CN102950004A - Carbon monoxide sulphur-tolerant pre-shift catalyst applicable under condition of low water-air ratio and preparation method - Google Patents
Carbon monoxide sulphur-tolerant pre-shift catalyst applicable under condition of low water-air ratio and preparation method Download PDFInfo
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Abstract
The invention relates to a carbon monoxide sulphur-tolerant pre-shift catalyst and a preparation method thereof. The catalyst is characterized by being suitable for a sulphur-tolerant pre-shift process with a low water-air ratio, and prepared by taking magnesium oxide, aluminium oxide and titanium dioxide as a composite carrier, taking Co-Mo-Ni as an active constituent, adding calcium aluminate cement as an auxiliary, and adopting a kneading method. The catalyst has the characteristics of being high in strength, good in strength stability, strong in erosion-resisting capacity and anti-toxicant capacity, uniform in the dispersion of the active constituent, has small possibility of losing the active constituent, and the like, as well as is high in pre-shift activity and stability, and capable of meeting the requirements of purifying synthesis gas and performing moderate pre-shift on carbon monoxide in the condition of a low water-air ratio. The catalyst is used in a pre-shift working section, and can be used for stabilizing gas flow distribution, filtering out catalyst toxicants, and effectively reducing the load of the main catalyst of a shift system, thus prolonging the service life of the subsequent sulphur-tolerant shift catalyst; therefore, the catalyst has good economic benefits.
Description
Technical field
The invention belongs to the carbon monodixe conversion technical field, particularly the carbon monoxide in the synthesis gas that makes with raw materials such as heavy oil, residual oil or coals is carried out catalyst and the preparation method of the pre-conversion process of anti-sulphur.
Background technology
In synthetic ammonia, methyl alcohol, hydrogen manufacturing and town gas industry, carbon monodixe conversion is important technical process.In this process, the exploitation of transformation catalyst receives much concern as key technology.Wherein, Co-Mo sulfur-tolerant shift catalyst because of its have serviceability temperature wide ranges, shift activity high, do not have the characteristics such as sulfur poisoning problem, over nearly 20 years in commercial Application achievement remarkable.
In recent years, along with being becoming tight petroleum resources day and the fast development of domestic Coal Chemical Industry, domestic coal generating gas scale continues to increase, and in China Petrochemical Industry's quadruplet chemical fertilizer reorganization and expansion device, the synthesis gas ability to transform increases more than 50% at least.In addition, carbon monoxide content also improves constantly in the process gas, reaches more than 55% such as carbon monoxide content in the GSP of the Siemens gasification technology process gas of introducing, and carbon monoxide content is up to more than 60% in the Shell fine coal gasification process.Gasification popularization and high-load carbon monodixe conversion cause the transformation system heat release to increase, and the bed temperature rise raises, and especially catalyst uses easy overtemperature of initial stage, causes catalyst at high temperature to move, to producing certain influence its service life; In addition, the variation of transformation system temperature also causes follow-up system parameter needs constantly to be adjusted, and misoperation just might cause the soaked or sintering of follow-up system catalyst.For this situation, solution is to adopt the mode that increases pre-conversion section that process gas is carried out pre-conversion, to reduce the burden of subsequent conversion system, reduces because of the unstable impact that follow-up main transformer catalyst changeout is caused of process gas.Simultaneously, increase pre-conversion section and can adsorb and remove the synthesis gas toxicity, prolong the follow-up main transformer catalyst changeout life-span.
Conventional pre-conversion section all adopts high WGR (more than 1.0) technique, and process conditions are harsh, and pre-change catalyzer need possess stronger hydration-resisting and antitoxin thing ability, the structure and activity stability requirement is high.In recent years, a kind of low WGR conversion process of new appearance, by reducing the conversion ratio of recently control change of aqueous vapor reaction, and then the hot(test)-spot temperature of control bed, to realize under lower hot(test)-spot temperature, carrying out the appropriate conversion of high-concentration carbon monoxide, not only can avoid the generation of methanation side reaction, and can reach the purpose of saving steam consumption energy consumption.This technique catalyst system therefor is stronger antitoxin thing ability except need possess, and outside structure and activity stability is better, also requires pre-transformation catalyst to have higher low temperature and middle temperature transformation activity.Therefore, for the pre-conversion process under the low WGR condition, the pre-transformation catalyst of anti-sulphur that exploitation matches with it has important industrial application value.
Patent CN90109711 discloses a kind of adsorbent of protecting transformation catalyst; this adsorbent is as the preposition protective layer of transformation catalyst; the absorption harmful components are with purification; reduction is to the murder by poisoning of subsequent conversion catalyst; prolong its service life; but this adsorbent only is used for purifying absorption, without pre-shift activity, can not reduce by in advance conversion the load of subsequent conversion system.Patent CN200610125452 discloses a kind of counterpoison and preparation method for the protection of cobalt molybdenum co surfer-resistant shift catalyst; this counterpoison can be protected the activity of transformation catalyst; by the infusion process preparation, because its active component content is higher, cost is higher.Patent CN 101791579 relates to a kind of preparation method who is applicable to the counterpoison of high pressure conversion, it is characterized in that providing a kind of spherical zinc aluminate carrier, with this carrier total immersion in ammoniacal liquor such as cobalt acetate and ammonium molybdate, add thiosulfuric acid in maceration extract, the dipping post-drying namely gets the high pressure conversion counterpoison.The activity of sulfur tolerant CO shift constituent content that patent CN96100935, CN101757941, CN101695662, CN1154271 etc. relate to is higher, so cost is higher, and is not suitable for pre-conversion section.
Summary of the invention
Technical problem to be solved by this invention provides a kind of low WGR condition that is applicable to, be pressure 2.0～6.0MPa, 250～450 ℃ of temperature, the pre-transformation catalyst of the anti-sulphur of carbon monoxide and the preparation method of WGR 0.2～0.8 o'clock, can under lower hot(test)-spot temperature, carry out appropriate conversion to high-concentration carbon monoxide, effectively reduce the conversion load of follow-up main transformer catalyst changeout, and absorption and remove the material harmful to the main transformer catalyst changeout, thereby main transformer catalyst changeout service life and device service cycle have been prolonged.
A kind of pre-transformation catalyst of the anti-sulphur of carbon monoxide that is applicable to low WGR condition of the present invention, it is characterized in that with magnesia, aluminium oxide and titanium dioxide complex carrier, take Co-Mo-Ni as active component, add aluminous cement and make auxiliary agent, the active component molybdenum, cobalt and the nickel mass percent in catalyst, count by oxide: molybdenum oxide is 1.5～5.0%, cobalt oxide is 0.5～3.0%, nickel oxide is 0.5～2%, alumina content is 20～60% of catalyst quality in the carrier, content of magnesia is 5～20% of catalyst quality, and titanium oxide content is 1～15% of catalyst quality, and aluminous cement content is 1～15% of catalyst quality.
The present invention makes it have stronger compression strength and anti-process gas erosion property take magnesia, aluminium oxide and titanium dioxide as complex carrier; Take Co-Mo-Ni as active component, add aluminous cement and make auxiliary agent, adopt kneading method to be prepared from.This catalyst has that intensity is high, strength stability good, erosion resistance and antitoxin thing ability is strong, active component is uniformly dispersed and be difficult for the characteristics such as loss, has higher pre-shift activity and stability.
Catalyst prepares as follows:
1. the preparation of active component solution:
A certain amount of ammonium molybdate is obtained solution A with deionized water dissolving, and its mass concentration is 10～25%.A certain amount of nickel nitrate and cobalt nitrate are dissolved in the deionized water; Binding agent is joined in the mentioned solution, stirring and dissolving obtains solution B again, and its mass concentration is 25～45%.
2. shaping of catalyst:
A certain amount of Powdered aluminum contained compound, Powdered magnesium-containing compound, Powdered titanium-containing compound, expanding agent and aluminous cement are mixed, add solution A, mediate evenly; Add again solution B, mediate evenly, after moulding, drying, roasting, make the catalyst semi-finished product.
3. catalyst strength is processed:
To place through the catalyst semi-finished product of roasting deionized water after soaking 2～8h under 10～80 ℃ of conditions, to take out, naturally dry, again through the roasting pre-transformation catalyst of anti-sulphur that gets product.
Active component molybdenum, cobalt and the nickel mass percent in catalyst described in the step 1 is (by oxide): molybdenum oxide is 1.5～5.0% (m/m), cobalt oxide is 0.5～3.0% (m/m), and nickel oxide is 0.5～2% (m/m).
In the above-mentioned steps 1, described binding agent is water, acetic acid, citric acid, oxalic acid or nitric acid etc., and optimization citric acid or oxalic acid, content are 2～4% (m/m) of catalyst quality.
In the above-mentioned steps 2, described Powdered aluminum contained compound is selected from the aluminum contained compounds such as boehmite, aluminium oxide, aluminium glue or aluminum acetate, and preferred boehmite or aluminium oxide are 20～60% (m/m) by its content of aluminium oxide.
Described Powdered magnesium-containing compound is selected from the magnesium-containing compounds such as magnesia, magnesium oxalate, magnesium carbonate or dolomol, and preferential oxidation magnesium is 5～20% (m/m) of catalyst quality by magnesia content.
Described Powdered titanium-containing compound is selected from the solid chemical compound that metatitanic acid, titanium oxide or anatase etc. contain titanium elements, and preferred metatitanic acid is 1～15% (m/m) of catalyst quality by titanium oxide content.
Described expanding agent is selected from field mountain valley with clumps of trees and bamboo powder, polyvinyl alcohol, poly amic acid, citric acid, sucrose or starch etc., preferred sesbania powder, and content is 2～4% (m/m) of catalyst quality.
Described cement is selected from 70#, 75#, 80# or 85# aluminous cement, preferred 85#, and content is 1～15% (m/m) of catalyst quality.Cement can improve catalyst structure stability, is conducive to improve low WGR active.
The sintering temperature that shaping of catalyst and intensity are processed is 200～600 ℃, roasting 2～4 hours.Catalyst finished product outward appearance is blueness or blue-green strip solid.The pore volume of catalyst should be greater than 0.30cm
3/ g is more preferably greater than 0.40cm
3/ g.Specific area should be greater than 100m
2/ g is more preferably greater than 120m
2/ g.
Advantage of the present invention:
Catalyst of the present invention prepares by kneading method, preparation technology is simple, production cost is lower, have that intensity is high, strength stability good, erosion resistance and antitoxin thing ability is strong, shift activity good, active component is uniformly dispersed and be difficult for the characteristics such as loss, can satisfy under low WGR condition, decontaminating syngas also carries out the requirement of pre-conversion to carbon monoxide.This catalyst is used for pre-conversion section, not only can distribute by steady air flow, and the filtration catalizer poisonous substance, and can effectively reduce the load of transformation system major catalyst, thus prolong the service life of follow-up sulfur-resistant transformation catalyst, have good economic benefit.
Description of drawings
Fig. 1 is normal pressure micro anti-evaluation device schematic diagram;
Among the figure: 1. contain H
2The S gas cylinder; 2. unstripped gas steel cylinder; 3. stop valve; 4. pressure maintaining valve; 5. spinner flowmeter; 6. triple valve; 7. threeway; 8. flow stabilizing valve; 9.CS
2Bubbler; 10. water-bath saturator; 11. hydrolysis stove; 12. reactor; 13. steam condensation separator; 14. soap-foam flowmeter
The specific embodiment
Embodiment 1
At first with ammonium molybdate 5.8g 40mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt nitrate 3.5g and nickel nitrate 72g 35mL deionized water dissolving, again citric acid 3.0g is joined in the mentioned solution, stirring and dissolving obtains containing the mixed solution B of cobalt nickel.
Take by weighing boehmite 75.0g, magnesia 20.0g, metatitanic acid 12.0g, sesbania powder 6.0g and 85# cement 15.0g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 550 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to take out after 6 hours 60 ℃ of lower immersions roasting catalyst, naturally dry, in 550 ℃ of lower roasting 3h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-1 of the anti-sulphur of finished product, its intensity sees Table 1.
At first with ammonium molybdate 12.5g 40mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt acetate 3.5g and nickel nitrate 14.6g 40mL deionized water dissolving, be that 20% acetic acid 5mL joins in the mentioned solution again with concentration, the heating stirring and dissolving gets mixed solution B.
Take by weighing aluminium oxide 80.0g, magnesium carbonate 18.0g, titanium oxide 12.0g, citric acid 64.0g and 75# cement 12.0g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 500 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to soak at normal temperatures after 6 hours roasting catalyst and take out, naturally dry, in 300 ℃ of lower roasting 3h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-2 of the anti-sulphur of finished product, its intensity sees Table 1.
Embodiment 3
At first with ammonium molybdate 7.4g 40mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt acetate 6.8g and nickel nitrate 11.5g 40mL deionized water dissolving, again oxalic acid 8.0g is joined in the mentioned solution, stirring and dissolving gets mixed solution B.
Take by weighing aluminium glue 65.0g, dolomol 24.0g, anatase 20.0g, sucrose 4.0g and 80# cement 8.0g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 530 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to soak at normal temperatures after 12 hours roasting catalyst and take out, naturally dry, in 500 ℃ of lower roasting 2h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-3 of the anti-sulphur of finished product, its intensity sees Table 1.
At first with 7.5g ammonium molybdate 40mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt nitrate 13.5g and nickel nitrate 7.6g 40mL deionized water dissolving, again citric acid 6.0g is joined in the mentioned solution, the heating stirring and dissolving gets mixed solution B.
Take by weighing boehmite 85.0g, magnesia 20.0g, metatitanic acid 12.0g, sesbania powder 6.0g and 85# cement 3.5g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 530 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to soak at normal temperatures after 12 hours roasting catalyst and take out, naturally dry, in 500 ℃ of lower roasting 3h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-4 of the anti-sulphur of finished product, its intensity sees Table 1.
At first with ammonium molybdate 9.5g 40mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt acetate 18.5g and nickel nitrate 4.0g 45mL deionized water dissolving, again citric acid 6.0g is joined in the mentioned solution, the heating stirring and dissolving gets mixed solution B.
Take by weighing boehmite 75.0g, magnesia 22.0g, metatitanic acid 9.0g, sesbania powder 6.0g and 85# cement 12.0g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 550 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to soak at normal temperatures after 6 hours roasting catalyst and take out, naturally dry, in 550 ℃ of lower roasting 1h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-5 of the anti-sulphur of finished product, its intensity sees Table 1.
At first with ammonium molybdate 9.8g 35mL deionized water dissolving, obtain containing the solution A of molybdenum; With cobalt nitrate 4g, nickel nitrate 2.5g 35mL deionized water dissolving is that rare nitric acid 5mL of 20% joins in the mentioned solution again with concentration, and stirring and dissolving obtains containing the mixed solution B of cobalt and auxiliary agent.
Take by weighing boehmite 85.0g, magnesium oxalate 15.0g, metatitanic acid 25.0g, starch 6.0g and 85# cement 3.0g and mix, add solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding dries naturally, in 500 ℃ of lower roasting 3h, naturally is cooled to room temperature.
Place deionized water to take out behind 40 ℃ of lower 8h of immersion roasting catalyst, naturally dry, in 550 ℃ of lower roasting 1h, naturally be cooled to room temperature, namely obtain the pre-transformation catalyst C-6 of the anti-sulphur of finished product, its intensity sees Table 1.
The catalyst strength of table 1 different formulations preparation
Catalyst normal pressure activity rating
Evaluation method:
Utilize conventional normal pressure micro anti-evaluation device, under the condition of far from equilibrium, the catalyst normal pressure intrinsic activity of spreading factor impact has been eliminated in test.The signal of normal pressure micro anti-evaluation device flow process as shown in Figure 1.The unstripped gas of employing take CO as main component allocated an amount of water and CS in reaction system
2, CS
2Through γ-Al is housed
2O
3Hydrolysis reactor, generate H in 350 ℃ of lower hydrolysis
2S enters shift-converter, and tail gas separates laggard chromatography through aqueous vapor after the reaction.
Catalyst normal pressure intrinsic activity rating condition: unstripped gas forms: CO 45～50% (V/V); CO
20～5% (V/V); H
2S 0.1～0.2% (V/V); Remaining is hydrogen.Air speed 5000h
-1Water/gas 1.0; 285 ℃, 350 ℃, 450 ℃ of temperature; Reaction pressure is normal pressure; Catalyst loading amount 0.6g.
CO interconversion rate computing formula is: X
CO=(Y
CO-Y
CO ')/[Y
CO(1+Y
CO ')] * 100%
Y
COThe molar fraction (butt) of-Reactor inlet gas CO
Y
CO 'The molar fraction of-reactor outlet gas CO (butt)
Catalyst normal pressure activity of the present invention sees Table 2.
Table 2 catalyst normal pressure is active
Catalyst pressurization activity rating
Adopt conventional pressurization activity rating device.This device is used for the simulation industrial condition, under certain pressure, measures " former granularity " catalyst CO concentration and variation thereof under different condition, the performances such as the shift activity of investigation catalyst and stability, the properties of overall merit catalyst.Reaction tube is the stainless steel tube of Φ 45 * 5mm, and there is the thermocouples tube of Φ 8 * 2mm in central authorities.Adopting the front process gas of certain synthetic ammonia workshop conversion is unstripped gas, allocates an amount of H into
2S adds a certain amount of water according to the requirement of different WGRs, behind high-temperature gasification, enters reaction tube with unstripped gas and carries out water gas shift reaction, tail gas chromatograph after the reaction.
The pressurization appreciation condition is: unstripped gas forms: CO 45～49% (V/V), CO
21～5% (V/V), H
2S＞0.10% (V/V), remaining is hydrogen; Dry gas air speed: 3000h
-1Pressure: 5.0MPa; Estimate inlet temperature: 250～500 ℃; WGR: 0.4; Catalyst loading amount: 100mL.
Catalyst pressurization activity of the present invention sees Table 3.
The pressurization of table 3 catalyst is active
CO interconversion rate computational methods are estimated active computational methods with normal pressure.
Claims (10)
1. pre-transformation catalyst of the anti-sulphur of carbon monoxide that is applicable to low WGR condition, it is characterized in that with magnesia, aluminium oxide and titanium dioxide are complex carrier, take Co-Mo-Ni as active component, add aluminous cement and make auxiliary agent, the active component molybdenum, cobalt and the nickel mass percent in catalyst, count by oxide: molybdenum oxide is 1.5～5.0%, cobalt oxide is 0.5～3.0%, nickel oxide is 0.5～2%, alumina content is 20～60% of catalyst quality in the carrier, content of magnesia is 5～20%, and titanium oxide content is 1～15%, and the content of aluminous cement is 1～15%.
2. catalyst according to claim 1 is characterized in that low WGR condition refers to pressure 2.0～6.0MPa, 250～450 ℃ of temperature, WGR 0.2～0.8.
3. the pre-transformation catalyst of the anti-sulphur of carbon monoxide according to claim 1 is characterized in that catalyst adopts kneading method to be prepared from.
4. a method for preparing claim 1 or 2 described catalyst is characterized in that comprising the steps:
(1) preparation of active component solution:
A certain amount of ammonium molybdate is obtained solution A with deionized water dissolving, and its mass concentration is 10～25%;
A certain amount of nickel nitrate and cobalt nitrate are dissolved in the deionized water, binding agent are joined in the mentioned solution again, stirring and dissolving obtains solution B, and its mass concentration is 25～45%;
(2) shaping of catalyst:
A certain amount of Powdered aluminum contained compound, Powdered magnesium-containing compound, Powdered titanium-containing compound, expanding agent and aluminous cement are mixed, add solution A, mediate evenly; Add again solution B, mediate evenly, after moulding, drying, roasting, make the catalyst semi-finished product;
(3) catalyst strength is processed:
To place through the catalyst semi-finished product of roasting deionized water after soaking 2～8h under 10～80 ℃ of conditions, to take out, naturally dry, get product through roasting again.
5. preparation method according to claim 4 is characterized in that the binding agent described in the step (1) is water, acetic acid, citric acid, oxalic acid or nitric acid, and content is 2～4% of catalyst quality.
6. preparation method according to claim 4, it is characterized in that the Powdered aluminum contained compound described in the step (2) is selected from boehmite, aluminium oxide, aluminium glue or aluminum acetate, Powdered magnesium-containing compound is selected from magnesia, magnesium oxalate, magnesium carbonate or dolomol, and Powdered titanium-containing compound is selected from metatitanic acid, titanium oxide or anatase.
7. preparation method according to claim 6 is characterized in that the Powdered aluminum contained compound described in the step (2) is selected from boehmite or aluminium oxide, and Powdered magnesium-containing compound is selected from magnesia, and Powdered titanium-containing compound is selected from metatitanic acid.
8. preparation method according to claim 4 is characterized in that the expanding agent described in the step (2) is selected from field mountain valley with clumps of trees and bamboo powder, polyvinyl alcohol, poly amic acid, citric acid, sucrose or starch, and content is 2～4% of catalyst quality.
9. preparation method according to claim 4 is characterized in that the aluminous cement described in the step (2) is selected from 70#, 75#, 80# or 85# aluminous cement.
10. preparation method according to claim 4 is characterized in that the sintering temperature that the middle shaping of catalyst of step (3) and intensity are processed is 200～600 ℃, roasting 2～4h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562022A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | High-air speed sulfur-resistant pre-shift catalyst and preparation method thereof |
| CN109201071A (en) * | 2017-07-04 | 2019-01-15 | 神华集团有限责任公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN109621984A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | Sulphur-resistant conversion methanation integration catalyst and preparation method |
| CN111085189A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift methanation bifunctional catalyst and preparation method thereof |
| CN111085190A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift and methanation dual-function catalyst and preparation method thereof |
| CN112916051A (en) * | 2021-01-25 | 2021-06-08 | 内蒙古中煤远兴能源化工有限公司 | Protective agent for sulfur-tolerant shift catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096494A (en) * | 1993-06-17 | 1994-12-21 | 中国石油化工总公司 | Sulfur-resistant CO conversion catalyst and method for making |
| CN1219500A (en) * | 1997-12-07 | 1999-06-16 | 中国石化齐鲁石油化工公司 | New CO sulphur-resistant transformation catalyst and its preparation method |
| CN1429763A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | CO sulfur resistant transformation catalyst and its preparation method |
| CN1485416A (en) * | 2002-09-27 | 2004-03-31 | 中国石化集团齐鲁石油化工公司 | Preparation process of immersion for water-gas sulfur-resistant transformation catalyst |
-
2011
- 2011-08-31 CN CN2011102554817A patent/CN102950004A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096494A (en) * | 1993-06-17 | 1994-12-21 | 中国石油化工总公司 | Sulfur-resistant CO conversion catalyst and method for making |
| CN1219500A (en) * | 1997-12-07 | 1999-06-16 | 中国石化齐鲁石油化工公司 | New CO sulphur-resistant transformation catalyst and its preparation method |
| CN1429763A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | CO sulfur resistant transformation catalyst and its preparation method |
| CN1485416A (en) * | 2002-09-27 | 2004-03-31 | 中国石化集团齐鲁石油化工公司 | Preparation process of immersion for water-gas sulfur-resistant transformation catalyst |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562022A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | High-air speed sulfur-resistant pre-shift catalyst and preparation method thereof |
| CN105562022B (en) * | 2014-10-09 | 2018-09-21 | 中国石油化工股份有限公司 | High-speed resistant to sulfur pre-transform catalyst and preparation method thereof |
| CN109201071A (en) * | 2017-07-04 | 2019-01-15 | 神华集团有限责任公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN109201071B (en) * | 2017-07-04 | 2021-08-03 | 神华集团有限责任公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN109621984A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | Sulphur-resistant conversion methanation integration catalyst and preparation method |
| CN111085189A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift methanation bifunctional catalyst and preparation method thereof |
| CN111085190A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift and methanation dual-function catalyst and preparation method thereof |
| CN111085190B (en) * | 2018-10-24 | 2022-10-14 | 中国石油化工股份有限公司 | Sulfur-tolerant shift and methanation dual-function catalyst and preparation method thereof |
| CN111085189B (en) * | 2018-10-24 | 2022-10-14 | 中国石油化工股份有限公司 | Sulfur-tolerant shift methanation bifunctional catalyst and preparation method thereof |
| CN112916051A (en) * | 2021-01-25 | 2021-06-08 | 内蒙古中煤远兴能源化工有限公司 | Protective agent for sulfur-tolerant shift catalyst and preparation method thereof |
| CN112916051B (en) * | 2021-01-25 | 2023-08-18 | 内蒙古中煤远兴能源化工有限公司 | Protective agent of sulfur-tolerant shift catalyst and preparation method thereof |
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