CN101810998A - Method for treating low-concentration sulfur dioxide waste gas - Google Patents
Method for treating low-concentration sulfur dioxide waste gas Download PDFInfo
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- CN101810998A CN101810998A CN 201010111778 CN201010111778A CN101810998A CN 101810998 A CN101810998 A CN 101810998A CN 201010111778 CN201010111778 CN 201010111778 CN 201010111778 A CN201010111778 A CN 201010111778A CN 101810998 A CN101810998 A CN 101810998A
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Abstract
The invention relates to a method for treating low-concentration sulfur dioxide waste gas. In the method, a sulfur compound containing hydrogen sulfide and low-concentration sulfur dioxide waste gas generate a chemical reaction under the function of an active aluminium oxide or titanium dioxide catalyst, and elemental sulfur is obtained by condensing and cooling a reaction product. The invention eliminates the influence of oxygen in the waste gas on the subsequent process, simplifies the tail gas treatment process, lowers the production cost, recovers sulfur resources, reduces the environmental pollution and has great economic benefit and social benefit.
Description
Technical field
The invention belongs to the industrial waste gas process field, be specifically related to a kind of processing method of low-concentration sulfur dioxide waste gas.
Background technology
In order to prevent and treat sulfur dioxide pollution and acid rain problem, the domestic and international method of taking is a lot, can be divided into dry method and wet method two big classes.Great majority use wet method at present, mainly contain gypsum method, soda method, ammonia process, metal oxide method, seawer washing method etc., though these sulfur methods have played positive role for alleviating sulfur dioxide pollution, but the byproduct of gained often is difficult for selling, cheap, the running expense is higher, and what have also causes secondary pollution.
Because dry desulfurization efficient is low, equipment is huge, operation requires height, develops slower.And wet desulfurizing process is numerous and diverse, operating difficulties, equipment corrosion are serious, and very easily produces equipment, line clogging phenomenon, exists short, critical defect such as investment is big in service life.In view of this, some factories rely on existing sulfur recovery facility, handle low concentration and contain the oxygen form waste gas of sulfur dioxide.Low concentration is contained the oxygen form waste gas of sulfur dioxide introduce burner for producing sulfur or system reaction of Salmon-Saxl device, utilize claus reaction to handle.Or low concentration is contained the oxygen form waste gas of sulfur dioxide introduce the tail gas hydrogenation reactor, utilize hydrogenation reaction that sulphur dioxide reduction is become hydrogen sulfide, absorb, to reach the purpose of desulfurization.Because it is more that low concentration contains in the oxygen form waste gas of sulfur dioxide inert component, not only influence the efficient of claus reaction, increase plant energy consumption, cause the catalyst overtemperature easily, threaten device normally to keep the safety in production, and increased equipment investment.Simultaneously, oxygen and sulfur dioxide are carried out hydrotreatment, consumed a large amount of hydrogen, strengthened production cost.
For fear of the bad reaction of sulfur dioxide, the invention provides that a kind of technical process is simple, equipment is simple, small investment, novel sulfur method that cost is low.
Summary of the invention
The present invention with low-concentration sulfur dioxide waste gas mix with hydrogen sulfide containing sulphur compound, preheating, under the effect of active alchlor or titanium deoxide catalyst, chemical reaction takes place, reacted gas obtains elemental sulfur through condensation, cooling, reduced the discharging of sulfur dioxide, reduced the influence of oxygen subsequent handling.
Its chemical equation is:
2H
2S+O
2＝＝＝2H
2O+2/nS
n
2H
2S+SO
2＝＝＝2H
2O+3/nS
n
xH
2S+NOx＝＝＝H
2O+1/2N
2+x/nS
n
The present invention is a raw material with containing sulphur compound and the low-concentration sulfur dioxide waste gas that mol ratio is a 1-99% hydrogen sulfide, its proportioning is that the mol ratio of the hydrogen sulfide in oxygen and sulfur dioxide sum and the sulphur compound in the waste gas is 1: 1.5-2.5, after 150 ℃-300 ℃ of Hybrid Heating, enter in the reactor that catalyst is housed, chemical reaction takes place, 180 ℃-450 ℃ of reaction temperature controls, time of staying 1-5 second, the gas that reaction generates is cooled to 130-160 ℃ through the cooler condensation, capture withdrawal liquid sulphur, be used for moulding, sale.Gas after the capture is handled with the tail gas hydrogenation reduction treatment system that the synthesis tail gas of sulfur recovery facility enters sulfur recovery facility, handles the tail gas qualified discharge after qualified.
According to SO in the waste gas
2And O
2Content, the addition of the hydrogen sulfide containing sulphur compound of corresponding adjustment, control H
2S and SO
2And O
2The ratio of sum is 1.5-2.5: 1 (mol%), preferred 1.9-2.1: 1 (mol%).
According to SO in the waste gas
2And O
2The height of content can be selected single-stage or multistage adiabatic reactor.SO in waste gas
2And O
2Content when high, select multistage reactor, according to the variation of reactor batch temperature, adjust the addition of the hydrogen sulfide containing sulphur compound of reactor inlets at different levels.The logistics that reactor reactions at different levels generate obtains sulphur through the condensation cooling, and remaining gas and hydrogen sulfide containing sulphur compound enter the next stage reactor after preheating.The afterbody reactor cools off remaining gas and enters the sulfur recovery facility exhaust treatment system and handle.
Described multistage reactor is not more than 5 grades, preferably is not more than 3 grades.
According to SO in the waste gas
2And O
2The height of content can be selected single-stage or multistage isothermal reactor.
In the described low-concentration sulfur dioxide waste gas, SO
2Concentration range is at 0.01-30% (mol%), O
2Concentration range is at 0.01-22% (mol%), other component be nitrogen, carbon dioxide, carbon monoxide, sulfur trioxide, hydrogen,, nitrogen oxide, at least a above component of water.
In the described hydrogen sulfide containing sulphur compound, H
2The S concentration range is at 1-99% (mol%).Described sulphur compound is the gas of refinery gas, natural gas, coal gas, synthetic gas desulfurization recovery back sulfur-bearing.
Described catalyst is a carrier with active alundum (Al, titanium dioxide, and the interpolation metal oxide is an active component, wherein the compound of metals such as iron, chromium, vanadium, manganese at least a more than.
The specific embodiment
Embodiment 1
A kind of low concentration contains the oxygen form waste gas of sulfur dioxide, and it consists of: SO
25.62%, CO
21.98%, CO 0.08%, H
2O 5.68%, N
286.44%, O
20.2%, with this kind of 100mol waste gas, consist of with 17.48mol: H
2S 65%, CO
234.8%, the hydrogen sulfide containing sulphur compound of hydro carbons 0.2% mixes, being preheated to 200 ℃ enters in the fixed bed reactors that active aluminum trioxide catalyst is housed and reacts, 300 ℃ of reaction temperature controls, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through the condensation of exhaust steam cooler, captures withdrawal liquid sulphur.Gas after the capture enters the tail gas hydrogenation system of sulfur recovery facility, after hydrogenation, chilling, absorption, tail gas burn, and qualified discharge.The conversion ratio of sulfur dioxide is 94.73%.
Embodiment 2
A kind of low concentration contains the oxygen form waste gas of sulfur dioxide, and it consists of: SO
25.62%, CO
21.98%, CO 0.08%, H
2O 5.68%, N
283.64%, O
23%, with this kind of 100mol waste gas, and consist of: H
2S 65%, CO
234.8%, the hydrogen sulfide containing sulphur compound of the 7.45mol of hydro carbons 0.2% mixes, being preheated to 200 ℃ enters to be equipped with in the first order fixed bed reactors that active alundum (Al and titanium dioxide mixture are catalyst and reacts, 363 ℃ of reaction temperatures, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through the condensation of exhaust steam cooler, captures withdrawal liquid sulphur.Gas after the capture mixes with the hydrogen sulfide containing sulphur compound of 19.07mol, being preheated to 200 ℃ enters to be equipped with in the second level fixed bed reactors that active alundum (Al and titanium dioxide mixture are catalyst and reacts, 372 ℃ of reaction temperatures, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through the condensation of exhaust steam cooler, captures withdrawal liquid sulphur.Gas after the capture enters the tail gas hydrogenation system of sulfur recovery facility, after hydrogenation, chilling, absorption, tail gas burn, and qualified discharge.The conversion ratio of sulfur dioxide is 91.92%.
Embodiment 3
A kind of low concentration contains the oxygen form waste gas of sulfur dioxide, and it consists of: SO
24.5%, CO
21.98%, CO0.08%, H
2O 5.68%, N
278.18%, O
25%, NOx0.0008%.With this kind of 100mol waste gas, and consist of: H
2S 65%, CO
234.8%, the hydrogen sulfide containing sulphur compound of the 7.1mol of hydro carbons 0.2% mixes, being preheated to 200 ℃ enters in the first order fixed bed reactors that titanium deoxide catalyst is housed and reacts, 357 ℃ of reaction temperatures, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through initiating the cooler condensation, captures withdrawal liquid sulphur.Gas after the capture mixes with the hydrogen sulfide containing sulphur compound of 7.1mol, being preheated to 200 ℃ enters in the fixed bed reactors of the second level and reacts, 357 ℃ of reaction temperatures, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through the condensation of exhaust steam cooler, captures withdrawal liquid sulphur.Gas after the capture mixes with the hydrogen sulfide containing sulphur compound of 14.83mol, being preheated to 200 ℃ enters in the third level fixed bed reactors and reacts, 343 ℃ of reaction temperatures, reaction pressure is controlled near the normal pressure, the gas that reaction generates is cooled to 160 ℃ through the condensation of exhaust steam cooler, captures withdrawal liquid sulphur.Do not detect NOx in the product, the gas after the capture enters the tail gas hydrogenation system of sulfur recovery facility, after hydrogenation, chilling, absorption, tail gas burn, and qualified discharge.The conversion ratio of sulfur dioxide is 93.03%.
Above-mentioned inventive method is compared with existing direct hydrogenation technique, has not only saved a large amount of hydrogen resources, has reduced production cost.And eliminated oxygen and sulfur dioxide to the influence of sulfur recovery facility, promoted the steady production of sulfur recovery facility.Can also reclaim the sulphur resource, reduce the discharging of sulfur dioxide and nitrogen oxide, have better economic and social benefit.
Claims (8)
1. the processing method of a low-concentration sulfur dioxide waste gas, it is characterized in that: it is to be raw material with hydrogen sulfide containing sulphur compound and low-concentration sulfur dioxide waste gas, wherein the content of hydrogen sulfide in described hydrogen sulfide containing sulphur compound is 1-99mol%, described proportion of raw materials is that the mol ratio of the hydrogen sulfide in oxygen and sulfur dioxide sum and the sulphur compound in the waste gas is 1: 1.5-2.5, after 150 ℃-300 ℃ of Hybrid Heating, enter in the reactor that catalyst is housed, chemical reaction takes place, 180 ℃-450 ℃ of reaction temperature controls, time of staying 1-5 second, the logistics that reaction generates is cooled to 130-160 ℃ through condensation and obtains sulphur, remaining gas is handled with the tail gas hydrogenation reduction treatment system that the synthesis tail gas of sulfur recovery facility enters sulfur recovery facility, handles the tail gas qualified discharge after qualified.
2. the processing method of low-concentration sulfur dioxide waste gas according to claim 1 is characterized in that: according to SO in the waste gas
2And O
2Content, the addition of the hydrogen sulfide containing sulphur compound of corresponding adjustment, control H
2S and SO
2And O
2The ratio of sum is 1.5-2.5: 1mol%, preferred 1.9-2.1: 1mol%.
3. the processing method of low-concentration sulfur dioxide waste gas according to claim 1 is characterized in that: according to SO in the waste gas
2And O
2The height of content can be selected single-stage or multistage adiabatic reactor. SO in waste gas
2And O
2Content when high, select multistage reactor, variation according to reactor batch temperature, adjust the addition of the hydrogen sulfide containing sulphur compound of reactor inlets at different levels. the logistics that reactor reactions at different levels generate obtains sulphur through the condensation cooling, remaining gas and hydrogen sulfide containing sulphur compound enter the next stage reactor after preheating. and the afterbody reactor cools off remaining gas and enters the sulfur recovery facility exhaust treatment system and handle.
4. the processing method of low-concentration sulfur dioxide waste gas according to claim 1, its feature also is: described multistage reactor is not more than 5 grades, preferably is not more than 3 grades.
5. the processing method of low-concentration sulfur dioxide waste gas according to claim 1 is characterized in that: according to SO in the waste gas
2And O
2The height of content can be selected single-stage or multistage isothermal reactor.
6. the processing method of low-concentration sulfur dioxide waste gas according to claim 1 is characterized in that: in the described low-concentration sulfur dioxide waste gas, and SO
2Concentration range is at 0.01-30mol%, O
2Concentration range is at 0.01-22mol%, and other component is at least a above component in nitrogen, carbon dioxide, carbon monoxide, sulfur trioxide, hydrogen, nitrogen oxide and the water.
7. the processing method of low-concentration sulfur dioxide waste gas according to claim 1 is characterized in that: in the described hydrogen sulfide containing sulphur compound, described sulphur compound is the gas that refinery gas, natural gas, coal gas or synthetic gas desulfurization reclaim the back sulfur-bearing.
8. the processing method of low-concentration sulfur dioxide waste gas according to claim 1, it is characterized in that: described catalyst is a carrier with active alundum (Al, titanium dioxide or alchlor and titanium dioxide mixture, the interpolation metal oxide is an active component, wherein the compound of iron, chromium, vanadium, manganese metal at least a more than.
Priority Applications (1)
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|---|---|---|---|
| CN 201010111778 CN101810998A (en) | 2010-02-22 | 2010-02-22 | Method for treating low-concentration sulfur dioxide waste gas |
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|---|---|---|---|
| CN 201010111778 CN101810998A (en) | 2010-02-22 | 2010-02-22 | Method for treating low-concentration sulfur dioxide waste gas |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307360A (en) * | 2014-10-28 | 2015-01-28 | 南京大学（苏州）高新技术研究院 | Gas-phase desulfurization oxidant and application thereof as well as method for removing hydrogen sulfide |
| CN104524968A (en) * | 2014-12-16 | 2015-04-22 | 杨楠 | Claus tail gas deep purification catalytic reduction oxidation process and catalyst used by claus tail gas deep purification catalytic reduction oxidation process |
| CN106629625A (en) * | 2016-12-14 | 2017-05-10 | 山东迅达化工集团有限公司 | Sulfur recovery process for treating low-concentration acidic gases |
| CN106698360A (en) * | 2016-12-14 | 2017-05-24 | 山东迅达化工集团有限公司 | Process for recycling sulfur from low-concentration acid gas |
| CN107281914A (en) * | 2016-04-05 | 2017-10-24 | 中国石油天然气集团公司 | The processing unit and method of a kind of regenerated flue gas |
| CN108310964A (en) * | 2017-01-16 | 2018-07-24 | 托普索公司 | The poor H of catalysis oxidation2The method and system of S streams |
| CN109395555A (en) * | 2018-12-27 | 2019-03-01 | 陈萌 | A kind of method of sulfur trioxide in removing flue gas during smelting |
| CN110605109A (en) * | 2018-06-14 | 2019-12-24 | 中国石油天然气股份有限公司 | Catalyst for waste gas treatment of liquid sulfur degassing process, preparation method and application process |
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| CN1155874A (en) * | 1995-05-30 | 1997-07-30 | 埃尔夫·阿奎坦生产公司 | Catalytic desulphurization process for a gas containing H2S and SO2 compounds, and catalyst for impelementing said process |
| CN1377294A (en) * | 1999-09-30 | 2002-10-30 | 加斯特克股份有限公司 | Process for the removal of sulphur compounds from gases |
| WO2009055104A2 (en) * | 2007-07-05 | 2009-04-30 | Worleyparsons Group, Inc. | Process for the thermal reduction of sulfur dioxide to sulfur |
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2010
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Patent Citations (3)
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| CN1155874A (en) * | 1995-05-30 | 1997-07-30 | 埃尔夫·阿奎坦生产公司 | Catalytic desulphurization process for a gas containing H2S and SO2 compounds, and catalyst for impelementing said process |
| CN1377294A (en) * | 1999-09-30 | 2002-10-30 | 加斯特克股份有限公司 | Process for the removal of sulphur compounds from gases |
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Non-Patent Citations (1)
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|---|
| 《Applied Catalysis A: General》 20030114 Anatoli A. Davydov et al. "Metal oxides in hydrogen sulfide oxidation by oxygen and sulfur dioxide I. The comparison study of the catalytic activity. Mechanism of the interactions between H2S and SO2 on some oxides " 第95页表1，第96页第3.1节 8 第244卷, 第1期 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307360A (en) * | 2014-10-28 | 2015-01-28 | 南京大学（苏州）高新技术研究院 | Gas-phase desulfurization oxidant and application thereof as well as method for removing hydrogen sulfide |
| CN104524968A (en) * | 2014-12-16 | 2015-04-22 | 杨楠 | Claus tail gas deep purification catalytic reduction oxidation process and catalyst used by claus tail gas deep purification catalytic reduction oxidation process |
| CN107281914A (en) * | 2016-04-05 | 2017-10-24 | 中国石油天然气集团公司 | The processing unit and method of a kind of regenerated flue gas |
| CN106629625A (en) * | 2016-12-14 | 2017-05-10 | 山东迅达化工集团有限公司 | Sulfur recovery process for treating low-concentration acidic gases |
| CN106698360A (en) * | 2016-12-14 | 2017-05-24 | 山东迅达化工集团有限公司 | Process for recycling sulfur from low-concentration acid gas |
| CN106629625B (en) * | 2016-12-14 | 2019-04-05 | 山东迅达化工集团有限公司 | Handle the recovery technology of sulfur of low concentration sour gas |
| CN106698360B (en) * | 2016-12-14 | 2019-04-09 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of low concentration sour gas |
| CN108310964A (en) * | 2017-01-16 | 2018-07-24 | 托普索公司 | The poor H of catalysis oxidation2The method and system of S streams |
| CN110605109A (en) * | 2018-06-14 | 2019-12-24 | 中国石油天然气股份有限公司 | Catalyst for waste gas treatment of liquid sulfur degassing process, preparation method and application process |
| CN110605109B (en) * | 2018-06-14 | 2022-05-10 | 中国石油天然气股份有限公司 | Catalyst for waste gas treatment of liquid sulfur degassing process, preparation method and application process |
| CN109395555A (en) * | 2018-12-27 | 2019-03-01 | 陈萌 | A kind of method of sulfur trioxide in removing flue gas during smelting |
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Application publication date: 20100825 |