CN102584533A - Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method - Google Patents
Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method Download PDFInfo
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- CN102584533A CN102584533A CN2012100146447A CN201210014644A CN102584533A CN 102584533 A CN102584533 A CN 102584533A CN 2012100146447 A CN2012100146447 A CN 2012100146447A CN 201210014644 A CN201210014644 A CN 201210014644A CN 102584533 A CN102584533 A CN 102584533A
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Abstract
The invention relates to a superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method. A cobalt-molybdenum catalyst is used to conduct the gas exchange sulfur supplementation, appropriate H2S is supplemented in CO mixture gas after finishing the gas exchange so as to conduct the adsorption concentration and desorption, thereafter, H2S treated through adsorption concentration is regenerated and recovered, and is supplemented in the CO mixture gas for cyclic use, so that the sulfur supplementation amount in the CO mixture gas is effectively decreased, the sulfur cyclic utilization in the system is improved, and adverse effects of sulfur on the follow-up system are reduced. The invention solves the problems that sulfide supplementation amount is large when the cobalt-molybdenum catalyst is used to conduct the gas exchange, and excess sulfide needs to be treated after the gas exchange is finished, and the method provided by the invention can be widely applied in the production process that a calcium carbide furnace tail gas is used to synthesize ethylene-glycol.
Description
Technical field:
The present invention relates to the high dense CO gas conversion of a kind of super low sulfur and mend sulphur and cyclic utilization method, particularly be applicable to and utilize in the calcium carbide stove exhaust synthesizing glycol production technique.
Background technology:
At present, CO gas conversion catalyzer mainly contains three major types, Fe-Cr series, copper zinc system, cobalt molybdenum system.The Fe-Cr series light-off temperature is high, and reaction is violent, and difficult control of temperature needs to use big water to steam ratio condition; The TR that copper zinc system uses is narrower, the gas that suitable virgin gas component is stable, foreign matter content is few; The cobalt molybdenum is that light-off temperature is medium, and wider range is active and stable for keeping it because of active constituent is a sulfide, needs certain sulphur content in the virgin gas.
For the lower high dense CO gas of sulphur content, it is relatively more scientific and reasonable to use cobalt-molybdenum catalyst to carry out gas conversion.But, in conversion process, generally need in gas mixture, mend and go into a large amount of sulfide, excessive sulfide need be handled behind the gas conversion, otherwise can have a negative impact to follow-up system, and the processing of excessive sulfide has certain degree of difficulty.
Summary of the invention:
This patent of the present invention has proposed a kind of method of mending sulphur and sulphur cycle utilization, is used for ultra-low sulfur (sulfide content≤100mgS/m
3), (CO content>=60% V/V) uses the benefit sulphur of cobalt-molybdenum catalyst conversion process to high dense CO gas mixture, can effectively fall doctor negative benefit and go into amount, carries the doctor positive cyclic utilization rate.
The technical scheme that the present invention adopts is: mend suitable H in the conversion forward direction CO gas mixture
2S, after the conversion to the H in the gas
2S adsorbs concentrated and removes, afterwards to adsorbing spissated H
2The S recovery of regenerating is mended in the CO gas mixture and is recycled, and then effectively reduces benefit sulfur content in the CO gas mixture, improves the recycle of sulphur in system, reduces the disadvantageous effect of sulphur to follow-up system.
Sulphur and cyclic utilization method are mended in the high dense CO gas conversion of described a kind of super low sulfur, mend the H of going in the CO gas mixture
2S is by sodium sulphite and sulfuric acid reaction and get.
Sulphur and cyclic utilization method, H in the CO gas mixture after the conversion are mended in the high dense CO gas conversion of described a kind of super low sulfur
2Liquid phase or solid phase adsorption are adopted in the absorption of S, through attemperation or the pressure H with absorption
2The S desorption comes out.
Sulphur and cyclic utilization method are mended in the high dense CO gas conversion of described a kind of super low sulfur, the desorption H that comes out after the conversion
2S adds in the CO gas mixture before returning shift conversion step, thereby realizes H
2S concentrating and recycling.
The present invention is through studying high dense CO gas conversion benefit sulphur of super low sulfur and recycle; The sulfide amount of benefit when using cobalt-molybdenum catalyst to carry out gas conversion of having solved reaches the difficult problem that excessive sulfide need be handled behind the gas conversion too greatly; Can effectively reduce the benefit sulfur content in the CO gas mixture; Improve the recycle of sulphur in system, reduce the disadvantageous effect of sulphur follow-up system.The present invention can be widely used in utilizing in the calcium carbide stove exhaust synthesizing glycol production technique.
Another embodiment difference is H
2S can be by sodium sulphite and nitric acid reaction and is got;
Another embodiment difference is H
2S can be by sodium sulphite and hydrochloric acid reaction and is got.
Claims (4)
1. sulphur and cyclic utilization method are mended in the high dense CO gas conversion of super low sulfur, it is characterized in that: use cobalt-molybdenum catalyst that the high dense CO gas mixture of super low sulfur is carried out conversion and mend sulphur, mend suitable H in the conversion forward direction CO gas mixture
2S, the desorption H that comes out after the conversion
2S adds in the CO gas mixture before returning shift conversion step, thereby realizes H
2S concentrating and recycling.
2. sulphur and cyclic utilization method are mended in high dense CO gas conversion according to claims 1 described a kind of super low sulfur, it is characterized in that: mend the H of going in the conversion forward direction CO gas mixture
2S is by sodium sulphite and sulfuric acid reaction and get.
3. sulphur and cyclic utilization method are mended in high dense CO gas conversion according to claims 2 described a kind of super low sulfur, it is characterized in that: H in the CO gas mixture after the conversion
2S adopts liquid phase or solid phase adsorption to adsorb.
4. sulphur and cyclic utilization method are mended in high dense CO gas conversion according to the described a kind of super low sulfur of claims 3, it is characterized in that: through attemperation or the pressure H with absorption
2The S desorption comes out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100146447A CN102584533A (en) | 2012-01-18 | 2012-01-18 | Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100146447A CN102584533A (en) | 2012-01-18 | 2012-01-18 | Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method |
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| CN102584533A true CN102584533A (en) | 2012-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012100146447A Pending CN102584533A (en) | 2012-01-18 | 2012-01-18 | Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776137A (en) * | 2016-02-17 | 2016-07-20 | 新疆天智辰业化工有限公司 | Method for supplementing sulfur to CO shift catalyst by replacing carbon disulfide with liquid sulfur |
| CN109592639A (en) * | 2019-01-24 | 2019-04-09 | 华陆工程科技有限责任公司 | The technique of low hydrogen gas low-sulfur high carbon monoxide mine furnace exhaust gas separating-purifying carbon monoxide and hydrogen |
Citations (4)
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| EP0016631A1 (en) * | 1979-03-19 | 1980-10-01 | Air Products And Chemicals, Inc. | Removal of hydrogen sulphide and carbonyl sulphide from gas stream |
| CN1035781A (en) * | 1987-11-14 | 1989-09-27 | 湖北省化学研究所 | The sulfuration method of cobalt-molybdenum carbon monoxide transformation catalyst |
| CN1051896A (en) * | 1989-11-16 | 1991-06-05 | 新金县化肥厂 | Sulfur tolerant low temperature shift process and reactor |
| CN101733171A (en) * | 2009-12-08 | 2010-06-16 | 华烁科技股份有限公司 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
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2012
- 2012-01-18 CN CN2012100146447A patent/CN102584533A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0016631A1 (en) * | 1979-03-19 | 1980-10-01 | Air Products And Chemicals, Inc. | Removal of hydrogen sulphide and carbonyl sulphide from gas stream |
| CN1035781A (en) * | 1987-11-14 | 1989-09-27 | 湖北省化学研究所 | The sulfuration method of cobalt-molybdenum carbon monoxide transformation catalyst |
| CN1051896A (en) * | 1989-11-16 | 1991-06-05 | 新金县化肥厂 | Sulfur tolerant low temperature shift process and reactor |
| CN101733171A (en) * | 2009-12-08 | 2010-06-16 | 华烁科技股份有限公司 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
Non-Patent Citations (2)
| Title |
|---|
| 余新等: "Co-Mo系耐硫变换催化剂的硫化研究", 《化工设计通讯》 * |
| 刘芹等: "CO变换单元开工硫化方案的选择", 《化肥工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776137A (en) * | 2016-02-17 | 2016-07-20 | 新疆天智辰业化工有限公司 | Method for supplementing sulfur to CO shift catalyst by replacing carbon disulfide with liquid sulfur |
| CN109592639A (en) * | 2019-01-24 | 2019-04-09 | 华陆工程科技有限责任公司 | The technique of low hydrogen gas low-sulfur high carbon monoxide mine furnace exhaust gas separating-purifying carbon monoxide and hydrogen |
| CN109592639B (en) * | 2019-01-24 | 2024-03-01 | 华陆工程科技有限责任公司 | Process for separating and purifying carbon monoxide and hydrogen from low-hydrogen low-sulfur high-carbon monoxide ore furnace tail gas |
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| DD01 | Delivery of document by public notice |
Addressee: Xinjiang Tianye (Group) Co., Ltd. Qin Mingyue Document name: Notification of Passing Preliminary Examination of the Application for Invention |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120718 |