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WO2007011251A1 - Procede de neutralisation de substances toxiques en produits non toxiques inoffensifs - Google Patents

Procede de neutralisation de substances toxiques en produits non toxiques inoffensifs Download PDF

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Publication number
WO2007011251A1
WO2007011251A1 PCT/RU2005/000384 RU2005000384W WO2007011251A1 WO 2007011251 A1 WO2007011251 A1 WO 2007011251A1 RU 2005000384 W RU2005000384 W RU 2005000384W WO 2007011251 A1 WO2007011251 A1 WO 2007011251A1
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WO
WIPO (PCT)
Prior art keywords
toxic
reagent
detoxification
amino acid
products
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/RU2005/000384
Other languages
English (en)
Russian (ru)
Inventor
Viktor Stanislavovich Polyakov
Valery Vasilievich Ermilov
Sergey Ivanovich Malekin
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.)
Zakrytoe Aktzionernoe Obschestvo 'elit Holding'
Original Assignee
Zakrytoe Aktzionernoe Obschestvo 'elit Holding'
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 Zakrytoe Aktzionernoe Obschestvo 'elit Holding' filed Critical Zakrytoe Aktzionernoe Obschestvo 'elit Holding'
Priority to PCT/RU2005/000384 priority Critical patent/WO2007011251A1/fr
Publication of WO2007011251A1 publication Critical patent/WO2007011251A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor

Definitions

  • the invention relates to a technology for processing toxic substances (OB).
  • the prior art method for processing pollutants the environment (US 6,039,882).
  • the method and composition are intended for the processing of substances that pollute the environment and are in the soil, in sediments, in aquifers, water.
  • the method and composition described in the patent can be used to treat containers containing contaminants.
  • the essence of the method is the reaction of a pollutant with a composition that includes a metal and a compound containing sulfur, resulting in environmentally acceptable chemically less active products.
  • the method is applicable for contaminants such as halogenated hydrocarbons, for pesticides, for chemical weapons and for dyes.
  • the composition in a preferred embodiment contains powdered iron and iron sulfide.
  • the addition of alcohol to the composition increases the efficiency of the processing reaction, especially for soil contaminants and sediments.
  • a method of processing a toxic substance by hydrolysis US
  • the method includes adding water to the chemical reagent (OB) so that the hydrolysis reaction of the chemical reagent with water occurs in the molar ratios indicated in the patent.
  • the method is carried out in the field in containers in which the processed substance (aminoalkylphosphonothiolates) is stored.
  • the method includes mixing the contents of the container after adding water.
  • the method includes reacting a chemical weapon with a nitrogen-containing base, such as anhydrous liquid ammonia, in which an active metal, for example, sodium, is dissolved.
  • a nitrogen-containing base such as anhydrous liquid ammonia, in which an active metal, for example, sodium, is dissolved.
  • Biodegradation of chemicals is a natural process that improves the environment.
  • scientists are also trying to obtain microorganisms and enzyme systems for direct biodegradation of OB.
  • microbial cells are still capable of destroying OBs only at the cost of their lives, which significantly increases the cost of biodegradation of OBs and makes them highly controversial from an environmental point of view.
  • the closest analogue to the invention is a method for processing a toxic substance (mustard gas) by alkaline hydrolysis followed by biodegradation of less toxic substances formed as a result of hydrolysis (US 6017750).
  • the method involves the processing of a mixture of 2,2'-dichlorodiethylcylphide and bis-2-2-chloroethylthioethyl ether (HT), the method comprising the following operations: combining HT with a hydrolyzing agent to form a mixture of thiodiglycol (TDG) and bis-2- ( 2-hydroxyethylthio) ethyl ester (s) (T-OH); - neutralizing the aforementioned mixture of TDG and T-OH to a pH that provides
  • SUBSTITUTE SHEET (RULE 26) the possibility of further biodegradation of the mixture; biodegradation of the aforementioned neutralized TDG and T-OH mixtures to obtain neutralized biomass and wastewater.
  • the disadvantages of the closest analogue include obtaining at the 1st stage (alkaline hydrolysis) toxic toxic products of neutralization, which significantly complicates and increases the cost of all processes associated with their further storage, transportation, etc., as well as increases the cost of their subsequent biodegradation, since special installations for biodegradation and continuous renewal of microorganisms that die due to the high toxicity of alkaline hydrolysis products are required.
  • the technical result of the invention is the completeness of detoxification, during which the toxicity of the initial OB is reduced so that it becomes possible further biodegradation of detoxification products.
  • the technical result is achieved by the method of neutralizing poisonous substances and Vx hydrolyzate set forth in the claims, based on their interaction with an amino acid reagent (AKP).
  • Amino acid reagent must contain at least one of the natural ⁇ -amino acids, such as alanine, arginine, aspartic acid, asparagine, valine, histidine, glycine, glutamic acid, glutamine, isoleucine, leucine, lysine, methionine, proline, series, tyrosine, threonine , tryptophan, phenylalanine, cysteine (see table 1). Amino acid reagent can also be obtained by alkaline hydrolysis of protein-containing industrial waste.
  • the natural ⁇ -amino acids such as alanine, arginine, aspartic acid, asparagine, valine, histidine, glycine, glutamic acid, glutamine, isoleucine, leucine, lysine, methionine, proline, series, tyrosine, threonine , tryptophan, phenylalanine, cysteine (
  • SUBSTITUTE SHEET (RULE 26) in the traditional way using microorganisms, including from “activated sludge", until neutralized biomass is obtained.
  • the described method does not have the disadvantages of the above methods of detoxification of OB and has in comparison with them a number of the following advantages: - ensuring the destruction of OB or hydrolyzate Vx with subsequent bio-utilization of their decomposition products, that is, with the possibility of
  • the first stage as low-toxic waste, and the possibility of their biodegradation in ordinary enterprises of biochemical wastewater treatment.
  • Example 1 Detoxification of mustard gas under the action of an amino acid reagent.
  • a mustard sample (2,2'-dichlorodiethyl sulfide) was prepared according to the method
  • Mustard detoxification was carried out according to the following method. In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, a solution of 80 mg of mustard gas in 10 ml of 0.1 M amino acid reagent was placed, which corresponds to their ratio of 1
  • Example 2 Detoxification and biodegradation of lewisite under the action of an amino acid reagent and microorganisms.
  • the detoxification of lewisite was carried out according to the following method.
  • a solution of 124 mg of lewisite and 12 ml of 0.1 M amino acid reagent (pH 7 - 12) was placed, the ratio of reagents was 1: 2, kept under stirring at room temperature for 0.5 hour,
  • reaction mass after detoxification of lewisite with 0.1 M solution of amino acid reagent was studied as a substrate for the activity of bacteria strottosossus thermorhulis and activated sludge. Both the initial solution and diluted to concentrations of 10 " ⁇ 10 " 3 were used. 10 ml of solution was placed in test tubes and 2 ml of bacterial cultures with a titer of 10 6 were added, then the tubes were incubated for one day at 37 ° ⁇ . day marked bacterial growth in all test tubes. Samples with the initial concentration of the reaction mass were transferred to the study of acute toxicity during intra-gastric administration in experiments on rats.
  • SUBSTITUTE SHEET (RULE 26) intragastric administration in experiments on rats, a re-lethal dose of LD 50 , of detoxification products exceeds 5000 mg / cr. Morphological studies of internal organs, conducted 14 days after the introduction of detoxification products, showed a complete absence of any manifestations of toxic effects. Mutagenic and carcinogenic properties were not found in detoxification products (Ames test with metabolic activation - Salmonella / microsome, strains TA-98 and TA-100). Example 4. Detoxification of lewisite under the action of cysteine.
  • Example 6 Detoxification of soman by the action of an amino acid reagent.
  • Example 7 Detoxification of soman under the action of phenylalanine.
  • Example 8 Detoxification of soman by sodium glycinate. Zoman detoxification was carried out according to the following procedure. Into the flask
  • Example 9 Detoxification and biodegradation of the hydrolyzate of substance Vx under the action of an amino acid reagent and microorganisms.
  • SUBSTITUTE SHEET (RULE 26) isobutyl-8-2-diethylaminoethyl-methylthiophosphonate in water at a ratio of 7: 100 (by volume) for 3 months at room temperature.
  • a study of acute toxicity during intragastric administration in experiments on rats showed that the lethal dose of LDs 0 , hydrolyzate of substance Vx, is 750 mg / kg.
  • the clinical picture of intoxication is curariform in depolarizing type.
  • the detoxification of the hydrolyzate of substance Vx was carried out as follows. A solution of 5. ml of a hydrolyzate of substance Vx, 10 ml of a 0.1 M amino acid reagent (pH 8 - 12) ratio and 35 ml of water was placed in a 100 ml Erlenmeyer flask equipped with a magnetic stirrer, stirred at room temperature for 0.5 hour. A study of acute toxicity during intra-gastric administration in experiments on rats showed that the re-lethal dose of LD 50 of the resulting reaction mass exceeds 5000 mg / kg.
  • Vx Hydrolyzate Vx (reg. Lethal dose LD 5O , 750 mg / kg) was studied as a possible substrate for the life of a number of microorganisms (strottosossus thermorhulis, basillus subtilis, escherisia coli, strossossus lactis). Tubes containing 10 ml of Vx hydrolyzate were seeded (2 ml of culture each) with all 4 strains.
  • the reaction mass obtained after detoxification of the hydrolyzate of substance Vx with an amino acid reagent was studied as a substrate for the activity of the bacteria strottosossus thermorhulis and activated sludge. Both the initial solution and dilution up to 10 "1 were used . 2 ml of bacteria cultures with a titer of 10 b were added to the tubes containing 10 ml of solutions; the tubes were incubated for 24 hours at 37 ° C. Bacteria grew in of all test samples, samples with the initial concentration of the reaction mass were transferred to the study of acute and chronic toxicity during intragastric administration in experiments on rats.
  • the table N ⁇ l shows the amino acid composition of the amino acid reagent (AKP) from the table shows that during alkaline hydrolysis of industrial white waste, 15 of the 20 natural ⁇ -amino acids are preserved, and this corresponds to the data presented in the monograph of ALinger Biochemistry. M. Mir: 1976.
  • Table N ° 2 shows the data of toxicometric measurements of the reaction mass obtained after the interaction of the OB with the amino acid reagent. From the data of the table it is seen that for all the studied OBs (mustard gas, lewisite, sarin, soman), these data for intragastric administration to rats is greater than 5000.0 mg / kg.
  • Table N ° 3 shows the toxic effects of the Vx hydrolyzate and reaction mass after its interaction with AKP. The table shows that the toxicity of the Vx hydrolyzate is ⁇ 750 mg / kg when administered intravenously to rats, a curariform clinical picture. Immediately after interaction
  • the minimum reaction time is determined by the time of neutralization of the toxicity of the ecotoxicant.
  • the increase in exposure time regardless of the temperature at which the reaction is carried out, does not affect the result - neutralization of toxicity.
  • the invention allows to neutralize toxic substances - mustard gas, lewisite, sarin, soman and Vx hydrolyzate under mild conditions using a cheap and affordable reagent - a composition containing a mixture of natural ⁇ -amino acids.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Microbiology (AREA)
  • Biomedical Technology (AREA)
  • Virology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention relève du domaine de la technologie de traitement de substances toxiques et concerne en particulier un procédé de neutralisation de substances toxiques comprenant les étapes suivantes: l'interaction de la substance toxique avec un réactif de détoxication; la neutralisation du produit ainsi obtenu jusqu'à ce que son pH atteigne 7 ou 8, garantissant ainsi sa biodégradation ultérieure; et sa biodégradation jusqu'à obtention d'une biomasse inoffensive et d'eaux usées. Dans cette invention, le réactif de détoxication se présente sous la forme d'une composition contenant au moins un type d'acide aminé α naturel, le rapport substance toxique - réactif de détoxication étant compris entre 1:1 et 1:3. L'interaction se produit lors d'un mélange à une température comprise entre 20 et 45 °C pendant une durée comprise entre une demi-heure et une heure. Cette invention permet de neutraliser pratiquement toute la substance toxique dans des conditions douces à l'aide d'un réactif peu coûteux et accessible.
PCT/RU2005/000384 2005-07-20 2005-07-20 Procede de neutralisation de substances toxiques en produits non toxiques inoffensifs Ceased WO2007011251A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/RU2005/000384 WO2007011251A1 (fr) 2005-07-20 2005-07-20 Procede de neutralisation de substances toxiques en produits non toxiques inoffensifs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2005/000384 WO2007011251A1 (fr) 2005-07-20 2005-07-20 Procede de neutralisation de substances toxiques en produits non toxiques inoffensifs

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WO2007011251A1 true WO2007011251A1 (fr) 2007-01-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107080916A (zh) * 2017-05-12 2017-08-22 贵州大学 用于煤矸石堆场污染释放原位控制的材料及方法
CN113087765A (zh) * 2021-04-02 2021-07-09 中国人民解放军军事科学院军事医学研究院 一种芥子气肽类加合物的制备新方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6017750A (en) * 1998-11-12 2000-01-25 The United States Of America As Represented By The Secretary Of The Army Hydrolysis and biodegradation of the chemical warfare vesicant agent HT
EP1059101A2 (fr) * 1999-06-07 2000-12-13 Kurita Water Industries Ltd. Méthode de décomposition des composés halogéniques
WO2004039456A1 (fr) * 2002-11-01 2004-05-13 Veckis Industries Ltd. Procede de neutralisation d'agents toxiques, de pesticides et de leurs hydrolysats et reactif correspondant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6017750A (en) * 1998-11-12 2000-01-25 The United States Of America As Represented By The Secretary Of The Army Hydrolysis and biodegradation of the chemical warfare vesicant agent HT
EP1059101A2 (fr) * 1999-06-07 2000-12-13 Kurita Water Industries Ltd. Méthode de décomposition des composés halogéniques
WO2004039456A1 (fr) * 2002-11-01 2004-05-13 Veckis Industries Ltd. Procede de neutralisation d'agents toxiques, de pesticides et de leurs hydrolysats et reactif correspondant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107080916A (zh) * 2017-05-12 2017-08-22 贵州大学 用于煤矸石堆场污染释放原位控制的材料及方法
CN113087765A (zh) * 2021-04-02 2021-07-09 中国人民解放军军事科学院军事医学研究院 一种芥子气肽类加合物的制备新方法
CN113087765B (zh) * 2021-04-02 2022-10-11 中国人民解放军军事科学院军事医学研究院 一种芥子气肽类加合物的制备方法

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