CN1463801A - Low cost sulfur transformation resistant deoxidizing agent - Google Patents
Low cost sulfur transformation resistant deoxidizing agent Download PDFInfo
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- CN1463801A CN1463801A CN 02135207 CN02135207A CN1463801A CN 1463801 A CN1463801 A CN 1463801A CN 02135207 CN02135207 CN 02135207 CN 02135207 A CN02135207 A CN 02135207A CN 1463801 A CN1463801 A CN 1463801A
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- deoxidier
- metal
- spent catalyst
- aqueous solution
- solvent
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Abstract
The low cost sulfur resistant converting deoxidant is prepared with waste Co-Mo system catalyst and through crushing, mixing with pore-creating agent and liquid and/or solid peptizator, kneading, forming, roasting and activating with activating liquid. The present invention can utilize the waste resource effectively to reduce the cost of producing deoxidant. The deoxidant may be used in the pressure range lower than 5.0 MPa and has deoxidation performance similar to that of industrial deoxidant and strength and strength stability higher than those of industrial deoxidant.
Description
Technical field
The present invention relates to a kind of sulfur transformation resistant deoxidizing agent, particularly a kind of low cost sulfur transformation resistant deoxidizing agent.
Background technology
In China is raw material with the coal, contain a spot of oxygen (being generally 0.5-0.8%) in the unstripped gas that " atmospheric fixed bed intermittent gasification " method of employing is produced, in the unstripped gas a spot of oxygen will with active component or the carrier generation sulfation reaction in the catalyst, make rapid catalyst deactivation, need above beds, load a large amount of sulfur transformation resistant deoxidizing agents for this reason, below the oxygen removal to 0.2% in the unstripped gas, to prolong the service life of catalyst.Now use industrial deoxidier all with γ-Al
2O
3Being carrier, is active component with the cobalt molybdenum, and its production cost is higher and intensity is lower, can not satisfy industrial requirement preferably.It is raw material that the present invention adopts waste and old cobalt-molybdenum series catalyst, can make the higher and lower-cost sulfur transformation resistant deoxidizing agent of intensity.
At present, both at home and abroad to the waste and old series catalysts of cobalt molybdenum utilize method a lot, the method described in U.S. Pat 5066469, US5013533; The waste and old series catalysts of China's cobalt molybdenum to utilize method to have following several: (1) reclaims cobalt and molybdenum wherein, (2) spent catalyst is sieved, melt down and continue to use (Henan chemical industry, 1992.12), (3) are processed into catalyst (Chinese patent CN98110476.2) again with spent catalyst.Said method substantially all is to reclaim cobalt and molybdenum wherein or it is processed use again.
Summary of the invention
The present invention utilizes spent catalyst, adopt special preparation method, prepare sulfur transformation resistant deoxidizing agent, not only reduced the production cost of deoxidier, and improved the intensity of deoxidier and effectively utilized the resource of spent catalyst, have tangible economic benefit and social benefit.
Details are as follows for the concrete technical scheme of the present invention: (1) pulverizes waste and old Co-Mo series catalysts; (2) add pore creating material and peptizing agent is mediated, moulding, roasting; (3) carrying out activation processing with activating solution makes.
At first spent catalyst is crushed to the 80-400 order, be preferably the 100-200 order, add that pore creating material and peptizing agent are mediated, extrusion and roasting again, the used peptizing agent of the present invention is solid gum solvent or liquid glue solvent, also can both use the solid gum solvent, use the liquid glue solvent again.The liquid glue solvent is nitric acid, I
A--III
AThe nitrate aqueous solution of metal and/or I
A--III
AThe sulfate solution of metal is preferably I
A--III
AThe nitrate aqueous solution of metal.The liquid glue solvent is if used nitric acid, and its consumption accounts for the 1-20% of spent catalyst weight; If used I
A--III
AThe nitrate aqueous solution of metal and/or I
A--III
AThe sulfate solution of metal, its consumption account for the 1-10% of spent catalyst weight in metal oxide.The solid gum solvent is Al (OH)
3, boehmite and/or gibbsite, its consumption accounts for the 5-80% of spent catalyst weight, is preferably 10-40%.
The used pore creating material of the present invention can be an organic pore-forming agents, also can be inorganic pore creating material, organic pore-forming agents such as sesbania powder, citric acid, methyl-prop diluted acid formicester and/or kapok preferably, and its consumption accounts for the 1-10% of spent catalyst weight.
Added the later mixture of above-mentioned peptizing agent and pore creating material through kneading, after the moulding at 400 ℃--700 ℃ of following roastings, and then product of roasting is carried out activation processing with activating solution, the used activating solution of the present invention is the hydroxide aqueous solution of alkali-metal hydroxide aqueous solution, alkali-metal carbonate aqueous solution, alkaline-earth metal, the soluble carbon acid salt aqueous solution and/or the ammoniacal liquor of alkaline-earth metal, its content is counted 1-20% with metal oxide or ammonia weight, can adopt incipient impregnation during activation processing, after super-dry, obtain the deoxidier product at last.Certainly can also pass through calcination process more at last, also can be without roasting, directly use dry back.
Outstanding advantage of the present invention is: utilizing waste and old Co-Mo is the material of sulfur-resistant transformation catalyst as deoxidier, can reduce the production cost of deoxidier greatly and effectively utilize the resource of spent catalyst.The deoxidier that the present invention makes can use in the pressure limit of≤5.0MPa, and its deoxy performance is suitable with industrial deoxidier, and intensity and strength stability all are higher than industrial deoxidier.
Deoxidier of the present invention can adopt following evaluation and test condition:
Strength test: get 20 samples at random, on QCY-602 type intensity meter, measure the radially crushing strength of deoxidier, represent the intensity of deoxidier with the mean value of unit length.
Intensity stabilization property testing: the strength stability that adopts the harsh The effects deoxidier of poach, poach experiment condition: take by weighing a certain amount of deoxidier and in boiling water, boiled 4 hours, measure the variation of intensity after the oven dry, represent deoxidier strength stability quality with the size of retention rate.
The test of normal pressure intrinsic deoxy performance: estimate the deoxy performance of deoxidier on the normal pressure micro-reactor, with under identical appreciation condition, the time that oxygen began to increase during tail gas was formed, promptly the length of deaeration time is represented the quality of deoxidier deoxy performance.Catalyst loading amount 0.6 gram, air speed 5000h
-1Water/gas is than 200 ℃ of 0.5 reaction temperatures; Unstripped gas is formed O
20.6-0.7%, CO 45%, and CO 25%, H
2S 2000PPm, surplus be H
2
The specific embodiment
Now further specify the present invention in conjunction with the embodiments, but scope of the present invention is not limited to following embodiment.
Embodiment 1
Spent catalyst is crushed to 120 orders, gets material 300 grams after the pulverizing, add 40 gram gibbsites and 12 gram methyl-prop diluted acid formicesters, the nitric acid that adds 10 weight % is again mediated, moulding, extrusion and 500 ℃ of following roastings.(potash content is with K to carry out activation processing with the equal-volume solution of potassium carbonate again
2O weight counts 12%), make product, deoxidier is numbered T-1, and its deoxy performance and intensity and strength stability contrast are as shown in table 1.
Embodiment 2
The deoxidier preparation method is with embodiment 1, and different is with Mg (OH)
2Solution replaces solution of potassium carbonate product of roasting to be carried out activation processing, Mg (OH)
2Content counts 3% with MgO weight, and deoxidier is numbered T-2, and its deoxy performance and intensity and strength stability contrast are as shown in table 1.Embodiment 3
The deoxidier preparation method is with embodiment 1, and the nitric acid that different is substitutes 10 weight % with 10 weight % potassium nitrate solutions is mediated, moulding, extrusion and roasting, and deoxidier is numbered T-3, and its deoxy performance and intensity and strength stability contrast are as shown in table 1.
Embodiment 4
The deoxidier preparation method is with embodiment 1, different is mediates, the sintering temperature after the extrusion adopts 600 ℃, and as activating solution product of roasting is carried out activation processing with the aqueous ammonia to replace solution of potassium carbonate of 10 weight %, and deoxidier is numbered T-4, and its performance comparison is as shown in table 1.
Table 1. deoxidier performance comparison
Deoxidier intensity poach experiment back deaeration time
N/cm intensity, the N/cm retention rate, (min)
％
T-1 108 102 94.4 210
T-2 121 117 96.7 215
T-3 118 112 94.9 220
T-4 112 108 96.4 224
Industry deoxidier 77 46 59.7 210
Claims (15)
1. low cost sulfur transformation resistant deoxidizing agent by following manner preparation, it is characterized in that: (1) pulverizes waste and old Co-Mo series catalysts; (2) add pore creating material and peptizing agent is mediated, moulding, roasting; (3) carrying out activation processing with activating solution makes.
2. by the deoxidier described in the claim 1, it is characterized in that spent catalyst is crushed to the 80-400 order.
3. by the deoxidier described in the claim 1, it is characterized in that spent catalyst is crushed to the 100-200 order.
4. by the deoxidier described in the claim 1, it is characterized in that peptizing agent is solid gum solvent and/or liquid glue solvent.
5. by the deoxidier described in the claim 4, it is characterized in that the liquid glue solvent is nitric acid, I
A--III
AThe nitrate aqueous solution of metal and/or I
A--III
AThe sulfate solution of metal.
6. by the deoxidier described in the claim 4, it is characterized in that the liquid glue solvent is I
A--III
AThe nitrate aqueous solution of metal.
7. by the deoxidier described in the claim 4, it is characterized in that the liquid glue solvent if used nitric acid, its consumption accounts for the 1-20% of spent catalyst weight; If used I
A--III
AThe nitrate aqueous solution of metal and/or I
A--III
AThe sulfate solution of metal, its consumption account for the 1-10% of spent catalyst weight in metal oxide.
8. by the deoxidier described in the claim 4, it is characterized in that the solid gum solvent is Al (OH)
3, boehmite and/or gibbsite.
9. by the deoxidier described in the claim 4, it is characterized in that the consumption of solid gum solvent accounts for the 5-80% of spent catalyst weight.
10. by the deoxidier described in the claim 4, it is characterized in that the consumption of solid gum solvent accounts for the 10-40% of spent catalyst weight.
11. the deoxidier by described in the claim 1 is characterized in that pore creating material is organic pore-forming agents such as sesbania powder, citric acid, methyl-prop diluted acid formicester and/or kapok.
12. the deoxidier by described in the claim 1,2,4 or 11 is characterized in that the consumption of pore creating material accounts for the 1-10% of spent catalyst weight.
13., it is characterized in that activating solution is the hydroxide aqueous solution of alkali-metal hydroxide aqueous solution, alkali-metal carbonate aqueous solution, alkaline-earth metal, the soluble carbon acid salt aqueous solution and/or the ammoniacal liquor of alkaline-earth metal according to claim 1,2,4 or 11 described deoxidiers.
14. deoxidier according to claim 13 is characterized in that activating solution content counts 1-20% with metal oxide or ammonia weight.
15. according to claim 1,2,4 or 11 described deoxidiers, it is characterized in that adding mediate behind pore creating material and the peptizing agent, when moulding, roasting, sintering temperature is 400 ℃--700 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021352070A CN1186117C (en) | 2002-06-12 | 2002-06-12 | Low cost sulfur transformation resistant deoxidizing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021352070A CN1186117C (en) | 2002-06-12 | 2002-06-12 | Low cost sulfur transformation resistant deoxidizing agent |
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| Publication Number | Publication Date |
|---|---|
| CN1463801A true CN1463801A (en) | 2003-12-31 |
| CN1186117C CN1186117C (en) | 2005-01-26 |
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ID=29744236
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021352070A Expired - Lifetime CN1186117C (en) | 2002-06-12 | 2002-06-12 | Low cost sulfur transformation resistant deoxidizing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100377990C (en) * | 2006-07-13 | 2008-04-02 | 本溪北方煤化工有限公司 | Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN103143315A (en) * | 2013-03-13 | 2013-06-12 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN111250100A (en) * | 2020-02-25 | 2020-06-09 | 山东科技大学 | Sulfur-tolerant shift deoxidation catalyst for synthesis gas and preparation method thereof |
| CN114602487A (en) * | 2022-04-13 | 2022-06-10 | 湖北禾谷环保有限公司 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
-
2002
- 2002-06-12 CN CNB021352070A patent/CN1186117C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100377990C (en) * | 2006-07-13 | 2008-04-02 | 本溪北方煤化工有限公司 | Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN102451701B (en) * | 2010-10-22 | 2014-08-06 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN103143315A (en) * | 2013-03-13 | 2013-06-12 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN103143315B (en) * | 2013-03-13 | 2015-01-21 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN111250100A (en) * | 2020-02-25 | 2020-06-09 | 山东科技大学 | Sulfur-tolerant shift deoxidation catalyst for synthesis gas and preparation method 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 |
| CN114602487A (en) * | 2022-04-13 | 2022-06-10 | 湖北禾谷环保有限公司 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
| CN114602487B (en) * | 2022-04-13 | 2022-11-15 | 湖北禾谷环保有限公司 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1186117C (en) | 2005-01-26 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20080104 |
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Effective date of registration: 20080104 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: Linzi District of Shandong city of Zibo province Huan Road No. 15 Patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. |
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Granted publication date: 20050126 |