CN112870964A - Hydrogenation catalyst and application thereof in treating sulfur-containing waste gas - Google Patents
Hydrogenation catalyst and application thereof in treating sulfur-containing waste gas Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 17
- 239000011593 sulfur Substances 0.000 title claims abstract description 17
- 239000002912 waste gas Substances 0.000 title abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20769—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
- B01D2255/504—ZSM 5 zeolites
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a hydrogenation catalyst and application thereof in treating sulfur-containing waste gas, wherein the hydrogenation catalyst comprises a hydrogenation active metal component and an ammonia type molecular sieve loaded with the hydrogenation active metal component; wherein the ammonia-type molecular sieve is obtained by ammonium ion exchange of a molecular sieve and ammonium salt. The hydrogenation catalyst provided by the invention can be used for remarkably improving the desulfurization efficiency in the sulfur-containing waste gas treatment process.
Description
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a hydrogenation catalyst and application thereof in treating sulfur-containing waste gas.
Background
The coke oven gas, the natural gas, the petroleum associated gas, the refinery waste gas and other gases contain a large amount of organic sulfur compounds including carbonyl sulfur, thioether, mercaptan, thiophene and the like, the organic sulfur compounds have toxicity, and can cause harm to the environment and human bodies along with the emission of the gases, and when the gases are continuously used for industrial production, the organic sulfur compounds can cause the inactivation of catalysts used in industrial reactions, and influence the catalytic performance of the catalysts, so that the industrial yield is reduced, for example, when the coke oven gas is used for preparing methanol, the general methanol synthesis catalysts require that the total sulfur content of the coke oven gas is lower than 0.1ppm, and even more advanced methanol synthesis catalysts require that the total sulfur content of the coke oven gas is lower than 0.05ppm, otherwise, the catalysts are inactivated due to poisoning in the coke oven gas with over-standard sulfur content, so that the gases are subjected to desulfurization treatment before being used for industrial production, including the removal of organic sulfur.
Common methods for removing organic sulfur include oxidation, hydroconversion, and hydroconversion, with hydroconversion being the most common. However, the hydrogenation catalyst used in the current industrial device generally has the defects of insufficient hydrogenation activity and desulfurization activity, higher production cost of the catalyst and the like, and the economic benefit is influenced.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a hydrogenation catalyst and application thereof in treating sulfur-containing waste gas, and the hydrogenation catalyst obviously improves the desulfurization efficiency in the sulfur-containing waste gas treatment process.
The invention provides a hydrogenation catalyst, which comprises a hydrogenation active metal component and an ammonia type molecular sieve loaded with the hydrogenation active metal component;
wherein the ammonia-type molecular sieve is obtained by ammonium ion exchange of the molecular sieve and ammonium salt.
Preferably, the hydrogenation-active metal component comprises at least one group VIII metal and at least one group VIB metal.
Preferably, the content of the hydrogenation active component of the VIII group metal in the hydrogenation catalyst is 1-10 wt%, and the content of the hydrogenation active component of the VIB group metal in the hydrogenation catalyst is 1-20 wt% calculated by oxide.
Preferably, the molecular sieve is at least one of a Y-type molecular sieve, a ZSM series molecular sieve or an MCM series molecular sieve.
Preferably, the molecular sieve is a ZSM-5 molecular sieve.
Preferably, the ammonium salt is ammonium nitrate and/or ammonium chloride.
Preferably, the ammonia type molecular sieve is obtained by adding the molecular sieve into an ammonium salt water solution, stirring for reaction, filtering, washing with water, and drying; preferably, the temperature of the stirring reaction is 60-100 ℃ and the time is 1-3 h.
Preferably, the hydrogenation catalyst is obtained by impregnating an ammonia molecular sieve with a metal salt solution corresponding to a hydrogenation active metal component, aging, drying and roasting.
Preferably, the drying temperature is 100-120 ℃, and the drying time is 1-6 h; the roasting temperature is 300-600 ℃, and the roasting time is 2-8 h.
The invention also provides an application of the hydrogenation catalyst in treating sulfur-containing waste gas.
The hydrogenation catalyst selects the ammonia type molecular sieve as a carrier, and the carrier is specifically characterized in that the molecular sieve is added into an ammonium salt solution in advance to realize NH on the surface of the molecular sieve4+Exchange, so that when the obtained ammonia type molecular sieve is impregnated with the metal salt of the hydrogenation active metal component for loading, the active metal component can be directionally exchanged on the ion exchange sites, the uniform distribution of the active metal component is facilitated, and different active metal components and NH are adopted4+The exchange efficiency is different, so the loading sequence and position of the active metal component can be regulated and controlled, and the utilization rate of the active metal component is obviously improved, thereby ensuring that the catalyst can achieve very high hydrogenation catalytic activity and being particularly suitable for deep hydrodesulfurization of sulfur-containing waste gas.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A hydrogenation catalyst comprises hydrogenation active metal components of cobalt and molybdenum and an ammonia type molecular sieve loaded with the hydrogenation active metal components of cobalt and molybdenum, and the preparation method specifically comprises the following steps:
s1, drying 15g of ZSM-5 molecular sieve raw powder at 500 ℃ for 5h, adding the dried powder into 200mL of ammonium nitrate solution (10 wt%), stirring the solution for 2h at 80 ℃, filtering the solution, washing the solution with deionized water, and drying the solution for 15h at 120 ℃ to obtain the ammonia type molecular sieve;
s2, adding the ammonia type molecular sieve into a mixed solution of cobalt nitrate and ammonium molybdate (specifically, 1.1148g of cobalt nitrate hexahydrate and 1.7623g of ammonium heptamolybdate tetrahydrate are dissolved in 20mL of deionized water), stirring uniformly, performing ultrasonic treatment for 0.5h, soaking at room temperature for 5h, drying at 120 ℃ for 3h, then placing in a muffle furnace, and roasting at 500 ℃ for 5h to obtain the hydrogenation catalyst.
Example 2
A hydrogenation catalyst comprises hydrogenation active metal components of nickel and molybdenum and an ammonia type molecular sieve loaded with the hydrogenation active metal components of nickel and molybdenum, and the preparation method specifically comprises the following steps:
s1, drying 15g of ZSM-5 molecular sieve raw powder at 500 ℃ for 5h, adding the dried powder into 200mL of ammonium nitrate solution (10 wt%), stirring the solution for 2h at 80 ℃, filtering the solution, washing the solution with deionized water, and drying the solution for 15h at 120 ℃ to obtain the ammonia type molecular sieve;
s2, adding the ammonia type molecular sieve into a mixed solution of nickel nitrate and ammonium molybdate (specifically, 1.0636g of nickel nitrate hexahydrate and 1.7623g of ammonium heptamolybdate tetrahydrate are dissolved in 20mL of deionized water), stirring uniformly, performing ultrasonic treatment for 0.5h, soaking at room temperature for 5h, drying at 120 ℃ for 3h, then placing in a muffle furnace, and roasting at 500 ℃ for 5h to obtain the hydrogenation catalyst.
Example 3
A hydrogenation catalyst comprises hydrogenation active metal components of nickel and molybdenum and an ammonia type molecular sieve loaded with the hydrogenation active metal components of nickel and molybdenum, and the preparation method specifically comprises the following steps:
s1, drying 15g of ZSM-5 molecular sieve raw powder at 500 ℃ for 5h, adding the dried powder into 200mL of ammonium nitrate solution (10 wt%), stirring the solution for 2h at 80 ℃, filtering the solution, washing the solution with deionized water, and drying the solution for 15h at 120 ℃ to obtain the ammonia type molecular sieve;
s2, adding the ammonia type molecular sieve into a mixed solution of nickel nitrate and ammonium metatungstate (specifically, 1.0636g of nickel nitrate hexahydrate and 2.6213g of ammonium metatungstate hexahydrate are dissolved in 20mL of deionized water), stirring uniformly, performing ultrasonic treatment for 0.5h, dipping for 5h at room temperature, drying for 3h at 120 ℃, then placing in a muffle furnace, and roasting for 5h at 500 ℃ to obtain the hydrogenation catalyst.
Example 4
A hydrogenation catalyst comprises hydrogenation active metal components of nickel and molybdenum and an ammonia type molecular sieve loaded with the hydrogenation active metal components of nickel and molybdenum, and the preparation method specifically comprises the following steps:
s1, drying 15g of ZSM-5 molecular sieve raw powder at 500 ℃ for 5h, adding the dried powder into 200mL of ammonium nitrate solution (10 wt%), stirring the solution for 2h at 80 ℃, filtering the solution, washing the solution with deionized water, and drying the solution for 15h at 120 ℃ to obtain the ammonia type molecular sieve;
s2, adding the ammonia type molecular sieve into a mixed solution of cobalt nitrate and ammonium metatungstate (specifically, 1.1148g of cobalt nitrate hexahydrate and 2.6213g of ammonium metatungstate hexahydrate are dissolved in 20mL of deionized water), stirring uniformly, performing ultrasonic treatment for 0.5h, soaking at room temperature for 5h, drying at 120 ℃ for 3h, then placing in a muffle furnace, and roasting at 500 ℃ for 5h to obtain the hydrogenation catalyst.
Comparative example 1
The preparation method of the hydrogenation catalyst specifically comprises the following steps: drying 15g of ZSM-5 molecular sieve raw powder at 500 ℃ for 5h, adding the dried powder into a mixed solution of cobalt nitrate and ammonium molybdate (specifically, 1.1148g of cobalt nitrate hexahydrate and 1.7623g of ammonium heptamolybdate tetrahydrate are dissolved in 20mL of deionized water), stirring uniformly, performing ultrasonic treatment for 0.5h, soaking at room temperature for 5h, drying at 120 ℃ for 3h, then placing the dried powder into a muffle furnace, and roasting at 500 ℃ for 5h to obtain the hydrogenation catalyst.
The compositions of the catalysts of examples 1-4 and comparative example 1 above were characterized and the results are shown in table 1 below:
TABLE 1 hydrogenation catalyst composition for the examples and comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| CoO(wt％) | 1.6 | 1.5 | 1.6 | ||
| NiO(wt％) | 1.5 | 1.5 | |||
| MoO3(wt％) | 8.6 | 8.6 | 8.6 | ||
| WO3(wt％) | 13.1 | 13.1 |
In order to more clearly illustrate the catalytic performance of the hydrogenation catalyst of the present invention in sulfur-containing exhaust gas treatment, the catalytic activity of the hydrogenation catalysts of examples and comparative examples was evaluated by the following methods: taking olefin mixed gas containing 50 percent (volume fraction) of thiophene as sulfur-containing waste gas, crushing the catalyst into particles with the particle size of 20-40 meshes, and filling 4 milliliters of catalyst into a micro reaction device; before the reaction, pre-sulfurizing with hydrogen mixture gas containing 2 vol% hydrogen sulfide in hydrogen atmosphere under the conditions: the pressure is normal pressure, the prevulcanization temperature is 280 ℃, and the volume space velocity is 1250h-1After the hydrogen sulfide at the inlet and outlet of the reaction device is balanced, the prevulcanization is finished, and the reaction device is switched to sulfur-containing waste gas for reaction under the following reaction conditions: the reaction pressure is normal pressure, the reaction temperature is 300 ℃, and the liquid hourly space velocity is 1250h-1The sulfur content of the gas at the inlet and outlet of the reactor was analyzed by gas chromatography and the thiophene conversion was calculated as shown in table 2 below:
table 2 catalytic evaluation effect of hydrogenation catalysts of examples and comparative examples
| Catalyst and process for preparing same | Conversion of thiophene (%) |
| Example 1 | 88.8 |
| Example 2 | 84.2 |
| Example 3 | 81.9 |
| Example 4 | 87.1 |
| Comparative example 1 | 42.1 |
From the data in the table above, it can be seen that the conversion rate of thiophene in the hydrogenation catalyst of the present invention is effectively improved compared with the hydrogenation catalyst in the comparative example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A hydrogenation catalyst is characterized by comprising a hydrogenation active metal component and an ammonia type molecular sieve loaded with the hydrogenation active metal component;
wherein the ammonia-type molecular sieve is obtained by ammonium ion exchange of the molecular sieve and ammonium salt.
2. The hydrogenation catalyst of claim 1 wherein said hydrogenation-active metal component comprises at least one group VIII metal and at least one group VIB metal.
3. The hydrogenation catalyst according to claim 2, wherein the content of the hydrogenation active component of the group VIII metal in the hydrogenation catalyst is 1-10 wt%, and the content of the hydrogenation active component of the group VIB metal in the hydrogenation catalyst is 1-20 wt%, calculated as oxide.
4. The hydrogenation catalyst according to any one of claims 1 to 3, wherein the molecular sieve is at least one of a Y-type molecular sieve, a ZSM-series molecular sieve or an MCM-series molecular sieve; preferably, the molecular sieve is a ZSM-5 molecular sieve.
5. Hydrogenation catalyst according to any of claims 1-4, characterized in that the ammonium salt is ammonium nitrate and/or ammonium chloride.
6. The hydrogenation catalyst according to any one of claims 1 to 5, wherein the ammonia-type molecular sieve is obtained by adding the molecular sieve into an aqueous solution of ammonium salt, stirring for reaction, filtering, washing with water, and drying; preferably, the temperature of the stirring reaction is 60-100 ℃ and the time is 1-3 h.
7. The hydrogenation catalyst according to any one of claims 1 to 6, wherein the hydrogenation catalyst is obtained by impregnating a metal salt solution corresponding to the hydrogenation active metal component with an ammonia type molecular sieve, followed by aging, drying and calcining.
8. The hydrogenation catalyst as claimed in claim 7, wherein the drying temperature is 100-120 ℃ and the drying time is 1-6 h; the roasting temperature is 300-600 ℃, and the roasting time is 2-8 h.
9. Use of a hydrogenation catalyst according to any one of claims 1 to 8 for the treatment of sulfur-containing exhaust gases.
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