CN1003979B - Sulfur resistant carbon monoxide transformation catalyst and its prepn - Google Patents
Sulfur resistant carbon monoxide transformation catalyst and its prepn Download PDFInfo
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- CN1003979B CN1003979B CN87107892.9A CN87107892A CN1003979B CN 1003979 B CN1003979 B CN 1003979B CN 87107892 A CN87107892 A CN 87107892A CN 1003979 B CN1003979 B CN 1003979B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 20
- 239000011593 sulfur Substances 0.000 title claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 title abstract description 4
- 230000009466 transformation Effects 0.000 title description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract 3
- 238000007598 dipping method Methods 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002803 maceration Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 239000000243 solution Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000007654 immersion Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 229910052770 Uranium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910020679 Co—K Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Abstract
The present invention relates to a sulfur resistant carbon monoxide conversion catalyst, and a preparation method and an application method thereof. The catalyst belongs to a catalyst in a Co-Mo system; the preparation method comprises the steps that active carriers, such as gamma-Al2O3, etc., are respectively immersed in a soluble cobalt salt solution, an ammonium molybdate solution and a soluble alkali metal salt solution or are immersed in the mixed solution thereof together, stabilizing agents (such as citric acid, etc.) are added to the immersion solution, and drying and roasting are carried out after immersion every time to obtain the catalyst. When used, the catalyst is resulphurized; the catalyst of the present invention has good low-temperature activity, high strength and low cost, wherein the low-temperature activity of the catalyst is obviously superior to that of US C25-2-02 and home-made similar products.
Description
The present invention relates to sulfur-resistant CO conversion catalyst and preparation thereof and application.
The technological process of present medium and small synthetic ammonia factory be gas making (～500 ℃) → gas holder (room temperature) → desulfurization (room temperature) → conversion (～350 ℃) → ... the unstripped gas that gas making gets is to shift conversion step, the trend of temperature has experienced the high shape of a saddle of height, obviously heat does not rationally utilize, and energy consumption is big.If make unstripped gas, carry out CO+H in the change furnace and directly enter without desulfurization
2O=CO
2+ H
2Reaction.Then can reduce energy consumption.But in the syngas for synthetic ammonia of making by oil or coal, H
2S content is generally～1.5 gram/standard meters
3, what have reaches 5 gram/standard meters
3Unstripped gas directly enters change furnace without desulfurization, and this is a low temperature conversion catalyst to the Cu-Zn that adopted in the past, because of being subject to very much sulfur poisoning, and inapplicable.Fe-Cr is a high temperature conversion catalyst because of ability high-sulfur amount not, the active temperature height, and transformationreation is incomplete, so also inapplicable.Therefore need correspondingly develop sulfur-resistant transformation catalyst.
U, S, Pat in recent years, No3,850,840, U, S, Pat, No3,957,962, U, S, Pat, No4,153,580 and U, S, Pat, No4,166,101 have reported with Al
2O
3For the Co-Mo of carrier is a sulfur-resistant transformation catalyst, and lower active temperature is arranged.
U, S, Pat, No3,850,840, U, S, Pat, No3, the Co-Mo-Me(Me of 957,962 developments represents alkali metal) carbon monoxide transformation catalyst, with the cobalt salt such as the Co(NO of solubility
3)
2, CoCl
2, Co(AC)
2, Co(HCOO)
2Flood (branch soaks) respectively or form mixed solution and soak (soaking altogether) jointly Deng salt, ammonium molybdate, alkali-metal solubility salt at cylindricality r-Al
2O
3On the carrier.In maceration extract, add stabilizing agents such as ammoniacal liquor, monoethanolamine, improve the stabilizing agent that maceration extract soaks solution especially altogether, with the r-Al behind the dipping
2O
3100-150 ℃ down dry, carried out roasting 1-3 hour under 400-700 ℃, promptly make new cylindricality catalyst.Dipping can divide a step or multistep to finish.U, S, Pat, No3, the composition of 850,840 catalyst:
CoO is the best 1-5% of being of 0.1-10%
MoO
3For 1-25% the best is 5-15%
＜10 the bests are 3
Though this catalyst has anti-sulphur, exist resistance big, intensity is lower, active lower deficiency.
The Co-Mo of the current development of China is transformation catalyst A, is to adopt cobalt salt, the preparation of molybdenum salt mixed grind forming method.The intensity of catalyst is lower, is the 150-200 kilograms per centimeter
2, active undesirable, cost is higher.
The purpose of this invention is to provide a kind of is sulfur-resistant CO conversion catalyst with immersion process for preparing support type (sphere) Co-Mo, and it is little that this catalyst should have a resistance, intensity height, active good, characteristics such as cost is low.
The objective of the invention is to adopt following method to realize, adopt the Co-Mo series catalysts, ball type carrier, orthogonal design proof catalyst cobalt content are counted 1-10% with CoO, 3-7% more preferably, and molybdenum content is with MoO
3Count 1-30%, 15-22% more preferably, alkali metal content is with oxide (K
2O is better) count 1-30%, more preferably 5-20%.Its preparation method is with active carrier such as SiO
2, Al
2O
3-SiO
2, MgO-Al
2O
3, r-Al
2O
3Deng, use the solubility cobalt salt (as Co(NO
3)
2, CoCl
2, Co(AC)
2, Co(HCOO)
2Deng), nitrate, the carbonate of ammonium molybdate, alkali metal (Na, K, Cs), acetate etc. divide to soak or form mixed liquor and soak altogether, have added ammoniacal liquor or monoethanolamine in the maceration extract, ethylenediamine, stabilizing agents such as citric acid, the also activity increase agent of catalyst.Each dipping back is 120-150 ℃ of oven dry 1-2 hour, 300-550 ℃ following roasting 0.5-2.0 hour.Add stabiliser content in the maceration extract and count 0.1-10% with compound, more preferably 1-5%(sees Table 3).
Catalyst carrier of the present invention can be SiO
2, Al
2O
3-SiO
2, MgO-Al
2O
3Or r-Al
2O
3, need satisfy following requirement and get final product.
Shape: spherical diameter 3-13 millimeter
Water absorption rate 0.3-0.6 milliliter/gram (weight method,
After soaking 30 minutes in the water, filter paper is dried)
Specific surface 150-300 rice
2/ gram (BET method)
Mechanical strength 〉=5 kilogram/(QCY-602 type intensity meter mensuration)
Catalyst of the present invention adopts Co, and Mo, K or K, Mo, Co order divide infuse to be equipped with, and activity of such catalysts is better.
This sulfur-resistant CO conversion catalyst.Need use through vulcanizing after, curing temperature 250-450 ℃, preferable curing temperature is 350-400 ℃, and vulcanizing agent is H
2S or CS
2, its concentration is 1-4%, in the test cure time 3.5-4.5 hour, cure time was 20-24 hour aborning.
No matter this catalyst is adopt to divide to soak or adopt altogether that the mode of soaking makes, its activity all is higher than U.S. C
25-2-02With homemade similar catalyst A, and the catalyst activity that divides the mode of soaking to make is higher, and good low temperature active is arranged, and can use under normal pressure 150-200 ℃, and cost also has very big decline (seeing Table 7).
The test of catalyst activity is carried out in microreactor, and condition is that reaction tube diameter is 3 millimeters, catalyst grain size 60-80 order.Catalyst volume is 0.25 milliliter, air speed 2000 hours
-1, normal pressure, unstripped gas are semiwater gas, are 400 ℃ in the probe temperature table 1, are 300 ℃ in table 2, the table 3, activity is represented with the interconversion rate of carbon monoxide.Listed U.S. C in the table together
25-2-02Data with homemade similar catalyst sample A.
The test of employing orthogonal design, CoO and MoO in the catalyst
3Content influences result such as Fig. 1 to its activity, and as seen from Figure 1, when CoO content was in 3-7% in the catalyst, its activity was along with the content of CoO increases and improves.Behind CoO content＞7%, the catalyst activity increase is very slow.Consider comprehensively that from catalyst activity cost and manufacturing process CoO content 3-7% is for well, to MoO in the catalyst
3, MoO in the catalyst
3Content is good at 15-22%.
Fig. 1 is CATALYST Co O and MoO
3Content is to the orthogonal design result of its activity influence.
Embodiment 1:
With spherical r-Al
2O
3Smash to pieces, get 60-80 order Al
2O
3, with 4%Co(NO
3)
2Solution (adding 1% citric acid used as stabilizers in addition), 10% ammonium molybdate solution, 12.5%K
2CO
3Solution by different impregnation sequence dipping, or is made into mixed solution with them and soaks altogether, and each dipping back is 120-150 ℃ of oven dry 1-2 hour down, 300-550 ℃ roasting 0.5-2.0 hour, catalyst that makes and activity see Table 1.
Annotate: 1, Co-Mo, Co-K, Co-Mo-K are expressed as altogether and soak in the impregnation method.
2, the Co0=4.5% in each catalyst, MoO
3=15.9%, K
2O=7.4%.
3, the curing temperature of catalyst is 400 ℃, and cure time is 4 hours.
As seen from Table 1, add K
2CO
3The back improves a lot to activity of such catalysts, divides infuse to be equipped with Co, Mo, K or K, Mo, Co order, and catalyst activity is better.
Embodiment 2:
As embodiment 1, get 60-80 purpose r-Al
2O
3, with 4.0%, 5.5%Co(NO
3)
2Solution (adding 1% citric acid in addition), 10% ammonium molybdate solution as stabilizing agent divide soak after, again with 12.5%K
2CO
3Solution floods, and changes the concentration of ammonium molybdate solution in addition, makes MoO in the catalyst
3Be respectively 15%, 18%, 22%, each dipping back is with 120-150 ℃ of oven dry 1-2 hour, 300-550 ℃ roasting 0.5-2.0 hour, catalyst that makes (No9-13) and activity thereof see Table 2.
Embodiment 3:
As embodiment 1, get 60-80 order r-Al
2O
3With 4.0%, Co(NO
3)
2Solution (citric acid or the monoethanolamine used as stabilizers that add variable concentrations in addition), 10% ammonium molybdate solution, 12.5%K
2CO
3Solution divides and soaks, and each dipping back is with 120-150 ℃ of oven dry 1-2 hour, 300-550 ℃ roasting 0.5-2.0 hour, catalyst that makes (No14-21) and activity thereof see Table 3.
Annotate: the catalyst vulcanization temperature is 300 ℃, 4 hours
, and do not add stabilizing agent and compare catalyst and have better activity respectively 3.0% and 2.0% o'clock by the visible citric acid of table 3 and monoethanolamine concentration.
Embodiment 4:
As embodiment 1, get 60-80 order r-Al
2O
3, with 3.5%Co(HCOO)
2Or 4.0%Co(AC)
2Solution (adding 1% citric acid used as stabilizers in addition), 10% ammonium molybdate solution divide soak after, again with 12.5%K
2CO
3Solution impregnation, each dipping back be with 120-150 ℃ of oven dry 1-2 hour, 300-550 ℃ roasting 0.5-2.0 hour, catalyst that makes (No22-23) and activity thereof see Table 4.
Embodiment 5:
As embodiment 1, get 60-80 order r-Al
2O
3, with 4.0%Co(NO
3)
2Solution (adding 1% citric acid used as stabilizers in addition), 10% ammonium molybdate solution divide soak after, flood with 16.5%KAC solution again, each dipping back was with 120-150 ℃ of oven dry 1-2 hour, 300-550 ℃ roasting 0.5-2.0 hour, catalyst that makes (No24) and activity see Table 4.
Annotate: No22,23 Co salt are respectively Co(HCOO)
2Co(AC)
2
The result of comparison sheet 2 and table 4 as can be known, with Co(HCOO)
2, Co(AC)
2Or KAC when dipping prepared catalyst activity also surpassed C
25-2-02With A, but with Co(NO
3)
2Or K
2CO
3The activity of such catalysts that makes during dipping is better.
The prepared catalyst of the present invention needs to use after vulcanizing, and vulcanizing agent is H
2S or CS
2, its concentration is 1-4%, curing temperature sees Table 5 to the influence of catalyst activity, from the table data as seen, curing temperature is good with 350-400 ℃.
Test condition: semiwater gas, normal pressure, catalyst grain size: former granularity (unbeaten r-Al
2O
3) 30 milliliters of volumes, air speed 500 hours
Use catalyst of the present invention, carry out the pilot production of 5 tons of samples in Wuhan Ammonia Making Factory, the activity data of its typical sample sees Table 6.Test condition: 32 * 2 millimeters of reaction tube diameter, catalyst are former granularity, 30 milliliters of volumes, air speed 500 hours
-1, normal pressure is made unstripped gas with semiwater gas.The result shows activity at 250,200,175 ℃ of following representative samples apparently higher than domestic sample A of the same type, and active temperature can reduce about 50 ℃, and cost also has very big decline, sees Table 7.
Different impregnation method catalyst of table 1 and activity
Table 2
| No | 9 | 10 | 11 | 12 | 13 | C 25-2-02 | A | |
| In the catalyst | MoO 3% | 16.2 | 16.3 | 15.0 | 18.1 | 22.1 | ||
| CoO% | 4.6 | 6.0 | 4.5 | 4.6 | 4.6 | |||
| K 2O% | 7.5 | 7.4 | 7.4 | 7.5 | 7.4 | |||
| Interconversion rate %300 ℃ | 70.3 | 75.6 | 66.4 | 75.8 | 71.7 | 57.8 | 61.2 | |
Table 3
| No | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | C 25-2-02 | A | |
| Soak stabilizing agent in the clear liquid | Citric acid % | 0 | 1.0 | 3.0 | 5.0 | ||||||
| Monoethanolamine % | 0 | 1.0 | 2.0 | 4.0 | |||||||
| Interconversion rate %300 ℃ | 68.0 | 70.3 | 30.5 | 75.1 | 68.0 | 71.5 | 76.2 | 70.1 | 57.8 | 61.2 | |
Table 4
| No | 22 | 23 | 24 | |
| In the catalyst | MoO 3% | 16.1 | 16.0 | 15.9 |
| CoO% | 4.0 | 4.1 | 4.3 | |
| K 2 O% | 7.3 | 7.4 | 7.4 | |
| 300 ℃ of interconversion rate % | 64.1 | 63.2 | 68.9 | |
Table 5 curing temperature is to the influence of catalyst activity
| Curing temperature ℃ | 250 | 300 | 350 | 400 | 450 |
| Exchange rate %200 ℃ | 89.5 | 92.1 | 96.3 | 97.2 | 92.5 |
Table 6
The sale price of each catalyst of table 7
| The catalyst model | Catalyst sample of the present invention | A | C 25-2-02 |
| Ten thousand yuan/meter of prices 3 | 2.0 | 2.75 | 3.1 |
Claims (8)
1, a kind of Co-Mo is a sulfur-resistant CO conversion catalyst, by 3-7%Co0.15-22%MoO
3, a kind of 5-20% alkali metal (Na, K, Cs) oxide and carrier are formed, and it is characterized in that carrier is selected from spherical SiO
2, Al
2O
3-SiO
2, MgO-Al
2O
3, r-Al
2O
3, and need satisfy following requirement:
Spherical diameter 3-13 millimeter
Water absorption rate 0.3-0.6 milliliter/gram
Specific surface 150-300 rice
2/ gram
Mechanical strength 〉=5 kilogram/
2, according to the catalyst of claim 1, wherein said alkali metal oxide is the oxide of potassium.
3, a kind of method for preparing the catalyst of claim 1, this method is to be selected from spherical SiO
2, Al
2O
3-SiO
2, MgO-Al
2O
3, r-Al
2O
3A kind of carrier, with a kind of Co(NO that is selected from
3)
2, CoCl
2, Co(AC)
2, Co(HCOO)
2The solubility cobalt salt, ammonium molybdate and be selected from a kind of nitrate, the carbonate of alkali metal (Na, K, Cs), or acetate divides and soaks or form mixed liquor and soak altogether, add in the maceration extract and be selected from ammoniacal liquor, monoethanolamine, ethylenediamine, a kind of stabilizing agent of citric acid, soak the back 120-150 ℃ of drying at every turn, 300-550 ℃ of following roasting, it is characterized in that each dipping back drying time is 1-2 hour, roasting time is 0.5-2.0 hour, and the amount (in compound) that adds stabilizing agent in the maceration extract is 0.1-10%.
4, according to the method for claim 3, wherein the amount of used stabilizing agent is 1-5%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107892.9A CN1003979B (en) | 1987-11-14 | 1987-11-14 | Sulfur resistant carbon monoxide transformation catalyst and its prepn |
| CN89100315A CN1009060B (en) | 1987-11-14 | 1987-11-14 | Sulphurization method of co-mo series carbon monoxide transducing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107892.9A CN1003979B (en) | 1987-11-14 | 1987-11-14 | Sulfur resistant carbon monoxide transformation catalyst and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87107892A CN87107892A (en) | 1988-05-04 |
| CN1003979B true CN1003979B (en) | 1989-04-26 |
Family
ID=4816282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107892.9A Expired CN1003979B (en) | 1987-11-14 | 1987-11-14 | Sulfur resistant carbon monoxide transformation catalyst and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003979B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067917C (en) * | 1996-01-11 | 2001-07-04 | 中国石化齐鲁石油化工公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN1087192C (en) * | 1998-07-15 | 2002-07-10 | 中国石化齐鲁石油化工公司 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| CN101342491B (en) * | 2008-08-18 | 2010-06-02 | 湖北双雄催化剂有限公司 | Preparation of spherical high-pressure sulphur resistant translation catalyst |
| CN103055907A (en) * | 2013-01-25 | 2013-04-24 | 华东理工大学 | High-water resistance catalyst for low-temperature oxidization of CO (Carbon Monoxide) and preparation method thereof |
| CN112439450B (en) * | 2019-09-02 | 2022-10-14 | 中国石油化工股份有限公司 | Modified sulfur-tolerant shift catalyst, preparation method and application |
| CN112439451B (en) * | 2019-09-02 | 2022-10-14 | 中国石油化工股份有限公司 | Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof |
| CN111250100B (en) * | 2020-02-25 | 2023-08-25 | 山东科技大学 | Sulfur-tolerant shift deoxidation catalyst for synthesis gas and preparation method thereof |
| CN115569663B (en) * | 2021-06-21 | 2023-10-20 | 中国石油化工股份有限公司 | Preparation method of novel sulfur-tolerant shift catalyst |
-
1987
- 1987-11-14 CN CN87107892.9A patent/CN1003979B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87107892A (en) | 1988-05-04 |
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International patent classification (main classification): B01J23/88 |