CN103480252A - Hydrogen sulfide-containing acid gas treatment method - Google Patents

Hydrogen sulfide-containing acid gas treatment method Download PDF

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Publication number
CN103480252A
CN103480252A CN201210194691.4A CN201210194691A CN103480252A CN 103480252 A CN103480252 A CN 103480252A CN 201210194691 A CN201210194691 A CN 201210194691A CN 103480252 A CN103480252 A CN 103480252A
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China
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gas
sulfur
hydrogen sulfide
enters
enter
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Inventor
温崇荣
何登华
何金龙
黄黎明
廖晓东
陈昌介
张晓雪
杨芳
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Petrochina Co Ltd
China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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Priority to CN201210194691.4A priority Critical patent/CN103480252A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/20Capture or disposal of greenhouse gases of methane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

Abstract

The invention relates to a hydrogen sulfide-containing acid gas treatment method, which comprises that: hydrogen sulfide-containing acid gas and air enter a burning furnace, are subjected to burning, and then enter a waste heat boiler to produce middle-high pressure steam; after the liquid sulfur-containing process gas is subjected to condensation separation to separate liquid sulfur, the process gas enters a first-stage Claus reactor, and the sulfur-containing process gas after the reaction is subjected to condensation separation to separate liquid sulfur; the obtained process gas enters a second-stage Claus reactor, and the liquid sulfur-containing process gas is subjected to condensation separation again; the obtained process gas enters a direct oxidation or catalysis reactor, the part of the air degassed through the liquid sulfur and combustible gas with a certain ratio enter the direct oxidation or catalysis reactor, and an oxidation reaction is performed, such that the sulfur-containing compound is converted into SO2; and the obtained process gas is introduced into an absorption bed layer, and the SO2 in the gas is subjected to absorption heat exchange, and then is directly discharged into atmosphere through a chimney. According to the method, a sulfur recovery rate is more than 99.9%, and the method is further suitable for other treatment processes for tail gases containing SO2 or sulfides, wherein the treated tail gas meets the new national emission standard.

Description

A kind of hydrogen sulfide containing Sour gas disposal method
Technical field
The present invention relates to a kind of hydrogen sulfide containing Sour gas disposal method, the tail gas after the method is processed does not need burning, directly qualified discharge.Applicable all sulfuric acid gas, belong to natural gas and refinery's acid gas manufacture field.
Background technology
Sulfur dioxide is one of major pollutants in atmosphere, is to weigh the important symbol whether atmosphere is polluted.The compulsory standard " discharge standard of air pollutants " that China came into effect in 1997 (GB16297-1996), is stipulated SO 2existing pollution sources and the new the highest permission discharge quality of pollution sources concentration are respectively 1200mg/m 3and 960mg/m 3.Standard increasingly stringent along with the countries in the world environment protection; " petroleum refining industry emission of industrial pollutants standard " the regulation sour gas retracting device concentration of emission limit value that is about to promulgate is: during 2011.7.1~2014.6.30, existing enterprise is 960mg/m 3, from the existing enterprise 2014.7.1 and the newly-built enterprise from 2011.7.1, be 400mg/m 3.Be about to " the Gas Purification Factory atmosphere pollutants emission standards " promulgated, the tail gas SO of its sulfur reclamation tail gas burning stove and acid gas incinerator 2the discharge standard regulation: during 2011.1.1~2014.12.31, existing enterprise is 1000mg/m 3, from the existing enterprise 2015.1.1 and the newly-built enterprise from 2011.1.1, be 500mg/m 3.This standard is to SO 2discharge stricter, if press New emission standard, implement, can allow existing Gas Purification Factory and refinery tail-gas discharge be faced with formidable challenges.
The Claus sulphur technique processed that the sulfide hydrogen Sour gas disposal proposes from Englishize scholar Claus in 1883 so far, the history of more than 100 year, the Claus recovery technology of sulfur also experiences a process made constant progress.Particularly, from the sixties in last century, abroad develop and realize that industrialized sulphur recovery and tail gas treatment process have tens of kinds.As: the low-temperature Claus techniques such as Sulfreen, MCRC, Clauspol; The H such as Seletox, Hi-Activity, SuperClaus, Clinsulf 2the direct selective oxidation process of S; And the selective catalytic oxidations such as Selectox, Modop and Super claus are basic sulfur recovery technique.These technique sulfur recovery rates all are being improved in various degree, but are difficult to meet the SO of substandard 2emission request.And SCOT technique and many improvement technique, the HCR technique of NIGI company, the BSR/MDEA technique of Parsons company, the tail gas Reducing and absorption techniques such as RAR technique of KTI company can, by absorbing after the sulfur-containing tail gas hydrogenation, obviously reduce SO in tail gas again 2discharge, even can hang down below 100ppm.Domestic some patented technologies that also form on recovery technology of sulfur, as: 96104817.4, ZL200710049014.2,200710048360.9,200710058567.4,24200810022175.7,200910058717.0 and 200910065268.2 etc., all being improved at existing recovery technology of sulfur, also all improve in various degree sulfur recovery rate, reduced the discharge of sulfur-containing compound in tail gas.
Due to the restriction that is subject to the claus reaction thermodynamical equilibrium, except tail gas reduction class technique and employing alkali liquor absorption mode, SO in the tail gas of all the other techniques discharges 2all do not reach and be about to the SO carried out 2country's New emission standard.Reducing and absorption tail gas treatment process complexity, investment, running cost and energy consumption are all quite high; Alkali cleaning absorbs shortcomings such as there being again secondary pollution.
Summary of the invention
The objective of the invention is to utilize the combination of renewable absorbing process and existing sulfide hydrogen recovery processing technique, propose a kind of hydrogen sulfide containing Sour gas disposal method, compare with Reducing and absorption class technique, can be implemented to tail gas SO 2in the time of minimum discharge, also there is significantly energy-saving and cost-reducing, saving and invest, reduce the advantages such as running cost.
Hydrogen sulfide containing Sour gas disposal method of the present invention, particular content is as follows:
(1) allocate air into containing the acid hydrogen sulfide gas of high concentration, enter combustion furnace, after condenser separates sulphur, enter one-level claus reaction device, separate through condenser A again that sulphur is laggard enters secondary claus reaction device, or enter again three grades of claus reaction devices, then separate through condenser B;
(2) secondary claus reaction device or three grades of claus reaction devices sulfur-bearing Process Gas out pass through direct oxidation or catalytic reactor again, and selective oxidation of sulfur containing compounds in particular is become to SO 2;
(3) containing SO 2high temperature gas flow directly enters SO 2adsorption reaction, occur in adsorption bed, and the tail gas after absorption is at SO 2content during lower than national standard, enters condenser C, reclaims after heat by smoke stack emission;
(4) SO in tail gas after absorption 2when content is above standard, adsorption bed is switched to reproduced state, passes into reducibility gas, and the sulfur-bearing Process Gas of regeneration, after condenser D separates molten sulfur, return to front any one-level claus reaction device, and the molten sulfur of condensation separation enters spout.
The hydrogen sulfide containing Sour gas disposal method of the second that the present invention proposes, particular content is as follows:
(1) the very low sour gas of sulfide hydrogen, the fuel gas that first proportioning is certain and air, through direct oxidation or catalytic reactor, enter adsorption bed after reaction, adsorption reaction occurs, and the gas after absorption is at SO 2content, lower than under national standard, enters heat reclaiming system, after the recovery heat, is discharged.
(2) when after absorption, tail gas is above standard, adsorption bed is switched to reproduced state, passes into reducibility gas, and regeneration sulfur-bearing Process Gas is after the condensation separation molten sulfur, and this Process Gas returns to combustion furnace again.
Technique of the present invention is carried out on existing technique basis, is mainly by the direct oxidation of tail gas high temperature or catalytic reaction, and selective oxidation of sulfur containing compounds in particular becomes SO 2after, carrying out high temperature adsorption, adsorbent can be regenerated, and regeneration gas is returned to claus reaction or the combustion furnace of front, can save investment 30%~50%, and Energy Intensity Reduction is more than 50%, simple to operate, easily miniaturization, the SO in tail gas 2can be controlled at reduced levels.This technique can also be processed other sulfurous gas.
Know-why: Claus tail gases or other sulfur-containing tail gas are after direct oxidation or catalytic reaction, and all sulfur-containing compounds change into SO 2, then by the SO in efficient adsorption bed absorption tail gas 2, the tail gas after absorption is meeting under national minimum discharge standard and can directly discharge; The SO of discharge after absorption 2while surpassing discharge standard, be switched to another adsorption bed absorption.The rear bed of absorption passes into reducibility gas and is regenerated, and the regeneration adsorption bed can be recycled, and the sulfur-bearing Process Gas born again returns to the claus reaction device after condensation separation sulphur, guarantees like this SO that exhaust emissions goes out 2in very low limit value, the sulfur recovery rate of device is greater than 99.9%.
The present invention has the following advantages:
(1) to the sulfide hydrogen sour gas out after, SO in emission 2content can reach the new environmental emission standard of country, even hang down and adsorbed fully, substantially realize zero-emission.
(2) SO after absorption 2through regeneration, return to again front claus reaction device after condensation separation, the sulfur recovery rate of this technique reaches more than 99.9%.
(3) this technique also is applicable to other containing SO 2perhaps the tail gas treatment process of sulfide, can make its tail gas meet the new discharge standard of country.
The accompanying drawing explanation
Fig. 1 the first sulfide hydrogen Sour gas disposal technique
The treatment process of Fig. 2 sulfur compound tail gas
Wherein: 1 combustion furnace, 2 waste heat boilers, 3 condensers, 4 liquid sulfur pits, 5 one-level claus reaction devices, 6 secondary claus reaction devices, 7 direct oxidations or catalytic reactor, 8 adsorption bed, 9 adsorption bed, 10 chimneys
The specific embodiment
As shown in Figure 1:
After the proportioning that hydrogen sulfide containing acid gas gas and air carry out, enter combustion furnace 1, contained H after burning 2s and SO 2volume ratio at 2: 1, then carry out energy recovery through waste heat boiler 2, produce mesohigh steam, enter condenser 3 containing the molten sulfur Process Gas, molten sulfur after condensation separation enters liquid sulfur pit 4, Process Gas enters one-level claus reaction device 5, reacted sulfur-bearing Process Gas enters condenser A, molten sulfur after condensation separation enters liquid sulfur pit 4, Process Gas enters secondary claus reaction device 6, reacted Process Gas enters condenser B, molten sulfur after condensation separation enters liquid sulfur pit 4, Process Gas enters direct oxidation or catalytic reactor 7, now, also enter reactor 7 through degassed air and a certain proportion of fuel gas of liquid sulfur pit 4, carry out oxidation reaction, make sulfur-containing compound all be transformed into SO 2, then this Process Gas is passed into to adsorption bed 8, SO in gas 2enter condenser C after absorption, heat exchange directly is discharged into atmosphere by chimney 10,
SO in the tail gas that adsorption bed is discharged 2when content surpasses emission request, the Process Gas of now being discharged by direct oxidation or catalytic reactor is switched to another bed and is adsorbed, and the bed 9 after absorption passes into reducibility gas, go out the air-flow of regenerator bed through condenser D, condensation and separation of molten sulfur enter liquid sulfur pit 4, Process Gas returns in one-level claus reaction device 5 or secondary claus reaction device 6, and the adsorption bed completely of regenerating can enter next sorption cycle again.
As shown in Figure 2:
After the tail gas of sulfur compound and air, fuel gas carry out proportioning, enter direct oxidation or catalytic reactor 7, the air of proportioning and fuel gas make sulfur compound be transformed into SO 2, then this Process Gas is passed into to adsorption bed 8, SO in gas 2enter condenser C after absorption, heat exchange directly is discharged into atmosphere by chimney 10.
SO in the tail gas that adsorption bed is discharged 2when content surpasses emission request, the Process Gas of now being discharged by reactor 7 is switched to another bed and is adsorbed, and the bed 9 after absorption passes into reducibility gas, go out the air-flow of regenerator bed through condenser D, condensation and separation of molten sulfur enter liquid sulfur pit 4, the regeneration air stream of now going back sulfur-bearing returns in one-level claus reaction device 5 or secondary claus reaction device 6.The adsorption bed completely of regenerating enters next sorption cycle.
The temperature of described adsorption bed is at 100~500 ° of C.
Described hydrogen sulfide containing acid gas gas space velocity is at 50~2000h -1.
The described regeneration gas volumetric concentration passed into is: 5~50%H 2s or 0.5~100%H 2perhaps overheated methane gas.
Described regeneration temperature is chosen in: 150~500 ° of C.

Claims (6)

1. a hydrogen sulfide containing Sour gas disposal method, is characterized in that: after hydrogen sulfide containing acid gas gas and air carry out proportioning, enter combustion furnace, contained H after burning 2s and SO 2volume ratio at 2: 1, then carry out energy recovery through waste heat boiler, produce mesohigh steam, enter condenser containing the molten sulfur Process Gas, the molten sulfur that condensation generates enters liquid sulfur pit, Process Gas after condensation separation enters one-level claus reaction device, reacted sulfur-bearing Process Gas enters condenser A, molten sulfur enters liquid sulfur pit, Process Gas after condensation separation enters secondary claus reaction device, enter condenser B containing the molten sulfur Process Gas, molten sulfur enters liquid sulfur pit, Process Gas after condensation separation enters direct oxidation or catalytic reactor, the part air enters this reactor after molten sulfur degasification, and the proportioning fuel gas is reacted, make sulfur-containing compound be transformed into SO 2, then this Process Gas is passed into to adsorption bed, SO in gas 2enter condenser C after absorption, heat exchange directly is discharged into atmosphere by chimney,
SO in the tail gas that adsorption bed is discharged 2when content surpasses emission request, the Process Gas of now being discharged by direct oxidation or catalytic reactor is switched to another bed and is adsorbed, and the bed after absorption passes into reducibility gas, go out the air-flow of regenerator bed through condenser D, condensation and separation of molten sulfur enter liquid sulfur pit, Process Gas returns in one-level claus reaction device or secondary claus reaction device, and the adsorption bed completely of regenerating enters next sorption cycle.
2. hydrogen sulfide containing Sour gas disposal method according to claim 1, it is characterized in that: the Process Gas that enters direct oxidation or catalytic reactor is the tail gas of claus reaction, or directly uses hydrogen sulfide gas or other sulfur compound tail gas of low concentration.
3. the Sour gas disposal method of hydrogen sulfide according to claim 1, it is characterized in that: the temperature of adsorption bed is at 100~500 ° of C.
4. hydrogen sulfide containing Sour gas disposal method according to claim 1, it is characterized in that: hydrogen sulfide containing acid gas gas space velocity is at 50~2000h -1.
5. hydrogen sulfide containing Sour gas disposal method according to claim 1, it is characterized in that: the regeneration gas volumetric concentration passed into is: 5~50%H 2s or 0.5~100%H 2perhaps overheated methane gas.
6. hydrogen sulfide containing Sour gas disposal method according to claim 1, it is characterized in that: regeneration temperature is chosen in: 150~500 ° of C.
CN201210194691.4A 2012-06-13 2012-06-13 Hydrogen sulfide-containing acid gas treatment method Pending CN103480252A (en)

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Cited By (11)

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CN105129741A (en) * 2014-06-06 2015-12-09 中国石油化工股份有限公司 Process for reducing SO2 emission concentration of sulfur recovery device
CN105293442A (en) * 2014-06-06 2016-02-03 中国石油化工股份有限公司 Method for decreasing flue gas SO2 emission concentration in sulphur apparatus
CN105293445A (en) * 2015-11-18 2016-02-03 山东迅达化工集团有限公司 Low sulfur emission sulphur recovery process
CN105314606A (en) * 2014-06-06 2016-02-10 中国石油化工股份有限公司 Liquid sulfur degassing technology
CN105314607A (en) * 2015-12-01 2016-02-10 山东迅达化工集团有限公司 Low-sulfur discharging and sulfur recycling process of intermediate concentration acid gas
CN105327599A (en) * 2014-06-06 2016-02-17 中国石油化工股份有限公司 Method for processing exhaust gas obtained by degasification of liquid sulfur
CN105399057A (en) * 2015-11-18 2016-03-16 山东迅达化工集团有限公司 Sulfur recovery technology realizing low sulfur emission
CN105480951A (en) * 2016-01-11 2016-04-13 神华集团有限责任公司 Liquid sulfur degassing system and liquid sulfur degassing method
CN106829875A (en) * 2017-03-08 2017-06-13 安徽宣城金宏化工有限公司 A kind of handling process and equipment for carbon disulphide production Process Gas
CN106955570A (en) * 2017-03-16 2017-07-18 盐城复华环保产业开发有限公司 A kind of catalytic oxidation process for treating for being used to handle gaseous contaminant
CN109982775A (en) * 2016-11-22 2019-07-05 奥图泰(芬兰)公司 For heat-treating methods in fluidized-bed reactor and equipment

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Cited By (16)

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CN105327599B (en) * 2014-06-06 2018-05-04 中国石油化工股份有限公司 The processing method of molten sulfur degasification exhaust gas
CN105293442A (en) * 2014-06-06 2016-02-03 中国石油化工股份有限公司 Method for decreasing flue gas SO2 emission concentration in sulphur apparatus
CN105293442B (en) * 2014-06-06 2018-03-20 中国石油化工股份有限公司 Sulphur unit reduces flue gas SO2The method of concentration of emission
CN105314606A (en) * 2014-06-06 2016-02-10 中国石油化工股份有限公司 Liquid sulfur degassing technology
CN105129741A (en) * 2014-06-06 2015-12-09 中国石油化工股份有限公司 Process for reducing SO2 emission concentration of sulfur recovery device
CN105327599A (en) * 2014-06-06 2016-02-17 中国石油化工股份有限公司 Method for processing exhaust gas obtained by degasification of liquid sulfur
CN105129741B (en) * 2014-06-06 2018-03-20 中国石油化工股份有限公司 Reduce sulfur recovery facility SO2The technique of concentration of emission
CN105399057B (en) * 2015-11-18 2018-02-23 山东迅达化工集团有限公司 The recovery technology of sulfur of low-sulfur discharge
CN105293445A (en) * 2015-11-18 2016-02-03 山东迅达化工集团有限公司 Low sulfur emission sulphur recovery process
CN105399057A (en) * 2015-11-18 2016-03-16 山东迅达化工集团有限公司 Sulfur recovery technology realizing low sulfur emission
CN105314607A (en) * 2015-12-01 2016-02-10 山东迅达化工集团有限公司 Low-sulfur discharging and sulfur recycling process of intermediate concentration acid gas
CN105314607B (en) * 2015-12-01 2018-05-08 山东迅达化工集团有限公司 The low-sulfur discharge recovery technology of sulfur of intermediate concentration sour gas
CN105480951A (en) * 2016-01-11 2016-04-13 神华集团有限责任公司 Liquid sulfur degassing system and liquid sulfur degassing method
CN109982775A (en) * 2016-11-22 2019-07-05 奥图泰(芬兰)公司 For heat-treating methods in fluidized-bed reactor and equipment
CN106829875A (en) * 2017-03-08 2017-06-13 安徽宣城金宏化工有限公司 A kind of handling process and equipment for carbon disulphide production Process Gas
CN106955570A (en) * 2017-03-16 2017-07-18 盐城复华环保产业开发有限公司 A kind of catalytic oxidation process for treating for being used to handle gaseous contaminant

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Application publication date: 20140101