CN1079035C - Process for regenerating used CO conversion catalyst resisting sulfur - Google Patents
Process for regenerating used CO conversion catalyst resisting sulfur Download PDFInfo
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- CN1079035C CN1079035C CN98110476A CN98110476A CN1079035C CN 1079035 C CN1079035 C CN 1079035C CN 98110476 A CN98110476 A CN 98110476A CN 98110476 A CN98110476 A CN 98110476A CN 1079035 C CN1079035 C CN 1079035C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011593 sulfur Substances 0.000 title claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 title abstract description 5
- 230000001172 regenerating effect Effects 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000009418 renovation Methods 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000008859 change Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 11
- 229910001648 diaspore Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100395824 Solanum lycopersicum HSC-2 gene Proteins 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a method for recovering and utilizing used conversion catalysts resisting sulfur. Most used conversion catalysts resisting sulfur serve as garbage and are tossed away, the environment is polluted and the resource is waste. In the present invention, firstly, used conversion catalysts resisting sulfur is pulverized, and then, solid gum solvents of analogy thin diaspore, etc. and liquid glue solvents of nitric acid, etc. are added for calcination. Next, an alkaline matter solution and a Co-Mo active constituent solution or a Co-Mo-alkali metal compound solution are activated, dried and/or calcined to obtain the regenerated catalyst which can satisfy the requirement of industrial production.
Description
The present invention relates to a kind of renovation process of waste and old sulfur-resistant transformation catalyst, specifically, the present invention relates to that a kind of to make waste and old Co-Mo be that the CO sulfur-resistant transformation catalyst recovers intensity and active method again.
At present, the waste and old Co-Mo of ton is the CO sulfur-resistant transformation catalyst surplus the annual approximately replacing 500 of China's fertilizer industry.These spent catalyst major parts are fallen as rubbish is processed.Like this, not only polluted environment, and, also caused the significant wastage of resource owing to bullion content height in the spent catalyst.
Be that the processing method of spent catalyst generally is cobalt and the molybdenum that reclaims wherein abroad to Co-Mo, as U.S. Pat 5,066,469 and US5, the method described in 013,533.China recycling Co-Mo is that the method for spent catalyst has following several: (1) reclaims cobalt and molybdenum wherein; (2) spent catalyst is sieved, remove particle and caking, continue in the stove of packing into then to use (seeing " Henan chemical industry " the 12nd phase in 1992); (3) regeneration of spent catalyst, as disclosed method among the open CN1128689A of Chinese patent, this method is carrier with the spent catalyst, soaks altogether with the solution of solubility cobalt salt, molybdenum salt and alkali metal compound, makes the product after the regeneration.The advantage of this method is to recover the activity of spent catalyst, but the insufficient strength ideal of regeneration rear catalyst is difficult to reach the requirement that industry is used.
The purpose of this invention is to provide a kind of method that waste and old Co-Mo is the CO sulfur-resistant transformation catalyst of handling, make the activity and the intensity of the spent catalyst after the regeneration all can reach and satisfy industrial requirement.
In the method for the invention, the first step is that spent catalyst is pulverized.The granularity of pulverizing the back spent catalyst can be in 80 orders～400 purpose scopes, and better particle size range is 100 orders～180 orders.Can earlier spent catalyst be carried out roasting before pulverizing, main purpose is to burn in original use or to make it dry attached to the pollutant on the spent catalyst; Certainly, carry out roasting after also can pulverizing.The advantage of pulverizing the back roasting is easier burn off pollutant, and shortcoming is than baking operation trouble before pulverizing.
Second step of the inventive method is to add the solid gum solvent in the spent catalyst after pulverizing to mix.The solid gum solvent can be selected aluminium hydroxide, iron hydroxide, magnesium hydroxide or boehmite for use, also can select in the above-claimed cpd two or more mixture for use, but boehmite or contain the said mixture of boehmite preferably.The solid gum solvent that adds is 0～10: 1 with the mass ratio of pulverizing back spent catalyst material, this means in the present invention and also can not add the solid peptizing agent, but add the intensity that the solid gum solvent can increase the regeneration rear catalyst, so preferably add the solid gum solvent.
The 3rd step of the inventive method is to add nitric acid in the mixture of gained to make the liquid glue solvent in second step, perhaps add the nitrate of alkali metal, alkaline-earth metal or transition metal or the aqueous solution of sulfate and make the liquid glue solvent, the aqueous solution that also can add two or more mixture in the sulfate of the nitrate of sulfate, transition metal of nitrate, the alkaline-earth metal of nitric acid, alkali-metal nitrate, alkali-metal sulfate, alkaline-earth metal or transition metal is made the liquid glue solvent.Add after the liquid glue solvent, mediate, moulding, then 400 ℃～700 ℃ following roastings.
The main purpose that adds the liquid glue solvent is further to improve the intensity of regeneration rear catalyst.
The better scope of sintering temperature is 450 ℃～650 ℃ after kneading, the moulding.
The 4th step of the inventive method is an activation processing, promptly with alkaline substance solution, Co-Mo active constituent solution or Co-Mo active constituent-alkali metal compound solution the material of the 3rd step gained is handled, then oven dry or roasting.
Used alkaline matter in the inventive method the 4th goes on foot, can be a kind of in the following material, also can be two or more mixture wherein: the hydroxide of ammonia, alkali-metal hydroxide, alkali-metal carbonate, alkaline-earth metal, the soluble carbon hydrochlorate of alkaline-earth metal.Used alkaline matter is two or more mixture of potassium hydroxide, NaOH, potash or sodium carbonate or its preferably.
Used Co-Mo active constituent is meant the soluble-salt of cobalt and molybdenum in the 4th step, as nitrate or acetate; Used Co-Mo active constituent-alkali metal compound is meant the soluble-salt and the alkali metal compound of cobalt and molybdenum, wherein alkali metal compound can be the compound of potassium and sodium, preferably two or more mixture of potassium hydroxide, NaOH, potash or sodium carbonate or its.
According to the present invention, the activation processing in the 4th step can only use a kind of method wherein to get final product, and promptly with a kind of solution in alkaline substance solution, Co-Mo active constituent solution or the Co-Mo active constituent-alkali metal compound solution material of the 3rd step gained is handled getting final product.But also can handle with Co-Mo active constituent solution after handling with alkaline substance solution, the purpose of doing like this is to improve the content of cobalt, molybdenum active constituent in the regeneration rear catalyst, with further increase activity of such catalysts again.In fact, only with alkaline substance solution the material of the 3rd step gained is handled, catalyst has just recovered activity.Soak with Co-Mo active constituent solution again, improved the active constituent content in the catalyst, activity also can increase certainly.
If handle with Co-Mo active constituent solution or Co-Mo active constituent-alkali metal compound solution in the 4th step, then cobalt that is added and molybdenum shared quality percentage composition in the regeneration rear catalyst is: CoO 0.1%～3%, MoO
31%～15%; The height of concrete content will be according to the situation decision of spent catalyst.
After the 4th step activation processing, the quality percentage composition of alkali in the regeneration rear catalyst is with M
2O (M is K or Na) counts 2%～15%, and better scope is 6%～12%.
Adopt method of the present invention, not only utilized waste and old sulfur-resistant transformation catalyst resource, reduced the pollution to environment, and the Catalyst Production after the regeneration is with low cost, properties of product are good, and its activity and intensity all are better than industrial catalyst C
25-02(see Table 1 and table 2).
Further specify the present invention below in conjunction with embodiment, but scope of the present invention is not limited to following embodiment.
Embodiment 1
With waste and old Co-Mo series catalysts roasting, be crushed to 180 orders, get material 400 grams after the pulverizing, add that 10% nitric acid is mediated, moulding, extrusion, and in 550 ℃ of roastings.Ammoniacal liquor with 18% and potassium hydroxide solution activation processing, the addition of potassium is with K
2O counts 8%, dries then, makes catalyst HSC-1.
Embodiment 2
With waste and old Co-Mo series catalysts roasting, be crushed to 120 orders, get material 200 grams after the pulverizing, add boehmite 40 grams, with 10% nitric acid mediate, moulding, extrusion, and in 500 ℃ of roastings.Ammoniacal liquor with 18% and potassium hydroxide solution activation processing, the addition of potassium is with K
2O counts 10%.Dry and/or roasting, make catalyst HSC-2.
Embodiment 3
With waste and old Co-Mo series catalysts roasting, be crushed to 120 orders, get material 200 grams after the pulverizing, add boehmite 20 grams, with 10% nitric acid mediate, moulding, extrusion and roasting.With Co-Mo active constituent-potassium hydroxide maceration extract dipping, oven dry or roasting make catalyst HSC-3, and its active constituent and alkali-metal addition (quality percentage composition) are respectively: CoO 0.2%, MoO
33%, K
2O 8%.
Embodiment 4
With waste and old Co-Mo series catalysts roasting, be crushed to 120 orders, get material 20 grams after the pulverizing, add boehmite 180 grams, with 10% nitric acid mediate, moulding, extrusion and roasting.With Co-Mo active constituent-potassium hydroxide maceration extract dipping, oven dry or roasting make catalyst HSC-4, and its active constituent and alkali-metal addition (quality percentage composition) are respectively: CoO 1.0%, MoO
35.5%, K
2O10%.The valence test of catalyst
Get 20 samples at random, on QCY-602 type strength tester, measure the radially crushing strength of catalyst, represent catalyst strength, the results are shown in Table 1 with unit length mean value.The poach experiment
Take by weighing a certain amount of catalyst and in boiling water, boiled 4 hours, measure the variation of intensity after the oven dry, investigate the catalyst intensity after hot-water soak and stability thereof under normal pressure, the results are shown in Table 2.The hydrothermal treatment consists experiment
On former granularity pressurization evaluating apparatus, be medium with nitrogen and water vapour, be that 5.0Mpa, temperature are that 500 ℃, air speed are 2000h at pressure
-1And water/gas is to handle 10 hours under 1.4 the condition.Measure the variation of oven dry back sample strength, relatively intensity and the stability thereof of catalyst after high pressure-temperature is handled the results are shown in Table 1.
Table 1 gained catalyst of the present invention and industrial catalyst C
25-02Intensity and stability
As can be seen from Table 1, utilizing the regenerating waste used Co-Mo of method of the present invention is sulfur-resistant transformation catalyst, and the intensity of gained catalyst and stability all are better than industrial catalyst C
25-02Activity rating
The condition of estimating is: catalyst loading amount 0.3 gram
Air speed 10000h
-1
Water/gas 1.0
265 ℃, 350 ℃, 450 ℃ of reaction temperatures
Unstripped gas is formed CO 45% (V/V)
CO
2 5％(V/V)
H
2S 2000 ppm
All the other are H
2
The catalyst of table 2 gained of the present invention and industrial catalyst C
25-02The active contrast of normal pressure intrinsic
| The title of catalyst | CO interconversion rate (%) | ||
| 265℃ | 350℃ | 450℃ | |
| HSC-1 | 8.9 | 41.4 | 30.8 |
| HSC-2 | 8.4 | 38.6 | 32.6 |
| HSC-3 | 9.6 | 36.8 | 35.8 |
| HSC-4 | 8.8 | 41.5 | 31.4 |
| Industrial catalyst C 25-02 | 8.6 | 38.9 | 26.2 |
Claims (7)
1. renovation process that waste and old Co-Mo is the CO sulfur-resistant transformation catalyst may further comprise the steps:
(1) be that to be crushed to granularity be 80 orders～400 purposes to sulfur-resistant transformation catalyst with waste and old Co-Mo
Material, and spent catalyst can carry out calcination process before or after pulverizing, can be not yet
Through calcination process;
(2) add the solid gum solvent in the spent catalyst after pulverizing and mix used solid gum solvent
Be Al (OH)
3, Fe (OH)
3, Mg (OH)
2Or boehmite, solid gum solvent and waste and old catalysis
The mass ratio of agent material is 0～10: 1;
(3) in said mixture, add nitric acid and make the liquid glue solvent, perhaps add alkali metal, alkaline-earth metal or
The nitrate of transition metal or one or more the aqueous solution of mixture in the sulfate are made liquid
The body peptizing agent is mediated, moulding, then 400 ℃～700 ℃ following roastings;
(4) with alkaline substance solution, Co-Mo active component solution or Co-Mo-alkali metal compound mixed liquor
The resulting material of step (3) is carried out activation processing, then oven dry and/or roasting; Described
Alkaline matter is the hydrogen-oxygen of ammonia, alkali-metal hydroxide, alkali-metal carbonate, alkaline-earth metal
The mixture of one or more in the meltability carbonate of change thing, alkaline-earth metal.
2. by the described method of claim 1, it is characterized in that in step (1) with waste and old Co-Mo being that anti-sulphur becomes
It is 100 orders～180 purpose materials that catalyst changeout is crushed to granularity.
3. press claim 1 or 2 described methods, giving up after it is characterized in that in step (2), joining pulverizing
Old Co-Mo is that the solid gum solvent in the sulfur-resistant transformation catalyst is a boehmite.
4. by claim 1 or 2 described methods, it is characterized in that the roasting after kneading, the moulding in step (3)
Burning temperature is 450 ℃～650 ℃.
5. by claim 1 or 2 described methods, it is characterized in that in step (4), adopting the active group of Co-Mo
Divide solution or Co-Mo-alkali metal compound mixed liquor that the resulting material of step (3) is activated the place
During reason, the Co-Mo active component of the adding in the end quality percentage composition in the catalyst of gained is: CoO
0.1％～3％，MoO
3 1％～15％。
6. by claim 1 or 2 described methods, it is characterized in that in step (4), adopting alkaline matter or Co-Mo
When-alkali metal compound mixed liquor carries out activation processing to the resulting material of step (3), used
Alkaline matter or alkali metal compound are the compound of K and/or Na.
7. by the described method of claim 6, the quality percentage composition that it is characterized in that the K that adds and/or Na is with gold
Belong to oxide and count 1%～15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110476A CN1079035C (en) | 1998-09-26 | 1998-09-26 | Process for regenerating used CO conversion catalyst resisting sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110476A CN1079035C (en) | 1998-09-26 | 1998-09-26 | Process for regenerating used CO conversion catalyst resisting sulfur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1249209A CN1249209A (en) | 2000-04-05 |
| CN1079035C true CN1079035C (en) | 2002-02-13 |
Family
ID=5220524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110476A Expired - Fee Related CN1079035C (en) | 1998-09-26 | 1998-09-26 | Process for regenerating used CO conversion catalyst resisting sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1079035C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950010B (en) * | 2011-08-31 | 2015-05-20 | 中国石油化工股份有限公司 | Method for utilizing molybdenum in waste cobalt-molybdenum-system sulfur-tolerant shift catalyst |
| CN114100622B (en) * | 2020-08-31 | 2023-08-11 | 中国石油化工股份有限公司 | Sulfur-tolerant pre-shift catalyst and preparation and vulcanization methods thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009887A1 (en) * | 1978-09-01 | 1980-04-16 | Exxon Research And Engineering Company | Process for regenerating spent hydrofining catalysts |
| SU738660A1 (en) * | 1978-02-15 | 1980-06-05 | Предприятие П/Я Р-6711 | Method of regenerating catalyst for hydropurification of petroleum feedstock |
| CN1128680A (en) * | 1995-02-09 | 1996-08-14 | 中国石化齐鲁石油化工公司 | Regeneration method of carbon monoxide sulfur-tolerant shift catalyst |
-
1998
- 1998-09-26 CN CN98110476A patent/CN1079035C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU738660A1 (en) * | 1978-02-15 | 1980-06-05 | Предприятие П/Я Р-6711 | Method of regenerating catalyst for hydropurification of petroleum feedstock |
| EP0009887A1 (en) * | 1978-09-01 | 1980-04-16 | Exxon Research And Engineering Company | Process for regenerating spent hydrofining catalysts |
| CN1128680A (en) * | 1995-02-09 | 1996-08-14 | 中国石化齐鲁石油化工公司 | Regeneration method of carbon monoxide sulfur-tolerant shift catalyst |
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| Publication number | Publication date |
|---|---|
| CN1249209A (en) | 2000-04-05 |
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