CN100469449C - Pretreating method for sulfur-resistant transforming catalyst and pretreating agent - Google Patents
Pretreating method for sulfur-resistant transforming catalyst and pretreating agent Download PDFInfo
- Publication number
- CN100469449C CN100469449C CNB031391583A CN03139158A CN100469449C CN 100469449 C CN100469449 C CN 100469449C CN B031391583 A CNB031391583 A CN B031391583A CN 03139158 A CN03139158 A CN 03139158A CN 100469449 C CN100469449 C CN 100469449C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preprocess method
- agent
- sulfur
- vulcanizing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
A process for pretreating the sulfur-resistant catalyst for the conversion of Co includs such steps as contacting it with the pretreating agent containing sulfurizing agent and the solvent able to dissolve said sulfurizing agent, passivating in H2 contained gas, inertial gas or steam, and sulfurizing. It has less damage to people and low pollution to environment.
Description
Technical field
The present invention relates generally to the outer at the scene use vulcanizing agent of sulfur-resistant CO conversion catalyst and carries out a kind of method of presulfurization and the pretreating agent of use.
Background technology
The preprocess method of traditional sulfur-resistant transformation catalyst is a preprocess method in the device.Be about to the burning attitude sulfur-resistant transformation catalyst reactor of packing into, at high temperature feed unstripped gas and vulcanizing agents such as hydrogen sulfide or carbon disulfide simultaneously, make metal active constituent become the metal sulphided state by oxidation state.Patent 90102615.8 has been described the interior vulcanization process of device of cobalt-molybdenum sulfur-resistant CO low change catalyzer.The shortcoming of preprocess method is that sulfuration cost height, cure time are long in the device, has used inflammable poisonous vulcanizing agent, and environment and operating personnel are caused very big injury.And vulcanization reaction is strong exothermal reaction, easily makes the catalyst overtemperature, damage activity of such catalysts, even whole furnace catalyst is scrapped.
The outer pre-curing technology of device was meant before catalyst is packed reactor into, a kind of method that sulfur-resistant transformation catalyst is contacted with vulcanizing agent, the outer pre-curing technology of 93111223.0 pairs of devices of patent possesses some special knowledge, utilize inorganic sulphide but not organic sulfur compound processing sulfur-resistant transformation catalyst, the sulfur-resistant transformation catalyst initial activity height that the method that this patent provides obtains, but the life-span is shorter, and promoting the use of of it is restricted.
Domestic and external a part of patent is described a lot to the outer pre-curing technology of the device of hydrogenation catalyst, as US5,215,954, CN85107953A, 93104406.5,97101805.7 etc. patent disclosure the outer preprocess method of device of hydrogenation catalyst or hydrocarbon processing catalysts, hydrogenation catalyst contains the metal component identical with the sulfur-resistant CO conversion catalyst part with hydrocarbon processing catalysts, as cobalt, molybdenum, tungsten, metal active constituents such as nickel, but in sulfur-resistant CO conversion catalyst, also contain and hydrogenation catalyst, the metal component that hydrocarbon processing catalysts is different, as alkali metal potassium, sodium, alkaline-earth metal magnesium, and Titanium, zinc etc., these metal components exist with different crystalline structures in the sulfur-resistant transformation catalyst carrier, affect cobalt, the sulfuration of metal active constituents such as molybdenum, for example alkali-metal interpolation can reduce the light-off temperature of the transformation catalyst of sulfur-resistant CO, make the content height of pentavalent molybdenum, the active component content height, but hinder cobalt, molybdenum changes sulphided state into by oxidation state, simultaneously, because the strong basicity of alkaline components, make anti-sulphur change catalyst and very easily contact sulfation behind the oxygen and inactivation.Though therefore hydrogenation catalyst, hydrocarbon processing catalysts have the identical metal component of part with sulfur-resistant transformation catalyst, belong to diverse catalyst.
This difference, show the incoherent separately field of catalyst simultaneously, hydrogenation catalyst and hydrocarbon processing catalysts are applied in the refining aspect of hydrofinishing and petroleum hydrocarbon, the petroleum component that is liquid phase contacts with catalyst, and sulfur-resistant CO conversion catalyst is the catalyst that nitrogen fertilizer industry is used, and raw material is semiwater gas (nitrogen 22-26%, carbon monoxide 28-32%, surplus is hydrogen), in reactor, the semiwater gas of gas phase contacts with catalyst and carbon monodixe conversion takes place and reacts.Therefore, hydrogenation catalyst, hydrocarbon processing catalysts are different catalyst with sulfur-resistant CO conversion catalyst, can not be applied to sulfur-resistant transformation catalyst simply to the outer pre-curing technology of the device of hydrogenation catalyst, hydrocarbon processing catalysts.
Summary of the invention
Technical problem to be solved by this invention provides a kind of outer at the scene preprocess method of sulfur-resistant transformation catalyst, and employed pretreating agent.Pretreated catalyst can directly heat up and incorporate system into or vulcanize according to conventional method.
The preprocess method of sulfur-resistant transformation catalyst of the present invention, it is characterized in that contacting with pretreating agent outside sulfur-resistant transformation catalyst at the scene, make vulcanizing agent in the pretreating agent enter into the hole of catalyst, vulcanizing agent in the described pretreating agent comprises elemental sulfur and organosulfur compound, the weight content of elemental sulfur is 0～80% of a vulcanizing agent total amount, and the solvent in the pretreating agent is for dissolving the organic solvent of vulcanizing agent.
The present invention has changed sulfur-resistant transformation catalyst and has generally adopted situation and the applicant's the patent 93111223.0 employing inorganic sulphide agent and the defective of vulcanizing in the device of inorganic solvent, adopt the form that is mixed of organic sulfur compound or elemental sulfur and organic sulfur compound under the effect of organic solvent, to be easy to infiltrate through in the catalyst pores, improve the shift activity of carbon monoxide, light-off temperature is low, when the reactor of packing into heats up, thermal discharge is little, long service life.
Sulfur-resistant transformation catalyst is with after pretreating agent contacts, and is preferably in hydrogeneous and/or inert gas or steam carry out passivation under existing.The operating condition of passivation is chosen as: be higher than under 100 ℃ the condition, general preferably be higher than 140 ℃ and be lower than under 400 ℃ that heatable catalyst carries out passivation more than 5 minutes in the presence of hydrogeneous and/or inert gas or steam, gas pressure hydrogeneous and/or inert gas or steam is 0.005-1.2Mpa; Passivation time is 0.1-10 hour, preferred 0.3-6 hour; When passivation gas was hydrogeneous, hydrogen content accounted for more than 2% of total gas volume at least, and is preferred more than 4%.Can be directly used in device after the catalyst structure drives.
In the presence of above-mentioned hydrogeneous and/or inert gas or steam, operating condition is chosen in to be higher than under 100 ℃ of temperature carries out, ad hoc proposal of the present invention adopts this measure, particularly when catalyst with after vulcanizing agent and the selected liquid that contains petroleum solvent or other solvents contact, heat treatment gained catalyst removes and desolvates then, and impels some the component generation combination reaction in sulphur and the organic solvent.Catalytic bed can adopt various catalyst beds, as fixed bed, revolving bed, thermopnore, expanded bed, fluid bed etc., all particles of the catalyst in the bed is all vulcanized under identical conditions, makes sulfuration more complete, and is more even.If contain elemental sulfur in the pretreating agent, then partially or completely be combined to polysulfide.Catalyst after handling is in these cases reduced to normal temperature naturally in air-flow, to prevent the metallic compound transition of sulphided state.
Described organosulfur compound is selected from organic polysulfide, mercaptan, carbon disulfide, sulfone, sulfoxide, thiophenyl compound or other any materials that in hydrogen, can decompose main generation hydrogen sulfide, preferred DMDS, dimethyl disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, a tetraethylthiuram sulfide, 2-benzothiazolyl mercaptan, one or more in sulfone, dimethyl sulfoxide (DMSO), dibenzothiazyl disulfide and mercaptan, the Thiourea organosulfur compound.When vulcanizing agent only adopted organic sulfur compound, preferred scheme was to choose wherein at least two kinds of organosulfur compounds, is more preferably at least three kinds.Adopt organic sulfur compound can reduce the cost of pretreating agent.Vulcanizing agent also can only adopt elemental sulfur, but the present invention does not advocate.
Organic solvent in the described pretreating agent can be a petroleum hydrocarbon, mixture as alkane or alkene or alkane and alkene, be exemplified as: gasoline, drippolene, diesel oil, naphtha, petroleum solvent, also can be the oil and the similar compounds of saturated or unsaturated fatty acid derived, have for example: organic compound of vegetable oil, oleic acid, nitrogenous and sulfur-bearing etc., or petroleum hydrocarbon therewith compounds mixed solvent.Should, to catalyst have no adverse effects can flood vulcanizing agent organic solvent all can, preferably select boiling point at 130～250 ℃ organic solvent.
Vulcanizing agent in the pretreating agent is introduced in the organic solvent, under temperature 60-135 ℃ between carries out usually, and heat more than 0.1 hour.Under this temperature, vulcanizing agent and organic solvent can be miscible or the unmixing state exist, and corresponding chemical reaction takes place in sulphur in the vulcanizing agent and organic solvent, form and sulfur-resistant transformation catalyst with liquid come in contact, make vulcanizing agent under the effect of organic solvent, at least a portion hole in the catalyst be full of, and with catalyst in metal component reaction, make metal oxide become metal sulfide or metal oxysulfide, i.e. the transition compound of metal sulfide.The metal active constituent of sulfur-resistant transformation catalyst contains in the IIB-VIB family of the periodic table of elements and the group VIII at least a metal and/or alkali metal, alkali earth metal, the most frequently used is metal components such as molybdenum, cobalt, tungsten, nickel, best composition content is cobalt oxide 0.2～4%, molybdenum oxide 1～10% (by weight), and the oxide content of alkali metal such as potassium oxide, alkaline-earth metal is 1～20%.Metal oxide is separately converted to Co in the catalyst
9S
8, MoS
2, WS
2, Ni
3S
2Deng, calculate the sulfur content of adding in the catalyst, the sulfur content of interpolation accounts for its theoretical 5-200% that calculates sulfur content, preferred 20-150%.
The mass ratio that is mixed of described vulcanizing agent and organic solvent is 1:1～1:50, preferred 1:1.5～1:20.
When catalyst was carried out preliminary treatment, described pretreating agent was 100～300 ℃ with the temperature that contacts of catalyst, preferred 110～200 ℃; Be 0.1～10 hour time of contact, preferred 0.5-6 hour.The 10-100% of catalyst, preferred 30～100% hole is full of vulcanizing agent by the osmosis of organic solvent on catalyst.
Compare with pre-curing technology in the device of present use, sulfur-resistant transformation catalyst provided by the invention and preprocess method have the following advantages:
(1) presulfurization of catalyst is outside the venue, and is simple to operate, makes the vulcanization reaction of catalyst more easy to control, thereby makes catalyst may reach higher shift activity.
(2) use method provided by the invention to handle catalyst, when the reactor of packing into heated up, thermal discharge was little, is not prone to overtemperature and burns catalyst.
(3) do not use hypertoxic sulfide such as traditional hydrogen sulfide, carbon disulfide, reduced people's the injury and the pollution of environment.
(4) presulfiding of catalyst process has significantly reduced the time of driving outside the venue, has also reduced the consumption of coal gas, electric power and vulcanizing agent simultaneously.Can directly heat up and incorporate system into, reach sulfuration level in the device, also can in device, vulcanize again according to a conventional method, reach higher activity.
(5) because sulfuration is complete, catalyst activity is better than sulfuration in the device, and light-off temperature reduces.
(6) catalyst can use at any time, and storge quality is good.
(7) catalyst long service life.
The specific embodiment
Following examples 1,2 explanation the present invention compare with pre-curing technology in the traditional device, the carbon monodixe conversion of the outer pre-curing technology of device active with device in the comparison of pre-sulfide catalyst carbon monodixe conversion activity.
Embodiment 1
Sulfur-resistant CO conversion catalyst, wherein carrier is γ-Al
2O
3, granularity is Φ 3-5mm, specific surface m
2/ g:210.8, pore volume ml/g:0.426, cobalt oxide (CoO, butt) is 1.2%, molybdenum trioxide (MoO
3, butt) and be 7.5%, potassium oxide (K
2O, 8.6%) carries out as catalyst A that sulfuration compares in the device.Evaluation method is according to " co surfer-resistant shift catalyst test method " chemical industry standard, and standard is numbered HG/T2780-1996.
Take by weighing catalyst A 300 grams, the vulcanizing agent of forming with elemental sulfur (12g), naphtha (130ml) is heated to 110 ℃, impregnated catalyst 40 minutes; Be divided into two parts, portion was handled 20 minutes under the steam of 160 ℃ (pressure is approximately 0.8Mpa), was catalyst B, and another part is 160
Under the temperature, contain in the nitrogen of 6% hydrogen and handled 20 minutes, be catalyst C.The former granularity activity of evaluate catalysts.The same catalyst A of the evaluation method of catalyst B, C is designated as B1, C1.Catalyst B, C pack into and do not vulcanize after the reactor, heat up after a period of stabilisation, directly estimate activity, are designated as B2, C2.
Embodiment 2
Above-mentioned catalyst 300 grams, vulcanizing agent tetraethylthiuram disulfide (25.7g), dimethyl disulfide (5.7g), pyrolysis gas oil (100ml), oleic acid (30ml) is dissolved in vulcanizing agent pyrolysis gas oil and contacts 15 minutes with catalyst A, obtains catalyst D; Is passivation under 0.01Mpa, 400 ℃ of nitrogen of temperature with part catalyst D at pressure, obtains catalyst E.Evaluation result and phenomenon are as follows:
| The catalyst title | Phenomenon | Appreciation condition | 200 ℃ of CO shift activity % |
| A | The pink colour bead | HG/T2780-1996 | 16.32% |
| B1 | Black | HG/T2780-1996 | 30.02% |
| B2 | Black | Do not vulcanize. | 16.58% |
| C1 | Greyish black | HG/T2780-1996 | 26.57% |
| C2 | Greyish black | Do not vulcanize. | 14.67% |
| D | Black | HG/T2780-1996 | 32.69% |
| E | Black | Do not vulcanize. | 16.77％ |
Above comparative example can find out that the outer presulfurization of device has reached the effect of presulfurization in the device, and after the outer presulfurization of device, the reactor of packing into directly heats up with going into unstripped gas, can obtain very high carbon monodixe conversion activity.
Embodiment 3
Sulfur-resistant CO conversion catalyst, wherein carrier is γ-Al
2O
3, granularity is Φ 4-6mm, specific surface m
2/ g:260, pore volume ml/g: 〉=0.4, nickel oxide (NiO, butt) is 1.8%, molybdenum trioxide (MoO
3, butt) and be 6.8%, titanium dioxide (TiO
2, butt) and be 1.8%, as catalyst F.
Above-mentioned catalyst F 800 grams use elemental sulfur (14.6g), dimethyl disulfide (10.7g), tetraethylthiuram disulfide (17g), the pretreating agent that rapeseed oil (350ml) is formed is heated to 130 ℃, impregnated catalyst B30 minute, handles 4 hours under 160 ℃ of steam conditions.Make catalyst G1.
Embodiment 4
The pretreating agent of forming according to embodiment 3 is heated to 180 ℃, and impregnated catalyst 30 minutes was handled 4 hours under 160 ℃ of steam conditions.Make catalyst G2.
Embodiment 5
The pretreating agent of forming according to embodiment 3 is heated to 130 ℃, and impregnated catalyst 4 hours was handled 4 hours under 160 ℃ of steam conditions.Make catalyst G3.
Embodiment 6
The pretreating agent of forming according to embodiment 3 is heated to 130 ℃, and impregnated catalyst 4 hours was handled 4 hours under 160 ℃, 0.01Mpa condition of nitrogen gas.Make catalyst G4.
Embodiment 7
Above-mentioned catalyst F 800 grams use the identical pretreating agent of embodiment 3, are heated to 130 ℃, and impregnated catalyst B6 hour is 20%, 99.7% at hydrogen respectively, and all the other are under the condition of nitrogen, and passivation is 6 hours when pressure 0.01Mpa.Make catalyst G5, G6.
Embodiment 8
Above-mentioned catalyst F 800 grams use benzothiazole disulfide (37g), dimethyl disulfide (10.7g), tetraethylthiuram disulfide (17g), the pretreating agent that pyrolysis gas oil (250ml), naphtha (100ml) are formed is heated to 190 ℃, and impregnated catalyst B10 minute, in temperature 500
The time, passivation is 4 hours under the 0.05Mpa nitrogen atmosphere.Make catalyst H.
Embodiment 9
Above-mentioned catalyst F800 gram, use benzothiazole disulfide (14.8g), dimethyl disulfide (3.5g), tetraethylthiuram disulfide (4g), the pretreating agent that one tetraethylthiuram sulfide (7g), lauryl mercaptan (12.8g), soybean fat acid esters (50ml), 200# solvent naphtha (300ml) are formed is heated to 200 ℃, impregnated catalyst B10 minute, passivation was 6 hours under 500 ℃ of temperature, pressure 0.01Mpa nitrogen atmosphere.Make catalyst I.
Embodiment 10
Above-mentioned catalyst F800 gram, use the identical pretreating agent of embodiment 3, reduce the pretreating agent consumption, benzothiazole disulfide (11g), dimethyl disulfide (8.1g), dimethyl sulfoxide (DMSO) (10.8g), the pretreating agent that a tetraethylthiuram sulfide (7g), lauryl mercaptan (12.4g), drippolene (400ml), soybean fat acid esters (50ml) are formed is heated to 130 ℃, impregnated catalyst B4 hour, in 500 ℃ of temperature, passivation 6 hours under pressure 0.01Mpa nitrogen atmosphere.Make catalyst J.
Embodiment 11
Above-mentioned catalyst F800 gram, use elemental sulfur (7.4g), lauryl mercaptan (29.1g), tetraethylthiuram disulfide (190.5g), naphtha (200ml), the pretreating agent that drippolene (200ml) soybean fat acid esters (30ml) is formed is heated to 110 ℃, impregnated catalyst B6 hour, handles 12 minutes under 160 ℃ of steam atmospheres.Make catalyst K.
Embodiment 12
Above-mentioned catalyst F800 gram, use DMDS (4.6g), thiocarbamide (23g), dimethyl sulfoxide (DMSO) (18.3g), the pretreating agent that drippolene (200ml), n-butylamine (200ml), oleic acid (30ml) are formed is heated to 110 ℃, impregnated catalyst B6 hour, under 160 ℃ of steam atmospheres, handled 12 minutes.Make catalyst L.
Embodiment 13
Above-mentioned catalyst F800 gram uses elemental sulfur (33.8g), dimethyl disulfide (7g), tetraethylthiuram disulfide (1.5g), the pretreating agent that rapeseed oil (350ml) is formed is heated to 130 ℃, impregnated catalyst B30 minute, handles 4 hours under 160 ℃ of steam conditions.Make catalyst M.
Claims (12)
1, a kind of preprocess method of sulfur-resistant transformation catalyst, it is characterized in that contacting with pretreating agent outside sulfur-resistant transformation catalyst at the scene, make vulcanizing agent in the pretreating agent enter into the hole of catalyst, vulcanizing agent in the described pretreating agent comprises elemental sulfur and organosulfur compound, the weight content of elemental sulfur is 0～80% of a vulcanizing agent total amount, solvent in the pretreating agent is for dissolving the organic solvent of vulcanizing agent, and the organosulfur compound in the vulcanizing agent is selected from tetramethylthiuram disulfide, tetraethylthiuram disulfide, one tetraethylthiuram sulfide, the 2-benzothiazolyl mercaptan, sulfone, dimethyl sulfoxide (DMSO), in dibenzothiazyl disulfide and the thiocarbamide one or more.
2, preprocess method according to claim 1 after it is characterized in that described sulfur-resistant transformation catalyst and pretreating agent contacting, carries out passivation in the presence of hydrogeneous and/or inert gas or steam.
3, preprocess method according to claim 1 is characterized in that vulcanizing agent is at least two kinds of organosulfur compounds.
4, preprocess method according to claim 1, it is characterized in that the organic solvent in the described pretreating agent is the oil of petroleum hydrocarbon, saturated or unsaturated fatty acid derived or their mixed solvent, described petroleum hydrocarbon is selected from the mixture of alkane or alkene or alkane and alkene.
5, preprocess method according to claim 4 is characterized in that described organic solvent is selected from drippolene, diesel oil, naphtha, petroleum solvent, vegetable oil, oleic acid.
6, preprocess method according to claim 1, the mass ratio that it is characterized in that described vulcanizing agent and organic solvent is 1:1～1:50.
7, preprocess method according to claim 6, the mass ratio that it is characterized in that described vulcanizing agent and organic solvent is 1:1.5～1:20.
8, preprocess method according to claim 1 is characterized in that the 10-100% hole of described catalyst is full of vulcanizing agent by the osmosis of organic solvent on catalyst.
9, preprocess method according to claim 1 is characterized in that described pretreating agent is 100～300 ℃ with the temperature that contacts of catalyst, and be 0.1～10 hour time of contact.
10, preprocess method according to claim 9 is characterized in that described pretreating agent is 110～200 ℃ with the temperature that contacts of catalyst.
11, preprocess method according to claim 2, the gas pressure that it is characterized in that catalyst deactivation is 0.005-1.2Mpa, the time is 0.1-10 hour.
12, preprocess method according to claim 2, when it is characterized in that passivation gas is hydrogeneous, hydrogen content accounts for more than 2% of total gas volume at least.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391583A CN100469449C (en) | 2003-08-22 | 2003-08-22 | Pretreating method for sulfur-resistant transforming catalyst and pretreating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391583A CN100469449C (en) | 2003-08-22 | 2003-08-22 | Pretreating method for sulfur-resistant transforming catalyst and pretreating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583272A CN1583272A (en) | 2005-02-23 |
| CN100469449C true CN100469449C (en) | 2009-03-18 |
Family
ID=34597244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031391583A Expired - Fee Related CN100469449C (en) | 2003-08-22 | 2003-08-22 | Pretreating method for sulfur-resistant transforming catalyst and pretreating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100469449C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417246B (en) * | 2007-10-26 | 2012-09-05 | 中国石油化工股份有限公司 | Processing method before using hydrogenation catalyst |
| CN103100395B (en) * | 2011-11-09 | 2016-01-20 | 中国石油化工股份有限公司 | The preparation method of sulfide type catalyst |
| CN103100445B (en) * | 2011-11-09 | 2015-09-30 | 中国石油化工股份有限公司 | The preparation method of presulfurization catalyst |
| FR3048965B1 (en) * | 2016-03-17 | 2023-06-09 | Arkema France | PROCESS FOR THE PRODUCTION OF SYNTHESIS GAS ENRICHED WITH HYDROGEN |
| FR3048964B1 (en) * | 2016-03-17 | 2023-06-09 | Arkema France | PROCESS FOR THE PRODUCTION OF SYNTHESIS GAS ENRICHED WITH HYDROGEN |
| CN107469873B (en) * | 2016-06-07 | 2020-07-10 | 中国石油化工股份有限公司 | Process and apparatus for treating presulfurized sulfur-resistant shift catalyst |
| CN106179524B (en) * | 2016-07-08 | 2018-02-13 | 昌邑凯特新材料有限公司 | A kind of method for pre-sulphuration of CO sulfur-resistant transformation catalysts |
| CN106955747A (en) * | 2017-03-24 | 2017-07-18 | 洛阳华张石化材料有限公司 | A kind of high sulfur-bearing environment-friendly type catalytic hydrogenation presulfurization agent |
| CN109387596B (en) * | 2017-08-02 | 2022-04-08 | 中国石油化工股份有限公司 | Small-sized evaluation device for sulfur-tolerant shift catalyst and method of using the same |
| CN111298811B (en) * | 2018-12-11 | 2023-02-28 | 中国石油天然气股份有限公司 | Environment-friendly pre-vulcanization reforming pre-hydrogenation catalyst and preparation method and application thereof |
-
2003
- 2003-08-22 CN CNB031391583A patent/CN100469449C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 耐硫变换催化剂硫化技术探讨. 高建国等.大氮肥，第25卷第4期. 2002 |
| 耐硫变换催化剂硫化技术探讨. 高建国等.大氮肥，第25卷第4期. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1583272A (en) | 2005-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100377056B1 (en) | Out-of-Site Preliminary Treatment of Hydrocarbon Treatment Catalyst | |
| US8431018B2 (en) | Carbon supported catalyst for demetallation of heavy crude oil and residue | |
| CN104646010B (en) | A kind of process modification method of sulfurized hydrogenation catalyst for refining | |
| CN100469449C (en) | Pretreating method for sulfur-resistant transforming catalyst and pretreating agent | |
| CN103059910B (en) | Vulcanization method of hydrofining catalyst | |
| KR101311968B1 (en) | Hydrogenation catalyst composition, process for preparing the same and use thereof | |
| CN101024204A (en) | Hydrogenation catalyst presulfurizing method | |
| CN104646034A (en) | Preparation method of vulcanization type hydrofining catalyst | |
| CN102051204B (en) | Work starting method for hydrogenation process | |
| CN102310006A (en) | Method for regenerating and pre-vulcanizing hydrogenation catalyst | |
| CN102039207B (en) | Method for regenerating and prevulcanizing hydrogenation catalysts | |
| CN100525915C (en) | preparation process of vulcanized hydrogenation catalyst | |
| CN108940248A (en) | A kind of organic sulfur hydroconversion catalyst and its preparation method and application | |
| CN100413587C (en) | Sulfurized type catalyst, and its prepn. method | |
| CN105498678A (en) | Desulfurization adsorbent, preparation method thereof, and gas desulfurization method | |
| CN108855116A (en) | A kind of low carrying capacity coking oven gas hydrodesulfurizationcatalyst catalyst and its preparation method and application | |
| CN111298811B (en) | Environment-friendly pre-vulcanization reforming pre-hydrogenation catalyst and preparation method and application thereof | |
| CN100413588C (en) | Hydrogenation catalyst composition and its prepn. method | |
| CN103769243B (en) | The ex situ presulfiding method of hydrogenation catalyst | |
| CN106179522B (en) | A kind of ex situ presulfiding method of hydrogenation catalyst | |
| RU2748975C1 (en) | Complex method for restoring activity of hydroprocess catalysts | |
| CN117504894A (en) | Preparation of hydrogenation catalyst and out-of-device presulfiding and catalytic pyrolysis gasoline start-up method | |
| JP2010214297A (en) | Carbon carrier catalyst for removing metal from heavy crude oil and residual oil | |
| CN115337939A (en) | Sulfurized aromatic hydrocarbon saturation catalyst, preparation method thereof and distillate oil hydrofining method | |
| CN115646529A (en) | Pre-vulcanized CO sulfur-tolerant shift catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090318 Termination date: 20130822 |