WO1994022563A1 - Capture de metaux volatils contenus dans des courants gazeux - Google Patents

Capture de metaux volatils contenus dans des courants gazeux Download PDF

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Publication number
WO1994022563A1
WO1994022563A1 PCT/US1994/003775 US9403775W WO9422563A1 WO 1994022563 A1 WO1994022563 A1 WO 1994022563A1 US 9403775 W US9403775 W US 9403775W WO 9422563 A1 WO9422563 A1 WO 9422563A1
Authority
WO
WIPO (PCT)
Prior art keywords
polysulfide
process according
contacting
synthesis gas
cadmium
Prior art date
Application number
PCT/US1994/003775
Other languages
English (en)
Inventor
Daniel Clark Baker
John William Gognat
Original Assignee
Shell Oil Company
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
Application filed by Shell Oil Company filed Critical Shell Oil Company
Priority to AU65560/94A priority Critical patent/AU6556094A/en
Publication of WO1994022563A1 publication Critical patent/WO1994022563A1/fr

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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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/103—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkali- or earth-alkali- or NH4 salts or inorganic acids derived from sulfur
    • 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
    • B01D53/14—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 absorption
    • 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
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury

Definitions

  • the invention relates to a process for removing volatile metals from a coal gasification synthesis gas stream.
  • the invention therefore is a process for removing volatile metals from a synthesis gas stream by (a) contacting in a contacting zone a synthesis gas stream containing zinc, lead, mercury, and cadmium with a polysulfide-containing aqueous solution under conditions to convert the zinc, lead, mercury, and cadmium to their respective metal sulfides; and (b) recovering the synthesis gas having reduced amounts of zinc, lead, mercury, and cadmium.
  • the particular type of gas stream treated according to the invention is not critical.
  • the gaseous stream is any stream containing zinc, lead, mercury, cadmium, nickel, antimony, or arsenic and which optionally contains other compounds, such as hydrogen cyanide, which react with polysulfides.
  • the gaseous stream does not contain compounds which interfere with the reaction between the metals and polysulfide, such as 0 2 found in the gaseous effluent of oxygen-rich coal-fired boilers/furnaces of conventional coal-fired power plants.
  • gaseous streams or effluents particularly suited to the invention include fuel gases produced by gasification procedures. Such gases include fuel or effluent gases derived from the gasification of coal, petroleum, shale, tar sands, etc.
  • the stream is a coal or petroleum coke synthesis gas stream.
  • the gaseous effluents are often quenched with water or gaseous liquids.
  • the volatile metals content of the treated gaseous stream will range from trace amounts to about one percent by volume. Preferably, such content is from about 0.05 ppm by weight to about 10 ppm by weight.
  • the first step, the contacting step, of the process is preferably done on a continuous basis. That is, the metal-containing gas and polysulfide-containing aqueous solution are both continuously supplied to a contacting zone.
  • the polysulfide-containing solution is added by injection into the gaseous stream or by adding it alone or adding it as part of a scrubbing solution or quenching solution.
  • it is added to a scrubber unit, such as a packed column scrubber.
  • the packing is any material, such as stainless steel rings, which is wetted by the polysulfide-containing solution.
  • the flow direction of the two streams in the scrubber unit is preferably counter- current.
  • the amount of the polysulfide-containing solution added is an effective amount to convert a substantial portion, e.g., at least 20% by weight, of the volatile metals to their respective sulfides.
  • the polysulfide-containing aqueous solution has at least a stoichiometric amount of polysulfide sulfur with respect to the zinc, lead, mercury, and cadmium.
  • a stoichiometric amount of polysulfide sulfur is present. Elemental sulfur is supplied to the contact zone as needed to maintain this concentration.
  • Typical concentrations of the polysulfide in the polysulfide-containing solution are from about 5 ppm to about 1,000 ppm. Preferable concentrations are from about 15 ppm to about 50 ppm. Where compounds, other than zinc, lead, mercury, cadmium, nickel, antimony, or arsenic, are present which react with the sulfides, higher concentrations of polysulfide must be used since some sulfides will react with the other compounds.
  • the contacting occurs at effective conditions for the conversion of the volatile metals to their respective sulfides.
  • Contacting temperature is preferably from ambient temperature to not more than about 200°F.
  • Contacting pressure is from about 1 atmosphere to about 30 atmospheres.
  • the pH of the contacting solution is from about 7 to about 9, preferably from about 7.5 to about 9.5.
  • the gas-liquid contacting time is from about 0.1 minute to about 1 minute, preferable from about 0.2 minute to about 0.5 minute.
  • the residence time of the polysulfide-containing solution is from about 10 minutes to about 60 minutes or longer.
  • any water-soluble polysulfide is suitable which does not contribute to the volatile metal concentration or add other environmentally hazardous compounds to the gaseous stream.
  • Ammonium polysulfide, sodium polysulfide, and mixtures thereof are preferred polysulfides. Where ammonium polysulfide is used and the pH is adjusted by the addition of an alkali such as NaOH, those skilled in the art will recognize that a mixture of polysulfides is also present.
  • the sulfides of the volatile metals which are largely insoluble in water, will concentrate on the packing material in the packed scrubbing bed. The packing material is then regenerated or disposed of in an environmentally safe manner. The synthesis gas is recovered having reduced amounts of volatile metals including reduced amounts of zinc, lead, mercury, and cadmium.
  • a bituminous coal feed Blacksville #2 coal
  • a bituminous coal feed Blacksville #2 coal
  • the synthesis gas was passed through a packed column scrubbing unit containing stainless steel packing rings having a 2-inch diameter.
  • An aqueous solution containing 100 ppm sodium polysulfide was fed to the scrubber in countercurrent flow.
  • the flow rate of synthesis gas was 65,000 lbs/hr.
  • the polysulfide solution was recirculated at a flow rate of 140,000 lbs/hr.
  • the liquid to gas flow rate was 2.1:1.
  • the gas-liquid contact time was 0.1 minute.
  • the residence time of the polysulfide solution was 60 minutes.
  • the temperature of the contacting zone was 200 ⁇ F.
  • the pressure was 280 psig.
  • the pH was 8.5.
  • the polysulfide solution effectively reduces the amount of volatile metals in the synthesis gas stream.

Landscapes

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

Abstract

L'invention concerne un procédé permettant d'extraire les métaux volatils d'un courant de gaz de synthèse en (a) mettant en contact, dans une zone de contact, un courant de gaz de synthèse contenant du zinc, du plomb, du mercure et du cadmium avec une solution contenant du polysulfure dans des conditions permettant la conversion du zinc, du plomb, du mercure et du cadmium; (b) produisant, suite à l'étape (a), les sulfures métalliques respectifs de zinc, plomb, mercure et cadmium; et (c) récupérant le gaz de synthèse dont les teneurs en zinc, plomb, mercure et cadmium ont été réduites.
PCT/US1994/003775 1993-04-06 1994-04-06 Capture de metaux volatils contenus dans des courants gazeux WO1994022563A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU65560/94A AU6556094A (en) 1993-04-06 1994-04-06 Volatile metals capture from gazeous streams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4317393A 1993-04-06 1993-04-06
US043,173 1993-04-06

Publications (1)

Publication Number Publication Date
WO1994022563A1 true WO1994022563A1 (fr) 1994-10-13

Family

ID=21925865

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/003775 WO1994022563A1 (fr) 1993-04-06 1994-04-06 Capture de metaux volatils contenus dans des courants gazeux

Country Status (2)

Country Link
AU (1) AU6556094A (fr)
WO (1) WO1994022563A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0846490A1 (fr) * 1996-12-02 1998-06-10 L. & C. Steinmüller GmbH Procédé pour éliminer le mercure d'un gaz contenant du mercure
DE19936930A1 (de) * 1999-08-19 2001-02-08 Ftu Gmbh Forschung Und Entwick Verfahren und Vorrichtung zur Abtrennung von Quecksilber aus heißen Pyrolysegasen
US6214304B1 (en) 1996-12-02 2001-04-10 L & C STEINMüLLER GMBH Method of removing mercury from a mercury-containing flue gas
DE19939382A1 (de) * 1999-08-05 2001-04-19 Ftu Gmbh Forschung Und Tech En Verfahren und Vorrichtung zur Abtrennung von Quecksilber aus heißen Pyrolysegasden
WO2006083942A2 (fr) * 2005-02-03 2006-08-10 Shell Internationale Research Maatschappij B.V. Procede pour inhiber un depot de matieres solides d'un flux gazeux
US7221170B2 (en) 2005-02-01 2007-05-22 Samsung Electronics Co., Ltd. Semiconductor test circuit
US7385090B2 (en) 2006-02-01 2008-06-10 Shell Oil Company Method of treating an aldehyde mixture, use of the treated aldehyde, and an alcohol
EP3476460A1 (fr) * 2012-09-07 2019-05-01 Chevron U.S.A. Inc. Procédés pour éliminer du mercure contenu dans du gaz naturel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2380339A1 (fr) * 1977-02-14 1978-09-08 Metallgesellschaft Ag Procede pour purifier des gaz
US4505881A (en) * 1983-11-29 1985-03-19 Shell Oil Company Ammonium polysulfide removal of HCN from gaseous streams, with subsequent production of NH3, H2 S, and CO2
US4671803A (en) * 1986-06-26 1987-06-09 Texaco Development Corp. Process for producing synthesis gas free-from volatile metal hydrides
US4748141A (en) * 1987-04-29 1988-05-31 Shell Oil Company Metal sulfide catalyst preparation
US5034203A (en) * 1989-04-27 1991-07-23 Mobil Oil Corporation Removal of mercury from natural gas utilizing a polysulfide scrubbing solution
DE4123907A1 (de) * 1991-07-18 1993-01-21 Gea Wiegand Gmbh Verfahren zur abscheidung von quecksilber und/oder quecksilber enthaltenden verbindungen aus rauch
JPH0691129A (ja) * 1991-01-21 1994-04-05 Jgc Corp 不飽和炭化水素含有ガス中の水銀の除去方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2380339A1 (fr) * 1977-02-14 1978-09-08 Metallgesellschaft Ag Procede pour purifier des gaz
US4505881A (en) * 1983-11-29 1985-03-19 Shell Oil Company Ammonium polysulfide removal of HCN from gaseous streams, with subsequent production of NH3, H2 S, and CO2
US4671803A (en) * 1986-06-26 1987-06-09 Texaco Development Corp. Process for producing synthesis gas free-from volatile metal hydrides
US4748141A (en) * 1987-04-29 1988-05-31 Shell Oil Company Metal sulfide catalyst preparation
US5034203A (en) * 1989-04-27 1991-07-23 Mobil Oil Corporation Removal of mercury from natural gas utilizing a polysulfide scrubbing solution
JPH0691129A (ja) * 1991-01-21 1994-04-05 Jgc Corp 不飽和炭化水素含有ガス中の水銀の除去方法
DE4123907A1 (de) * 1991-07-18 1993-01-21 Gea Wiegand Gmbh Verfahren zur abscheidung von quecksilber und/oder quecksilber enthaltenden verbindungen aus rauch

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9418, Derwent World Patents Index; Class A41, AN 94-147100 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0846490A1 (fr) * 1996-12-02 1998-06-10 L. & C. Steinmüller GmbH Procédé pour éliminer le mercure d'un gaz contenant du mercure
US6214304B1 (en) 1996-12-02 2001-04-10 L & C STEINMüLLER GMBH Method of removing mercury from a mercury-containing flue gas
DE19939382A1 (de) * 1999-08-05 2001-04-19 Ftu Gmbh Forschung Und Tech En Verfahren und Vorrichtung zur Abtrennung von Quecksilber aus heißen Pyrolysegasden
DE19936930A1 (de) * 1999-08-19 2001-02-08 Ftu Gmbh Forschung Und Entwick Verfahren und Vorrichtung zur Abtrennung von Quecksilber aus heißen Pyrolysegasen
US7221170B2 (en) 2005-02-01 2007-05-22 Samsung Electronics Co., Ltd. Semiconductor test circuit
WO2006083942A2 (fr) * 2005-02-03 2006-08-10 Shell Internationale Research Maatschappij B.V. Procede pour inhiber un depot de matieres solides d'un flux gazeux
WO2006083942A3 (fr) * 2005-02-03 2006-09-28 Shell Oil Co Procede pour inhiber un depot de matieres solides d'un flux gazeux
US7488372B2 (en) * 2005-02-03 2009-02-10 Shell Oil Company Process for inhibiting deposition of solids from a gaseous stream
US7385090B2 (en) 2006-02-01 2008-06-10 Shell Oil Company Method of treating an aldehyde mixture, use of the treated aldehyde, and an alcohol
EP3476460A1 (fr) * 2012-09-07 2019-05-01 Chevron U.S.A. Inc. Procédés pour éliminer du mercure contenu dans du gaz naturel

Also Published As

Publication number Publication date
AU6556094A (en) 1994-10-24

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