EP0467053B1 - Verfahren zur Enthalogenierung organischer Verbindungen mittels Alkalimetall auf festen Trägern - Google Patents

Verfahren zur Enthalogenierung organischer Verbindungen mittels Alkalimetall auf festen Trägern Download PDF

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Publication number
EP0467053B1
EP0467053B1 EP91108627A EP91108627A EP0467053B1 EP 0467053 B1 EP0467053 B1 EP 0467053B1 EP 91108627 A EP91108627 A EP 91108627A EP 91108627 A EP91108627 A EP 91108627A EP 0467053 B1 EP0467053 B1 EP 0467053B1
Authority
EP
European Patent Office
Prior art keywords
treated
sodium
column
treating agent
alkali metal
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
EP91108627A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0467053A1 (de
Inventor
Burkhard Frenzel
Sybille Parr
Edgar Dr. Bilger
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0467053A1 publication Critical patent/EP0467053A1/de
Application granted granted Critical
Publication of EP0467053B1 publication Critical patent/EP0467053B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/32—Processes 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
    • 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
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • 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 invention relates to a method for dehalogenating a material to be treated from dissolved or gaseous or organohalogen compounds present in gas mixtures by contacting the material to be treated with sodium or potassium carried by particles of an inert solid as a treatment agent at room temperature or elevated temperature, optionally under inert gas and for recovering the carrier.
  • halogen-containing transformer oils essentially two types of processes: In the first method, the contaminated transformer oil is burned in a high-temperature incineration plant, with the loss of this valuable substance. This procedure is technically very complex, natural raw materials are destroyed and removed from the material cycle.
  • the contaminated transformer oil is detoxified by treatment with a sodium dispersion (DE-PS 28 13 200).
  • the transformer oil must be removed from the temporarily closed transformer and transported to the treatment plant.
  • U.S. Patent 4,639,309 describes the possibility. Destroy solutions of organic halogen compounds by adding sodium and then sand or by adding a sand doped with sodium and then to separate the liquid material to be treated from solids.
  • organochlorine compounds are reacted quantitatively in strongly dilute solutions in a batch mode with sodium in a stirred tank.
  • work must always be carried out above the melting point of sodium or potassium and with a large excess thereof.
  • the stirred tank has mechanically moving parts and sand has an abrasive effect, damage to the container material and agitator can be expected.
  • the finest suspended solids can result from the abrasion, which can cause difficulties in separating the liquid phase.
  • the abrasive properties of the sand are said to be necessary to make the total amount of sodium available through ongoing abrasion by stirring.
  • the object of the invention is to avoid such disadvantages and to find an improved method.
  • the atomic ratio of sodium to chlorine in the material to be treated depends on the respective reactant for the sodium. It varies from 1: 1 to 3: 1, the higher ratios being used if sodium consumption for side reactions (such as ethylate formation) is to be expected at the same time.
  • the process according to the invention makes it possible to choose temperatures which are substantially lower than the reaction temperatures which have hitherto been customary in known relevant processes. Compared to the otherwise often chosen use of sodium dispersion, the process according to the invention has the advantage that a liquid dispersant can be dispensed with as an auxiliary. Furthermore, the method does not contain any moving parts, which means that maintenance work in particular can be significantly reduced.
  • all customary ceramic supports as used in catalysis can advantageously be used as an inert support for the alkali metal.
  • Aluminum oxides, activated carbon, common salt, calcined soda, silicas or zeolites in powder form or in the form of granules with a diameter of up to 6 mm are preferred.
  • the provisions for treatment temperature, residence time and alkali metal content of the treatment agent according to the invention are to be adapted to the particular material to be treated.
  • the reactivity to the chosen alkali metal is to be taken as a basis.
  • the treatment temperature, residence time and alkali metal content of the treatment agent are chosen to be low with a higher chemical reactivity of the material to be treated, and vice versa.
  • the apparatus design of the reactor column follows the requirements of the process according to the invention. It can be provided that a heatable column is used in order to achieve a favorable rate of reaction in the case of inert treatment material.
  • the cross section of the reaction column has a gas- and liquid-permeable plate-shaped element in the lower part, which serves as a support for the bed of treatment agent.
  • PCB polychlorinated biphenyls
  • the replacement transformer oil is usually contaminated with residues of PCB that were left in the transformer and must therefore also be considered problematic. It also happens that uncontaminated insulating oils are contaminated with PCBs from the cleaning system when cleaning takes place at intervals (drying, separation of solids). This also makes detoxification treatment necessary.
  • transformer oil detoxification the entire process is explained, starting with the preparation of the treatment agent up to the regeneration of the carrier.
  • the carrier material ⁇ -Al2O3 (type XL 129, Rhône Poulenc) in the form of granules with an average diameter of 3 mm and a surface area of 95 m2 / g is first dried in a muffle furnace at 400 ° C. under normal pressure for 2 hours. In parallel, sodium is liquefied by heating under inert gas.
  • the granules placed in a rotary tube and mixed are heated to 150 ° C under an inert gas stream. 30% by weight of sodium, based on the weight of the inert carrier, are melted and added to the agitated granules. After 30 minutes, the granules are coated with finely divided sodium, recognizable by their black color.
  • the sodium-coated carrier material is then filled into a heatable vertical treatment column (height 50 cm) made of steel with a capacity of 1 l.
  • the material to be treated a mineral transformer oil with a content of 1% by weight of PCB, is then pumped from bottom to top through the column (column temperature 120 ° C, contact time 1 h). The PCB content of the transformer oil could thus be reduced to below the detection limit in one pass.
  • Example 1 regenerated granules from the process of Example 1 have also proven to be extremely suitable. Both the recoatability with 30% by weight of sodium, based on the weight of the granules, and the dehalogenation of the same material to be treated as in Example 1 were unexpectedly successful.
  • the correct coating of the carrier material is of particular importance in the context of the invention. It has been shown in the course of development that with some seemingly possible working methods no satisfactory dehalogenation results could be achieved. It has not proven particularly useful to add and liquefy sodium, then to add pellets, to add pellets and to add solid sodium, to subsequently heat up, to add pellets, to add sodium purified with isopropanol and then to heat up.
  • a zeolite powder (trade name Wessalith P, Degussa AG, surface area: approx. 30 m 2 / g) was used for coating with sodium.
  • the powder was dried for 2 hours at 600 ° C. under normal pressure in a muffle furnace and coated with 5% by weight sodium, based on the amount of zeolite powder used.
  • the reactivity of the sodium is increased so that work must be carried out under the strictest exclusion of oxygen.
  • the coated powder is excellently suited for the decomposition of organically bound halogens, which are otherwise very difficult to decompose.
  • the powder coated with sodium is filled into the treatment column mentioned in Example 1 and heated to 50 ° C.
  • a solution of 5000 ppm of organically bound chlorine-containing methylene chloride in hexane is pumped up and down the column, the contact time being 40 minutes.
  • the decomposition rate of the organically bound chlorine is> 99% after passing the solution through twice.
  • Example 1 The ⁇ -Al2O3 granules used in Example 1 are dried for 3 hours at 150 ° C and 32 mbar in a vacuum drying cabinet and then coated with 31% by weight sodium, based on the amount of Al2O3 granules used.
  • a regenerated according to Example 1 ⁇ -Al2O3 granules of the type SCM 99 XT (average particle diameter 2.5 mm and specific surface 110 m2 / g) is dried at 150 ° C and 26 mbar for 2 hours.
  • the granules are heated to 150 ° C. under an inert gas stream and liquid sodium is added until 30% by weight sodium, based on the amount of granules used, has been taken up.
  • Sodium chloride with a grain size of 0.3 - 0.6 mm is dried for 2 hours at 200 ° C in a vacuum drying cabinet. Then it is filled into a stirred flask and sodium is added with stirring at 120 ° C. under an inert gas (argon) until a loading of 10%, based on sodium chloride, is reached.
  • argon inert gas
  • the sodium-coated table salt is colored gray and free-flowing.
  • a solution of 3-chloro-1-propene (equivalent to 8900 ppm organic chlorine) in hexane is passed through a column filled with the sodium-coated common salt.
  • Sodium is liquefied under an inert gas stream and added to the granules, which is in a rotary tube furnace at 150 ° C. in a mixing movement until a loading of the ⁇ -Al2O3 granules of 25% by weight sodium, based on the amount of granules used, is reached.
  • the sodium-coated granulate is filled into the treatment column made of steel (according to Example 1) and heated to 50 ° C.
  • the gas is passed through the column mentioned at a flow rate of 15 l / h. A degradation rate of 85% is achieved.
  • Anhydrous Na2CO3 is placed in a stirred vessel under argon and mixed with liquid sodium while stirring at 125 ° C until a sodium content of 7%, based on Na2CO3, is reached.
  • the gray, free-flowing, sodium-coated Na2CO3 is filled into the heatable treatment column according to Example 1.
  • a solution of chlorobenzene with 10,000 ppm organically bound chlorine in hexane is then passed over the treatment column with a contact time of 20 minutes.
  • the organic chlorine content of the eluate is 5,100 ppm.
  • the organic chlorine content of the leaking solution is below the detection limit.
  • activated carbon type Epanit, powdered
  • 200 g of activated carbon, type Epanit, powdered are dried for 3 hours at 180 ° C. in a vacuum drying cabinet and placed in a stirred vessel under an inert gas at 130 ° C. While stirring, liquid sodium is added until 35% sodium, based on activated carbon, has been added.
  • the coated activated carbon is gray-black and free-flowing. A sample taken into the air will glow after a few moments.
  • the coated activated carbon is filled into a treatment column (as in Example 1) and then a chlorobenzene solution in hexane (10,000 ppm organically bound chlorine) is chlorinated to 83% at room temperature and a contact time of 20 minutes.
  • the degradation rate can be increased to> 99% in the same experimental arrangement.
  • SiO2 pellets with a diameter of 4-7 mm are dried for 2 hours at 400 ° C in a muffle furnace, placed under argon at 140 ° C in a stirred vessel and mixed with 5% liquid sodium, based on the pellets. After stirring for 60 minutes, the pellets are coated evenly black.
  • the sodium-coated SiO2 pellets were introduced into the heatable treatment column described in Example 1. A chlorobenzene solution in hexane (10,000 ppm organically bound chlorine) is allowed to flow from bottom to top through this at 120 ° C. and a contact time of 20 minutes.
  • the Cl content in the eluate is below the detection limit.
  • the sodium excess, based on chlorine, is 8: 1, which is due to poor wetting (low surface area and high layer thickness).

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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)
  • Fire-Extinguishing Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP91108627A 1990-07-16 1991-05-28 Verfahren zur Enthalogenierung organischer Verbindungen mittels Alkalimetall auf festen Trägern Expired - Lifetime EP0467053B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4022526 1990-07-16
DE4022526A DE4022526C2 (de) 1990-07-16 1990-07-16 Verfahren zur Enthalogenierung organischer Verbindungen mittels Alkalimetall auf festen Trägern

Publications (2)

Publication Number Publication Date
EP0467053A1 EP0467053A1 (de) 1992-01-22
EP0467053B1 true EP0467053B1 (de) 1995-04-05

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EP91108627A Expired - Lifetime EP0467053B1 (de) 1990-07-16 1991-05-28 Verfahren zur Enthalogenierung organischer Verbindungen mittels Alkalimetall auf festen Trägern

Country Status (4)

Country Link
EP (1) EP0467053B1 (es)
AT (1) ATE120650T1 (es)
DE (2) DE4022526C2 (es)
ES (1) ES2070367T3 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5936137A (en) * 1997-06-06 1999-08-10 The United States Of America As Represented By The Secretary Of Commerce Process for destroying halogenated compounds

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4236382A1 (de) * 1992-10-28 1994-05-05 Degussa Verfahren zur Umsetzung von FCKW's mit Dispersionen von Alkalimetallen
DE4406588A1 (de) * 1994-03-01 1995-09-07 Solvay Deutschland Verfahren zur katalytischen Behandlung von Abwasser sowie ein Verfahren zur Regenerierung eines Katalysators
DE19501597C1 (de) * 1995-01-20 1996-04-25 Edgar Dr Bilger Verwendung von Alkalimetallen zur Zerstörung chemischer Kampfstoffe
GB2299080A (en) * 1995-03-24 1996-09-25 Ea Tech Ltd Process for the destruction of halocarbons
DE19742297C2 (de) 1997-09-25 2000-06-29 Volker Birke Verfahren zur reduktiven Dehalogenierung von halogenorganischen Stoffen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379746A (en) * 1980-08-18 1983-04-12 Sun-Ohio, Inc. Method of destruction of polychlorinated biphenyls
US4612404A (en) * 1982-05-24 1986-09-16 Thyagarajan Budalur S Process for treatment of fluids contaminated with polychlorinated biphenyls
IT1206508B (it) * 1983-07-22 1989-04-27 Sea Marconi Decontamin Srl Processo continuo per la decomposizione e decontaminazione di composti organici e agenti tossici alogenati.
DE3447066A1 (de) * 1984-12-22 1986-07-03 Bergwerksverband Gmbh Verfahren zur katalytischen entfernung von chlorkohlenwasserstoffen aus deponiegasen
US4639309A (en) * 1985-09-18 1987-01-27 Hydro-Quebec Process for the dehalogenation of polyhalogenated hydrocarbon containing fluids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5936137A (en) * 1997-06-06 1999-08-10 The United States Of America As Represented By The Secretary Of Commerce Process for destroying halogenated compounds

Also Published As

Publication number Publication date
ES2070367T3 (es) 1995-06-01
EP0467053A1 (de) 1992-01-22
DE4022526A1 (de) 1992-01-23
ATE120650T1 (de) 1995-04-15
DE4022526C2 (de) 1994-03-24
DE59105087D1 (de) 1995-05-11

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