CN106902614A - A kind of method of organic sulfur in removing coke-stove gas - Google Patents

A kind of method of organic sulfur in removing coke-stove gas Download PDF

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Publication number
CN106902614A
CN106902614A CN201710186572.7A CN201710186572A CN106902614A CN 106902614 A CN106902614 A CN 106902614A CN 201710186572 A CN201710186572 A CN 201710186572A CN 106902614 A CN106902614 A CN 106902614A
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CN
China
Prior art keywords
coke
gas
organic sulfur
naphthalene
stove gas
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Application number
CN201710186572.7A
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CN106902614B (en
Inventor
郭亮
田旺远
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SD Steel Rizhao Co Ltd
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SD Steel Rizhao Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons

Abstract

Include the de- naphthalene operation of pretreatment process, TSA, boosting operation, organic sulfur conversion operation, desulfurization process the present invention relates to a kind of method for removing organic sulfur in coke-stove gas, inorganic sulfur, the organic sulfur content in fuel can effectively be reduced, improve board quality, reduce product fraction defective, the fuel of high-quality can be provided for each user of iron and steel enterprise, especially there is crucial effect to producing the automobile of high added value, the cold hot rolling line of household electrical appliances thin plate.

Description

A kind of method of organic sulfur in removing coke-stove gas
Technical field
The invention belongs to coke oven gas purification field, and in particular to a kind of method of organic sulfur in removing coke-stove gas.
Background technology
Generally, the inorganic sulfur portion based on hydrogen sulfide during iron and steel enterprise uses dry process to remove coke-stove gas Point, generally using the box or towers units filled with adsorbent, there is followingization in the hydrogen sulfide in coke-stove gas in a device Learn reaction：Fe2O3·H2O+3H2S=Fe2S3·H2O+3H2O, and then removed.
Prior art only has removal effect to the inorganic sulfur part based on hydrogen sulfide, to being with cos, carbon disulfide Main organic sulfur part does not have removal effect.
The content of the invention
Only there is removal effect to the inorganic sulfur part based on hydrogen sulfide and to cos, two to overcome in the prior art Not the drawbacks of organic sulfur part based on nitric sulfid does not have removal effect, it is an object of the invention to provide one kind removing coke-stove gas The method of middle organic sulfur.
The technical solution adopted for the present invention to solve the technical problems is：The side of organic sulfur in a kind of removing coke-stove gas Method, comprises the following steps：
1) pretreatment process：
Coke-stove gas is processed with preprocessor, point two parts in preprocessor a, part sets silk screen and coke, removes Remove tar, washing oil and the free water component of wherein most；Another part sets desulfurizing agent, the H in removing unstripped gas2S, protection The adsorbent of the de- naphthalene operations of TSA；
2) naphthalene operation is taken off：Hydrogen sulfide, the naphthalene impurity, TSA of coke gas are removed using " temp.-change adsorptive process (TSA) " purification technique Operation is made up of regenerative heater, combination tower, and coke-stove gas enters the combination tower for being in adsorbed state, the sulphur in coke-stove gas The flourishing hole system for changing various adsorbents that hydrogen, tar, washing oil mist, benzene, naphthalene are loaded is adsorbed, so that coal gas is purified, The continuous operation that each combination tower is adsorbed and regenerated by program-controlled valve automatic switchover, after complexing agent adsorption saturation, using net Coal gas after change regenerates to adsorbent；
3) boosting operation：Compression system is boosted unstripped gas using roots blower, to meet next procedure to raw material The need for atmospheric pressure；
4) organic sulfur conversion operation：Organic sulfur after taking off naphthalene operation in coke-stove gas is mainly cos and curing Carbon, is translated into the inorganic sulfur of easy removing in the presence of hydrolyst；
5) desulfurization process：Using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, coke-stove gas bottom in and top out is changed to the desulfurizing agent later stage Upper entering and lower leaving, when hydrogen sulfide again will be exceeded, changes to desulfurizing agent, goes out the coal gas as product gas of desulfurizing tower.
The invention has the advantages that：The method of the present invention can effectively reduce inorganic sulfur, organic sulfur in fuel Content, improves board quality, reduces product fraction defective, and the fuel of high-quality, especially opposite can be provided for each user of iron and steel enterprise Producing the automobile of high added value, the cold hot rolling line of household electrical appliances thin plate has crucial effect.
Specific embodiment
The following is specific embodiment of the invention, technical scheme is described further, but it is of the invention Protection domain is not limited to these embodiments.It is every to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute Protection domain within.
First, unstripped gas condition
Unstripped gas is the coke-stove gas that operation is produced from coke ovenization, pressure~8kPa (G), normal temperature.Coal gas is constituted and impurity Content is as follows：
Coke-stove gas is constituted
Component CO CmHn Pressure kPa
Average content (V%) 58.8 25.6 5.9 3.8 2.1 3.4 0.4 ~8
Impurity content table
Component Organic sulfur HCN Benzene Naphthalene Tar
150 200-300 80 300 2000 300 20
Organic sulfur is constituted
Component COS Methyl mercaptan Thiophene Other organic sulfurs
~120 ~107 ~3 ~30 ~40
2nd, technical scheme
This method is made up of five operations, including the de- naphthalene operation of pretreatment process, TSA, boosting operation, organic sulfur conversion work Sequence, desulfurization process.
1st, pretreatment process：
Coke-stove gas first passes around pretreatment process and carries out the impurity such as detar and washing oil, it is therefore an objective in preventing coke-stove gas Tar, washing oil harmful effect is produced to various adsorbents in hereafter operation.Point two parts in preprocessor a, part sets silk screen And coke, to remove the component such as tar, washing oil and free water of wherein most, while playing cushioning effect；Another part sets Desulfurizing agent, the H in removing unstripped gas2S, to protect the adsorbent of the de- naphthalene operations of TSA.
2nd, naphthalene operation is taken off：The impurity such as hydrogen sulfide, naphthalene using " temp.-change adsorptive process (TSA) " purification technique removing coke gas, TSA operations are made up of regenerative heater, combination tower.Coke-stove gas enters the combination tower for being in adsorbed state, in coke-stove gas The flourishing hole system of various adsorbents that is loaded of the component such as hydrogen sulfide, tar, washing oil mist, benzene, naphthalene adsorbed so that coal gas It is purified, the continuous operation that each combination tower is adsorbed and regenerated by program-controlled valve automatic switchover, when complexing agent adsorption saturation Afterwards, adsorbent is regenerated using the coal gas after purification.
3rd, boosting operation：Compression system is boosted unstripped gas using roots blower, to meet next procedure to raw material The need for atmospheric pressure.
4th, organic sulfur conversion operation：Organic sulfur after taking off naphthalene operation in coke-stove gas is mainly cos and curing Carbon, this part organic sulfur can not directly use dry removal, it is necessary to the nothing of easy removing is translated into the presence of catalyst Machine sulphur, then uses dry removal again.
The principle of organic sulfur conversion：Using cos and carbon disulfide and water reaction generation hydrogen sulfide, key reaction is： COS+H2O=CO2+H2S, CS2+2H2O====CO2+2H2S, HCN+H2O=====NH3+CO。
5th, desulfurization process：Using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, coke-stove gas bottom in and top out is changed to the desulfurizing agent later stage Upper entering and lower leaving, when hydrogen sulfide again will be exceeded, you can changed to desulfurizing agent.Go out the coal gas as product of desulfurizing tower Gas.
The principle of dry desulfurization：Using hydrated ferric oxide and hydrogen sulfide reaction generation iron sulfide, key reaction is：Fe2O3· H2O+3H2S=Fe2S3·H2O+3H2O。
3rd, capital equipment
4th, each operation index
5th, product gas index
Product gas outlet pressure >=20kPa, normal temperature, index is as follows：

Claims (1)

1. it is a kind of remove coke-stove gas in organic sulfur method, it is characterised in that comprise the following steps：
1) pretreatment process：
Coke-stove gas is processed with preprocessor, point two parts in preprocessor a, part sets silk screen and coke, removes it In most tar, washing oil and free water component；Another part sets desulfurizing agent, the H in removing unstripped gas2S, protection TSA takes off The adsorbent of naphthalene operation；
2) naphthalene operation is taken off：Hydrogen sulfide, the naphthalene impurity of coke gas, TSA operations are removed using " temp.-change adsorptive process (TSA) " purification technique It is made up of regenerative heater, combination tower, coke-stove gas enters the combination tower for being in adsorbed state, the vulcanization in coke-stove gas The flourishing hole system of various adsorbents that hydrogen, tar, washing oil mist, benzene, naphthalene are loaded is adsorbed, so that coal gas is purified, respectively The continuous operation that platform combination tower is adsorbed and regenerated by program-controlled valve automatic switchover, after complexing agent adsorption saturation, using purification Coal gas afterwards regenerates to adsorbent；
3) boosting operation：Compression system is boosted unstripped gas using roots blower, to meet next procedure to material pressure The need for power；
4) organic sulfur conversion operation：Organic sulfur after taking off naphthalene operation in coke-stove gas is mainly cos and carbon disulfide, The inorganic sulfur of easy removing is translated into the presence of hydrolyst；
5) desulfurization process：Using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, coke-stove gas bottom in and top out is changed to enterprising to the desulfurizing agent later stage Under go out, when hydrogen sulfide again will be exceeded, desulfurizing agent is changed, go out the coal gas as product gas of desulfurizing tower.
CN201710186572.7A 2017-03-27 2017-03-27 A kind of method of organic sulfur in removing coke-stove gas Active CN106902614B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101749A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The method that coke-stove gas produces methanol
CN109277075A (en) * 2017-07-19 2019-01-29 湖北申昙环保新材料有限公司 Coke oven gas purification adsorbent and its purification method
CN109825334A (en) * 2019-03-26 2019-05-31 马鞍山钢铁股份有限公司 A kind of coke-stove gas process for refining security system and its control method
CN113265275A (en) * 2021-05-31 2021-08-17 中冶东方工程技术有限公司 Coke oven gas purification device and method
CN114752719A (en) * 2022-04-26 2022-07-15 酒泉钢铁(集团)有限责任公司 Pretreatment process based on hydrogen-rich metallurgical gas

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130009A1 (en) * 2005-07-08 2009-05-21 Chiyoda Corporation Method of removing sulfur compounds from natural gas
CN102642810A (en) * 2011-02-22 2012-08-22 上海寰球石油化学工程有限公司 Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas
CN102816609A (en) * 2012-09-13 2012-12-12 上海梅山工业民用工程设计研究院有限公司 Dry-wet combination process refining and purifying technology of coke oven gas
CN102139860B (en) * 2011-03-03 2013-03-20 韩城市黑猫能源利用有限公司 Device and method for purifying coke oven gas
CN102994171A (en) * 2011-09-17 2013-03-27 河南利源煤焦集团有限公司 Gas turbine generating coke oven gas comprehensive purification system and purification method thereof
US20140271451A1 (en) * 2013-03-13 2014-09-18 Terravire, Corp. Method for removing sulfur compounds from sour gas streams and hydrogen rich streams
CN104263421A (en) * 2014-09-16 2015-01-07 山东洪达化工有限公司 Coke oven gas purification method
CN104388138A (en) * 2014-11-05 2015-03-04 新奥能源贸易有限公司 Method for co-producing natural gas and hydrogen by utilizing coke oven gas
CN105253899A (en) * 2014-07-15 2016-01-20 宝鸡市泰和化工科技有限公司 Coke oven coat gas comprehensive utilization method
CN106520177A (en) * 2015-09-14 2017-03-22 上海华西化工科技有限公司 Method of directly preparing fuel oil from coke oven gas

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130009A1 (en) * 2005-07-08 2009-05-21 Chiyoda Corporation Method of removing sulfur compounds from natural gas
CN102642810A (en) * 2011-02-22 2012-08-22 上海寰球石油化学工程有限公司 Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas
CN102139860B (en) * 2011-03-03 2013-03-20 韩城市黑猫能源利用有限公司 Device and method for purifying coke oven gas
CN102994171A (en) * 2011-09-17 2013-03-27 河南利源煤焦集团有限公司 Gas turbine generating coke oven gas comprehensive purification system and purification method thereof
CN102816609A (en) * 2012-09-13 2012-12-12 上海梅山工业民用工程设计研究院有限公司 Dry-wet combination process refining and purifying technology of coke oven gas
US20140271451A1 (en) * 2013-03-13 2014-09-18 Terravire, Corp. Method for removing sulfur compounds from sour gas streams and hydrogen rich streams
CN105253899A (en) * 2014-07-15 2016-01-20 宝鸡市泰和化工科技有限公司 Coke oven coat gas comprehensive utilization method
CN104263421A (en) * 2014-09-16 2015-01-07 山东洪达化工有限公司 Coke oven gas purification method
CN104388138A (en) * 2014-11-05 2015-03-04 新奥能源贸易有限公司 Method for co-producing natural gas and hydrogen by utilizing coke oven gas
CN106520177A (en) * 2015-09-14 2017-03-22 上海华西化工科技有限公司 Method of directly preparing fuel oil from coke oven gas

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101749A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The method that coke-stove gas produces methanol
CN109277075A (en) * 2017-07-19 2019-01-29 湖北申昙环保新材料有限公司 Coke oven gas purification adsorbent and its purification method
CN109825334A (en) * 2019-03-26 2019-05-31 马鞍山钢铁股份有限公司 A kind of coke-stove gas process for refining security system and its control method
CN113265275A (en) * 2021-05-31 2021-08-17 中冶东方工程技术有限公司 Coke oven gas purification device and method
CN114752719A (en) * 2022-04-26 2022-07-15 酒泉钢铁(集团)有限责任公司 Pretreatment process based on hydrogen-rich metallurgical gas
CN114752719B (en) * 2022-04-26 2023-07-07 酒泉钢铁(集团)有限责任公司 Pretreatment process based on hydrogen-rich metallurgical gas

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Address after: 276800 Shandong Province, Rizhao City Arashiyama District Shugang Avenue

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