WO1998048901A1 - Verfharen zum abbau von halogenierten kohlenwasserstoffen - Google Patents
Verfharen zum abbau von halogenierten kohlenwasserstoffen Download PDFInfo
- Publication number
- WO1998048901A1 WO1998048901A1 PCT/EP1998/002541 EP9802541W WO9848901A1 WO 1998048901 A1 WO1998048901 A1 WO 1998048901A1 EP 9802541 W EP9802541 W EP 9802541W WO 9848901 A1 WO9848901 A1 WO 9848901A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- degradation
- catalyst
- partially
- halogenated hydrocarbons
- 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
Links
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
- A62D3/20—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by hydropyrolysis or destructive steam gasification, e.g. using water and heat or supercritical water, to effect chemical change
-
- 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
- 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
Definitions
- the invention relates to a process for the degradation of partially and / or completely halogenated hydrocarbons by reaction with water in the presence of a catalyst.
- Chlorofluorocarbons (CFRP) (also known as chlorofluorocarbons (CFCs)) are of great technical and economic importance. Individually or as azeotropes in liquefied form, they are used in particular as blowing agents for aerosols, as refrigerants, fire extinguishing agents, solvents for chemical cleaning, for metal degreasing and for foaming plastics. However, for some years now there have been considerable concerns about their uncontrolled use: the ones that remain unchanged into
- CFRP entering the stratosphere are photolyzed there by hard solar UV radiation, with the formation of, for example, chlorine radicals; these react with the ozone, causing a weakening of the ozone jacket, which acts as a UV radiation shield (so-called ozone hole). It is no longer seriously disputed that CFRP, at least in part, is responsible for the depletion of the ozone layer in the stratosphere. In addition, there is also the natural greenhouse effect Warming beyond the earth's atmosphere, at least in part, is attributable to the increase in the concentration of CFRP.
- CFCs CFRP
- zeolites a catalyst for example zeolites
- CFRPs are mainly broken down by thermal fission at high temperatures, for example at approx. 2000 ° C; however, this method has the disadvantage that it is very energy-intensive. It was an object of the present invention to provide a process for the degradation of partially and / or completely halogenated hydrocarbons which can be carried out simply, safely and with the lowest possible energy consumption and which leads to end products which can be easily and completely disposed of or which can be returned to the material cycle can. The end products are therefore not harmful to the environment.
- the present invention relates to a process according to claim 1 for the degradation of partially and / or fully halogenated hydrocarbons by reaction with water in the presence of a catalyst, which is characterized in that a zeolite H-ZSM 5 with a S ⁇ 0 2 / Al 2 0 3 -Verhaltn ⁇ s (module) of large 15 used.
- a zeolite H-ZSM 5 with a SiO 2 / Al 2 O 3 ratio (module) of a large 15 is used as the catalyst for the process according to the invention.
- a zeolite H-ZSM 5 is preferred a module from 20 to 100, in particular from 25 to 35, and primarily from 28.
- the halogenated hydrocarbons used are primarily those having 1 or 2 carbon atoms, such as fully halogenated chlorofluoromethane, methylene chloride or equivalent ethane derivatives.
- the partially or fully halogenated hydrocarbons used are preferably derived from saturated hydrocarbons.
- the process according to the invention expediently also comprises a step for neutralizing the hydrohalic acids formed during the decomposition.
- This neutralization can take place simultaneously, i.e. during mining to form the
- Hydrogen halides are carried out, or such a neutralization stage can be expediently connected to the decomposition stage, because in this way the used neutralizing agent can be exchanged independently of the catalyst.
- the hydrogen halide and carbon oxide products formed in the degradation stage are expediently passed in gaseous form through absorption or scrubbing chambers.
- This process can be carried out in one or more stages, and the absorbent can be solid or liquid.
- the absorbent can be solid or liquid.
- an aqueous solution of sodium hydroxide solution or slurry of milk of lime is used.
- a solid absorbent such.
- B. calcium hydroxide or calcium chloride can be used.
- the carbon oxides can also, at least partially, be converted into salts. It is also possible to carry out the neutralization stage at the same time as the degradation stage, that is to say during the formation of hydrogen halides and carbon oxides.
- the temperature of the reaction is preferably between 200 ° C and 500 ° C, and in particular between 300 ° C and 400 ° C.
- a tubular reactor is equipped with zeolite H-ZSM 5 with a module of 28 and heated to 340 ° C.
- the CFRP R12 to be converted is brought into a gaseous state by evaporation and mixed with water vapor in an at least stoichiometric ratio. This gas mixture then flows through the tubular reactor at a temperature of 340 ° C.
- the tube reactor is filled with 500 g of zeolite and a flow rate of 25 l / hour, complete CFRP degradation can be achieved.
- the gas mixture leaving the tubular reactor is then fed to a gas scrubber with aqueous sodium hydroxide solution.
- the gas stream leaving this scrubber is carbon-free and contains no halogenated products.
- the gas mixture leaving the tubular reactor can be passed through the tubular reactor (zeolite bed) one or more times before the gas scrubbing, and in particular after the gas scrubbing .
- Zeolites H-ZSM 5 with a module of 20 to 100 are characterized by a particularly high effectiveness. They also have high temperature stability and, as studies have shown, they are also insensitive to the corrosive degradation products HBr, HC1 and HF.
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98929274A EP0981394A1 (de) | 1997-04-30 | 1998-04-29 | Verfharen zum abbau von halogenierten kohlenwasserstoffen |
| AU79101/98A AU7910198A (en) | 1997-04-30 | 1998-04-29 | Process for decomposing halogenated hydrocarbons |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19718373.5 | 1997-04-30 | ||
| DE19718373 | 1997-04-30 | ||
| DE19750546.5 | 1997-11-14 | ||
| DE19750546A DE19750546C2 (de) | 1997-04-30 | 1997-11-14 | Verfahren zur Konversion voll- und teilhalogenierter Kohlenwasserstoffe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998048901A1 true WO1998048901A1 (de) | 1998-11-05 |
Family
ID=26036225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/002541 Ceased WO1998048901A1 (de) | 1997-04-30 | 1998-04-29 | Verfharen zum abbau von halogenierten kohlenwasserstoffen |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0981394A1 (de) |
| AU (1) | AU7910198A (de) |
| WO (1) | WO1998048901A1 (de) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| EP0089579A1 (de) * | 1982-03-12 | 1983-09-28 | The Dow Chemical Company | Katalytisches Dehydrohalogenierungsverfahren |
| JPH01155946A (ja) * | 1987-12-14 | 1989-06-19 | Idemitsu Kosan Co Ltd | ハロゲン化低級炭化水素除去用吸着剤 |
| EP0516850A1 (de) * | 1990-12-27 | 1992-12-09 | JAPAN as represented by DIRECTOR GENERAL, AGENCY OF INDUSTRIAL SCIENCE AND TECHNOLOGY | Verfahren zum entfernen organischer halide |
-
1998
- 1998-04-29 EP EP98929274A patent/EP0981394A1/de not_active Withdrawn
- 1998-04-29 AU AU79101/98A patent/AU7910198A/en not_active Abandoned
- 1998-04-29 WO PCT/EP1998/002541 patent/WO1998048901A1/de not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| EP0089579A1 (de) * | 1982-03-12 | 1983-09-28 | The Dow Chemical Company | Katalytisches Dehydrohalogenierungsverfahren |
| JPH01155946A (ja) * | 1987-12-14 | 1989-06-19 | Idemitsu Kosan Co Ltd | ハロゲン化低級炭化水素除去用吸着剤 |
| EP0516850A1 (de) * | 1990-12-27 | 1992-12-09 | JAPAN as represented by DIRECTOR GENERAL, AGENCY OF INDUSTRIAL SCIENCE AND TECHNOLOGY | Verfahren zum entfernen organischer halide |
Non-Patent Citations (3)
| Title |
|---|
| APPL. CATAL., B (1996), 9(1-4), 167-177 CODEN: ACBEE3;ISSN: 0926-3373, 1996 * |
| CHEMICAL ABSTRACTS, vol. 112, no. 6, 5 February 1990, Columbus, Ohio, US; abstract no. 42193, SATO, HARUHITO ET AL: "Adsorbent for halogenated lower hydrocarbons removal from water" XP002079098 * |
| CHEMICAL ABSTRACTS, vol. 125, no. 21, 18 November 1996, Columbus, Ohio, US; abstract no. 275108, TAJIMA, MASAHIRO ET AL: "Decomposition of chlorofluorocarbons in the presence of water over zeolite catalyst" XP002079099 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0981394A1 (de) | 2000-03-01 |
| AU7910198A (en) | 1998-11-24 |
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