DE3804265A1 - Process for the preparation of trichloroethylene - Google Patents
Process for the preparation of trichloroethyleneInfo
- Publication number
- DE3804265A1 DE3804265A1 DE19883804265 DE3804265A DE3804265A1 DE 3804265 A1 DE3804265 A1 DE 3804265A1 DE 19883804265 DE19883804265 DE 19883804265 DE 3804265 A DE3804265 A DE 3804265A DE 3804265 A1 DE3804265 A1 DE 3804265A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- weight
- organic phosphine
- perchlorethylene
- rhodium
- 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.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein neues Verfahren zur Herstellung von Trichlorethylen aus Perchlorethylen und Wasserstoff mittels eines Kupfer/Rhodium-Katalysators, der mit Phospinen bzw. Phosphiten imprägniert ist.The invention relates to a new method of manufacture of trichlorethylene from perchlorethylene and hydrogen using of a copper / rhodium catalyst with phospines or phosphites is impregnated.
In der EP-PS 5 263 wird ein Verfahren zur Herstellung von Trichlorethylen aus Perchlorethylen und Wasserstoff unter Verwendung eines Katalysators beschrieben, der aus einem Aktivkohleträger, Kupfer in elementarer oder chemisch gebundener Form und Palladium, Ruthenium oder Rhodium in elementarer oder chemisch gebundener Form besteht. Wie in dieser Publikation dargelegt, ist ein wesentlicher Punkt der katalytischen Hydrierung von Perchlorethylen zu Trichlorethylen, die Reaktion bei möglichst niederer Temperatur zu starten, um dem Aktivitätsabfall des Katalysators bei längerer Betriebsdauer durch Temperaturerhöhung gegensteuern zu können.In EP-PS 5 263 a process for the production of Trichlorethylene from perchlorethylene and hydrogen under Using a catalyst described, which consists of a Activated carbon carrier, copper in elementary or chemically bound Form and palladium, ruthenium or rhodium in elementary or chemically bound form. Like this one Publication is an essential point of catalytic Hydrogenation of perchlorethylene to trichlorethylene, start the reaction at the lowest possible temperature, the decrease in activity of the catalyst over a longer operating period to be able to counteract this by increasing the temperature.
Aufgabe der Erfindung war es daher einen Katalysator zu entwickeln, der gegenüber bekannten Systemen zur Herstellung von Trichlorethylen aus Perchlorethylen bei niedrigeren Temperaturen zu höherem Umsatz führt.The object of the invention was therefore to provide a catalyst develop compared to known systems for manufacturing of trichlorethylene from perchlorethylene at lower Temperatures lead to higher sales.
Überraschenderweise wurde das Problem durch die Verwendung von Kupfer/Rhodium-Kontakten, die mit Phosphinen bzw. Phosphiten imprägniert wurden, gelöst. Surprisingly, the problem came through using it of copper / rhodium contacts, which with phosphines or Phosphites have been impregnated.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Trichlorethylen aus Perchlorethylen und Wasserstoff mittels eines Trägerkatalysators, bestehend aus Aktivkohle mit mehr als 500 m²/g BET-Oberfläche, 0,5 bis 20 Gew.-% Kupfer in elementarer oder chemisch gebundener Form und 0,01 bis 0,5 Gew.-% Rhodium in elementarer oder chemisch gebundener Form, bei einer Temperatur von 150 bis 300°C und einem Wasserstoffdruck von 1 bis 10 bar, dadurch gekennzeichnet, daß der Katalysator mit 0,05 bis 5 Gew.-% einer organischen Phosphin- oder Phosphitverbindung imprägniert wird.The invention relates to a method for manufacturing of trichlorethylene from perchlorethylene and hydrogen using a supported catalyst consisting of activated carbon more than 500 m² / g BET surface area, 0.5 to 20% by weight copper in elementary or chemically bound form and 0.01 to 0.5 % By weight of rhodium in elemental or chemically bound form, at a temperature of 150 to 300 ° C and one Hydrogen pressure from 1 to 10 bar, characterized in that the catalyst with 0.05 to 5 wt .-% of an organic Phosphine or phosphite compound is impregnated.
Als Katalysatorträger wird Aktivkohle, vorzugsweise in gekörnter Form, mit einer BET-Oberfläche von mehr als 500 m²/g und einer Korngröße von 1 bis 5 mm eingesetzt.Activated carbon, preferably granular, is used as the catalyst support Form, with a BET surface area of more than 500 m² / g and a grain size of 1 to 5 mm.
Das Kupfer wird zu 0,5 bis 20 Gew.-%, vorzugsweise zu 5 bis 15 Gew.-%, in elementarer oder chemisch gebundener Form auf den Träger aufgetragen. Vorzugsweise werden wasserlösliche Kupfersalze eingesetzt. Besonders bevorzugt wird CuCl₂ verwendet.The copper is 0.5 to 20 wt .-%, preferably 5 to 15 wt .-%, in elemental or chemically bound form applied the carrier. Preferably water-soluble Copper salts used. CuCl₂ is particularly preferably used.
Rhodium wird zu 0,01 bis 0,5 Gew.-%, vorzugsweise zu 0,02 bis 0,2 Gew.-%, in elementarer oder chemisch gebundener Form aufgetragen. Vorzugsweise werden wasserlösliche Rhodiumverbindungen verwendet. Besonders bevorzugt sind Komplexsalze des Rh(III)-chlorids.Rhodium is 0.01 to 0.5 wt .-%, preferably 0.02 to 0.2% by weight, in elemental or chemically bound form applied. Water-soluble rhodium compounds are preferred used. Complex salts are particularly preferred of the Rh (III) chloride.
Der mit Kupfer und Rhodium belegte Katalysatorträger wird mit 0,05 bis 5,0 Gew.-%, vorzugsweise mit 0,2 bis 2,0 Gew.-%, organischer Phosphin- und/oder Phosphitverbindungen imprägniert. Vorzugsweise werden Triarylphosphine und Triarylphosphite eingesetzt. Besonders bevorzugt sind Triphenylphosphin und Triphenylphosphit. The catalyst support covered with copper and rhodium becomes with 0.05 to 5.0% by weight, preferably with 0.2 to 2.0% by weight, impregnated organic phosphine and / or phosphite compounds. Triarylphosphines and triarylphosphites are preferred used. Triphenylphosphine is particularly preferred and triphenyl phosphite.
Zur Herstellung des Katalysators wird die Aktivkohle, vorzugsweise mit wäßrigen Lösungen des Kupfer- bzw. Rhodiumsalzes, besprüht und anschließend im Stickstoffstrom getrocknet. Zur Imprägnierung kann der Kontakt mit einer Lösung des Phosphins oder Phosphits in Perchlorethylen getränkt und anschließend getrocknet werden. Andere Imprägniermethoden, z. B. Sprühimprägnierung, sind ebenfalls zulässig. Eine weitere Variante besteht darin, daß über das zur Reaktion eingesetzte Perchlorethylen die Phosphine oder Phosphite in den Reaktor eingeschleust werden.To produce the catalyst, the activated carbon is preferred with aqueous solutions of the copper or rhodium salt, sprayed and then dried in a stream of nitrogen. Contact with a solution can be used for impregnation of the phosphine or phosphite soaked in perchlorethylene and then dried. Other impregnation methods, e.g. B. Spray impregnation are also permitted. Another variant is that the perchlorethylene used for the reaction, the phosphines or Phosphites are introduced into the reactor.
Zur Umsetzung des Perchlorethylens wird der Katalysator in geschütteter Form in ein Reaktionsrohr gebracht. Die Reaktion wird bei einer Temperatur von 150 bis 300°C und unter einem Druck von 1 bis 10 bar durchgeführt. Das Perchlorethylen wird in Mengen von 0,5 bis 5 Mol pro Stunde und pro Liter an Kontaktmasse zusammen mit der 0,1- bis 1 fachen molaren Menge an Wasserstoff zur Reaktion gebracht.To convert the perchlorethylene, the catalyst is in poured into a reaction tube. The Reaction is carried out at a temperature of 150 to 300 ° C and carried out under a pressure of 1 to 10 bar. The Perchlorethylene is used in amounts of 0.5 to 5 moles per hour and per liter of contact mass together with the 0.1 to 1 times the molar amount of hydrogen reacted.
Gekörnte Aktivkohle der Bezeichnung Degusorb WS IV Spezial, Fa. Degussa, wird mit einer wäßrigen CuCl₂-Lösung und einer wäßrigen Na₃RhCl₆-Lösung getränkt und getrocknet, so daß der Rh-Gehalt bei 0,044 Gew.-% und der Cu-Gehalt bei 10 Gew.-% liegt. Der getrocknete Katalysator wird mit in Perchlorethylen gelöstem Triphenylphosphin angeteigt, anschließend das Lösungsmittel verdampft. Die Mengen wurden so gewählt, daß 1 Gew.-% Triphenylphosphin, bezogen auf Aktivkohle, vorliegt. Die Trichlorethylenherstellung wird in einem Einrohrreaktor mit einem Katalysatorvolumen von 400 ml durchgeführt. Der Reaktor wird mit 48 g/h Perchlorethylen und 10 l/h Wasserstoff belastet. Der Reaktionsdruck beträgt 1 barabs. Die Umsatzraten zu Trichlorethylen in Abhängigkeit von der Reaktionstemperatur sind in Tabelle 1 aufgeführt.Grained activated carbon of the name Degusorb WS IV Spezial, from Degussa, is soaked with an aqueous CuCl₂ solution and an aqueous Na₃RhCl₆ solution and dried so that the Rh content is 0.044% by weight and the Cu content is 10% .-% lies. The dried catalyst is pasted with triphenylphosphine dissolved in perchlorethylene, then the solvent is evaporated. The amounts were chosen so that 1 wt .-% triphenylphosphine, based on activated carbon, is present. The trichlorethylene production is carried out in a single-tube reactor with a catalyst volume of 400 ml. The reactor is charged with 48 g / h perchlorethylene and 10 l / h hydrogen. The reaction pressure is 1 bar abs . The conversion rates to trichlorethylene depending on the reaction temperature are listed in Table 1.
Analog Beispiel 1, anstelle von Triphenylphosphin wird der Katalysator mit Triphenylphosphit imprägniert.Analogous to Example 1, instead of triphenylphosphine Impregnated catalyst with triphenyl phosphite.
Analog Beispiel 1, jedoch ohne Phosphin- oder Phosphitzusatz.Analogous to Example 1, but without the addition of phosphine or phosphite.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19883804265 DE3804265A1 (en) | 1988-02-11 | 1988-02-11 | Process for the preparation of trichloroethylene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19883804265 DE3804265A1 (en) | 1988-02-11 | 1988-02-11 | Process for the preparation of trichloroethylene |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3804265A1 true DE3804265A1 (en) | 1989-08-24 |
Family
ID=6347206
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19883804265 Withdrawn DE3804265A1 (en) | 1988-02-11 | 1988-02-11 | Process for the preparation of trichloroethylene |
Country Status (1)
Country | Link |
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DE (1) | DE3804265A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0432636A1 (en) * | 1989-12-12 | 1991-06-19 | Wacker-Chemie Gmbh | Process for preparing trichloroethylene |
EP0496446A1 (en) * | 1991-01-25 | 1992-07-29 | SOLVAY (Société Anonyme) | Process for the preparation of chlorotrifluoroethylene and of trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalytic composition used in this process |
WO1994007825A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Processes for converting chlorinated alkene byproducts or waste products to useful, less chlorinated alkanes |
US5453557A (en) * | 1992-10-01 | 1995-09-26 | The Dow Chemical Company | Processes for converting chlorinated byproducts and waste products to useful materials |
EP0679438A1 (en) * | 1994-04-28 | 1995-11-02 | Wacker-Chemie GmbH | Catalyst for the preparation of 1-chloro-3-methyl-2-butene |
US5613783A (en) * | 1995-03-27 | 1997-03-25 | International Business Machines Corporation | Point of sale printer with magnetic reader |
-
1988
- 1988-02-11 DE DE19883804265 patent/DE3804265A1/en not_active Withdrawn
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE34761E (en) * | 1989-12-12 | 1994-10-18 | Wacker-Chemie Gmbh | Process for the preparation of trichloroethylene |
US5091603A (en) * | 1989-12-12 | 1992-02-25 | Wacker-Chemie Gmbh | Process for the preparation of trichloroethylene |
EP0432636A1 (en) * | 1989-12-12 | 1991-06-19 | Wacker-Chemie Gmbh | Process for preparing trichloroethylene |
EP0496446A1 (en) * | 1991-01-25 | 1992-07-29 | SOLVAY (Société Anonyme) | Process for the preparation of chlorotrifluoroethylene and of trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalytic composition used in this process |
WO1994007825A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Processes for converting chlorinated alkene byproducts or waste products to useful, less chlorinated alkanes |
WO1994007828A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Processes for converting chlorinated byproducts and waste products to useful materials |
WO1994007817A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Process for converting 2-chloropropene to propylene |
WO1994007824A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Process for converting perchloroethylene to trichloroethylene |
WO1994007816A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Process for converting 1,3-dichloropropene to propylene |
WO1994007826A1 (en) * | 1992-10-01 | 1994-04-14 | The Dow Chemical Company | Processes for converting chlorinated alkenes to corresponding useful, less chlorinated alkenes |
US5453557A (en) * | 1992-10-01 | 1995-09-26 | The Dow Chemical Company | Processes for converting chlorinated byproducts and waste products to useful materials |
EP0679438A1 (en) * | 1994-04-28 | 1995-11-02 | Wacker-Chemie GmbH | Catalyst for the preparation of 1-chloro-3-methyl-2-butene |
US5613783A (en) * | 1995-03-27 | 1997-03-25 | International Business Machines Corporation | Point of sale printer with magnetic reader |
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Legal Events
Date | Code | Title | Description |
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8141 | Disposal/no request for examination |