CN103446861A - Circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization - Google Patents
Circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization Download PDFInfo
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- CN103446861A CN103446861A CN2013104157515A CN201310415751A CN103446861A CN 103446861 A CN103446861 A CN 103446861A CN 2013104157515 A CN2013104157515 A CN 2013104157515A CN 201310415751 A CN201310415751 A CN 201310415751A CN 103446861 A CN103446861 A CN 103446861A
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Abstract
The invention discloses a circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization. The circulating treatment method comprises the steps: firstly, carrying out organic sulfur conversion on regenerated waste gas with high sulfur content to enable organic sulfides in the regenerated waste gas to be converted into H2S, wherein the regenerated waste gas is generated in a temperature swing adsorption desulfurization process; then, carrying out wet desulfurization to remove the H2S, and furthermore, oxidizing the removed and absorbed sulfides to form sulfur to be recovered; and returning the regenerated waste gas subjected to wet desulfurization to a temperature swing adsorption system to be recycled. By using the method, the sulfur in the regenerated waste gas with high sulfur content can be recovered as a useful resource, and the treated gas can be returned to the temperature swing adsorption system and recycled, so that the aims of zero emission and no pollution are achieved really.
Description
Technical field
A kind of method that the present invention relates to high sulfur-bearing regeneration off gases circular treatment that the Temp .-changing adsorption sweetening process is produced and recycle.
Background technology
Temp .-changing adsorption is a kind of simple and efficient gas separation/purification style, existing application widely in to many industrial circles such as coke oven gas purification, natural gas purification, Semi-water Gas Purification, water-gas purification, polysilicon tail gas purification, purifying exhausting gas of yellow phosphorus, calcium carbide tail gas purifications at present.
The Temp .-changing adsorption sweetening process is a kind of sulfur removal technology commonly used to sulfurous gas, especially height is contained to removing of organic sulfur compound, and the unrivaled advantage of conventional sulfur removal technology is arranged.The flow process of Temp .-changing adsorption desulfurization, be generally make sulfur-bearing unstripped gas in being filled with the adsorption tower of adsorbent, successively through absorption, step-down, heating, blast-cold, the step such as boost.Sulfide composition wherein is adsorbed agent absorption and removes through adsorption tower adsorbent bed the time, and the thing that cures until adsorbent bed penetrates.For the Temp .-changing adsorption bed can be recycled, adsorbent bed must the regeneration that the thing that cured penetrates, need the desulfurization adsorption tower is heated and blast-cold.The heat air and the blast-cold gas that enter adsorption tower in regenerative process are regeneration gas, it can be the desulfurizing and purifying gas from this desulphurization system, can be also as the outer gas of other systems such as hydrogen, nitrogen, natural gas, Utilization of PSA Relief Gas and the various venting of speeding.General regeneration gas accounts for processes 2 ~ 8% of tolerance.Regeneration gas is by after adsorption tower, and adsorbent bed middle adsorbed sulfide is heated desorb and takes out of, becomes the regeneration off gases of load high-sulfur, and the content of its sulfide can be the decades of times of unstripped gas.For the processing of regeneration off gases, as publication number CN101323799A etc. relates to the bibliographical informations such as temperature swing adsorption process to coke oven gas purification, be all generally direct emptying or burnt as combustion gas.No matter the regeneration off gases of high sulfur-bearing is direct emptying or burned processing, does not in fact all have really sulfide " is removed ", and be only sulfide to be separated concentrate and shift rear discharge, still will cause severe contamination to environment.
Summary of the invention
For above-mentioned situation, a kind of method that the invention provides circular treatment to the regeneration off gases that produces in the Temp .-changing adsorption sweetening process and recycle, can make the sulphur in high sulfur-bearing regeneration off gases be recovered as useful resource, regeneration gas after processing can be returned to again temperature swing adsorption system and recycle, and has really realized the purpose of Zero-discharge non-pollution.
The circulation process method of Temp .-changing adsorption desulfurization regeneration waste gas of the present invention, basic process and principle are that the high sulfur-bearing regeneration off gases that the Temp .-changing adsorption sweetening process is produced is first carried out the organic sulfur conversion, and organic sulfur compound is wherein changed into to H
2s, and then it is removed through wet desulphurization, and the sulfide that will remove after absorption is further oxidized to sulphur recovery, the regeneration gas after wet desulphurization is processed is returned to temperature swing adsorption system and is recycled.
Under heating and catalytic condition, realize organic sulfur is converted into to H
2s, be common method currently reported and/or that use, that is, after described high sulfur-bearing regeneration off gases is heated to the required temperature of hydroconversion of organic sulfur, the organic sulfur converter through being provided with the catalyzed conversion filling batch changes into H
2s.Report to some extent all in comprising the existing document such as CN1130151A.Also preferred this mode of said organic sulfur conversion processing process in said method of the present invention.Wherein, to the heating-up temperature of said high sulfur-bearing regeneration off gases is general controlled, be made as 150 ~ 450 ℃, further preferably heating-up temperature is 300 ~ 400 ℃.
After said high sulfur-bearing regeneration off gases is heated to the required temperature of catalyzed conversion, the present invention preferably adopts at least one in being provided with ferrimanganic molybdenum series catalyst, iron molybdenum series hydrocatalyst, cobalt molybdenum series hydrocatalyst or cobalt molybdenum nickel series hydrogenating catalyst for the organic sulfur converter of filling batch, and organic sulfur compound is converted into to H
2s.Using and operating of above-mentioned reforming catalyst is all routine techniques currently reported and/or that use.
As above-mentioned, to being converted into H
2the wet desulphurization of S is processed, and also can adopt the conventional method of currently reported/use, particularly can adopt alkaline solution absorption pattern the most commonly used, under 30 ~ 60 ℃, will be converted into H
2after gas after S absorbs with akaline liquid, when resulting this sulfur removing pregnant solution regeneration, and the sulfide that will remove after absorption is further oxidized to sulphur recovery.Wherein, it is any in hot potash method at present commonly used, amine method (as the MDEA method etc.) or ammonia process, tannin extract method that wet desulphurization of the present invention is processed what preferably adopt, and the sulfide will remove absorption when sulfur removing pregnant solution is regenerated after is oxidized to sulphur recovery.
Except aforesaid way, to the said H changed into by organic sulfur compound
2s gas removes with the wet desulphurization mode, and a kind of more easy optimal way is saidly should contain H
2s gas returns to the front wet desulfurization system of Temp .-changing adsorption sweetening process in said this regeneration off gases source and processes and Recovered sulphur.
Be appreciated that thus, the regeneration off gases processing method that the present invention is above-mentioned, can solve satisfactorily the difficult problem that in current Temp .-changing adsorption sulfur removal technology, regeneration off gases is processed, not only make all can cause the sulfide of severe environmental pollution " to turn waste into wealth " emptying in regeneration off gases or burning at present, after being converted into sulphur recovery, utilize, and the regeneration gas after processing can return to temperature swing adsorption system and recycle, really realized the effect of Zero-discharge non-pollution.
The specific embodiment by the following examples is described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Without departing from the idea case in the present invention described above, various replacements or the change according to ordinary skill knowledge and customary means, made, all should comprise within the scope of the invention.
The specific embodiment
embodiment 1
The present embodiment is for take sulfur-containing gas as the LNG of raw material through Temp .-changing adsorption sulfur removal technology 57kt/a processed.Sulfur-containing gas medium sulphide content component is organic sulfur ~ 250mg/Nm
3, COS ~ 50
mg/Nm
3; The regeneration gas source of the gas is the natural gas after desulfurization, regeneration off gases tolerance 500Nm
3/ h, pressure 0.1Mpa(G), the sulfide content in regeneration off gases is: organic sulfur ~ 5g/Nm
3, COS ~ 1g/Nm
3.Handling process to regeneration off gases is:
At first, this regeneration off gases is heated and adjusts the temperature to 320-390 ℃ through gas-fired heater, then enter the organic sulfur converter, pass through the reforming catalyst bed from top to bottom, the converter filler is that the JT201 cobalt molybdenum nickel that Jingjiang catalyst total Co., Ltd., Factory in Jiangsu produces is organic sulfur hydroconversion catalyst (CN102886265A report).In regeneration off gases after conversion, most organic sulfurs are converted into H
2s.Two organic sulfur converters are set in this step of converting altogether, and two towers are in parallel, one open one standby.
This regeneration off gases after completing organic sulfur and transforming enters heat exchanger and carries out the heat exchange cooling, and simultaneously to the cold regeneration gas heating of need heating.Through cooled this transformation tissue culture EGT of heat exchanger, be 80-100 ℃, again through being water-cooled to ~ 40 ℃, send into diethanol amine (MDEA) method desulfurizer, the regeneration off gases that enters absorption tower fully contacts with desulfurization lean solution adverse current from top to bottom from the bottom to top, and the gas after desulfurization is flowed out by the absorption tower tower top.Absorbed H
2the doctor solution of S is called rich solution, and rich solution goes out by flash tank hydro carbons is wherein removed from the absorbing tower underflow.Rich solution after flash distillation enters, and poor-rich solution heat exchanger is heated up, and then enters the regenerator top, from top to bottom with steam, contacts, by the H in rich solution
2the S air lift out, is separated sucking-off H
2the doctor solution of S is called lean solution, lean solution through above-mentioned poor-can deliver to absorption tower after rich solution heat exchanger cooling to recycle.The regeneration overhead effluent air is mainly H
2s and steam, after cooling by most of water vapor condensation and remove.Fixed gas is the sulphur foam, through the sulphur foam pump, sends into the sulfur melting kettle heating and melting, and the sulphur slurry is discharged from sulfur discharging valve, is solidified as sulfur in lump form and reclaims.The clear liquid of being discharged by still top after the cooling precipitation of defecator, the clear liquid deallocation liquid bath overflowed from top.Regeneration gas after processing can be returned to temperature swing adsorption system and recycle.
embodiment 2
The present embodiment is for take coke-stove gas as unstripped gas, send into routinely and take sodium carbonate as alkali source, the wet desulphurization device that the PDS+ tannin extract is composite catalyst, sulfur removing pregnant solution is regenerated with wet oxidation manner, the recovery of sulphur is reclaimed sulphur cream, vertical sieve plate column ammonia still process by embodiment 1 continuous sulfur melting kettle mode.Wet desulphurization gas is processed and is purified oven gas 40kNm through temperature swing adsorption system again
3/ h, for the production of the synthetic ammonia of 200kt/a.After the part of take purifies, coke-stove gas is the regeneration gas source of the gas, and Temp .-changing adsorption agent bed is regenerated, and the regeneration off gases tolerance of generation is about 2000Nm
3/ h, pressure is 0.05Mpa(G), temperature is 250 ~ 300 ℃, the sulfide content in regeneration off gases is: organic sulfur: ~ 5g/Nm
3, H
2s: ~ 2g/Nm
3, S ~ 1g/Nm
3.Handling process to regeneration off gases is:
At first, high sulfur-bearing regeneration off gases heats and adjusts the temperature to 380-395 ℃ through gas-fired heater.Concrete operation method can arrange from Temp .-changing adsorption regeneration off gases outlet header to organic sulfur converter inlet manifold a bypass duct, by control valve, a part of regeneration off gases is heated through heater, another part directly through this bypass duct be heated after gas mix, with control and the adjusting that realizes temperature.Be provided with control valve on pipeline, enter the temperature of organic sulfur converter in order to control regeneration gas.
The above-mentioned regeneration off gases be heated to after temperature required, through the organic sulfur converter, the top inlet manifold enters the organic sulfur converter, pass through the reforming catalyst bed from top to bottom, the converter filler is that the JT-4 type cobalt molybdenum that Xibei Chemical Inst produces is coking catalysis drying gas hydrogenation catalyst.Most organic sulfurs in regeneration off gases are converted into to H
2s.Be provided with two organic sulfur converters in step of converting, two towers are in parallel, one open one standby.
Regeneration off gases after above-mentioned conversion is sent into heat exchanger (gas-to-gas heat exchanger and/or water cooling heat exchanger) and is carried out the heat exchange cooling, needs the cold regeneration gas of preheating for heating.
This regeneration off gases after cooling is with after the coke-stove gas from coke-oven plant mixes, and the wet desulfurization system returned before above-mentioned Temp .-changing adsorption device is processed and Recovered sulphur in the lump, realizes that zero-emission circulates.
Claims (7)
1. the circulation process method of Temp .-changing adsorption desulfurization regeneration waste gas, is characterized in that making the high sulfur-bearing regeneration off gases of Temp .-changing adsorption sweetening process generation first to carry out the organic sulfur conversion, and organic sulfur compound is wherein changed into to H
2s, and then it is removed through wet desulphurization, and the sulfide that will remove after absorption is further oxidized to sulphur recovery, the regeneration off gases after wet desulphurization is processed is returned to temperature swing adsorption system and is recycled.
2. the method for claim 1, is characterized in that said organic sulfur transforms, and is that after the regeneration off gases of described high sulfur-bearing is heated to the required temperature of hydroconversion of organic sulfur, the organic sulfur converter through being provided with the catalyzed conversion filling batch changes into H
2s.
3. method as claimed in claim 2, the hydroconversion of organic sulfur heating-up temperature that it is characterized in that said high sulfur-bearing regeneration off gases is 150 ~ 450 ℃, preferably heating-up temperature is 300 ~ 400 ℃.
4. method as claimed in claim 2, it is characterized in that the said high sulfur-bearing regeneration off gases be heated to after said temperature, at least one in being provided with ferrimanganic molybdenum series hydrocatalyst, iron molybdenum series hydrocatalyst, cobalt molybdenum series hydrocatalyst or cobalt molybdenum nickel series hydrogenating catalyst carried out catalyzed conversion for the organic sulfur converter of filling batch.
5. method as described as one of claim 1 to 4, is characterized in that said wet desulphurization for will be converted into H under 30 ~ 60 ℃
2after gas after S absorbs with akaline liquid, when resulting this sulfur removing pregnant solution regeneration, the sulfide removed after absorption is changed into to sulphur recovery by air oxygen.
6. method as claimed in claim 5, is characterized in that said wet desulphurization adopts any in hot potash method, amine method or ammonia process, tannin extract method.
7. method as described as one of claim 1 to 4, is characterized in that the said H changed into by organic sulfur compound
2the wet desulphurization of S gas is processed, for by this H
2s gas returns to the front wet desulfurization system of Temp .-changing adsorption sweetening process in said this regeneration off gases source and processes and Recovered sulphur.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126573A (en) * | 2015-07-22 | 2015-12-09 | 江苏新世纪江南环保股份有限公司 | Integrated ammonia-process desulfurization method of various acidic gases in oil refining device |
| CN106190386A (en) * | 2016-08-26 | 2016-12-07 | 成都巨涛油气工程有限公司 | A kind of method of deep natural gas removing organic sulfur |
| CN106367146A (en) * | 2016-08-26 | 2017-02-01 | 成都巨涛油气工程有限公司 | Method of organic sulfur removal for natural gas |
| CN111362229A (en) * | 2020-04-24 | 2020-07-03 | 西南化工研究设计院有限公司 | Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas |
| CN113881464A (en) * | 2021-11-25 | 2022-01-04 | 安徽工业大学 | Fine desulfurization device and method for coke oven gas |
| CN114920386A (en) * | 2022-05-17 | 2022-08-19 | 四川省银河化学股份有限公司 | Method for desulfurizing hot spring water and co-producing sulfur soap |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126573A (en) * | 2015-07-22 | 2015-12-09 | 江苏新世纪江南环保股份有限公司 | Integrated ammonia-process desulfurization method of various acidic gases in oil refining device |
| CN106190386A (en) * | 2016-08-26 | 2016-12-07 | 成都巨涛油气工程有限公司 | A kind of method of deep natural gas removing organic sulfur |
| CN106367146A (en) * | 2016-08-26 | 2017-02-01 | 成都巨涛油气工程有限公司 | Method of organic sulfur removal for natural gas |
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| CN111362229A (en) * | 2020-04-24 | 2020-07-03 | 西南化工研究设计院有限公司 | Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas |
| CN113881464A (en) * | 2021-11-25 | 2022-01-04 | 安徽工业大学 | Fine desulfurization device and method for coke oven gas |
| CN113881464B (en) * | 2021-11-25 | 2023-08-15 | 安徽工业大学 | Fine desulfurization device and method for coke oven gas |
| CN114920386A (en) * | 2022-05-17 | 2022-08-19 | 四川省银河化学股份有限公司 | Method for desulfurizing hot spring water and co-producing sulfur soap |
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Application publication date: 20131218 |