WO2002090268A1 - Organoboron waste stream treatment using hydrogen peroxide - Google Patents

Organoboron waste stream treatment using hydrogen peroxide Download PDF

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Publication number
WO2002090268A1
WO2002090268A1 PCT/US2002/014122 US0214122W WO02090268A1 WO 2002090268 A1 WO2002090268 A1 WO 2002090268A1 US 0214122 W US0214122 W US 0214122W WO 02090268 A1 WO02090268 A1 WO 02090268A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
organoboron
ppm
compounds
para
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.)
Ceased
Application number
PCT/US2002/014122
Other languages
English (en)
French (fr)
Inventor
Ronald A. Reimer
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to KR1020037014441A priority Critical patent/KR100838449B1/ko
Priority to DE60205606T priority patent/DE60205606T2/de
Priority to EP02736651A priority patent/EP1385793B1/en
Priority to JP2002587354A priority patent/JP4159367B2/ja
Publication of WO2002090268A1 publication Critical patent/WO2002090268A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F1/025—Thermal hydrolysis
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/908—Organic

Definitions

  • the present invention relates to the treatment of aqueous waste streams containing organoboron compounds in order to convert the organoboron compounds to boric acid and organic compounds.
  • this invention relates to the hydrolysis of phenylated boron compounds to boric acid and benzene .
  • Organoboron compounds such as triphenylborane, are suitable for use as promoters in the hydrocyanation of butadiene .
  • Arylboron compounds used in hydrocyanation reactions can be prepared by the process described in U.S. Patents 4,046,815 and 4,076,756. The preparation of such compounds can produce an aqueous waste stream that contains various amounts of organoboron compounds. For environmental reasons, it is desirable to reduce the level of organoboron compounds in such streams .
  • U-. S. Patent 5,709,841 discloses a process in which aqueous waste streams containing organoboron compounds of the formula R 3 B, RB _1 , and R 2 BOH are treated to hydrolyze the compounds to boric acid and the corresponding hydrocarbons.
  • the process involves treatment of the waste streams to adjust the pH of the stream to a value between 5 and 9 and elevating the temperature to at least 150° C, at a pressure sufficiently high to prevent substantial evaporation of the aqueous solution. This process may not be sufficient for complete RB _1 hydrolysis within a reasonable period of time.
  • U.S. Patent 4,840,765 discloses a process for acid hydrolysis of 4PBS (sodium tetraphenylborate) contained in nuclear waste. The hydrolysis is performed in the presence of a copper (II) cation catalyst and formic acid.
  • 4PBS sodium tetraphenylborate
  • the present invention is a process for treating an aqueous waste steam containing an organoboron compound of the formula R 4 B _1 M + , comprising adjusting the pH of said stream to a value between 5 and 11, and contacting said stream with hydrogen peroxide at a temperature of at least 150° C; wherein:
  • R is selected from the group consisting of phenyl, ortho-tolyl, para-tolyl, naphthyl, para-methoxyphenyl, para-aminophenyl and biphenyl , and wherein R is optionally substituted with Br or Cl , and
  • M + is selected from the group consisting of Na + , K + ,
  • Aqueous waste streams containing RB _:L M + may result from preparing triphenylboron by the method described in U.S. Patent 4,046,815.
  • Organoboron compounds of the formula R 3 B, R 2 BOH, and RB (OH) 2 also are typical components of such waste streams.
  • the R 4 B ⁇ X compound requires a counter ion, M + .
  • M + is Na + .
  • the organic groups (R) of R 4 B "1 M + can be the same or different .
  • R can be aryl or substituted aryl having 6 to 12 carbon atoms.
  • R groups are phenyl, orthotolyl, paratolyl, naphthyl, para- methoxyphenyl, para-aminophenyl, biphenyl, chlorophenyl , and bromophenyl .
  • Such waste streams will usually contain, in addition to the organoboron compound(s), (1) alkali metal halides, (2) lower alkyl alcohols (ie, those with 1 to 6 carbon atoms) , and (3) boric acid.
  • the aforementioned waste streams containing the organoboron compounds can be treated to hydrolyze the organoboron compounds to boric acid and an organic compound, and then subjected to a distillation to remove the resulting organic compound (benzene, for example, in the case of phenylated boron compounds) .
  • the resulting product is then amenable to biotreatment .
  • Hydrogen peroxide is preferred over other oxygen sources because of its high solubility which allows 200 ppm or greater levels to be used in the process.
  • concentration of hydrogen peroxide is at least 200 ppm. More preferably, the concentration is greater than 2000 ppm.
  • the hydrolysis reaction can be performed at a pH of 5 to 11.
  • the temperature should be at least 150°C.
  • the temperature is 200 to 250°C.
  • the preferred pressure of the hydrolysis is 150 to 4000 psig (1.14 to 27.7 MPa) .
  • the pressure is chosen to minmize vaporization of the aqueous solution.
  • a metal catalyst may be used to promote the hydrolysis of R 4 B -1 compounds. However, due to potential bio-toxicity issues, it is preferred that no such catalyst be used.
  • Examples 1 to 3 were carried out in 10 ml, 316 stainless steel, mini-bomb reactors heated by a 200°C sand bath. Ten reactors, charged with 6 ml each of identical 4PBS (sodium tetraphenylborate) solutions, were simultaneously placed in the 200°C bath and then removed intermittently at predetermined times. In all runs, solution pH was maintained at about 9.3 using a buffer solution made by mixing 882 ml of 0. IN NaOH solution with 9.27g H 3 B0 3 , and diluting to 1000 ml total volume with de-ionized water.
  • 4PBS sodium tetraphenylborate
  • Example 1 A solution containing 2000 ppm sodium tetraphenylborate (4PBS) in pH 9.3 buffer solution declined to about 600 ppm 4PBS after 120 minutes holdup time. For comparison, this experiment was repeated, except that 200 ppm H 2 0 2 was present. In this latter case, the final 4PBS concentration was about 3 ppm.

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)
  • General Health & Medical Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Emergency Management (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
PCT/US2002/014122 2001-05-07 2002-05-02 Organoboron waste stream treatment using hydrogen peroxide Ceased WO2002090268A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020037014441A KR100838449B1 (ko) 2001-05-07 2002-05-02 과산화수소를 사용하는 유기붕소 폐기 스트림의 처리 방법
DE60205606T DE60205606T2 (de) 2001-05-07 2002-05-02 Organoborverbindungsabfallstrombehandlung durch wasserstoffperoxid
EP02736651A EP1385793B1 (en) 2001-05-07 2002-05-02 Organoboron waste stream treatment using hydrogen peroxide
JP2002587354A JP4159367B2 (ja) 2001-05-07 2002-05-02 過酸化水素を用いる有機ホウ素廃棄物流処理

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/850,549 US6372147B1 (en) 2001-05-07 2001-05-07 Organoboron waste stream treatment using hydrogen peroxide
US09/850,549 2001-05-07

Publications (1)

Publication Number Publication Date
WO2002090268A1 true WO2002090268A1 (en) 2002-11-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/014122 Ceased WO2002090268A1 (en) 2001-05-07 2002-05-02 Organoboron waste stream treatment using hydrogen peroxide

Country Status (9)

Country Link
US (1) US6372147B1 (https=)
EP (1) EP1385793B1 (https=)
JP (1) JP4159367B2 (https=)
KR (1) KR100838449B1 (https=)
CN (1) CN1228257C (https=)
DE (1) DE60205606T2 (https=)
MY (1) MY124849A (https=)
TW (1) TWI229054B (https=)
WO (1) WO2002090268A1 (https=)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6911916B1 (en) * 1996-06-24 2005-06-28 The Cleveland Clinic Foundation Method and apparatus for accessing medical data over a network
FR2849027B1 (fr) * 2002-12-23 2005-01-21 Rhodia Polyamide Intermediates Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques
FR2850966B1 (fr) 2003-02-10 2005-03-18 Rhodia Polyamide Intermediates Procede de fabrication de composes dinitriles
FR2854891B1 (fr) 2003-05-12 2006-07-07 Rhodia Polyamide Intermediates Procede de preparation de dinitriles
FR2854892B1 (fr) * 2003-05-12 2005-06-24 Rhodia Polyamide Intermediates Procede de fabrication de dinitriles
US20050139548A1 (en) * 2003-12-31 2005-06-30 The Boc Group, Inc. Extraction and oxidation process
US6977049B2 (en) * 2003-12-31 2005-12-20 The Boc Group, Inc. Treatment process for industrial waste stream
WO2007109005A2 (en) * 2006-03-17 2007-09-27 Invista Technologies S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US7709674B2 (en) * 2006-07-14 2010-05-04 Invista North America S.A R.L Hydrocyanation process with reduced yield losses

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5564105A (en) * 1995-05-22 1996-10-08 Westinghouse Electric Corporation Method of treating a contaminated aqueous solution
US5709841A (en) * 1996-02-23 1998-01-20 E.I. Du Pont De Nemours And Company Waste stream treatment
US5868945A (en) * 1996-08-29 1999-02-09 Texaco Inc Process of treating produced water with ozone

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076756A (en) 1975-11-12 1978-02-28 E. I. Du Pont De Nemours And Company Process for the preparation of triarylborane
US4046815A (en) 1975-11-12 1977-09-06 E. I. Du Pont De Nemours And Company Process for the preparation of triarylborane
DE2553840C3 (de) * 1975-11-29 1981-01-29 Bayer Ag, 5090 Leverkusen Druckhydrolytische Behandlung von Abwasser
JPS6012970B2 (ja) * 1978-12-22 1985-04-04 日鉄化工機株式会社 廃液のホウ酸含有物の焼却方法
US4840765A (en) 1987-02-25 1989-06-20 The United States Of America As Represented By The United States Department Of Energy Precipitate hydrolysis process for the removal of organic compounds from nuclear waste slurries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5564105A (en) * 1995-05-22 1996-10-08 Westinghouse Electric Corporation Method of treating a contaminated aqueous solution
US5709841A (en) * 1996-02-23 1998-01-20 E.I. Du Pont De Nemours And Company Waste stream treatment
US5868945A (en) * 1996-08-29 1999-02-09 Texaco Inc Process of treating produced water with ozone

Also Published As

Publication number Publication date
KR100838449B1 (ko) 2008-06-16
US6372147B1 (en) 2002-04-16
EP1385793B1 (en) 2005-08-17
CN1507418A (zh) 2004-06-23
JP2004532111A (ja) 2004-10-21
DE60205606D1 (de) 2005-09-22
DE60205606T2 (de) 2006-06-08
MY124849A (en) 2006-07-31
TWI229054B (en) 2005-03-11
EP1385793A1 (en) 2004-02-04
KR20040017811A (ko) 2004-02-27
JP4159367B2 (ja) 2008-10-01
CN1228257C (zh) 2005-11-23

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