CA1119203A - Process for preparation of trichloroethylene - Google Patents
Process for preparation of trichloroethyleneInfo
- Publication number
- CA1119203A CA1119203A CA000326608A CA326608A CA1119203A CA 1119203 A CA1119203 A CA 1119203A CA 000326608 A CA000326608 A CA 000326608A CA 326608 A CA326608 A CA 326608A CA 1119203 A CA1119203 A CA 1119203A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- weight
- copper
- tetrachloroethylene
- compound
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
PROCESS FOR PREPARATION OF TRICHLOROETHYLENE ABSTRACT OF THE DISCLOSURE Process for the preparation of trichloroethylene from tetrachloroethylene and hydrogen at an elevated temp-erature by means of a carrier catalyst containing a copper compound and optionally an alkali metal compound, wherein the tetrachloroethylene is reacted at 150°to 250°C and a hydrogen pressure of 1-100 bar in an amount of 0.5 to 5 mol per hour and per liter catalyst mass. The catalyst consists of an activated carbon carrier with over 500m2/g BET-surface, 0.5 to 20% by weight of copper in elemental state or as chemical compound, 0.01 to 1% by weight of palladium as metal or chemical compound, and if desired up to 20% by weight of a member of the group consisting of potassium, rubidium and cesium. Instead of palladium, ruthenium or rhodium may be used in the same amount.
Description
The present invention relates to a process for preparing trichloroethylene from tetrachloroethylene and hydrogen at an elevated temperature in the presence of a catalyst containing a copper compound and, optionally, an alkali metal compound on a carrier.
In a conventional process, tetrachloroethylene is reacted with hydrogen in the presence of copper salts distributed on aluminum oxide. The addition to tetrachloro-ethylene of alkali metal salts, e.g. potassium-,rubidium-and cesium salts has also been previously disclosed. How-ever, German Auslegeschrift 11 94 403 mentions that the system aluminum oxide/copper salt produces only low yields which cannot be reproduced. The activation with alkali metal salts likewise results only in a modest improvement at temperatures from 200 to 325C.
It is therefore the object of the present in-vention to provide a process for preparing trichloroethy-lene from tetrachloroethylene which permits one to obtain good yields at low temperatures and high selectivity.
This object is fulfilled according to the pre-sent invention when tetrachloroethylene is reacted at temperatures between 150 and 250C in an amount of 0.5 to 5 mol per hour and per liter of catalyst mass over a catalyst consisting of an activated carbon carrier with more than 500m /g BET surface, 0.5 to 20% by weight of copper in elementar~ or chemically bound form, 0.01 to 1% by weight of one or more of the group consisting of palladium, ruthen-ium or rhodium in elemental form or in the form of a chemical compound, and with up to 20% by wei~ht of one or several of the metals potassium,rubidium or cesium, in the form of a ~119Z03 chemical compound, and with hydro~en at a pressure of 1 to 100 bar.
These new catalysts exhibit a surprising improve-ment over catalysts known and used up to now. It could in no way be expected that with a changeover from aluminum ox-ide to activated carbon with surfaces of more than 500 m2/g and the addition of 0.01 to 1% by weight of one or several metals of the group of palladium, ruthenium or rhodium in elemental form or as a chemical compound, the selectivity, the yield, and space-time output could be so drastically improved.
The catalyst according to the invention consists of activated carbon as a carrier material and it has a BET-surface of more than 500 m2/g; materials with surfaces of up to 1400 m2/g are commercially available. The activated car-bon is generally used in grain sizes of between 2 and 10 mm diameter. The catalyst is coated with finely dispersed salts of one or several of the metals palladium, ruthenium or rhodium, as well as copper and if desired, the salts of alkali metals, e.g. potassium, rubidium or cesium. As salts, one may use any ino-rganic or organic salts highly soluble in water or acids, with the proviso:that for the preparation of, e.g. 1 kg of catalyst, the necessary salt quantities should be dissolved in 0.5-- 10 liters of water.
The catalyst carrier is coated with 0.5 to 20~ by weight of copper in elemental or chemical compound form, 0.01%
to 1~ by weight of one of the metals palladium, ruthenium or rhodiu~ in elemental or chemical compound form, as well as a compound of potassium, rubidium or cesium of U2 to 20~. At the start or during the reaction, there occurs a partial or ~1~9203 or complete reduction of the salts of copper, palladium, ruthenium or rhodium with formation of the respective metals.
The preparation of the catalyst is carried out, for instance, by starting ith 160 g of activated carbon grains (BET-surfaces 500 m ~g) of a commerical product, soaking or sprinkling it with 140 ml of an aqueous so-lution which contains 260 mg palladium chloride, and 43 g copper chloride dihydrate and subsequently drying it in a nitrogen current. If desired, this solution may also con-tain the alkali metal salts desirable in certain cases, such as the potassium, rubidium or cesium chlorides. The treat-ment of the activated carbon may also occur separately in se-~uence with the salt solutions.
The preparation of the novel catal~st is much simpler than the one of the known catalyst, as described in ; the German Offenlegungsschrift 11 94 403. The cumbersome and dangerous treatment there applied with hydrogen and oxy-gen at 300C is completely omitted in the catalyst according to the invention.
Preferably, catalysts with a copper content between 3 and 15~ by weight are used. The catalyst in final form has a bulk weight of 200 to 600 ~liter.
The activity of the catalyst depends almost linearly on the content of one or several of the metals Pd,Ru or Rh.
For instance, under otherwise comparable conditions, the in-crease from 0.01% Pd to 0.1% Pd in the novel catalyst raises the yield in the desired product 10-fold; with a content of 0.2% Pd the yield is doubled again. With further increase in the amount of Pd the yield further increases, and a peak ~1192()3 yield is already obtained at 0.8% Pd.
In amounts of below 1% by weight of copper, the volatility of the copper component can be diminished by the presence of small amounts of alkali metal chloride.
For carrying out the process, the newly-developed catalyst is introduced into a reaction tube by shaking.
Tetrachloroethylene, which is gaseous at the reaction tempera-ture, is fed-in in quantities of 0.5-5 mol per hour and per liter of catalyst mass, and reacted with the 0.1-1 fold equi-molar quantity of hydrogen gas. The reaction sets-in notice-ably at temperatures above 150C; at 180C in the initial phase of the catalyst formation, 98-99~ by weight of the theoretical conversion is already occurring, whereas with the catalysts known in this field, only 95~ can be maximally obtained. The space-time yields are considerably higher than the values obtained by the known processes even at temperatures 50C below those employed in these known pro-cesses.
Reaction temperatures above 250C are in general not necessary. It is a further advantage of the novel pro-cess that, contrary to known processes, operations can be carried out at elevated hydrogen pressure. It is desirable to operate at pressures of 1-100 bar: for best results, pressures of 1-10 bar and especially between 3 and 10 bar, are frequently used. The hydrogen chloride obtained in the pressure process can be used in other suitable processes, e.g. oxychlorination, without being pre-compressed. The separation of the reaction products is also much simpler.
If the catalyst is used over a longer period, a decrease in activity may be compensated by raising the tempera-ture. It is advantageous to start the reaction at low !
temperature,e.g., 180C, and increase the temperature ~;lowly, as the activity of the catalyst drops. The stability of the catalyst is good for more than one year.
The process according to the invention will be more fully described in a number of examples, but it should be understood that these are given by way of illustration and not of limitation.
160 g of granular activated carbon (grain size 2- -lOmm) of the brand EKT-IV, made by the firm LURGI,
In a conventional process, tetrachloroethylene is reacted with hydrogen in the presence of copper salts distributed on aluminum oxide. The addition to tetrachloro-ethylene of alkali metal salts, e.g. potassium-,rubidium-and cesium salts has also been previously disclosed. How-ever, German Auslegeschrift 11 94 403 mentions that the system aluminum oxide/copper salt produces only low yields which cannot be reproduced. The activation with alkali metal salts likewise results only in a modest improvement at temperatures from 200 to 325C.
It is therefore the object of the present in-vention to provide a process for preparing trichloroethy-lene from tetrachloroethylene which permits one to obtain good yields at low temperatures and high selectivity.
This object is fulfilled according to the pre-sent invention when tetrachloroethylene is reacted at temperatures between 150 and 250C in an amount of 0.5 to 5 mol per hour and per liter of catalyst mass over a catalyst consisting of an activated carbon carrier with more than 500m /g BET surface, 0.5 to 20% by weight of copper in elementar~ or chemically bound form, 0.01 to 1% by weight of one or more of the group consisting of palladium, ruthen-ium or rhodium in elemental form or in the form of a chemical compound, and with up to 20% by wei~ht of one or several of the metals potassium,rubidium or cesium, in the form of a ~119Z03 chemical compound, and with hydro~en at a pressure of 1 to 100 bar.
These new catalysts exhibit a surprising improve-ment over catalysts known and used up to now. It could in no way be expected that with a changeover from aluminum ox-ide to activated carbon with surfaces of more than 500 m2/g and the addition of 0.01 to 1% by weight of one or several metals of the group of palladium, ruthenium or rhodium in elemental form or as a chemical compound, the selectivity, the yield, and space-time output could be so drastically improved.
The catalyst according to the invention consists of activated carbon as a carrier material and it has a BET-surface of more than 500 m2/g; materials with surfaces of up to 1400 m2/g are commercially available. The activated car-bon is generally used in grain sizes of between 2 and 10 mm diameter. The catalyst is coated with finely dispersed salts of one or several of the metals palladium, ruthenium or rhodium, as well as copper and if desired, the salts of alkali metals, e.g. potassium, rubidium or cesium. As salts, one may use any ino-rganic or organic salts highly soluble in water or acids, with the proviso:that for the preparation of, e.g. 1 kg of catalyst, the necessary salt quantities should be dissolved in 0.5-- 10 liters of water.
The catalyst carrier is coated with 0.5 to 20~ by weight of copper in elemental or chemical compound form, 0.01%
to 1~ by weight of one of the metals palladium, ruthenium or rhodiu~ in elemental or chemical compound form, as well as a compound of potassium, rubidium or cesium of U2 to 20~. At the start or during the reaction, there occurs a partial or ~1~9203 or complete reduction of the salts of copper, palladium, ruthenium or rhodium with formation of the respective metals.
The preparation of the catalyst is carried out, for instance, by starting ith 160 g of activated carbon grains (BET-surfaces 500 m ~g) of a commerical product, soaking or sprinkling it with 140 ml of an aqueous so-lution which contains 260 mg palladium chloride, and 43 g copper chloride dihydrate and subsequently drying it in a nitrogen current. If desired, this solution may also con-tain the alkali metal salts desirable in certain cases, such as the potassium, rubidium or cesium chlorides. The treat-ment of the activated carbon may also occur separately in se-~uence with the salt solutions.
The preparation of the novel catal~st is much simpler than the one of the known catalyst, as described in ; the German Offenlegungsschrift 11 94 403. The cumbersome and dangerous treatment there applied with hydrogen and oxy-gen at 300C is completely omitted in the catalyst according to the invention.
Preferably, catalysts with a copper content between 3 and 15~ by weight are used. The catalyst in final form has a bulk weight of 200 to 600 ~liter.
The activity of the catalyst depends almost linearly on the content of one or several of the metals Pd,Ru or Rh.
For instance, under otherwise comparable conditions, the in-crease from 0.01% Pd to 0.1% Pd in the novel catalyst raises the yield in the desired product 10-fold; with a content of 0.2% Pd the yield is doubled again. With further increase in the amount of Pd the yield further increases, and a peak ~1192()3 yield is already obtained at 0.8% Pd.
In amounts of below 1% by weight of copper, the volatility of the copper component can be diminished by the presence of small amounts of alkali metal chloride.
For carrying out the process, the newly-developed catalyst is introduced into a reaction tube by shaking.
Tetrachloroethylene, which is gaseous at the reaction tempera-ture, is fed-in in quantities of 0.5-5 mol per hour and per liter of catalyst mass, and reacted with the 0.1-1 fold equi-molar quantity of hydrogen gas. The reaction sets-in notice-ably at temperatures above 150C; at 180C in the initial phase of the catalyst formation, 98-99~ by weight of the theoretical conversion is already occurring, whereas with the catalysts known in this field, only 95~ can be maximally obtained. The space-time yields are considerably higher than the values obtained by the known processes even at temperatures 50C below those employed in these known pro-cesses.
Reaction temperatures above 250C are in general not necessary. It is a further advantage of the novel pro-cess that, contrary to known processes, operations can be carried out at elevated hydrogen pressure. It is desirable to operate at pressures of 1-100 bar: for best results, pressures of 1-10 bar and especially between 3 and 10 bar, are frequently used. The hydrogen chloride obtained in the pressure process can be used in other suitable processes, e.g. oxychlorination, without being pre-compressed. The separation of the reaction products is also much simpler.
If the catalyst is used over a longer period, a decrease in activity may be compensated by raising the tempera-ture. It is advantageous to start the reaction at low !
temperature,e.g., 180C, and increase the temperature ~;lowly, as the activity of the catalyst drops. The stability of the catalyst is good for more than one year.
The process according to the invention will be more fully described in a number of examples, but it should be understood that these are given by way of illustration and not of limitation.
160 g of granular activated carbon (grain size 2- -lOmm) of the brand EKT-IV, made by the firm LURGI,
2 ~:
having a surface of 1200 m /g were steeped with 14Q ml of ~;
an aqueous solution of 260 mg pd chloride and 43 g copper chloride dihydrate. After having been dried in a nltrogen current at 160C for one hour the catalyst is ready for use.
EXAMPLE 2 (Comparison test, German Ausle~sschrift 11 94 403) 335 g of aluminum oxide with a BET-surface of 190 m2/g were steeped with a solution-of 32 g of copper chlo-ride dihydrate and 150 gof potassium chloride in 450 ml water, dried, and after-treated first for 30 minutes with oxygen at 290C and then, after an intermediate rinsing with nitrogen, treated for 30 minutes with hydrogen.
EXA~lPLE 3 (Comparison Test) An activated carbon carrier as used in Example 1 was coated with 0.1% by weight of Pd in the form of its chloride.
EXAMPLE 4 (Comparison Test) An activated carbon carrier as used in Example 1, was coated with lQ~ by weight of copper as chloride. With the same conditions as in Example 1, only a low conversion 111~;~03 of tetrachloro- to trichloroethylene was achieved.
EX~PLE 5 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12-2 H20) and 385 mg of sodium hexachlororhodinate (Na3~ICl6 12 H20) in 130 ml of water. After drying for one hour at 160C, the catalyst is ready for use.
EX~PLE 6 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12~2 H20) and 366 mg of Ruthenium trichloride (RuC13 2 1~20) in 130 ml water. After drying for one hour at 160, the catalyst is ready for use.
EX~IPLE 7 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12-HzO) and 175 mg of sodiumhexachlororhodinate (Na3RhC16 12 H20) in 130 ml water. After drying for one hour at 160C, the catalyst was ready for use.
151 g of granular activated carbon as in Example 1, was steeped in a solution of 21.1 g of copper chloride and 260 mg of palladium chloride in 130 ml of water.
After drying for one hour at 160C, the catalyst is ready for use.
From the examples, the superiority of the process according to the invention with the use of the novel cata-lysts is clearly noticeable. (See the compilation in the Table below.) ~ ~ ~ ~ ¦ ~ ~ ~ 1' ~ .- ¦ ~ ~ ~ .
~3 ~.~ o~3 ~n3 ~P~ w~ ,-3 ~
Z Z o Z o o ~ o P) t~ Q ~ ~ Q ~D
~SO) Qu~ _ 1~ ,~
O ~ ~ c W 1- 1- ~ ~_ .~P I CO ~ ~ ~
~D ~.
; I I l ~
`' ~~q ~ ; ~ 3 ~
lo I 1- I ~ol oc~ o I I w~ ~OOnO I
~ :1 n ~ ~y B-I` I ~ ~ ~ol o~_l 1- 1 1 ~l IhO I ~ g~ -~ lo ~'~;
W ~ I_~ ~0 I ~ Ul O I ~W~n ina~ a~ i~ I~wl~~
_, I_ ~
K
TABLE FOOTNOTES:
. .
1. According to Example la, only 0.3 g cis-, 0.06 g trans-dichloroethylene, 0.08 g vinylidene chloride, 0.023 g ethylene, and 0.002 g ethane were formed.
2. There the work was done at 5 bar. Formed were: 1.18 g cis-, 0.38 g trans-dichloroethylene, and 0.36 g vinylidene chloride.
having a surface of 1200 m /g were steeped with 14Q ml of ~;
an aqueous solution of 260 mg pd chloride and 43 g copper chloride dihydrate. After having been dried in a nltrogen current at 160C for one hour the catalyst is ready for use.
EXAMPLE 2 (Comparison test, German Ausle~sschrift 11 94 403) 335 g of aluminum oxide with a BET-surface of 190 m2/g were steeped with a solution-of 32 g of copper chlo-ride dihydrate and 150 gof potassium chloride in 450 ml water, dried, and after-treated first for 30 minutes with oxygen at 290C and then, after an intermediate rinsing with nitrogen, treated for 30 minutes with hydrogen.
EXA~lPLE 3 (Comparison Test) An activated carbon carrier as used in Example 1 was coated with 0.1% by weight of Pd in the form of its chloride.
EXAMPLE 4 (Comparison Test) An activated carbon carrier as used in Example 1, was coated with lQ~ by weight of copper as chloride. With the same conditions as in Example 1, only a low conversion 111~;~03 of tetrachloro- to trichloroethylene was achieved.
EX~PLE 5 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12-2 H20) and 385 mg of sodium hexachlororhodinate (Na3~ICl6 12 H20) in 130 ml of water. After drying for one hour at 160C, the catalyst is ready for use.
EX~PLE 6 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12~2 H20) and 366 mg of Ruthenium trichloride (RuC13 2 1~20) in 130 ml water. After drying for one hour at 160, the catalyst is ready for use.
EX~IPLE 7 151 g of granular activated carbon as in Example 1, was steeped with a solution of 42.2 g of copper chloride (CuC12-HzO) and 175 mg of sodiumhexachlororhodinate (Na3RhC16 12 H20) in 130 ml water. After drying for one hour at 160C, the catalyst was ready for use.
151 g of granular activated carbon as in Example 1, was steeped in a solution of 21.1 g of copper chloride and 260 mg of palladium chloride in 130 ml of water.
After drying for one hour at 160C, the catalyst is ready for use.
From the examples, the superiority of the process according to the invention with the use of the novel cata-lysts is clearly noticeable. (See the compilation in the Table below.) ~ ~ ~ ~ ¦ ~ ~ ~ 1' ~ .- ¦ ~ ~ ~ .
~3 ~.~ o~3 ~n3 ~P~ w~ ,-3 ~
Z Z o Z o o ~ o P) t~ Q ~ ~ Q ~D
~SO) Qu~ _ 1~ ,~
O ~ ~ c W 1- 1- ~ ~_ .~P I CO ~ ~ ~
~D ~.
; I I l ~
`' ~~q ~ ; ~ 3 ~
lo I 1- I ~ol oc~ o I I w~ ~OOnO I
~ :1 n ~ ~y B-I` I ~ ~ ~ol o~_l 1- 1 1 ~l IhO I ~ g~ -~ lo ~'~;
W ~ I_~ ~0 I ~ Ul O I ~W~n ina~ a~ i~ I~wl~~
_, I_ ~
K
TABLE FOOTNOTES:
. .
1. According to Example la, only 0.3 g cis-, 0.06 g trans-dichloroethylene, 0.08 g vinylidene chloride, 0.023 g ethylene, and 0.002 g ethane were formed.
2. There the work was done at 5 bar. Formed were: 1.18 g cis-, 0.38 g trans-dichloroethylene, and 0.36 g vinylidene chloride.
3. As by-products 0.3 g cis-dichloroethylene, 0.15 g vinyliden~
chloride, 0.79 g ethane and 0.74gethylene were formed.
chloride, 0.79 g ethane and 0.74gethylene were formed.
4. As by-products 0.015 g vinylidene chloride, 0.17 g cis-dichloroethylene, 0.023 g trans-dichloroethylene, 1.4 mg ethy-lene, and 0.1 mg ethane.
5. There the hydrogen pressure during the operation was 10.5 bar. As by-products 0.17 g vinylidene chloride, 1.2 g cis- and 0.24 g trans-dichloroethylene were formed.
": -
": -
Claims (2)
1. A process for the preparation of trichloroethy-lene from tetrachloroethylene and hydrogen at an elevated temperature by means of a carrier catalyst containing a copper compound, wherein the tetrachloroethylene is reac-ed at 150° to 250°C and a hydrogen pressure of 1-100 bar in an amount of 0.5 to 5 mol per hour and per liter catalyst mass, the catalyst consisting of an activated car-bon carrier with over 500 m2/g BET-surfaee, 0.5 to 20%
by weight of copper in elemental state or as chemical compound, 0.01 to 1.0% by weight of a member selected from the group consisting of ruthenium, rhodium and palladium as metal or chemical compound, and up to 20%
by weight of a member of the group consisting of potas-sium, rubidium and cesium.
by weight of copper in elemental state or as chemical compound, 0.01 to 1.0% by weight of a member selected from the group consisting of ruthenium, rhodium and palladium as metal or chemical compound, and up to 20%
by weight of a member of the group consisting of potas-sium, rubidium and cesium.
2. The process according to claim 1 wherein said carrier catalyst also contains an alkali metal compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2819209.8 | 1978-05-02 | ||
| DE19782819209 DE2819209A1 (en) | 1978-05-02 | 1978-05-02 | CATALYST AND METHOD FOR PRODUCING TRICHLOROETHYLENE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119203A true CA1119203A (en) | 1982-03-02 |
Family
ID=6038497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000326608A Expired CA1119203A (en) | 1978-05-02 | 1979-04-30 | Process for preparation of trichloroethylene |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0005263B1 (en) |
| JP (1) | JPS5811408B2 (en) |
| AT (1) | AT369728B (en) |
| CA (1) | CA1119203A (en) |
| DE (2) | DE2819209A1 (en) |
| ES (1) | ES480095A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453557A (en) * | 1992-10-01 | 1995-09-26 | The Dow Chemical Company | Processes for converting chlorinated byproducts and waste products to useful materials |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6097507U (en) * | 1983-12-08 | 1985-07-03 | 株式会社資生堂 | Cosmetic container lid opening/closing device |
| US4797382A (en) * | 1987-11-27 | 1989-01-10 | Gaf Corporation | Hydrogenation catalyst and process for preparing the catalyst |
| DE3941037A1 (en) * | 1989-12-12 | 1991-06-13 | Wacker Chemie Gmbh | METHOD FOR PRODUCING TRICHLORETHYLENE |
| WO1994007817A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Process for converting 2-chloropropene to propylene |
| JP2008510831A (en) * | 2004-08-26 | 2008-04-10 | グレート・レイクス・ケミカル・コーポレイション | Compound generation method and compound generation system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2967835A (en) * | 1957-08-01 | 1961-01-10 | Gen Aniline & Film Corp | Hydrogenation catalyst |
| NL277576A (en) * | 1961-04-24 |
-
1978
- 1978-05-02 DE DE19782819209 patent/DE2819209A1/en not_active Withdrawn
-
1979
- 1979-03-15 JP JP54029442A patent/JPS5811408B2/en not_active Expired
- 1979-04-30 CA CA000326608A patent/CA1119203A/en not_active Expired
- 1979-04-30 AT AT0322779A patent/AT369728B/en not_active IP Right Cessation
- 1979-04-30 ES ES480095A patent/ES480095A1/en not_active Expired
- 1979-05-02 DE DE7979101330T patent/DE2960150D1/en not_active Expired
- 1979-05-02 EP EP79101330A patent/EP0005263B1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453557A (en) * | 1992-10-01 | 1995-09-26 | The Dow Chemical Company | Processes for converting chlorinated byproducts and waste products to useful materials |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0005263B1 (en) | 1981-02-11 |
| JPS5811408B2 (en) | 1983-03-02 |
| DE2960150D1 (en) | 1981-03-26 |
| EP0005263A2 (en) | 1979-11-14 |
| JPS54144303A (en) | 1979-11-10 |
| EP0005263A3 (en) | 1979-11-28 |
| ATA322779A (en) | 1982-06-15 |
| DE2819209A1 (en) | 1979-11-08 |
| ES480095A1 (en) | 1980-03-01 |
| AT369728B (en) | 1983-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19990302 |