CN88100299A - The method of destroying chlorinated products at low temp - Google Patents
The method of destroying chlorinated products at low temp Download PDFInfo
- Publication number
- CN88100299A CN88100299A CN88100299.2A CN88100299A CN88100299A CN 88100299 A CN88100299 A CN 88100299A CN 88100299 A CN88100299 A CN 88100299A CN 88100299 A CN88100299 A CN 88100299A
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- CN
- China
- Prior art keywords
- aluminate
- chloro
- products
- chloride
- chlorinated 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.)
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- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic 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)
- Dental Preparations (AREA)
- Developing Agents For Electrophotography (AREA)
- Photoreceptors In Electrophotography (AREA)
- Paper (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Fire-Extinguishing Compositions (AREA)
- Luminescent Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Glass Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
The invention relates to the method for a kind of destruction chlorinated products, particularly aromatic product and many aromatic products.
This method is chlorinated products is contacted with the Sodium Tetrachloroaluminate bath that contains aluminium powder.
Description
The invention relates to the method for a kind of destruction chloride organic products, particularly aromatic product and Polychlorinated biphenyls.
Some dielectric fluids contain some chloride organic products, and generation is decomposed and needed to change after the work certain hour.They may be regenerated sometimes fully or partly.Often have to destroy this class I liquid I of a part.
Chloride organic products, as some agricultural chemicals, chloride aromatic hydrocarbons such as hexachloro-benzene, or some Polychlorinated biphenyls (PCB), when they when the common product that can burn is burnt, can generate poisonous product.
For avoiding generating poisonous product, people destroy these chlorinated products under high temperature and specified conditions.
Narrated the method for destroying Polychlorinated biphenyls (PCB) with burning method in one piece of article of Sci.Total Environ.1987 10 volumes the 1st phase 51-59 page or leaf, the time of staying spent for 2 seconds slightly.
The method of destroying 99.9995% Polychlorinated biphenyls down at 1000 ℃ narrated in another piece article in the article of 1977 2 the 33rd phases of volume of PROC.ANNU.MEET-AIR POLLUT.CONTROL ASSOC., the time of staying was 2 seconds.
European patent EP 170 714 has been narrated by with the aluminium of fusion or a kind ofly destroy the method for Polychlorinated biphenyls based on the eutectic mixture reaction of aluminium, is reflected at more than 382 ℃ and carries out.
Find a kind of method of more simply destroying these products at present, can operate below 300 ℃.
The present invention is the method that a kind of destruction is contained the chloride organic products of 2 above carbon atoms 2, it is characterized in that these products are contacted with at least a chloro-aluminate bath.
Can use various chloro-aluminates or their mixture.The chloro-aluminate of chlorine potassium aluminate or lithium, sodium, calcium, strontium or ammonium for example.
Claim that in this article any mixture of anhydrous Aluminum chloride and one or more metal chlorides is a chloro-aluminate.
What be suitable for using is Sodium Tetrachloroaluminate, and it is meant that aluminium chloride and sodium chloride are not only equimolar mixture with any ratio.Sodium Tetrachloroaluminate also can contain lithium chloride and/or potassium chloride.Thereby can adopt the mixture arbitrarily of aluminium chloride, sodium chloride and lithium chloride, be referred to as the Sodium Tetrachloroaluminate lithium.
At least containing 50% mole of aluminium chloride and fusing point, to be lower than 200 ℃ Sodium Tetrachloroaluminate then better.
The present invention is applicable to that all contain the chloride organic products of 2 above carbon atoms, and is specially adapted to aliphatic series, ring-type, the aromatics of monocycle or many rings, the product of heterocycle.Particularly with excessively chlorine aliphatic series product is relevant in the present invention, and relevant with Polychlorinated biphenyls in aromatic product.
The waste of organic chloride product is preferably 5000ppm (in chloro-aluminate), and 2000ppm is better.
These products can exist in any form.They especially can a kind of solid mutually in, for example be absorbed on the active carbon.
Method of the present invention is chlorinated products is contacted with the chloro-aluminate bath.
When chlorinated products be in solid mutually in, this solid can be poured into mutually during chloro-aluminate bathes, if stir then better.Note making salt bath to keep fusion, if necessary, can heat salt bath.If chlorinated products in liquid phase, is operated equally.
Most applications is that the chlorinated products that will destroy mixes in gas phase or with low weight chlorinated products and/or carrier gas separately mutually.For example this may be the gas that burning produces, thereby is the nitrogen that contains carbon dioxide, carbon monoxide, chlorinated products and may go back aerobic.In a word, it can be any a kind of admixture of gas that any process is discharged.
If chlorinated products is at no aqueous phase then better.The gas that contains chlorinated products can contact with a kind of absorbent such as alumina or ethylene glycol does behaviour.
With this gas phase that contains the chlorinated products that will destroy, the method with any gas-liquid contact contacts with chloro-aluminate then.This can be a plate column or packed tower.Equally also can be in a chloro-aluminate container that has a stirring with a liquid under pipe or with a pipe feeding gas phase that feeds from container bottom.
Various chloride organic products can be distributed between the liquid and gas of chloro-aluminate bath.For the product of following these chlorinated products, also be same.Can adopt plate column or packed tower to bathe excellent contact to guarantee continuous circulation of liquid and gas and stirring and gas products and chloro-aluminate.The equally also reactor operation that can stir with the band of series connection.Keep chloride organic products and chloro-aluminate to bathe and touch their the required time of destruction.The time of staying can change within wide scope, but is generally between a few minutes to several hours.
Though as long as chloro-aluminate is a liquid, just can under any temperature, operate,, and be preferably in 200～300 ℃ better below 300 ℃.
The breakdown speed of chlorinated products, particularly aromatic product improves along with the rising of chloro-aluminate temperature.
The lighter product that the chlorization product that can find to destroy in the gas phase that chloro-aluminate is bathed decomposes; For example carbon tetrachloride and/or carbon trichloride.In the gas phase that chloro-aluminate is bathed, can not find the chlorinated products that will destroy originally.At in accordance with regulations chlorinated products and chloro-aluminate after time of contact, when analyzing chloro-aluminate and bathing, do not find the organic products that will destroy.
Equally also can regularly clean chloro-aluminate bathes to avoid undissolved product or can not keep the product deposition of suspension in bath.In cleaning, do not find the chloride organic products of any trace yet.Thereby confirm that the chlorinated products that will destroy has disappeared.
Preferably in the specific embodiment, in bathing, chloro-aluminate adds one or more reducing metal powder, one of the present invention as aluminium powder or zinc powder.Better with particle mean size less than 500 microns powder.If use metal, can remove chloride organic products fully as previously described, but speed improves obviously, be several times to tens times of preceding face velocity.
Observe metal (or multiple metal) powder consumption, this expression therefrom obtains chlorine and has generated chloride when chloride organic products destroys.To the metal dust quantity in the feeding chloro-aluminate without limits.Better with aluminium powder; Can in bathing, put into chloro-aluminate aluminium powder until 5% or 10% (weight).The breakdown speed of observing chlorinated products improves along with the rising of aluminium powder quantity and chloro-aluminate bath temperature.For metal dust is dispersed in the bath well, stir better.The metal chloride (one or more) that generates can be sneaked in the chloro-aluminate bath, and is distributed between the liquid and gas.If desired, can use a kind of hydroxide,, metal chloride therefrom be removed as NaOH or potassium hydroxide treatment gas phase.By the following examples the present invention can be described:
Embodiment 1
At one rotating speed being housed is that 500 gram Sodium Tetrachloroaluminate, wherein AlCl pack in 300 rev/mins the Pyrex round-bottomed flask of 1 liter of volume of spiral agitator, electric heater
3The ratio of/NaCl counts 1 with mole.Product by heating to 200 ℃ stirs, and adds 0.2 gram hexachloro-benzene and 0.1 gram, ten chlordiphenyls then.In 200 ℃ after following 1 hour, blew down molten baths 15 minutes with 50 liters of/hour nitrogen streams, air-flow washs in a bubbler that contains 100 milliliters of hexanes.
Amount with gas Chromatographic Determination chlorine-containing organic compounds in final the bath and in the hexane.The result lists in the table 1.
Embodiment 2
Carry out same test, but in chloro-aluminate is bathed, add 5% atomized aluminium (grade is PECHINEY XY 49) again.In 200 ℃ after 1 hour,, get salt bath and the hexane sample carries out quantitative assay with 50 liters/hour nitrogen blow-offs 15 minutes.The result lists table 1 in.
Table 1
| Chloride organic products | Do not add aluminium powder | Add 5% aluminium powder | ||||||
| In the salt bath | In the hexane | The product % that disappears | In the salt bath | In the hexane | The product % that disappears | |||
| Beginning | Finally | Beginning | Finally | |||||
| C 6Cl 6Ten chlordiphenyls | ?200 ?100 | ?111 ?41.3 | ??13.2 ??0.40 | ??37.7 ??58.3 | ??200 ??100 | ????29 ????3.8 | ?3.5 ?0.2 | ?83.7 ?96 |
Numeral is represented with milligram in the table
Embodiment 3
In embodiment 1 and 2 used same equipment, operate, but operating condition is changed into:
Bathe temperature: 250 ℃
Chloro-aluminate is bathed weight: 500 grams
Add 5% aluminium powder (PECHINEY XY 49)
Test period: 2 hours
Blow down with nitrogen after 2 hours: 15 minutes
Begin to add: 500 milligrams of hexachloro-benzenes, 500 milligram of ten chlordiphenyl
The result lists in the table 2.
Embodiment 4
Test similarly to Example 3, but test period is 4 hours.The results are shown in Table 2.
Table 2
PS: numeral is represented with milligram in the polystream ethene table
| Chloride organic products | Through 2 hours | Through 4 hours | ||||||
| In the salt bath | In the hexane | The product % that disappears | In the salt bath | In the hexane | The product % that disappears | |||
| Beginning | Finally | Beginning | Finally | |||||
| ?C 6H 2Cl 4?C 6HCl 5?C 6Cl 6Ten chlordiphenyl PS* | ??500 ??500 | ??2.5 ??10 ??8 ??6 ??0.02 | 0.7 5 3 0.2 0.002 | ?97.8 ?98.8 | ??500 ??500 | 0.3 1.5 1.3 3 0.1 | ?0.1 ?1.3 ?3 ?0.16 ?0.008 | ??99.15 ??99.4 |
Claims (7)
1. destroy the method for the chloride organic products that contains 2 above carbon atoms, it is characterized in that these products are contacted with at least a chloro-aluminate bath.
2. according to the method for claim 1, it is characterized in that chloro-aluminate is a Sodium Tetrachloroaluminate.
3. according to the method for claim 2, it is characterized in that Sodium Tetrachloroaluminate contains the aluminium chloride of 50% (mole) at least.
4. according to any one method in the claim 1 to 3, it is characterized in that the chloro-aluminate bath temperature is lower than 300 ℃, and better between 200 and 300 ℃.
5. according to any one method in the claim 1 to 4, it is characterized in that chloro-aluminate contains a kind of metal dust at least.
6. according to the method for claim 5, it is characterized in that preferably aluminium of described metal.
7. according to any one method in claim 5 or 6, the particle mean size that it is characterized in that powder is less than 500 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8700669 | 1987-01-21 | ||
| FR8700669A FR2609652B1 (en) | 1987-01-21 | 1987-01-21 | PROCESS FOR THE DESTRUCTION OF LOW TEMPERATURE CHLORINE PRODUCTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88100299A true CN88100299A (en) | 1988-08-03 |
| CN1012142B CN1012142B (en) | 1991-03-27 |
Family
ID=9347122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88100299A Expired CN1012142B (en) | 1987-01-21 | 1988-01-20 | Process for destroying chlorinated products at low temp. |
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) | FI880241A (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)
| 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 |
Family Cites Families (3)
| 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 |
| US4469661A (en) * | 1982-04-06 | 1984-09-04 | Shultz Clifford G | 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 |
-
1987
- 1987-01-21 FR FR8700669A patent/FR2609652B1/en not_active Expired - Lifetime
-
1988
- 1988-01-12 NO NO880104A patent/NO174088C/en unknown
- 1988-01-13 CA CA000556427A patent/CA1333404C/en not_active Expired - Fee Related
- 1988-01-14 ES ES88400074T patent/ES2014508B3/en not_active Expired - Lifetime
- 1988-01-14 AT AT88400074T patent/ATE51531T1/en not_active IP Right Cessation
- 1988-01-14 DE DE8888400074T patent/DE3860064D1/en not_active Expired - Fee Related
- 1988-01-14 EP EP88400074A patent/EP0277858B1/en not_active Expired - Lifetime
- 1988-01-19 IN IN34/MAS/88A patent/IN170563B/en unknown
- 1988-01-19 NZ NZ223232A patent/NZ223232A/en unknown
- 1988-01-19 JP JP63009439A patent/JPS63192468A/en active Pending
- 1988-01-20 FI FI880241A patent/FI880241A/en not_active Application Discontinuation
- 1988-01-20 DK DK023288A patent/DK166432B1/en not_active IP Right Cessation
- 1988-01-20 CN CN88100299A patent/CN1012142B/en not_active Expired
- 1988-01-20 AU AU10621/88A patent/AU610552B2/en not_active Ceased
- 1988-01-20 PT PT86577A patent/PT86577B/en unknown
- 1988-01-20 IE IE13788A patent/IE60535B1/en not_active IP Right Cessation
-
1990
- 1990-04-18 GR GR90400235T patent/GR3000437T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK23288D0 (en) | 1988-01-20 |
| PT86577A (en) | 1988-02-01 |
| DK23288A (en) | 1988-07-22 |
| ATE51531T1 (en) | 1990-04-15 |
| AU610552B2 (en) | 1991-05-23 |
| FR2609652A1 (en) | 1988-07-22 |
| CA1333404C (en) | 1994-12-06 |
| AU1062188A (en) | 1988-07-28 |
| NZ223232A (en) | 1991-05-28 |
| GR3000437T3 (en) | 1991-06-28 |
| DK166432B1 (en) | 1993-05-24 |
| NO174088C (en) | 1994-03-16 |
| IE880137L (en) | 1988-07-21 |
| FI880241A (en) | 1988-07-22 |
| NO174088B (en) | 1993-12-06 |
| ES2014508B3 (en) | 1990-07-16 |
| JPS63192468A (en) | 1988-08-09 |
| FR2609652B1 (en) | 1992-05-15 |
| IN170563B (en) | 1992-04-11 |
| EP0277858A1 (en) | 1988-08-10 |
| NO880104D0 (en) | 1988-01-12 |
| PT86577B (en) | 1991-12-31 |
| IE60535B1 (en) | 1994-07-27 |
| NO880104L (en) | 1988-07-22 |
| CN1012142B (en) | 1991-03-27 |
| EP0277858B1 (en) | 1990-04-04 |
| FI880241A0 (en) | 1988-01-20 |
| DE3860064D1 (en) | 1990-05-10 |
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