EP0116423B1 - Traitement de résidu - Google Patents

Traitement de résidu Download PDF

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Publication number
EP0116423B1
EP0116423B1 EP19840300445 EP84300445A EP0116423B1 EP 0116423 B1 EP0116423 B1 EP 0116423B1 EP 19840300445 EP19840300445 EP 19840300445 EP 84300445 A EP84300445 A EP 84300445A EP 0116423 B1 EP0116423 B1 EP 0116423B1
Authority
EP
European Patent Office
Prior art keywords
cyanide
acetone cyanohydrin
micro
weight
organism
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
Application number
EP19840300445
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German (de)
English (en)
Other versions
EP0116423A1 (fr
Inventor
William Rhodes Rodger
Thomas William Naylor
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0116423A1 publication Critical patent/EP0116423A1/fr
Application granted granted Critical
Publication of EP0116423B1 publication Critical patent/EP0116423B1/fr
Expired legal-status Critical Current

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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
    • A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
    • 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
    • A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
    • 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
    • A62D2101/26—Organic substances containing nitrogen or phosphorus
    • 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
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • This invention relates to the treatment of residues and in particular to the treatment of residual quantities of acetone cyanohydrin remaining in tanks or other containers.
  • Acetone cyanohydrin which is used in the manufacture of methacrylic acid esters, is often transported in bulk, for example by road, rail, or ship, tanker. After discharge of the acetone cyanohydrin from the tank, generally a small residual amount thereof remains in the tank. It is often necessary to dispose of this residual amount of acetone cyanohydrin before the tank can be returned for refilling or for use with another material.
  • Acetone cyanohydrin not only is itself toxic but readily decomposes, especially in conditions that are not highly acidic, to acetone and hydrogen cyanide which presents an even greater toxicity hazard.
  • acetone cyanohydrin is usually stabilised by a small amount of a suitable acid, e.g. sulphuric acid.
  • the residue is usually treated . with an excess of an aqueous alkali to produce the corresponding cyanide and acetone, and then the cyanide is decomposed by treatment with, e.g. hypochlorite.
  • hypochlorite treatment represents a considerable expense.
  • the treatment may be performed inside the original tank, but frequently this is not convenient because of the corrosive nature of hypochlorite: the transfer of the residues to a suitable treatment tank may itself present a hazard. It is generally required that the effluent contains less than 10 ppm (by weight) of cyanide ions, and often a concentration of less than 1 ppm is required.
  • cyanide-containing solution Because of volume limitations, it is generally necessary to perform the treatment of the cyanide-containing solution at relatively high cyanide ion concentrations, e.g. containing 0.1 to 2% by weight of cyanide ions. Such solutions will also have a relatively high acetone concentration: thus a solution containing 1% by weight of cyanide ions will also contain about 2.2% by weight of acetone.
  • acetone is a powerful solvent for micro-organism cell constituents.
  • a process for the treatment of acetone cyanohydrin residues comprising adding sufficient water and alkali to the residues to give a solution containing between 0.1 and 2% by weight of cyanide ions and having a pH within the range 6 to 10, adding to the solution a culture containing a cyanide-degrading micro-organism, in which the enzyme cyanide hydratase has been induced, in an amount of at least 0.005 g of micro-organism (dry weight) per g of cyanide ions, and maintaining the resultant mixture at between 5 and 35°C until the cyanide ion concentration is below 10 ppm by weight.
  • Micro-organisms that may be used include Stemphylium loti, e.g. ATCC 11718; Mycolep- todiscus terrestris, e.g. CBS 231.53; Fusarium moniliforme, e.g. No. 3104.SA.49a available from the Canadian Department of Agriculture, Culture Collection, Ottawa, and which has also been deposited as CBS 161.82; Helminthosporium sorghicola, otherwise known as Drechslera sorghicola, e.g. CBS 249.49; Periconia circinata, e.g. CBS 263.37; and Glomerella tucamanensis, e.g. CBS 132.37. (ATCC No.
  • Fungi can be made to grow in two distinct forms, namely a ball or pellet form or in a mycelial form where the fungal cells are diffuse filamentous strands dispersed in the growth medium. It is desirable, though not essential, that the fungus is grown in the mycelial, as opposed to ball or pellet, form since, with the fungus in pellet or ball form, diffusion into, and out of the fungal pellet or ball, may be restricted, thereby preventing efficient utilisation of the active enzyme within the ball or pellet.
  • the preferred carbon sources are carbohydrates, particularly gluclose.
  • the enzyme cyanide hydratase may be induced by adding to the culture a low concentration of cyanide ions, e.g. 0.05 to 5, preferably 0.1 to 1 mM per gram of cells (dry weight) and continuing culturing for 1 to 24, preferably about 12 hours, at 20 to 40°C.
  • a low concentration of cyanide ions e.g. 0.05 to 5, preferably 0.1 to 1 mM per gram of cells (dry weight) and continuing culturing for 1 to 24, preferably about 12 hours, at 20 to 40°C.
  • the culture may then be concentrated if desired in readiness for use.
  • the micro-organism may be harvested and stored, e.g. by freeze drying.
  • the acetone cyanohydrin treatment process comprises a first step involving dilution and pH modification in order to convert the acetone cyanohydrin to cyanide and acetone, and then a biological degradation step.
  • the dilution and pH modification may conveniently be performed by adding a dilute aqueous alkali, for example sodium hydroxide, to the acetone cyanohydrin residue: where residues remain in several tanks it may be convenient to wash all the residues into a single tank wherein the treatment process is performed.
  • the aqueous alkali may be added as such or the acetone cyanohydrin first diluted with water and then solid, or more concentrated, alkali added to give the requisite pH.
  • the water used may be mains water or sea water if a supply thereof is available. However, the degradation process may take longer if sea water is utilised.
  • the cyanide degradation process should be carried out at a pH between 6 and 10, preferably between 7 and 9, and in particular at about pH 8. We have found that there is some buffering action so that a pH of about 8 can be achieved even with a significant excess of alkali.
  • the acetone cyanohydrin residues normally comprise in excess of 95% by weight acetone cyanohydrin and should be diluted with the aqueous alkali so that the solution contains 0.1 to 2% by weight of cyanide ions. This corresponds approximately to dilution of the acetone cyanohydrin by at least 15 times its volume.
  • the acetone cyanohydrin is diluted until the solution contains 0.1 to 1% by weight (1000-10,000 ppm, i.e. approx. 40-400 mM) of cyanide ions.
  • the culture, in which the cyanide hydratase has been induced, is then added, e.g. as a slurry or as dried cells.
  • the amount of culture should be at least 0.005 g of micro-organism dry weight per g of cyanide ions. This corresponds approximately to at least 1.5 g of micro-organism dry weight per litre of acetone cyanohydrin residue. If smaller amounts of the culture are employed, we have found that there will probably be insufficient cyanide degradation even if the mixture is left for 24 hours or more.
  • the amount of culture is at least 0.02 g of micro-organism dry weight per g of cyanide ions.
  • the mixture After adding the culture, the mixture is left for sufficient time for the cyanide ions to be degraded to the desired level, below 10, preferably below 1 ppm.
  • the mixture is agitated during the cyanide degradation, e.g. by sparging with compressed air.
  • the time taken for the cyanide degradation will depend on the proportion of cells to cyanide ions, the desired degree of treatment, the pH, the temperature, and, as mentioned hereinbefore, the type of water employed.
  • the temperature employed may range between 5 and 35°C and is preferably between 10 and 30°C, and in particular is above 20°C. If necessary the mixture can be heated, for example by injecting steam to achieve the desired temperature, prior to addition of the culture.
  • fungicide As an insurance against release of biologically active spores upon discharge of the aqueous mixture.
  • fungicide is not necessary.
  • the invention is of particular utility in the cleaning of vessels used to transport acetone cyanohydrin: after discharge of the bulk of the transported acetone cyanohydrin, the acetone cyanohydrin residues in the vessel are treated by the method described hereinbefore and then the aqueous mixture having a cyanide ion concentration below 10 ppm by weight is discharged.
  • the aqueous mixture can be discharged, depending on local regulations into waterways, e.g. rivers or the sea, or into a conventional sewage treatment plant. Discharge of the diluted acetone cyanohydrin residues before microbiological degradation of the cyanide ions into a conventional sewage treatment plant would not normally be possible since the latter can not normally tolerate influents containing such large concentrations of cyanide.
  • Fusarium moniliforme (CBS 161.82) was aerobically grown in an aqueous nutrient medium containing, per litre
  • the trace element solution had the following composition, per litre
  • the cultivation was conducted at 28°C and pH 5.5 to give a culture containing 20 g/I of cells.
  • the pH was then raised to 7.8 and cyanide hydratase induced by adding 0.2 m moles of cyanide ions (as acetone cyanohydrin) per gram of cell dry weight and incubating at 28°C for 12 hours.
  • Example 1 A slurry containing 45 g of Fusarium moniliforme (CBS 181.82) in which cyanide hydratase had been induced as described in Example 1 was then added.
  • CBS 181.82 Fusarium moniliforme

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Business, Economics & Management (AREA)
  • General Health & Medical Sciences (AREA)
  • Emergency Management (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Claims (6)

1. Procédé pour le traitement de résidus d'acétonecyanohydrine, comprenant l'addition de suffisamment d'eau et d'alcali à ces résidus pour donner une solution contenant entre 0,1 et 2% en poids d'ions cyanure et ayant un pH dans la gamme de 6 à 10, l'addition à cette solution d'une culture contenant un microorganisme dégradant le cyanure dans laquelle a été induite l'enzyme cyanure hydratase, à raison d'au moins 0,005 g de microorganisme (poids sec) par gramme d'ions cyanure, et le maintien du mélange résultant entre 5 et 35°C jusqu'à ce que la concentration des ions cyanure soit inférieure à 10 ppm en poids.
2. Procédé suivant la revendication 1, caractérisé en ce que ce microorganisme est un mycélium fongique.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que ce résidu d'acétonecyano- hydrine est dilué avec une quantité d'eau et d'alcali telle que la solution contient 0,1 à 1% en poids d'ions cyanure.
4. Procédé suivant l'une quelconque des revendications 1 à 3, caractérisé en ce que la quantité de la culture du microorganisme employée est d'au moins 0,02 g de microorganisme (poids sec) par gramme d'ions cyanure.
5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que le mélange de résidus dilués d'acétonecyanohydrine et de la culture, est maintenu entre 10 et 30°C pour effectuer la dégradation des ions cyanure.
6. Méthode pour nettoyer un récipient utilisé pour le transport d'acétonecyanohydrine, caractérisée en ce qu'après avoir déchargé du récipient la masse de l'acétonecyanohydrine transportée, on traite l'acétonecyanohydrine résiduelle dans ce récipient selon un procédé suivant l'une quelconque des revendications 1 à 5, pour produire un mélange aqueux contenant moins de 10 ppm en poids d'ions cyanure et ensuite, on décharge ce mélange aqueux du récipient.
EP19840300445 1983-02-11 1984-01-25 Traitement de résidu Expired EP0116423B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB838303818A GB8303818D0 (en) 1983-02-11 1983-02-11 Residue treatment
GB8303818 1983-02-11

Publications (2)

Publication Number Publication Date
EP0116423A1 EP0116423A1 (fr) 1984-08-22
EP0116423B1 true EP0116423B1 (fr) 1986-07-30

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EP19840300445 Expired EP0116423B1 (fr) 1983-02-11 1984-01-25 Traitement de résidu

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EP (1) EP0116423B1 (fr)
JP (1) JPS59155272A (fr)
DE (1) DE3460363D1 (fr)
GB (1) GB8303818D0 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8702138D0 (en) * 1986-02-19 1987-03-04 Ici Plc Cyanide hydratase
US5219750A (en) * 1986-02-19 1993-06-15 Imperial Chemical Industries Plc Production of cyanide hydratase

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2299275A1 (fr) * 1975-01-31 1976-08-27 Degussa Procede pour rendre atoxiques des cyanures et des nitriles au moyen de peroxydes
EP0061249B1 (fr) * 1981-03-20 1985-05-08 Imperial Chemical Industries Plc Traitement d'eaux résiduaires

Also Published As

Publication number Publication date
EP0116423A1 (fr) 1984-08-22
DE3460363D1 (en) 1986-09-04
JPS59155272A (ja) 1984-09-04
GB8303818D0 (en) 1983-03-16

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