WO1993014033A1 - Detoxification of aqueous cyanide solutions - Google Patents

Detoxification of aqueous cyanide solutions Download PDF

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Publication number
WO1993014033A1
WO1993014033A1 PCT/US1992/005064 US9205064W WO9314033A1 WO 1993014033 A1 WO1993014033 A1 WO 1993014033A1 US 9205064 W US9205064 W US 9205064W WO 9314033 A1 WO9314033 A1 WO 9314033A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyanide
aqueous solution
hydrogen peroxide
citric acid
solution
Prior art date
Application number
PCT/US1992/005064
Other languages
English (en)
French (fr)
Inventor
Harry Marcus Castrantas
Michael R. Fagan
Original Assignee
Fmc Corporation
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 Fmc Corporation filed Critical Fmc Corporation
Priority to JP5512397A priority Critical patent/JPH084788B2/ja
Priority to KR1019940702484A priority patent/KR970006498B1/ko
Priority to KR1019940702484A priority patent/KR940703784A/ko
Publication of WO1993014033A1 publication Critical patent/WO1993014033A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/903Nitrogenous
    • Y10S210/904-CN containing

Definitions

  • the present invention relates to a process for detoxifying aqueous solutions containing cyanide and metals with a peroxygen.
  • it relates to detoxifying solutions of metal cyanide complexes.
  • Purification of waste waters is of major impor ⁇ tance for the protection of the environment. Efflu ⁇ ents from many industries, including electroplating, steel-hardening and mining operations, often contain cyanide in various forms together with toxic metals.
  • the detoxification of these waste waters is of para ⁇ mount importance before such waste waters are dis ⁇ charged, in order to avoid serious damage to the environment and adverse impact on public health and safety.
  • U.S. Patent No. 4,070,281 discloses free cyanide ions in organic wastes can be oxidized in the pre ⁇ sence of certain copper and ammonium salts. Sodium hypochlorite was the most effective oxidizing agent followed by potassium persulfate and ozone. The least effective oxidant was found to be hydrogen peroxide. The toxic copper must be removed from the effluent prior to discharge. Further, the process requires oxidizing the organic wastes at 170°C to 30 0 oC at pressures of 20 to 150 kg/crr ⁇ , making it impractical for large scale installations.
  • the present invention overcomes the problems of the prior art by providing a long-sought process for detoxifying an aqueous solution containing weak acid dissociable (WAD) cyanide complexes of metals, the process comprising incorporating hydrogen peroxide and citric acid or a soluble salt thereof into the aqueous solution and maintaining the aqueous solution between pH 8 and pH 12 for a sufficient time to oxi ⁇ dize at least part of the cyanide contained therein, the hydrogen peroxide being provided in an amount sufficient to maintain a concentration of at least 1 millimole per liter of the aqueous solution, and the citric acid being provided in an amount to complex substantially all of the metal in the WAD cyanide complexes.
  • WAD weak acid dissociable
  • the biodegradable citric acid chelant may be incorporated into the solution in any convenient form, such as solid citric acid, its hydrate or a solution of citric acid. On the other hand, it may be introduced as a suitable salt of citric acid, either as a solution or as a solid salt.
  • the cation in the salt may be an alkali metal salt, such as sodium, potassium, or an alkaline earth salt, such as a magnesium or calcium salt.
  • the amount of hydrogen peroxide to be added will vary with the amount of cyanide to be destroyed and the decomposition rate of hydrogen peroxide in the solution. It is usually desirable to make successive additions of hydrogen peroxide to maintain a residual concentration of at least 1 millimole per liter.
  • citrate ion At least about 1 mole to 2 moles of citrate ion should be added per mole of complexed metal ion in the solution. Adding more than 2 moles citrate ion per mole of complexed metal ion does not provide sufficient additional benefit to justify the added cost. About 1 mole of citrate ion is economically preferred.
  • the pH may vary over a wide range be- tween 8 and 12, it is desirable for the pH to be maintained between about 9 and 10, preferably about pH 9.5.
  • the temperature is not critical, and usually ambient temperature is satisfactory. However, the rate of reaction decreases with a decreased tempera ⁇ ture while the rate of decomposition of hydrogen peroxide increases with temperature.
  • One skilled in the art can readily determine the optimum temperature for the particular WAD cyanide solution being treat- ed. Generally a temperature of about 10°C to about 40°C may be employed.
  • Hydrogen peroxide (50% w/w) was then added to the solutions with mixing, to provide approximately a 2:1 wt. ratio of H 2 0 2 :WAD CN ( ⁇ 430 mg/1 H 0 2 ) .
  • the reac ⁇ tions were allowed to commence with periodic agita- tion. Measurements of H 2 0 2 , pH and WAD cyanide ion (WAD CN) were taken over the course of the reaction. When the initial H 2 0 was depleted or at approximate ⁇ ly 30 minute intervals, 105 mg/1 aliquots were added, with the total H 0 2 dose not exceeding 640 mg/1 ( ⁇ 3 ⁇ l wt. ratio H 2 0 :WAD CN) . Results are provided in Table I.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Removal Of Specific Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US1992/005064 1992-01-21 1992-06-17 Detoxification of aqueous cyanide solutions WO1993014033A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP5512397A JPH084788B2 (ja) 1992-01-21 1992-06-17 シアン化物水溶液の無毒化
KR1019940702484A KR970006498B1 (ko) 1992-01-21 1992-06-17 수성 시아나이드 용액의 해독방법
KR1019940702484A KR940703784A (ko) 1992-01-21 1992-06-17 수성 시아나이드 용액의 해독방법(detoxifcation of aqueous cyanide solutions)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/823,400 US5137642A (en) 1992-01-21 1992-01-21 Detoxification of aqueous cyanide solutions
US823,400 1992-01-21

Publications (1)

Publication Number Publication Date
WO1993014033A1 true WO1993014033A1 (en) 1993-07-22

Family

ID=25238659

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/005064 WO1993014033A1 (en) 1992-01-21 1992-06-17 Detoxification of aqueous cyanide solutions

Country Status (6)

Country Link
US (1) US5137642A (en, 2012)
JP (1) JPH084788B2 (en, 2012)
KR (2) KR940703784A (en, 2012)
AU (1) AU2267092A (en, 2012)
TW (1) TW249222B (en, 2012)
WO (1) WO1993014033A1 (en, 2012)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05329489A (ja) * 1992-04-01 1993-12-14 Fuji Electric Co Ltd オゾンを用いた水処理方法
US5415785A (en) * 1992-12-11 1995-05-16 Nalco Chemical Company Method for removing a cyanide contaminant from refinery waste water streams
US5397482A (en) * 1993-08-03 1995-03-14 Fmc Corporation Treatment of cyanides in effluents with Caro's acid
DE29617981U1 (de) * 1996-10-16 1997-01-30 Lipp, Herbert, 76327 Pfinztal Wasserentkeimungsanlage
WO2000034288A1 (en) * 1998-12-08 2000-06-15 E.I. Du Pont De Nemours And Company Process for removal of cyanide from reactions producing 1,3 diones
WO2013149197A1 (en) 2012-03-30 2013-10-03 Saint-Gobain Abrasives, Inc. Abrasive products and methods for fine polishing of ophthalmic lenses

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417987A (en) * 1980-12-12 1983-11-29 Interox Chemicals Limited Process for detoxification
US4822496A (en) * 1988-08-18 1989-04-18 Degussa Aktiengesellschaft Process for the treatment of effluent containing cyanide and toxic metals, using hydrogen peroxide and trimercaptotriazine

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1560450A (en, 2012) * 1968-01-16 1969-03-21
US3617567A (en) * 1969-05-15 1971-11-02 Du Pont Destruction of cyanide in aqueous solutions
US4070281A (en) * 1974-08-05 1978-01-24 Asahi Kasei Kogyo Kabushiki Kaisha Method for treating waste water
US4419246A (en) * 1982-09-30 1983-12-06 E. I. Du Pont De Nemours & Co. Removal of heavy metal ions
US4512900A (en) * 1983-12-13 1985-04-23 International Business Machines Corporation Method for treating waste compositions
US4851129A (en) * 1988-04-19 1989-07-25 Degussa Aktiengesellschaft Process for the detoxification of effluents from ore processing operations with hydrogen peroxide, using a magnetic pre-separation stage
US4966715A (en) * 1989-05-19 1990-10-30 Degussa Aktiengesellschaft Process for the removal of cyanide from wastewaters
US5006262A (en) * 1989-11-21 1991-04-09 Met. Rev. Inc. Process for recovering copper from copper ion containing aqueous solutions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417987A (en) * 1980-12-12 1983-11-29 Interox Chemicals Limited Process for detoxification
US4822496A (en) * 1988-08-18 1989-04-18 Degussa Aktiengesellschaft Process for the treatment of effluent containing cyanide and toxic metals, using hydrogen peroxide and trimercaptotriazine

Also Published As

Publication number Publication date
KR940703784A (ko) 1994-12-12
JPH084788B2 (ja) 1996-01-24
KR970006498B1 (ko) 1997-04-28
AU2267092A (en) 1993-08-03
TW249222B (en, 2012) 1995-06-11
US5137642A (en) 1992-08-11
JPH06510946A (ja) 1994-12-08

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