AU610552B2 - Process for destroying chlorinated products at low temperature - Google Patents

Process for destroying chlorinated products at low temperature Download PDF

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Publication number
AU610552B2
AU610552B2 AU10621/88A AU1062188A AU610552B2 AU 610552 B2 AU610552 B2 AU 610552B2 AU 10621/88 A AU10621/88 A AU 10621/88A AU 1062188 A AU1062188 A AU 1062188A AU 610552 B2 AU610552 B2 AU 610552B2
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AU
Australia
Prior art keywords
products
bath
chlorinated
chloroaluminate
sodium
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
AU10621/88A
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AU1062188A (en
Inventor
Jacques Dugua
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Arkema France SA
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Atochem SA
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Filing date
Publication date
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Application granted granted Critical
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Anticipated expiration legal-status Critical
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Classifications

    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/32Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or metals
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/22Organic substances containing halogen

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  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Dental Preparations (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Glass Compositions (AREA)
  • Luminescent Compositions (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Paper (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Processing Of Solid Wastes (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

1. Process for destroying chlorinated organic products containing more than 2 carbon atoms, in which these products are brought into contact with a bath of at least one chloroaluminate, characterized in that the initial concentration of the chlorinated organic products in the bath is 4000 ppm or less and preferably 2000 ppm or less.

Description

10552 Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952469 COMPLETE SPECIFICATION
(ORIGINAL)
Class Application Number: Lodged: I t. Class I4Cdiiipleto Specification Lodged: Priority: Accepted; Published: Iielpted Art: 0 Address of Applicant: 0 Actual Inventor.
Address for Service: ATOCH EM La Defense 10 4 8 Cours Michelet 92800 Puteaux, France JACQUES DUGUA EDWD. WATERS SONS, 50 QUEEQN STREET, NIELBOURNE, AUSTRALIA, 3000.
Complete Specification for the Invention entitled: PROCESS FOR DESTROYING CHLORINATED PRODUCTS AT LOW
TEMPERATURE
The following statement Is a full descriptio~n of this invention, Including the best method of performing It known to us s 1- PROCESS FOR DESTROYING CHLORINATED PRODUCTS AT LOW TEMPERATURE The present invention relates to a process for destroying chlorinated organic products and more particularly aromatic products and polychLorobiphenyls.
Certain dielectric liquids contain chlorinated organic products and after a certain period of operation a* s they decompose and need to be replaced. It is sometimes SSSr possible to regenerate them completely or partially. It 10 is often necessary to destroy a proportion of these liquids.
Chlorinated organic products, as well as certain pesticides and chlorinated aromatics .such as hexachlorobenzene or polychlorobiphenyls (PCB) can give rise to toxic products when they ar burnt like an ordinary flamo mable product.
0oo In order to avoid generating toxic products these oo chlorinated products are destroyed at a high temperature o Go and under specific conditions.
A paper in Sci. Total Environ. 1978, 10 51-9 describes the destruction of polychlorobiphenyls (PCB) by incineration with a residence time of more than 2 seconds.
Another paper, Proc. Ann. Meet Air Pollut.
Control Assoc. 1977 (Vol 2) paper No. 33, describes a 99.9995% destruction of PCBs at 1000C with a residence time of 2 seconds.
European Patent EP 170,714 describes the destruction of PCes by reaction with molten aluminium or an 1 -2aluminium-base eutectic; the reaction takes place above 382°C.
A much simpler process for destroying these products, capable of operating below 300 0 C, has now been found, The present .invention is a process for destroying chlorinated organic products containing more than 2 car- 0 0 bon atoms, characterized in that these products are placed in contact with a bath of at Least one chloroalumindte.
Various chloroaluminates or their mixtures can be 0 10 employed. For example, potassium, lithium, sodium, calcium, strontium or ammonium chloroaluminates.
*o In this text, the name chloroaluminate is given 0 p to any mixture of anhydrous aluminium chloride and one or more metal chlorides.
Sodium chLoroaluminate, which is preferably em- *ooo ployed, denotes a mixture of aluminium chloride and of 0oo00 6 0 sodium chloride in any proportions and not only the equimolar mixture. Sodium chloroaluminate may also contain lithium and/or potassium chlorides. It is therefore possible to have a mixture of aluminium chloride, sodium chloride and lithium chloride, which is called sodium lithium chloroaluminate.
It is also preferred that the sodium chloroaluminate should contain at least 50 mol% of aluminium chloride and should have a melting point below 200 0
C.
The invention applies to all chlorinated organic products containing more than 2 carbon atoms, but it is, first and foremost, usable in the case of aliphatic, cyclic, mono- or polycyclic aromatic and heterocyclic products.
The invention relates most especially to perchlorinated aliphatic products and, among aromatic products, to poLychlorobiphenyls.
The quantity of chlorinated organic products to be destroyed is advantageously less than 5000 ppm of -he chloroaluminate and preferably less than 2000 ppm.
These products may be in any form. They may,, in t c Oc particular be in a solid phase, for example absorbed on active charcoal.
4 o The process according to the invention consists 9 9 in placing the chlorinated product in contact with the bath of chloroaLuminate.
99 When the chlorinated product is in a solid phase, 9 o0 this solid phase may be poured into the bath of chloroaluminate, preferably stirred. Care is taken to keep the bath molten, by heating if necessary. The procedure is 0..0 similar if the chlorinated products are in a liquid phase.
o o- 0* s In most cases the chlorinated products which are to be destroyed are in a gaseous phase by themselves or mixed with light chlorinated products and/or carrier gases.
For example, this may be a gas produced by a combustion and will then consist of nitrogen containing carbon dioxide, carbon monoxide, chlorinated products and possibly oxygen.
However, it may be any gaseous mixture taken from any process.
It is preferable that the chlorinated products should be in an anhydrous phase. The gas containing the chlorinated products may be dried by contact with an IC-C- -I 4 absorbent, for example alumina or glycol.
This gaseous phase containing the chlorinated products to be destroyed is then placed in contact with the chloroaluminate using any means for placing a liquid phase in contact with a gaseous phase. This may be a plate- or packed column. The gaseous phase may also be •introduced into a stirred vat of chloroalurminate through a dip tube or through a tube entering via the bottom of or@o 0o"0 the vat.
0000 10 The various chlorinated organic products may partition between the liquid and vapour phases of the chloro- 0 atuminate bath. Similarly, in the case of the products which accompany these chlorinated products. A plate- or packed column may bo employed in order to ensure continuous 0 0 circulation and stirring of the liquid and gaseous phases a00. and good contact between the gaseous products and the S o .0 o chloroaluminate bath. It is also possible to operate o oo using a cascade of stirred reactors. The chlorinated organic products are kept in contact with the chloroaluminate bath for the period required to destroy them. The residence time may vary within wide limits but is generally between a few minutes and a few hours.
Although i is possible to operate at any temperature, provided chat the chloroaluminate is liquid, it is preferable for this to be done below 300°C and preferably between 200 and 300 0
C.
The rate of destruction of the chlorinated products, i I I c especially aromatic products, increases with the temperature of the chloroaluminate.
Light products of decomposition of the chlorinated products which it was intended to destroy may be found in the gaseous phase of the chloroaluminate bath; for example carbon tetrachloride and/or hexachloroethane. The chlorinated organic products which it was intended to destroy o are not to be found in the vapour phase of the chl roaluminate bath. When the chloroaluminate bath is analysed 10 after the period of contact between the chlorinated products and the chloroatuminate has been observed, the organic products which it was intended to destroy are not found.
The chloroaluminate bath may also be purged at o regular intervals to avoid the accumulation of products which are insoluble or which cannot remain in suspension in the bath. No trace of the chlorinated organic products 9oo o o 0 .ooo is found in this purge either. It is concluded, therefore, that the chlorinated products which it was intended to destroy h.ave disappeared.
In a preferred embodiment of the invention, one or more powdered metals chosen from reducing metals such as, for example, aluminium or zinc, are added to the chloroaluminate bath. It is preferable to employ a powder whose mean particle size is less than 500 u. When metals are employed, the chlorinated organic products are completely eliminated as previously but at a markedly higher rate, of the order of several times to several tens of 6- 0 0O S 0° *9 1g 5 aPe 0@006o 0 5 *0 8 0 *0 0 0 0 o o 0000 00 0 9 0 0o a so ao o orc times the previous rate.
A consumption of the powdered metal (or metals) is observed, and this may mean that chloride has formed, taking up chlorine from the chlorin.ated organic products when they are being destroyed. There is no limit to the quantity of metal powder to be introduced into the chloroaluminate. It is preferable to employ aluminium powder; up to 5 or 10% by weight of aluminium powder may be placed in the chloroaluminate bath. It is found that the rate of destruction of the chlorinated products increases with the quantity of aluminium powder and with the temperature of the chloroaluminate bath. It is preferable to stir the bath so that the metal powder is well dispersed in the bath. The metal chloride or chlorides which have been produced may mix with the chLoroatuminate bath and may partition between the liquid and gaseous phases. If necessary, the metal chlorides may be removed from the gaseous phase by treating it with a hydroxide, such as sodium hydroxide or potassium hydroxide.
The following examples illustrate the invention: EXAMPLE 1 500 g of sodium chtoroaluminate in which the ratio
ALCL
3 /Nati I are introduced into an electrically heated i-litre Pyrex round flask fitted with a propeller stirrer rotating at 300 rev/min. The product is heated to 200 C, stirred, and then 0.2 g of hexachlorobenzene and 0.1 g of decachlorobiphenyl are introduced. After 1 hour at 200 0
C,
7the moLten bath is purged for 15 minutes with a stream of L/h of N2, which is washed in a bubbler containing 100 mL of hex~ane.
The, chlorinated organic compounds in the finaL bath and in the hexane are determined by gas phase ~.trO chromatography.
The results are shown in Table 1.
EXAMPLE 2 The same test is carried out, but 5% of fine alum- 10 inium powder (Pechiney XY 49 grade) are additionally introduced into the chioroaLuminate bath. After I hour at 200 0 C followed by purging with 50 L/h of N 2 for 15 min, 0 a sampke of the bath and of hexane is taken for quantitative analysis.
The resutts are shown in Table 1.
too TABLE 1 CHLOR WITHOUT At WITH 5% Al ORGANIC 1 %of-l Y. I of PRO&LOCTS I BATH lhexane I product I BATH thexane I product! s t ta r t f ina( srmo st ar t f 1inaL~ removed' 6 I C 6 1 200 lift 1 13.2 1 37.7 ZI 2,00 129 1 3.5 1 83.7 1 1 I DCBP* 1 100 141.3 1 0.40! 58.3 2! 100 1 3.8 t 0.2 196 *DCBPi decachiorobiphenyt -VaLues in mg L I_ Li I~-r
I
-8o a 0 O 0 0n 0 0 60 00 0 0 00 00 0 0 00 p 00Q EXAMPLE 3 The operation is carried out in the same apparatus employed for Examples 1 and 2, but the operating conditions are changed: bath temperature: 250 0
C
weight of the chdoroaLuminate bath: 500 g addition of 5% of Al powder (Pechiney XY 49) duration of the test: 2 hours nitrogen purge after 2 hours: 15 mini initial addition of: 500 mg of hexachtorobenzene 500 mg of decachtorobiphenyL The resuLts are given in Table 2.
EXAMPLE 4 Same test as in Example no. 3 but the duration of the test is 4 hours.
The results are shown in Table 2.
TABLE 2 3- 1 I jCHLOR- I DURATION 2 h DURATION 4 h I INATEO D 1
ORGANIC
1 3 1 f I I I rof I IPRODCUTS1 BATH I hexane Iproductl BATH Ihexane I productl 1 3 1 1 remoyedl I tremoved I I 3start I finaL! I i start If ina 3 1 I Q 2.5 1 0.7 1 1 1 0.3 1 0.1 1 1 1 C 4 I I I I I I I 1 I ic I 1 110 3 5 1 t 1 1.5 1 1.3 1 6 5 1 1 I 1 1 1 i CVCl 1 500 1 n a 3 1 97ie 1 500 1 1.3 1 3 1 99.15 1 1 1 6 t 1 1 1 I I t I DCBP 1 500 1 6 1 0.2 1 94.8 1 500 1 3 1 0.16 t9f.4 1, I PS* 1 1 0.021 0.0021 1 1 0.11 0.0081 1 I I I I I- Irr*y Ir I 3 PS: perchlorostyrene Values in mg

Claims (4)

1.Pr-~cess for (,omplete one-step destruction of J chloriaated organic products containing more than 2 carbon At~oms characterized in that these products are placed in contact with a bath of at least one chioroaluminate as hereinbefore defined containing at least one metal powder and at a temperature between 2501C 300 0 C, said chlorinated organic produ-,ts b~ing present in an amount of less than 2000 ppm of the chioroaluminate.
2. Process according to claim 1, characterized in that the chloroaluiuinate is sodium chloroaminAte. 4404 *0 4,040
3. Process atccording t claim 2, characteriziad in the 0 the sodium chioroaluminate contains at least 50 zuol% of aluminium chloride.
4. Process according to cJlaim 1, characterized in that oooooo the metal powder is preferably aluminium, Process according to, either of claimis I and 4, characteriOO4 in that~ the mean parti~cle size of the powder is bel~ow 5O00p. 00 00 DATED this 12th day of February, 1991. 0.00000 4, ATOCIUEIl WATERMARK PATENT a TR~ADE~ MAR~K ATTORNEYS f THE ATVttJM', 20D FLOOR 290 BURWOOO ROAD V.2.T~THC-RN VIC. 3122.
AU10621/88A 1987-01-21 1988-01-20 Process for destroying chlorinated products at low temperature Ceased AU610552B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8700669A FR2609652B1 (en) 1987-01-21 1987-01-21 PROCESS FOR THE DESTRUCTION OF LOW TEMPERATURE CHLORINE PRODUCTS
FR8700669 1987-01-21

Publications (2)

Publication Number Publication Date
AU1062188A AU1062188A (en) 1988-07-28
AU610552B2 true AU610552B2 (en) 1991-05-23

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AU10621/88A Ceased AU610552B2 (en) 1987-01-21 1988-01-20 Process for destroying chlorinated products at low temperature

Country Status (17)

Country Link
EP (1) EP0277858B1 (en)
JP (1) JPS63192468A (en)
CN (1) CN1012142B (en)
AT (1) ATE51531T1 (en)
AU (1) AU610552B2 (en)
CA (1) CA1333404C (en)
DE (1) DE3860064D1 (en)
DK (1) DK166432B1 (en)
ES (1) ES2014508B3 (en)
FI (1) FI880241L (en)
FR (1) FR2609652B1 (en)
GR (1) GR3000437T3 (en)
IE (1) IE60535B1 (en)
IN (1) IN170563B (en)
NO (1) NO174088C (en)
NZ (1) NZ223232A (en)
PT (1) PT86577B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931167A (en) * 1987-10-13 1990-06-05 Advanced Refinery Technology Degradation of polychlorinated biphenyls
US5490919A (en) * 1990-08-14 1996-02-13 State Of Isreal, Atomic Energy Commission Process for the dehalogenation of organic compounds
JP4458585B2 (en) * 1999-09-09 2010-04-28 祝治 朝倉 Methods for decomposing and detoxifying harmful organic compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447262A (en) * 1983-05-16 1984-05-08 Rockwell International Corporation Destruction of halogen-containing materials
EP0170714A1 (en) * 1982-04-06 1986-02-12 Clifford G. Shultz Destruction of polychlorinated biphenyls and other hazardous halogenated hydrocarbons

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5257149A (en) * 1975-11-07 1977-05-11 Gunma Daigakuchiyou Method of decomposing halogenated aromatic compounds to carboneous substance using molten salts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170714A1 (en) * 1982-04-06 1986-02-12 Clifford G. Shultz Destruction of polychlorinated biphenyls and other hazardous halogenated hydrocarbons
US4447262A (en) * 1983-05-16 1984-05-08 Rockwell International Corporation Destruction of halogen-containing materials

Also Published As

Publication number Publication date
FI880241A7 (en) 1988-07-22
FI880241L (en) 1988-07-22
IN170563B (en) 1992-04-11
ES2014508B3 (en) 1990-07-16
NO174088B (en) 1993-12-06
NZ223232A (en) 1991-05-28
PT86577A (en) 1988-02-01
PT86577B (en) 1991-12-31
EP0277858A1 (en) 1988-08-10
FI880241A0 (en) 1988-01-20
DK23288D0 (en) 1988-01-20
FR2609652B1 (en) 1992-05-15
CN1012142B (en) 1991-03-27
JPS63192468A (en) 1988-08-09
NO174088C (en) 1994-03-16
IE880137L (en) 1988-07-21
DE3860064D1 (en) 1990-05-10
FR2609652A1 (en) 1988-07-22
IE60535B1 (en) 1994-07-27
GR3000437T3 (en) 1991-06-28
CN88100299A (en) 1988-08-03
ATE51531T1 (en) 1990-04-15
EP0277858B1 (en) 1990-04-04
CA1333404C (en) 1994-12-06
NO880104L (en) 1988-07-22
AU1062188A (en) 1988-07-28
DK166432B1 (en) 1993-05-24
DK23288A (en) 1988-07-22
NO880104D0 (en) 1988-01-12

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