CN1112256C - Application of pre-sulfurization process inside a built-in container - Google Patents
Application of pre-sulfurization process inside a built-in container Download PDFInfo
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- CN1112256C CN1112256C CN 99122905 CN99122905A CN1112256C CN 1112256 C CN1112256 C CN 1112256C CN 99122905 CN99122905 CN 99122905 CN 99122905 A CN99122905 A CN 99122905A CN 1112256 C CN1112256 C CN 1112256C
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- Prior art keywords
- hydrogen
- hydrogenation
- filled
- stabilized
- built
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- 238000000034 method Methods 0.000 title claims abstract description 7
- 238000005987 sulfurization reaction Methods 0.000 title description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000005486 sulfidation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- 230000008676 import Effects 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to the application of a new prevulcanizing technique in a built-in device, which is characterized in that firstly, hydrogenation catalysts are filled to a hydrogenation reactor, and a certain quantity of solid vulcanizing agents are filled to the upper part of the hydrogenation reactor according to the quantity which is 0.5 to 2.0 times more than the theoretical quantity required by the complete vulcanization of the hydrogenation catalysts. Then, nitrogen gas whose content is 99.999% is used as supporting gas to increase temperature to 160 to 180 DEG C, hydrogen gas is filled in the nitrogen gas, an initial hydrogen filling concentration is from 1 to 2%, and the temperature of a catalyst bed is increased to 300 to 350 DEG C at a rate of 30 DEG C/hr. System pressure is controlled to be 0.8 to 1.5MPa, hydrogen gas concentrations at inlets and outlets are stabilized to be 60 to 80%, and the temperature of the catalyst bed is stabilized to be 300 to 350 DEG C. When the concentration of hydrogen sulfide at the outlets is decreased to be 0.2 to 50 ppm, vulcanization processes end.
Description
Technical field
The present invention relates to the application of pre-vulcanization process in the built-in device.
Background technology
The hydrogenation catalyst of industries such as synthetic ammonia, oil refining hydrogen manufacturing adopts MO, CO, Ni, elements such as w to make component mostly, and is dispersed in oxidation state on the carrier of porous.A large amount of development test results show that the catalyst hydrogenation activity of this form is low, and activity stability is poor.Catalyst is handled through presulfurization, promptly made the oxidation state metal be converted into the sulphided state metal under catalyst and hydrogen existence condition, then sulphided state activity of such catalysts and stability all are higher than oxidized catalyst.So the pre-curing technology of hydrogenation catalyst and effect directly have influence on the serviceability of catalyst and the economic benefit of device.Before the presulfurization new process development was used in built-in device, it is long that traditional pre-vulcanization process has the time, big etc. scarce to equipment corrosion and environmental pollution.
It is reported that the technology of at present pre-ruleization mainly contains two kinds, a kind of is sulfuration in the device, and another kind is that device vulcanizes outward.The process of presulfurization is in the device, earlier hydrogenation catalyst is filled on request and is warmed up to a certain degree, then, gas or liquid curing agent is injected in the hydrogenation reactor, realizes the sulfidation of catalyst in hydrogenation reactor.The shortcoming of this technology is the difficult control of sulfidation, and the time is long, at 2-3 days, and vulcanizing agent particularly the liquid curing agent is big to equipment and environmental pollution.The process of the outer presulfurization of device is that elder generation vulcanizes hydrogenation catalyst in special reactor with vulcanizing agent, make the catalyst of sulphided state, then, installs in the hydrogenation reactor on request and comes into operation.The shortcoming of this technology is catalyst spontaneous combustion easily in air of sulphided state, and storage and transportation are very inconvenient.It is investigated newly the present domestic commercial Application identical of still not having with the present invention.
Summary of the invention
The objective of the invention is to shorten the presulfurization time, reduce the pollution of sulfide, shorten the driving cycle of device, for enterprise creates favorable economic benefit equipment and environment.
The present invention is achieved in that and earlier hydrogenation catalyst is filled in the hydrogenation reactor, and get a certain amount of (by the hydrogenation catalyst complete cure in theory needed amount 0.5-2.0 doubly) solid sulfurizing agent be seated in the top of hydrogenation catalyst, then, be warming up to 160-180 ℃ of control system pressure 0.8-1.5MPa with chlorine (99.999%) do carrier gas, in nitrogen, allocate hydrogen into, the initial hydrogen concentration of joining is 1-2%, speed with 5-20%/hr improves density of hydrogen to 60-80%, speed with 30 ℃/hr carries bed temperature to 300 ℃-350 ℃, simultaneously, analysis reactor outlet concentration of hydrogen sulfide, equate when importing and exporting density of hydrogen, reaction bed temperature is stabilized in 300 ℃-350 ℃, and when the outlet concentration of hydrogen sulfide dropped to 0.2-50PPm, sulfidation finished.Close with the lotus root of the sulfuration exothermic reaction of hydrogenation catalyst owing to realized the endothermic reaction that vulcanizing agent generates hydrogen sulfide in a reactor, the beds temperature rise is little, and sulfidation is controlled easily, and the time lacks; And, in reactor, the hydrogen sulfide of generation in time and hydrogenation catalyst react, the reactor outlet concentration of hydrogen sulfide is low, the hydrogen sulfide that has reduced high concentration is to the corrosion of equipment with to the pollution of environment.
Details are as follows for concrete technology: earlier hydrogenation catalyst is filled in the hydrogenation reactor, and get a certain amount of (by the hydrogenation catalyst complete cure in theory needed amount 0.5-2.0 doubly) solid sulfurizing agent be seated in the top of hydrogenation catalyst, with nitrogen (99.999%) system is purged totally (O of displacement
2Content is less than 0.2%), get through the flow process that the hydrogenation catalyst circulation heats up and vulcanizes, start the compressor that goes into operation and set up nitrogen circulation, control system pressure 0.8-1.5Mpa.Then, the heating furnace igniting heats up with the speed of 30 ℃/hr, when being warming up to 160-180 ℃, in nitrogen, allocate hydrogen into, the initial hydrogen concentration of joining is 1-2%, speed with 5-20%/hr improves density of hydrogen to 60-80%, speed with 30 ℃/hr improves bed temperature to 300-350 ℃, simultaneously, analyze once reactor inlet density of hydrogen and outlet concentration of hydrogen sulfide per half an hour, equate when importing and exporting density of hydrogen, reaction bed temperature is stabilized in 300-350 ℃, when the outlet concentration of hydrogen sulfide dropped to 0.2-50PPm, sulfidation finished, and whole sulfidation needs 8-15 hour.Then, heating furnace is flame-out, stops worker's compressor, system decompression, and clean with nitrogen replacement, hydrogenation catalyst just can drop into normal the use.
Good effect of the present invention has been to realize that the reaction that vulcanizing agent generates hydrogen sulfide closes with the lotus root of the vulcanization reaction of hydrogenation catalyst in hydrogenation reactor, small investment, and to equipment and environmental nonpollution, and the activity of hydrocatalyst height after vulcanizing, activity stability is good.
The specific embodiment
Embodiment 1: when the device for producing hydrogen general overhaul, the hydrogenation catalyst of new replacing is carried out presulfurization.1 ton of solid sulfurizing agent and 9 tons of hydrogenation catalysts are divided up and down in the two-layer hydrogenation reactor of packing into, with nitrogen replacement clean after, when being warming up to 180 ℃ do carrier gas with nitrogen, control system pressure 0.8-1.5Mpa allocates 2% hydrogen in nitrogen, speed with 30 ℃/hr rises to 350 ℃, be 75% when importing and exporting density of hydrogen, when the outlet concentration of hydrogen sulfide was 0.2PPm, sulfidation finished.12 hours consuming time of whole sulfidation.After the hydrogenation catalyst of process presulfurization put into operation, bed temperature was stable; Reforming catalyst initial operating stage piebald obviously reduces, and illustrates that presence of unsaturates obviously descends through in the feedstock oil behind the hydrogenation; Before not adopting the interior presulfurization new technology of built-in device to vulcanize, desulfurization reactor outlet sulphur resultant is at 0.4-0.5PPm, after adopting the interior presulfurization new technology of built-in device to vulcanize, desulfurization reactor outlet sulfur content has dropped to 0.2PPm, and the activity of hydrocatalyst height is described.
Claims (2)
1. the application of presulfurization new technology in the built-in device, it is characterized in that earlier hydrogenation catalyst being filled in the hydrogenation reactor, and get by the hydrogenation catalyst complete cure in theory 0.5～2.0 times solid sulfurizing agent of needed amount be seated in the top of hydrogenation reactor, then, be that 99.999% nitrogen is warming up to 160 ℃～180 ℃ do carrier gas with content, in nitrogen, allocate hydrogen into, the initial hydrogen concentration of joining is 1%～2%, reaction bed temperature is warming up to 300 ℃～350 ℃ with the speed of 30 ℃/hr, control system pressure 0.8MPa～1.5MPa, import and export density of hydrogen and be stabilized in 60%～80%, reaction bed temperature is stabilized in 30 ℃～350 ℃, when the outlet concentration of hydrogen sulfide dropped to 0.2PPm～50PPm, sulfidation finished.
2. method according to claim 1 is characterized in that improving density of hydrogen to 60%～70% with the speed of 5%～20%/hr, with the speed of 30 ℃/hr bed temperature is carried to 300 ℃～350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99122905 CN1112256C (en) | 1999-12-15 | 1999-12-15 | Application of pre-sulfurization process inside a built-in container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99122905 CN1112256C (en) | 1999-12-15 | 1999-12-15 | Application of pre-sulfurization process inside a built-in container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1299706A CN1299706A (en) | 2001-06-20 |
| CN1112256C true CN1112256C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99122905 Expired - Fee Related CN1112256C (en) | 1999-12-15 | 1999-12-15 | Application of pre-sulfurization process inside a built-in container |
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| Country | Link |
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| CN (1) | CN1112256C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260319B (en) * | 2008-04-25 | 2011-08-24 | 江苏佳誉信实业有限公司 | Vulcanization method for hydrogenation catalyst |
| CN103551208B (en) * | 2013-11-13 | 2017-12-15 | 天津渤化永利化工股份有限公司 | A kind of vulcanization process of sulfur-resistant transformation catalyst |
| CN106031856B (en) * | 2015-03-19 | 2018-10-09 | 上海宝钢化工有限公司 | In-situ activation method for hydrogenation reactor catalyst after ex-situ vulcanization |
| CN106925356B (en) * | 2015-12-30 | 2020-06-09 | 中国石油天然气股份有限公司 | Pre-sulfurizing method of hydrogenation catalyst |
| CN110694696A (en) * | 2019-09-11 | 2020-01-17 | 河北华丰能源科技发展有限公司 | System and method for vulcanizing heating furnace and drying furnace synchronous hydrogenation catalyst |
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1999
- 1999-12-15 CN CN 99122905 patent/CN1112256C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1299706A (en) | 2001-06-20 |
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Owner name: CHINA PETROLEUM + CHEMICAL CORPORATION Free format text: FORMER OWNER: BALIN BRANCH CORP. SINOPEC Effective date: 20090605 |
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Effective date of registration: 20090605 Address after: Chaoyang District, Chaoyangmen, North Street, No. 22, No. Patentee after: Sinopec Corp. Address before: No. 1 Dongting Road, Yueyang, Hunan Patentee before: Baling Branch, China Petro-Chemical Co., Ltd. |
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Granted publication date: 20030625 Termination date: 20171215 |
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