CN106902614B - 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
CN106902614B
CN106902614B CN201710186572.7A CN201710186572A CN106902614B CN 106902614 B CN106902614 B CN 106902614B CN 201710186572 A CN201710186572 A CN 201710186572A CN 106902614 B CN106902614 B CN 106902614B
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coke
gas
stove gas
organic sulfur
naphthalene
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CN201710186572.7A
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CN106902614A (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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    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Industrial Gases (AREA)

Abstract

Method the present invention relates to organic sulfur in a kind of removing coke-stove gas includes pretreatment process, the de- naphthalene process of TSA, boosting process, organic sulfur conversion process, desulfurization process, inorganic sulfur, the organic sulfur content in fuel can be effectively reduced, improve board quality, reduce product defect rate, good fuel can be provided for each user of iron and steel enterprise, especially have the function of key to the automobile of production 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 fields, and in particular to a method of organic sulfur in removing coke-stove gas.
Background technique
Under normal circumstances, iron and steel enterprise uses the inorganic sulfur portion based on hydrogen sulfide in dry process removing coke-stove gas Point, the box or towers units filled with adsorbent are generallyd use, followingization occurs in a device for the hydrogen sulfide in coke-stove gas Learn reaction: Fe2O3·H2O+3H2S=Fe2S3·H2O+3H2O, and then removed.
The prior art only has removal effect to the inorganic sulfur part based on hydrogen sulfide, is to carbonyl sulfur, carbon disulfide Main organic sulfur part does not have removal effect.
Summary of the invention
Only there is removal effect to the inorganic sulfur part based on hydrogen sulfide and to carbonyl sulfur, two to overcome in the prior art Organic sulfur part based on nitric sulfid does not have the drawbacks of removal effect, and the purpose of the present invention is to provide a kind of removing coke-stove gas The method of middle organic sulfur.
The technical solution adopted by the present invention to solve the technical problems is: a kind of side removing organic sulfur in coke-stove gas Method, comprising the following steps:
1) pretreatment process:
Coke-stove gas is handled with preprocessor, is divided into two parts in preprocessor, a part sets silk screen and coke, removes Remove the tar, washing oil and free water component of wherein most；Another part sets desulfurizing agent, removes the H in unstripped gas2S, protection TSA takes off the adsorbent of naphthalene process；
2) naphthalene process is taken off: using hydrogen sulfide, the naphthalene impurity of " temp.-change adsorptive process (TSA) " purification process removing coke gas, TSA Process is made 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 a variety of adsorbents that hydrogen, tar, washing oil mist, benzene, naphthalene are loaded is adsorbed, so that coal gas is made to be purified, Each combination tower automatically switches absorption and regenerated continuous operation by program-controlled valve, after complexing agent adsorption saturation, using net Coal gas after change regenerates adsorbent；
3) boosting process: compression system is boosted unstripped gas using roots blower, to meet next procedure to raw material The needs of atmospheric pressure；
4) organic sulfur conversion process: the organic sulfur after taking off naphthalene process in coke-stove gas is mainly carbonyl sulfur and curing Carbon is translated into the inorganic sulfur easily removed under the action of hydrolyst；
5) desulfurization process: using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, and coke-stove gas bottom in and top out is changed to the desulfurizing agent later period Upper entering and lower leaving replaces desulfurizing agent when hydrogen sulfide again will be exceeded, and the coal gas of desulfurizing tower is product gas out.
The invention has the following advantages: inorganic sulfur, organic sulfur in fuel can be effectively reduced in method of the invention Content improves board quality, reduces product defect rate, good fuel can be provided for each user of iron and steel enterprise, especially to life The cold hot rolling line of the automobile, household electrical appliances thin plate that produce high added value has the function of key.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute Protection scope within.
One, unstripped gas condition
Unstripped gas is the coke-stove gas that process is produced from coke ovenization, pressure~8kPa (G), room temperature.Coal gas composition and impurity Content is as follows:
Coke-stove gas composition
Component H2 CH4 CO N2 CO2 CmHn O2 Pressure kPa
Average content (V%) 58.8 25.6 5.9 3.8 2.1 3.4 0.4 ~8
Impurity content table
Component H2S Organic sulfur NH3 HCN Benzene Naphthalene Tar
Average content (mg/Nm3) 150 200-300 80 300 2000 300 20
Organic sulfur composition
Component COS CS2 Methyl mercaptan Thiophene Other organic sulfurs
Average content (mg/Nm3) ~120 ~107 ~3 ~30 ~40
Two, technical solution
This method is made of five processes, including pretreatment process, TSA take off naphthalene process, boosting process, organic sulfur conversion work Sequence, desulfurization process.
1, 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 to prevent in coke-stove gas Tar, washing oil to adsorbents various in hereafter process generate adverse effect.It is divided into two parts in preprocessor, a part sets silk screen And coke, with components such as the tar, washing oil and free water that remove wherein most, while playing buffer function；Another part is set Desulfurizing agent removes the H in unstripped gas2S, to protect TSA to take off the adsorbent of naphthalene process.
2, it takes off naphthalene process: the impurity such as hydrogen sulfide, the naphthalene of coke gas is removed using " temp.-change adsorptive process (TSA) " purification process, TSA process is made of regenerative heater, combination tower.Coke-stove gas, which enters, is in the combination tower of adsorbed state, in coke-stove gas The flourishing hole system of a variety of adsorbents that is loaded of the components such as hydrogen sulfide, tar, washing oil mist, benzene, naphthalene adsorbed, to make coal gas It is purified, each combination tower automatically switches absorption and regenerated continuous operation by program-controlled valve, when complexing agent adsorption saturation Afterwards, adsorbent is regenerated using purified coal gas.
3, boosting process: compression system is boosted unstripped gas using roots blower, to meet next procedure to raw material The needs of atmospheric pressure.
4, organic sulfur conversion process: the organic sulfur after taking off naphthalene process in coke-stove gas is mainly carbonyl sulfur and curing Carbon, this part organic sulfur cannot directly adopt dry removal, it is necessary to be translated into the nothing easily removed under the effect of the catalyst Machine sulphur, then uses dry removal again.
The principle of organic sulfur conversion: it is reacted using carbonyl sulfur and carbon disulfide with water and generates hydrogen sulfide, key reaction are as follows: COS+H2O=CO2+H2S, CS2+2H2O====CO2+2H2S, HCN+H2O=====NH3+CO。
5, desulfurization process: using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, and coke-stove gas bottom in and top out is changed to the desulfurizing agent later period Upper entering and lower leaving can replace desulfurizing agent when hydrogen sulfide again will be exceeded.The coal gas of desulfurizing tower is product out Gas.
The principle of dry desulfurization: iron sulfide, key reaction are as follows: Fe are generated using hydrated ferric oxide and hydrogen sulfide reaction2O3· H2O+3H2S=Fe2S3·H2O+3H2O。
Three, capital equipment
Four, each process index
Five, product gas index
Product gas outlet pressure >=20kPa, room temperature, index are as follows:

Claims (1)

1. a kind of method of organic sulfur in removing coke-stove gas, which comprises the following steps:
1) pretreatment process:
Coke-stove gas is handled with preprocessor, is divided into 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, removes the H in unstripped gas2S, protection TSA are de- The adsorbent of naphthalene process；
2) naphthalene process is taken off: using hydrogen sulfide, the naphthalene impurity of " temp.-change adsorptive process (TSA) " purification process removing coke-stove gas, TSA work Sequence is made of regenerative heater, combination tower, and coke-stove gas enters the combination tower for being in adsorbed state, the vulcanization in coke-stove gas The flourishing hole system for a variety of adsorbents that hydrogen, tar, washing oil mist, benzene, naphthalene are loaded is adsorbed, to make coal gas be purified, respectively Platform combination tower automatically switches absorption and regenerated continuous operation by program-controlled valve, after adsorbent adsorption saturation, using purification Coal gas afterwards regenerates adsorbent；
3) boosting process: compression system is boosted unstripped gas using roots blower, to meet next procedure to material pressure The needs of power；
4) organic sulfur conversion process: the organic sulfur after taking off naphthalene process in coke-stove gas is mainly carbonyl sulfur and carbon disulfide, The inorganic sulfur easily removed is translated under the action of hydrolyst；
5) desulfurization process: using desulfurizing tower Removing Hydrogen Sulfide by Dry Process, and coke-stove gas bottom in and top out is changed to enterprising to the desulfurizing agent later period Go out down, when hydrogen sulfide again will be exceeded, desulfurizing agent is replaced, the coal gas of desulfurizing tower is product gas out.
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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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
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

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4845438B2 (en) * 2005-07-08 2011-12-28 千代田化工建設株式会社 Method for removing sulfur compounds from natural gas
US20140271451A1 (en) * 2013-03-13 2014-09-18 Terravire, Corp. Method for removing sulfur compounds from sour gas streams and hydrogen rich streams

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

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