CN1228257C - 应用过氧化氢处理有机硼的废气 - Google Patents

应用过氧化氢处理有机硼的废气 Download PDF

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CN1228257C
CN1228257C CNB028094360A CN02809436A CN1228257C CN 1228257 C CN1228257 C CN 1228257C CN B028094360 A CNB028094360 A CN B028094360A CN 02809436 A CN02809436 A CN 02809436A CN 1228257 C CN1228257 C CN 1228257C
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hydrogen peroxide
waste gas
organoboron
compound
treamtent
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CN1507418A (zh
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R·A·雷默
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INVISTA TECHNOLOGIES Sarl
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EI Du Pont de Nemours and Co
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    • 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

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  • 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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

一种用过氧化氢处理含水废气的方法，该所述废气pH值为5-11，其含有通式为R4B-1M+的有机硼化合物。该方法是将所述有机硼化合物转变为硼酸和有机化合物。

Description

应用过氧化氢处理有机硼的废气
                        背景技术
                       1.发明领域
本发明涉及对含有有机硼化合物的含水废气的处理，是将有机硼化合物转变为硼酸和有机化合物。特别是，本发明涉及将苯基硼化合物水解为硼酸和苯。
                   2.相关现有技术的描述
有机硼化合物，例如三苯基硼烷，适用于在丁二烯的氢氰化反应中作助催化剂。用于氢氰化反应的芳基硼化合物是按照美国专利4046815和4076756所描述的方法制备的。这类化合物的制备会产生含有各种不同量有机硼化合物的含水废气。由于环保的原因，需要降低这些废气中有机硼化合物的水平。
美国专利5,709,841披露了一种将含有以通式R3B、R4B-1、及R2BOH表示的有机硼化合物的含水废气水解为硼酸和相应的烃的方法。该方法包括调整废气的pH值至5-9，升温至至少150℃，压力调整至足够高以防止水溶液的大量蒸发。该方法不能充分地在适当的时间内完成R4B-1的水解。
美国专利4,840,765披露了一种酸水解包含在核废料中的4PBS(四苯基硼酸钠)的方法。该水解是在铜(II)阳离子催化剂和甲酸存在的条件下完成的。
                        发明概述
本发明公开了一种处理含有通式为R4B-1M+的有机硼化合物的含水废气的方法，包括调节所述废气的pH值至5-11，用过氧化氢在至少150℃温度下接触该废气；其中：R选自由苯基、邻甲苯基、对甲苯基、萘基、对甲氧基苯基、对氨基苯基及联苯基组成的组，并且R基任选被Br或Cl取代，M+选自由Na+、K+、NH4 +、Li+、H+和Cs+组成的组。
                        发明详述
含有R4B-1M+的含水废气产生于用美国专利4,046,815所描述的方法制备三苯基硼的过程中。通式R3B、R2BOH和RB(OH)2表示的有机硼化合物也是所述的废气的典型成分。R4B-1表示的化合物需要一反电荷离子，M+。典型的M+是Na+。R4B-1M+的有机基团(R)可以相同或不同，。R可以是具有6-12个碳原子的芳基或取代的芳基。R基团的例子有苯基、邻甲苯基、对甲苯基、萘基、对甲氧基苯基、对氨基苯基、联苯基、氯代苯基和溴代苯基。所述废气除有机硼化合物以外，通常还含有(1)碱金属卤化物，(2)低级烷基醇(即含有1-6个碳原子的)，和(3)硼酸。
如上所述的含有有机硼化合物的废气可以通过有机硼化合物水解为硼酸和有机化合物，并然后通过蒸馏去除所产生的有机化合物(例如苯，是指在苯基硼化合物的情况下)。所得产物可以随后生物处理。在生物处理之前将有机硼物质基本上完全水解是十分重要的。通式R4B-1M+表示的化合物(例如四苯硼酸钠)特别难以水解。四苯基硼酸钠可以抑制废水的生物处理体系。
加入过氧化氢可以增加R4B-1化合物水解反应的程度。这可使得更多的水解产物进行生物处理。
过氧化氢因其在使用过程中具有较高的可达到200ppm或更高浓度的溶解度而优于其它的氧源。优选的是，过氧化氢的浓度至少200ppm，更优选的是，其浓度至少2000ppm。
水解反应可在pH5-11条件下进行。温度至少在150℃。优选的是，温度在200-250℃。优选的水解反应压力在150-4000psig(1.14-27.7MPa)。优选的是，所选择的压力使得水溶液的蒸发达到最小。
任选的，可以使用金属催化剂促进R4B-1化合物的水解。然而，由于可能的生物毒性的结果，优选不使用所述的催化剂。
本发明的方法适合于前述的R4B-1M+化合物，其中M+为K+、NH4 +、Li+、H+、和Cs+。该方法还适用于R基团被Br和Cl取代的有机硼化合物。
                        实施例
实施例1-3是在10ml、316不锈钢小型反应釜中用沙浴加热至200℃下进行的。10个反应器，分别加入6ml相同的4PBS(四苯基硼酸钠)溶液，同时置于200℃沙浴中，随后按预定的间隔时间取出。在所有的操作中，溶液的pH值用缓冲溶液控制在大约9.3，其中缓冲溶液的配制是通过将882ml的0.1N的NaOH溶液与9.27g的H2BO3混合，并用去离子水稀释至总体积1000ml制得。
                        实施例1
包含2000ppm四苯基硼酸钠(4PBS)的溶液在pH为9.3的缓冲溶液中在120分钟内稀释至约600ppm 4PBS。作为对比，该实验重复进行，并加入200ppm的H2O2。在后一个实验中，最终的4PBS浓度为大约3ppm。
                        实施例2
包含2000ppm 4PBS的溶液在pH为9.3的缓冲溶液(加入第二相苯1ml)中在120分钟内稀释至约700ppm 4PBS。作为对比，该实验重复进行，并加入200ppm的H2O2。在后一个实验中，最终的4PBS浓度为大约60ppm。
                        实施例3
在pH为9.3的缓冲液中包含2000ppm 4PBS的溶液，以1ml含大约90％苯加环己烷，大约6-12％的异丙醇，和大约1％的其它有机物如苯基异丙醇、苯酚和联苯的第二有机相在140分钟内稀释至1300ppm 4PBS。作为对比，该实验重复进行，并加入200ppm的H2O2。在后一个实验中，最终的4PBS浓度为大约10ppm。

Claims (5)

1.一种处理含有通式为R4B-1M+的有机硼化合物的含水废气的方法，包括调节所述废气的pH值至5-11，用过氧化氢在至少150℃温度下接触该废气，其中：R为苯基、邻甲苯基、对甲苯基、萘基、对甲氧基苯基、对氨基苯基或联苯基，并且R基任选被Br或Cl取代，M+为Na+、K+、NH4 +、Li+、H+或Cs+。
2.如权利要求1所述的方法，其中过氧化氢的浓度为至少200ppm。
3.如权利要求2所述方法，其中所述温度在200-250℃。
4.如权利要求3所述方法，其中R4B-1M+是四苯基硼酸钠。
5.如权利要求4所述方法，其中过氧化氢的浓度为至少2000ppm。
CNB028094360A 2001-05-07 2002-05-02 应用过氧化氢处理有机硼的废气 Expired - Fee Related CN1228257C (zh)

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US09/850,549 US6372147B1 (en) 2001-05-07 2001-05-07 Organoboron waste stream treatment using hydrogen peroxide
US09/850,549 2001-05-07

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EP (1) EP1385793B1 (zh)
JP (1) JP4159367B2 (zh)
KR (1) KR100838449B1 (zh)
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DE (1) DE60205606T2 (zh)
MY (1) MY124849A (zh)
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WO (1) WO2002090268A1 (zh)

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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
FR2854892B1 (fr) * 2003-05-12 2005-06-24 Rhodia Polyamide Intermediates Procede de fabrication de dinitriles
FR2854891B1 (fr) 2003-05-12 2006-07-07 Rhodia Polyamide Intermediates Procede de preparation de dinitriles
US6977049B2 (en) * 2003-12-31 2005-12-20 The Boc Group, Inc. Treatment process for industrial waste stream
US20050139548A1 (en) * 2003-12-31 2005-06-30 The Boc Group, Inc. Extraction and oxidation process
CZ2008547A3 (cs) * 2006-03-17 2009-06-10 Invista Technologies S. A. R. L. Zpusob purifikace triorganofosfitu ošetrením bazickým aditivem
US7709674B2 (en) * 2006-07-14 2010-05-04 Invista North America S.A R.L Hydrocyanation process with reduced yield losses

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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
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US5868945A (en) * 1996-08-29 1999-02-09 Texaco Inc Process of treating produced water with ozone

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DE60205606T2 (de) 2006-06-08
TWI229054B (en) 2005-03-11
EP1385793B1 (en) 2005-08-17
KR20040017811A (ko) 2004-02-27
JP4159367B2 (ja) 2008-10-01
JP2004532111A (ja) 2004-10-21
DE60205606D1 (de) 2005-09-22
US6372147B1 (en) 2002-04-16
CN1507418A (zh) 2004-06-23
MY124849A (en) 2006-07-31
KR100838449B1 (ko) 2008-06-16
EP1385793A1 (en) 2004-02-04
WO2002090268A1 (en) 2002-11-14

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