US3923965A - Process for eliminating waste liquors accumulated in the desulfurization of coke oven gas - Google Patents

Process for eliminating waste liquors accumulated in the desulfurization of coke oven gas Download PDF

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Publication number
US3923965A
US3923965A US519563A US51956374A US3923965A US 3923965 A US3923965 A US 3923965A US 519563 A US519563 A US 519563A US 51956374 A US51956374 A US 51956374A US 3923965 A US3923965 A US 3923965A
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US
United States
Prior art keywords
coke oven
oven gas
waste liquor
accumulated
desulfurization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US519563A
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English (en)
Inventor
Peter Diemer
Gerhard Preusser
Paul Radusch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heinrich Koppers GmbH
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Heinrich Koppers GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2361910A external-priority patent/DE2361910C3/de
Application filed by Heinrich Koppers GmbH filed Critical Heinrich Koppers GmbH
Application granted granted Critical
Publication of US3923965A publication Critical patent/US3923965A/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

Definitions

  • ABSTRACT A process for eliminating waste liquors accumulated in the desulfurization of coke oven gas with a washing solution containing an organic oxygen carrier includes evaporating between 30 and 70% of the water from the waste liquor to provide a concentrated waste liquor solution.
  • the concentrated waste liquor is introduced into a combustion chamber with air and coke oven gas.
  • the concentrated waste liquor is thermally decomposed in the combustion chamber and eliminated sulfur is separated from the gaseous products of combustion.
  • the gaseous products of combustion are admixed with the coke oven gas evolved during the coking process.
  • washing processes utilizing alkaline or ammoniacal washing solutions containing organic oxygen carriers have proven to be excellent in desulfurizing coke oven gas, that is, primarily removing the hydrogen sulfide from the coke oven gas.
  • Useful organic oxygen carriers are quinones or compounds of quinoid character, such as hydroquinone, naphthoquinone, anthraquinone and their sulfonic acids. Other organic compounds with a suitable redox potential are also suitable.
  • the process includes first washing the hydrogen sulfide from the coke oven gas in a washer of suitable design by means of the washing solution containing the organic oxygen carrier.
  • the spent washing solution is then regenerated with air in an oxidizer where the oxygen of the air oxidizes the hydrogen sulfide to sulfur and water by means of the oxygen carrier contained in the washing solution.
  • the sulfur is then removed from the washing solution by flotation and the regenerated washing solution is recycled to the hydrogen sulfide washer.
  • hydrocyanic acid that is also contained in the coke oven gas is removed by the above described washing process.
  • the hydrocyanic acid is converted with the elemental sulfur to thiocyanates in the oxidizer. Also secondary reactions occur in the oxidization of hydrogen sulfide to sulfur to form sulfates, thiosulfates and other sulfur compounds.
  • the washing solution is recycled and after an extended period of time the washing solution is enriched with the above compounds.
  • This invention is directed to a process for eliminating the enriched waste liquor and avoiding discharging waste liquor into the sewer.
  • the process includes first evaporating from the enriched waste liquor between 30 and 70% of the water contained in the enriched waste liquor to provide a concentrated enriched waste liquor.
  • the concentrated enriched waste liquor is introduced into a combustion chamber where it is thermally decomposed with the addition of air in a reducing atmosphere.
  • the reducing atmosphere is produced in the combustion chamber by combustion of coke oven gas evolved during the coking process.
  • the sulfur is separated from the lean gas during the thermal decomposition of the waste liquor and the subsequent cooling of the lean gas.
  • the discarded enriched waste liquor is thus decomposed in a reducing atmosphere in which the sulfur compounds contained in the enriched waste liquor are converted essentially to hydrogen sultide and sulfur dioxide.
  • the lean gas formed during the thermal decomposition is cooled and the elemental sulfur is separated from the lean gas and discharged from the process.
  • the lean gas, together with the ammonia vapors formed during the thermal decomposition of the waste liquor is added to the coke oven gas before the primary coolers so that the lean gas and ammonia vapors participate in the complete treatment of the coke oven gas. Since the ammonia vapors accumulated in the treatment of the coke oven gas are simultaneously decomposed, another advantage of the process is the elimination of additional ammonia combustion equipnce which otherwise would be required for the destruction of the ammonia contained in the coke oven gas.
  • FIGURE is a flow diagram illustrating the process for thermally decomposing enriched waste liquor.
  • the waste liquor discarded from the desulfurization system is conveyed through conduit 1 into the thickener 2.
  • the thickener 2 is preferably in the form of a column provided with plates or trays.
  • the waste liquor is introduced into the top of the thickener and flows downwardly on the plates or trays.
  • the waste liquor discharged from the sump of the thickener 2 is circulated by pump 3 through conduits 4 and 6 between thickener 2 and the heater 5.
  • the heated waste liquor is allowed to expand by means of an expansion valve 7 before it reenters the thickener 2 so that a portion of the water in the waste liquor vaporizes.
  • the ammonia vapors accumulated during the vaporization are discharged from the thickener 2 through conduit 8 adjacent the upper portion of the thickener 2.
  • the combustion chamber 10 includes a burner 11 that has an air feed conduit 12 for the primary combustion air.
  • a conduit 13 is provided for the ammonia vapors, and coke oven gas is supplied through conduit 14.
  • the feed conduit 12 for the combustion air has branch conduits 12a and 12b through which additional amounts of secondary air are injected into the combustion chamber 10.
  • the air flowing through conduits 12a and 12b can be the waste air that forms in the oxidizers during the regeneration of the spent Washing solution.
  • the reducing atmosphere in the combustion chamber 10 is produced by combining in burner 11 the coke oven gas as well as the ammonia vapors accumulated during the treatment of coke oven gas with a deficiency of air, i.e. with a deficiency of oxygen.
  • the sensible heat of the gas produced in this manner is sufficient to thermally decompose the thickened waste liquor that is injected into the combustion chamber through the conduits 9 and 9a with the simultaneous addition of air through conduits 12a and 12b.
  • the resultant gas of combustion referred to as a lean gas is discharged from the combustion chamber through conduit 15 and is introduced into a waste heat boiler 16 for cooling.
  • the waste heat boiler 16 is connected by means of conduits 17 with the steam cylinder 18 in which the heater 5 is positioned.
  • the necessary feed water for the boiler 18 is introduced to the system through conduit 19. It is possible by this arrangement to utilize the sensible heat of the lean gas for thickening the waste liquor and for simultaneously producing steam.
  • the saturated steam produced in steam cylinder 18 is withdrawn through conduit 23 for subsequent use.
  • the sulfur accumulated in the waste heat boiler 16 during the cooling of the lean gas is discharged through conduit 20.
  • the sulfur is conveyed through a submerged pot 21 and conduit 22 to a sulfur pit of the desulfurization system (not illustrated).
  • the cooled and desulfurized lean gas leaves the waste heat boiler 16 through conduit 24.
  • Conduit 8 carrying the ammonia vapors accumulated in thickener 2 is connected to the conduit 24 and is admixed with the lean gas conveyed therethrough.
  • the mixture of cooled lean gas and ammonia vapors is then added to coke oven gas evolved during the coking process before the coke oven gas is introduced into the primary coolers (not illustrated).
  • the slurry formed in the waste heat boiler 16 is discharged through conduit 25.
  • the process of the invention is distinguished by the fact that the ammonia vapors NH accumulated in the treatment of the coke oven gas can be simultaneously eliminated so that the construction of an additional system for the combustion of ammonia is unnecessary.
  • the ammonia vapors are not burned during the process of the present invention but are decomposed as lean gas and again added to the coke oven gas, no nitrogen oxides appear and lead to an undesired pollution of the atmosphere, as is present in the combustion of ammonia.
  • the amount of gas to be treated is increased by about 6% because of the addition of the lean gas accumulated in the process of the invention to the coke oven gas.
  • the resultant costs, however, are minimal.
  • a process for the elimination of waste liquors accumulated in the desulfurization of coke oven gas with a washing solution containing an organic oxygen carrier comprising,
  • a process for the elimination of waste liquors accumulated in the desulfurization of coke oven gas with a washing solution containing an organic oxygen carrier as set forth in claim 1 which includes,
  • a process for the elimination of waste liquors accumulated in the desulfurization of coke oven gas with a washing solution containing an organic oxygen carrier as set forth in claim 2 which includes,

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Industrial Gases (AREA)
  • Treating Waste Gases (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
US519563A 1973-12-13 1974-10-31 Process for eliminating waste liquors accumulated in the desulfurization of coke oven gas Expired - Lifetime US3923965A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2361910A DE2361910C3 (de) 1973-12-13 1973-12-13 Verfahren zur Beseitigung von Abwässern, die bei der Entschwefelung von Koksofengas mit einer organische Sauerstofffiberträger enthaltenden Waschlösung anfallen

Publications (1)

Publication Number Publication Date
US3923965A true US3923965A (en) 1975-12-02

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US519563A Expired - Lifetime US3923965A (en) 1973-12-13 1974-10-31 Process for eliminating waste liquors accumulated in the desulfurization of coke oven gas

Country Status (7)

Country Link
US (1) US3923965A (enrdf_load_stackoverflow)
JP (1) JPS5746910B2 (enrdf_load_stackoverflow)
BE (1) BE821247A (enrdf_load_stackoverflow)
BR (1) BR7410270A (enrdf_load_stackoverflow)
ES (1) ES431384A1 (enrdf_load_stackoverflow)
FR (1) FR2254522B1 (enrdf_load_stackoverflow)
SE (1) SE398512B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103571503A (zh) * 2013-11-13 2014-02-12 山西中天煤化有限公司 用于炭化室顶部荒煤气废热热解脱硫废液喷射器
CN103571505A (zh) * 2013-11-13 2014-02-12 太原理工大学 一种炭化室顶部脱硫废液热解器
CN106675585A (zh) * 2016-07-15 2017-05-17 太原理工大学 一种带有保护装置的脱硫废液热解器
WO2020135136A1 (zh) * 2018-12-27 2020-07-02 中冶焦耐(大连)工程技术有限公司 真空蒸发处理焦化硫泡沫制取硫浆的工艺及装置

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2411805A2 (fr) * 1977-12-15 1979-07-13 Krupp Koppers Gmbh Procede pour eliminer les eaux usees produites par la desulfuration du gaz de four a coke au moyen d'une solution de lavage contenant des donneurs d'oxygene organiques
JPS5622389A (en) * 1979-07-31 1981-03-02 Tsukishima Kikai Co Ltd Treatment of pyrolysis gas
JPS6150835A (ja) * 1984-08-18 1986-03-13 Tsuda Kogyo Kk シフトポジシヨン表示装置
JPS62154520U (enrdf_load_stackoverflow) * 1986-03-20 1987-10-01

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798308A (en) * 1972-01-19 1974-03-19 Koppers Co Inc Method for treating coke oven gas
US3840653A (en) * 1971-11-19 1974-10-08 Koppers Gmbh Heinrich Process for eliminating the formation of waste liquor during the desulfurization of coke oven gas

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2218292A1 (en) * 1973-02-20 1974-09-13 Texaco Development Corp Waste water contng sulphide - removal of sulphide as sulphur by hydrocarbon and oxidn
NL176160C (nl) * 1973-10-10 1985-03-01 Comprimo Bv Werkwijze voor het verbranden van een ammoniak en waterstofsulfide bevattend mengsel van gassen.
US3966876A (en) * 1973-12-18 1976-06-29 Woodall-Duckham, Limited Gas purification

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3840653A (en) * 1971-11-19 1974-10-08 Koppers Gmbh Heinrich Process for eliminating the formation of waste liquor during the desulfurization of coke oven gas
US3798308A (en) * 1972-01-19 1974-03-19 Koppers Co Inc Method for treating coke oven gas

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103571503A (zh) * 2013-11-13 2014-02-12 山西中天煤化有限公司 用于炭化室顶部荒煤气废热热解脱硫废液喷射器
CN103571505A (zh) * 2013-11-13 2014-02-12 太原理工大学 一种炭化室顶部脱硫废液热解器
CN103571505B (zh) * 2013-11-13 2014-11-05 太原理工大学 一种炭化室顶部脱硫废液热解器
CN106675585A (zh) * 2016-07-15 2017-05-17 太原理工大学 一种带有保护装置的脱硫废液热解器
CN106675585B (zh) * 2016-07-15 2019-02-26 太原理工大学 一种带有保护装置的脱硫废液热解器
WO2020135136A1 (zh) * 2018-12-27 2020-07-02 中冶焦耐(大连)工程技术有限公司 真空蒸发处理焦化硫泡沫制取硫浆的工艺及装置

Also Published As

Publication number Publication date
JPS5746910B2 (enrdf_load_stackoverflow) 1982-10-06
JPS5092861A (enrdf_load_stackoverflow) 1975-07-24
FR2254522B1 (enrdf_load_stackoverflow) 1978-06-09
ES431384A1 (es) 1976-11-01
FR2254522A1 (enrdf_load_stackoverflow) 1975-07-11
SE398512B (sv) 1977-12-27
SE7413797L (enrdf_load_stackoverflow) 1975-06-16
BR7410270A (pt) 1976-06-29
BE821247A (fr) 1975-04-18

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