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EP0238735B1 - Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre - Google Patents

Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre Download PDF

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Publication number
EP0238735B1
EP0238735B1 EP86301671A EP86301671A EP0238735B1 EP 0238735 B1 EP0238735 B1 EP 0238735B1 EP 86301671 A EP86301671 A EP 86301671A EP 86301671 A EP86301671 A EP 86301671A EP 0238735 B1 EP0238735 B1 EP 0238735B1
Authority
EP
European Patent Office
Prior art keywords
sulphur
carbonaceous material
reaction
reaction vessel
temperature
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.)
Expired - Lifetime
Application number
EP86301671A
Other languages
German (de)
English (en)
Other versions
EP0238735A1 (fr
Inventor
Harold W. Adams
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.)
Sultech Inc
Original Assignee
Sultech Inc
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
Priority to US06/644,545 priority Critical patent/US4581442A/en
Application filed by Sultech Inc filed Critical Sultech Inc
Priority to EP86301671A priority patent/EP0238735B1/fr
Priority to DE8686301671T priority patent/DE3679986D1/de
Publication of EP0238735A1 publication Critical patent/EP0238735A1/fr
Application granted granted Critical
Publication of EP0238735B1 publication Critical patent/EP0238735B1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • 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
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to a method of destruction of carbonaceous materials, which may be toxic and/or hazardous chemicals, and the conversion of such materials to safe, inert and useful non-toxic products.
  • PCBs polychlorinated biphenyls
  • Japanese specification 74/127954 discloses detoxification of PCBs by reaction with sulphur for several hours; no further broad details of the method are given, although the examples suggest refluxing sulphur and a PCB in a flask at 285° to 315°C for three to five hours.
  • Japanese specification 82/29373 discloses a vapour phase reaction between sulphur vapour and vapourised PCB, in the absence of oxygen.
  • the batch method described is said to result in instantaneous reaction between the PCB and the sulphur.
  • the present invention accordingly comprises a method of destruction of a carbonaceous material, which comprises feeding sulphur at a temperature in the range of 135 to 1500°c to a reaction vessel together with a flow of inert gas so as to maintain a substantially oxygen-free inert gas in the reaction vessel; separately feeding the carbonaceous material to the reaction vessel for reaction therein with the sulphur at a temperature between 500°C and 1500°C so as to form a substantially inert solid material comprising sulphur and carbon and containing unreacted residues of the carbonaceous material in an amount not exceeding a few parts per million; and separately removing vapour phase material and the solid material from the reaction vessel.
  • the resulting solid material is refractory, inert, non-inflammable and insoluble in organic solvents.
  • the present invention further comprises a substantially inert solid material formed by reaction of sulphur with carbonaceous material at an elevated temperature in a substantially oxygen-free atmosphere, which solid material comprises carbon and sulphur in approximately equal proportions by weight, has no observable melting point, is substantially unaffected by aqua regia, is electrically conductive, and is substantially free of residue of the carbonaceous material.
  • the carbonaceous material to be destroyed according to the invention may be inorganic or organic chemicals; halogen-containing materials, such as polychlorinated biphenyls, are preferred in many embodiments of the present invention.
  • mass spectral analysis of the product indicates less than one part per million of unreacted PCB.
  • the sulphur is fed to the reaction vessel at a temperature in the range of 135 to 1500°C; it is preferably supplied as a vapour at a temperature in the range 450 to 1500°C.
  • the sulphur is fed into the reactor through a nozzle or spray nozzle.
  • the inert gas used in the method according to the invention is typically nitrogen, and the pressure in the reaction vessel is between one and two atmospheres.
  • the sulphur-containing gases are typically recycled to the sulphur which is fed to the reaction vessel and the reaction time is less than five minutes.
  • Chemical waste such as an inorganic or organic material, typically a halogen-containing compound such as a PCB
  • a reactor 20 is fed, either via preheater 30 and heater 40, or directly, to a reactor 20.
  • Sulphur (which may be fresh or recycled) is introduced into a heated melt tank 50, where the sulphur is melted, and then fed to a heater 60 (which may effect vapourisation) to be supplied into reactor 20 as a separate stream relative to the waste stream.
  • Liquid sulphur 4 may be fed directly to heater 60.
  • An inert gas stream (such as nitrogen) is also fed to the reactor 20 so as to maintain an inert, substantially oxygen-free atmosphere in the reactor.
  • Pressurised nitrogen gas may also be introduced into preheater 30, heater 40, melt tank 50 and heater 60, so as to pump or drive the liquid waste material and the sulphur into the reactor 20.
  • Reactor 20 is preferably a rotating screw-type oven, typically heated by electric induction heating coils to a temperature in the range of 500 to 1500°C inside the reactor. Within a matter of minutes at this temperature in less than five minutes) the waste organic material and the sulphur completely react together to produce a black solid reaction product, which generally contains less than one part per million of unreacted organic material.
  • Vapour products comprising unreacted sulphur and hydrogen sulphide, carbon disulphide and sulphur chloride gases are fed to a condenser 70, from which condensed sulphur is recycled to melt tank 50.
  • the remaining gases 9 from the condenser are then passed to a pollution recovery scrubber apparatus 80, from which a stream of clean effluent gas, and a stream of chemical intermediates is obtained.
  • the solid reaction product from reactor 20 is supplied to a post-reactor cooler unit, from which the solid may be transferred to appropriate grinding and mixing equipment.
  • the by-product gases 11 may include hydrogen sulphide, carbon disulphide, and sulphur chlorides, which may be recovered and removed from the effluent in a conventional manner. Sulphur vapours may also be recovered, condensed and recycled to the sulphur supply stream.
  • the sulphur may be fed to the reactor in molten form at a temperature of 135 to 450°C, or in vapour form at a temperature of 450 to 1500°C, again through a nozzle or spray nozzle.
  • the resulting black solid reaction product has a typical analysis as follows:
  • the black solid comprises substantially equal proportions by weight of sulphur and carbon; the exact molecular structure of the material is not known, but the following properties have been determined:
  • this solid material mean that it is suitable for use as a filler for non-corrosive coatings, for solar energy absorber devices, for cements and asphalt, and for body implants; and as electronic resistors and conductors.
  • the combination of electrical conductive properties, absorption of infra-red, and chemical inertness mean that the material is particularly suitable for solar energy conversion devices, such as photovoltaic devices and thermo-electric conversion devices.

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  • Health & Medical Sciences (AREA)
  • 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)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)

Claims (11)

  1. Procédé de destruction d'une matière carbonée, qui comprend L'introduction de soufre à une température ente 135 et 1500°C dans un récipient, en même temps qu'un courant de gaz inerte de manière à maintenir dans ce récipient une atmosphère inerte pratiquement exempte d'oxygène; L'introduction séparée de la matière carbonée dans ledit récipient pour La réaction dans celui-ci avec le soufre à une température comprise entre 500 et 1500°C, de manière à former une matière solide pratiquement inerte comprenant du soufre et du carbone et contenant des résidus de la matière carbonée, n'ayant pas réagi dans une quantité ne dépassant pas quelques parties par million; et l'élimination séparée de la matière en phase vapeur et de ladite matière en phase solide dudit récipient.
  2. Procédé selon la revendication 1, caractérisé en ce que ledit gaz inerte est de l'azote.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le soufre est introduit dans le récipient sous forme de vapeur à une température entre 450 et 1500°C.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la réaction est effectuée sous une pression comprise entre un et deux atmosphères.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les gaz contenant du soufre sont recyclés dans le soufre introduit dans le récipient.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le temps de réaction pour la réaction du soufre avec la matière carbonée est inférieur à cinq minutes.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la matière carbonée est préchauffée avant d'être introduite dans le récipient.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la matière carbonée est un produit chimique organique.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la matière contient un halogène.
  10. Procédé selon la revendication 9, caractérisé en ce que la matière carbonée comprend un diphényle polychloré.
  11. Matière solide pratiquement inerte formée par réaction du soufre avec une matière carbonée à température élevée, dans une atmosphère pratiquement exempte d'oxygène, laquelle matière solide comprend du carbone et du soufre dans des proportions pondérales approximativement égales, n'a pas de point de fusion observable, est pratiquement non affectée par l'eau régale, est conductrice de l'électricité et est pratiquement exempte de résidu de la matière carbonée.
EP86301671A 1984-08-27 1986-03-10 Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre Expired - Lifetime EP0238735B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US06/644,545 US4581442A (en) 1984-08-27 1984-08-27 Process for destruction of toxic organic chemicals and the resultant inert polymer by-product
EP86301671A EP0238735B1 (fr) 1986-03-10 1986-03-10 Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre
DE8686301671T DE3679986D1 (de) 1986-03-10 1986-03-10 Vernichtung kohlenartigen stoffes und aus der reaktion kohlenartigen stoffes mit schwefel gebildeter traeger feststoff.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86301671A EP0238735B1 (fr) 1986-03-10 1986-03-10 Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre

Publications (2)

Publication Number Publication Date
EP0238735A1 EP0238735A1 (fr) 1987-09-30
EP0238735B1 true EP0238735B1 (fr) 1991-06-26

Family

ID=8195921

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86301671A Expired - Lifetime EP0238735B1 (fr) 1984-08-27 1986-03-10 Destruction de matière carbonée et matière solide inerte formée par la réaction de la matière carbonée avec du soufre

Country Status (2)

Country Link
EP (1) EP0238735B1 (fr)
DE (1) DE3679986D1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491046A (en) * 1967-02-24 1970-01-20 Thiokol Chemical Corp Lead dioxide/manganese dioxide/sulfur cure for polysulfide-bituminous compositions
US4581442A (en) * 1984-08-27 1986-04-08 Adams Harold W Process for destruction of toxic organic chemicals and the resultant inert polymer by-product

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CENTRAL PATENT INDEX, Basic Abstracts Journal, Section E, Week E13, March 1982, ref. no. 24635; London, GB & JP-A-82 029 373 (T. ITO) 17-02-1982. *
CHEMICAL ABSTRACTS, vol. 82, no. 23, June 9, 1975, page 553, ref. no. 155718g; Columbus, Ohio, US & JP-A-74 127 954 (MITSUBISHI MONSANTO CHEMICAL CO.) 07-12-1974 *
Japanese Specification 74/127954 and 82/29373 *

Also Published As

Publication number Publication date
EP0238735A1 (fr) 1987-09-30
DE3679986D1 (de) 1991-08-01

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