards, and the hydrolysis conversion rate of the catalyst is rapidly reduced after 200 min.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
The present invention has been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Many other changes and modifications may be made without departing from the spirit and scope of the invention and should be considered as within the scope of the invention.
The particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A method for activating a carbonyl sulfide hydrolysis catalyst is characterized by comprising the following steps:
(1) Putting carbonyl sulfide hydrolysis catalyst with alumina as carrier into deionized water or hydrogen peroxide solution and stirring;
(2) Washing the catalyst which participates in stirring with deionized water to obtain a washed catalyst;
(3) And drying the washed catalyst at 100-120 ℃ to obtain the activated carbonyl sulfide hydrolysis catalyst.
2. The method of claim 1, wherein the carbonyl sulfide hydrolysis catalyst in step (1) is a bare alumina or a metal-supported alumina.
3. The method for activating carbonyl sulfide hydrolysis catalyst according to claim 1 or 2, wherein the metal-loaded alumina has one or more of lanthanum, titanium, copper, nickel and cobalt, and the metal loading is 0.5-5 wt%.
4. The method of claim 1, wherein the hydrogen peroxide solution has a concentration of 3 to 30wt%.
5. The method of claim 1, wherein the stirring is performed at 30 to 80 ℃ for 1 to 2 hours.
6. The method of claim 1, wherein the drying time is 3 to 4 hours.
7. The method of claim 1, wherein the washing is a plurality of times.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143959A (en) * | 2004-11-24 | 2006-06-08 | Matsushita Electric Works Ltd | Desulfurization equipment and regeneration method of alumina catalyst |
| CN101961654A (en) * | 2010-09-15 | 2011-02-02 | 昆明理工大学 | Method for regenerating carbonyl sulfide hydrolysis catalyst after inactivation |
| CN102921477A (en) * | 2012-10-18 | 2013-02-13 | 昆明理工大学 | Method for regenerating inactivated carbonyl sulfide hydrolysis catalyst |
| US20160136636A1 (en) * | 2013-12-27 | 2016-05-19 | Mitsubishi Heavy Industries, Ltd. | Method for regenerating cos hydrolysis catalyst |
| CN107791274A (en) * | 2017-08-29 | 2018-03-13 | 宁波华源精特金属制品有限公司 | A kind of Robot wrist and preparation method thereof |
| CN108906098A (en) * | 2018-05-29 | 2018-11-30 | 东北石油大学 | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst |
| CN112206835A (en) * | 2020-09-18 | 2021-01-12 | 中国石化扬子石油化工有限公司 | Regeneration method of carbonyl sulfide hydrolysis catalyst |
| CN114146699A (en) * | 2020-08-17 | 2022-03-08 | 中国石油天然气股份有限公司 | Catalyst for organic sulfur hydrolysis and preparation method thereof |
-
2022
- 2022-12-28 CN CN202211716750.XA patent/CN115945227A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143959A (en) * | 2004-11-24 | 2006-06-08 | Matsushita Electric Works Ltd | Desulfurization equipment and regeneration method of alumina catalyst |
| CN101961654A (en) * | 2010-09-15 | 2011-02-02 | 昆明理工大学 | Method for regenerating carbonyl sulfide hydrolysis catalyst after inactivation |
| CN102921477A (en) * | 2012-10-18 | 2013-02-13 | 昆明理工大学 | Method for regenerating inactivated carbonyl sulfide hydrolysis catalyst |
| US20160136636A1 (en) * | 2013-12-27 | 2016-05-19 | Mitsubishi Heavy Industries, Ltd. | Method for regenerating cos hydrolysis catalyst |
| CN107791274A (en) * | 2017-08-29 | 2018-03-13 | 宁波华源精特金属制品有限公司 | A kind of Robot wrist and preparation method thereof |
| CN108906098A (en) * | 2018-05-29 | 2018-11-30 | 东北石油大学 | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst |
| CN114146699A (en) * | 2020-08-17 | 2022-03-08 | 中国石油天然气股份有限公司 | Catalyst for organic sulfur hydrolysis and preparation method thereof |
| CN112206835A (en) * | 2020-09-18 | 2021-01-12 | 中国石化扬子石油化工有限公司 | Regeneration method of carbonyl sulfide hydrolysis catalyst |
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