US2538723A - Process for producing perchlorethylene - Google Patents

Process for producing perchlorethylene Download PDF

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Publication number
US2538723A
US2538723A US764050A US76405047A US2538723A US 2538723 A US2538723 A US 2538723A US 764050 A US764050 A US 764050A US 76405047 A US76405047 A US 76405047A US 2538723 A US2538723 A US 2538723A
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perchlorethylene
combustion
gases
flame
acetylene
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US764050A
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Fruhwirth Otto
Walla Heinrich
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Donau Chemie AG
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Donau Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens

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  • This invention relates to an improved process for the production of perchlorethylene
  • Perchlorethylene has been produced till nowv so far as made from acetylene, according to complicated technical processes.
  • Acetylene has been an inert gas such as gaseous hydrochloric acid.
  • perchlorethylene can also be obtained with a very good yield by burning acetylene and chlorine in one working step.
  • the process according to our invention consists in burning an intimate mixture of about one part by volume of acetylene and 3 to 3.5 parts by volume of chlorine, in the form of a flame.
  • the combustion chamber in which this flame is produced may be, as shown in the accompanying drawing, a vertical cylindrical, tubular chamber, having a diameter substantially larger than the diameter of the flame, and the gas mixture may be introduced in an upward direction through piping located at the bottom of said combustion chamber.
  • the temperature in the reaction zone should rise slowly, measured from the entrance of the gaseous mixture into said reaction'zone, up to the point where the flame itself begins.
  • the regulation of the rise of temperature in the reaction zone can be effected by different measures. It is essential, above all, that the speed of the gaseous mixture, when leaving the nozzle in order to enter the combustion space, he as great as possible. Preferably, it must be blown in at a speed above 20 m./sec. in order to avoid the formation of by-products.
  • the reaction zone flame
  • the reaction zone is necessarily extended so that there is a relatively slow rise of temperature between the point of arrival of the gas mixture into the reaction zone and the extreme end of the flame.
  • Another means in order to retard the rise of temperature is to avoid a reflection of heat from the wall of the combustion space into the flame, especially into the first part of the reaction zone.
  • the walls of the combustion room may be cooled throughout their whole length or locally, but the cooling must be regulated so that there is no separation of intermediate products of a lower degree of chlorination upon the interior wall. Care is also to be taken that the distance between the wall of the combustion chamber and the flame islarge enough in order to maintain the latter stable. If this distance is large enough, it is not necessary to cool the wall.
  • the first part of the reaction zone can be cooled for instance by evaporating inert liquids, especially by pulverizing (e. g. atomizing) liquid reaction products, such as perchlorethylene.
  • pulverizing e. g. atomizing liquid reaction products
  • the pulverization is preferably effected by means of the gaseous mixture coming out of the nozzle.
  • Cooling may be effected by any suitable technical means.
  • the reaction gases may be conducted into a gas cooler. It has proved to be of special advantage to bring the reaction gases into contact with water.
  • the hydrochloric acid formed by the combustion is thereby absorbed and the chlorinated hydrocarbons are simultaneously condensed.
  • Perchlorethylene which is insoluble in water, separates as a layer.
  • perchlorethylene can be produced in a continuous manner with a, yield up to -85%. Furthermore, in conhexachlorethane/tetrachlormethane, at the corresponding combustion temperature about 2% of hexachlorethane and 7-9% of tetrachlormethane are formed by further chlorination. Owing to the special measures described, the decomposition and the polymerization of acetylene is avoided, whereas the formation of hexachlorbutadiene and hexachlorbenzene, which generally takes place at the same time, is retarded to a large extent.
  • the gas mixture which is burned' contains other substances besides acetylene and chlorine which .account, so that always enough acetylene and chlorine are present for the formation of perchlorethylene.
  • the concentration of these two gases in the mixture to be burned must be high enough to furnish enough heat so that the reaction will go on as a combustion.
  • acetylene or chlorine must be added (if an insufilcient amount of one is present) to the mixture prior to the combustion.
  • perchlorethylene For a good yield of perchlorethylene, it is essential that gas mixtures are used which contain acetylene and chlorine in the proportion by volume of about 1:13-1:35. It more chlorine is used, the proportion of perchlorethylene in the final product decreases slowly and more hexachlorethane is formed. If less than 3 volumes of chlorine are used per one volume of acetylene, the yield of perchlorethylene diminishes and more hexachlorbutadiene is formed.
  • our new process is distinguished by the simplicity of the method and of the apparatus to be used, by the fact that large amounts of the starting components may be reacted with each other per unit of time as well as by the possibility to use technical gas mixtures as starting components without any inconvenience.
  • Example 1 This mixture becomes sured in the liquid state) by the current of the gas mixture. In order to avoid a further chlorination of the perchlorethylene formed by the combustion, the combustion gases are cooled immediately after complete combustion. Then, the
  • the reaction product consists essentially of perchlorethylene. It may be purified in the usual manner.
  • Example 2 Through a gas-mixing nozzle are blown with a, speed of m'./sec. on the one hand 8 mfi/h. of a mixture of waste gases containing 50% of acetylene, 30% of nitrogen, 10% of carbon dioxide and 10% of hydrogen, on the other hand 14 mfi/h. of chlorine, into a combustion pipe of 30 centimeters diameter and of 3 meters length, the outer walls of which are cooled with water. The mixture is inflamed. The combustion pipe leads into a gas refrigerator, in which the gasesscoming out are cooled to room temperature. The greatest part of the perchlorethylene is condensed thereby, whereas the rest is separated (condensed), during the following absorption of the hydrochloric acid.
  • Example 3 An intimate gaseous mixture of 4 mfi/h. oi
  • the separation of the main product and the byproducts, respectively, may be carried out in accordance with the invention in different ways.
  • solid bodies maintained at temperatures approximately between and 80 C. may be provided within the chamber containing the combustion gases.
  • a fluid of the above mentioned These temperatures, which does not mix and does not react with them for example sulphuric acid or phosphoric acid.
  • the combustion gases may be washed for instance with a fluid miscible with the condensate, which preferably is a product of the combustion itself.
  • a fluid miscible with the condensate which preferably is a product of the combustion itself.
  • the gases are necessarily cooled by evaporation of a part of theaddediiquid perchlorethylene to approximately 120 C.
  • the high boiling components especially hexachlorbutadiene and hexachlorbenzene, are dissolved by the part, of perchlorethylene which is not evaporated and suitably is circulating, or are enriched in it, but are precipitated after the cooling of the perchlorethylene nearly completely in coarse crystalline form and may be isolated in pure state.
  • the separation of the main product of the reaction. (perchlorethylene) as a. fraction boiling between 120-80? C. is for example attained by bringing the remaining gases into contact with solid bodies, or better with a fluid, not miscible and not reacting with the condensate, which bodies or fluids are kept at temperatures of about 78-80 C.
  • the still remaining part of the gases is either cooled to room temperature, the components boiling below 80 0., especially carbon tetrachloride, being separated thereby or by irrigating the gases with cold water, the hydrochloric acid being absorbed thereby and simultaneously the reaction products boiling below 80 C. being condensed.
  • acetylene and chlorine respectively, in a proportion corresponding substantially to the ratio of about one part of volume of acetylene to about 3 to 3.5 parts by volume of chlorine are introduced into a mixing pipe I. After thorough mixing the gaseous mixture is discharged through a combustion nozzle 5 provided in the head of a burner 4 and ignited and burned.
  • the outside wall of the combustion chamber 6 is cooled with water supplied through a, perforated ring I and flowing oil from the collector 8. At times, some liquid may condense on the inside of 6, and may flow downwardly and out through 9a.
  • the head of the burner l is cooled e. g. by means of the cooling Jacket 9 situated around it.
  • the combustion gases pass from the combustion chamber to the column 10 containing Raschig rings which are irrigated with perchlorethylene introduced by a sprayer II. A part of the perchlorethylene introduced evaporates when meeting the hot combustion gases, another part flows 03 from the column I0 through a pipe l4 located v below the perforated plate l2.
  • the perchlorethylene not vaporized in H] is led in a liquid form, from the bottom of the perforated hood l3 and leaves the bottom of ill by a pipe line It.
  • the high boiling components carried along with it are separated (solidlfled) by cooling (say with cold water) in II and are retained in solid state by a filter it. They consist essentially of hexachlorbutadiene and hexachlorbenzene.
  • the perchlorethylene flowing out of the filter i6 is returned by a pump l'l through a reservoir l8 to the sprayer ii and again used for washing and cooling the combustion.gas.es-.
  • The'separation of the perchlorethylene out of gases and vapors leaving the column 10 by a pipe line I9 may be effected in a similar way by circulating sulphuric acid in contact with the gases and vapors.
  • the gases and vapors from i9 enter a column 20, filled with Raschig rings, through which warm sulphuric acid of Vii- C. trickles down from a sprayer 2
  • the perchlorethylene is condensed and flows with the sulphuric acid out through a perforated plate 22 into a separator 23.
  • the perchlorethylene flows off through an overflow 20 to storage, while the sulphuric acid in the bottom of the separator 23 flows of! by the pipe 25 and is returned to the sprayer 2
  • the condensation of the components boiling below 78-80" C. (C014 and HCl etc. is effected by introducing the gases leaving the column 20 by a pipe line 29 into an absorber 30, irrigated with cold water.
  • the hydrochloric acid is absorbed in this water, and the carbon tetrachloride vapor is condensed in this absorber.
  • the watery hydrochloric acid is allowed to flow off by the pipe line 3
  • a process of producing perchlorethylene which comprises burning an intimate mixture of acetylene and chlorine in the proportion by volume of about 1:3 to 1:35, in the form of a flame in which flame the temperature at the cooler end is about 600 C., and the temperature at the hottest part of the flame, l. e. at its end, is about 750 C. to about 950 C.
  • a process of producing perchlorethylene which comprises burning an intimate mixture of acetylene and chlorine in the proportions of about 1:3 and 1:35, in the form of a-flame the temperature of which flame, at its beginning is about 600 C. and the temperature of which flame increases to between about 750 C. and about 950 C., and in which process the mixture of acetylene and chlorine is blown into the combustion zone at a speed of more than 20 meters per second.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US764050A 1940-08-07 1947-07-28 Process for producing perchlorethylene Expired - Lifetime US2538723A (en)

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DED83082D DE734024C (de) 1940-08-07 1940-08-07 Verfahren zur Herstellung von Perchloraethylen

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734926A (en) * 1956-02-14 Agitation of hflloqenffteo liquid
US2843638A (en) * 1954-11-15 1958-07-15 Columbia Southern Chem Corp Dehydrochlorination of tetrachloroethane
US2858347A (en) * 1954-08-26 1958-10-28 Pure Oil Co Process for manufacturing aliphatic chlorides
US2895999A (en) * 1955-12-01 1959-07-21 Allied Chem Production of carbon tetrafluoride
US2919296A (en) * 1956-04-17 1959-12-29 Electro Chimie Metal Method of obtaining tetrachlorethylene and tetrachloride of carbon
US2938931A (en) * 1957-02-19 1960-05-31 Electro Chimie Metal Manufacture of tri-and tetrachlorethylene
US2960543A (en) * 1953-09-28 1960-11-15 Wyandotte Chemicals Corp Total chlorination of c4 and higher aliphatic hydrocarbons
US3065279A (en) * 1960-08-24 1962-11-20 Pittsburgh Plate Giass Company Resolution of trichloroethylene from reaction products

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE868294C (de) * 1950-09-22 1953-02-23 Chloberag Chlor Betr Rheinfeld Verfahren und Vorrichtung zur direkten Herstellung von Perchloraethylen aus Acetylen und Chlor
BE552063A (de) * 1955-10-31
BE564260A (de) * 1957-02-19
DE1275040C2 (de) * 1957-07-04 1979-12-13 Stauffer Chemical Company, San Francisco, Calif. (V.StA.) Verfahren zur herstellung von mischungen aus tetrachlormethan und perchloraethylen

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US730703A (en) * 1902-01-27 1903-06-09 Alexander Sydney Ramage Process of producing lactose from whey.
FR358146A (fr) * 1905-04-28 1906-01-29 Alby Carbidfabriks Aktiebolag Procédé de production de composés ou combinaisons entre l'acétylène et le chlore, et produits ainsi obtenus
US1418882A (en) * 1922-02-03 1922-06-06 Firm Method for the chlorination of acetylene
US1516350A (en) * 1922-09-01 1924-11-18 Firm Of Holzverkohlungs Ind Ak Method of chlorinating acetylene
US1895086A (en) * 1927-04-27 1933-01-24 Continental Oil Co Apparatus for the manufacture of benzol and valuable by-products from a gas containing either butane, propane, or ethane, or portions of each
US2140551A (en) * 1938-02-11 1938-12-20 Dow Chemical Co Chlorination of acetylene
US2160574A (en) * 1937-05-10 1939-05-30 Ig Farbenindustrie Ag Manufacture of carbon tetrachloride
US2178622A (en) * 1937-02-22 1939-11-07 Wacker Chemie Gmbh Process for producing tetrachlorethylene
US2255752A (en) * 1937-06-19 1941-09-16 Wacker Chemie Gmbh Process for producing tetrachlorethylene
CH224640A (de) * 1940-08-06 1942-12-15 Donau Chemie Ag Verfahren zur Herstellung von Perchloräthylen.
US2442324A (en) * 1945-01-22 1948-05-25 Dow Chemical Co Process of making carbon tetrachloride and perchlorethylene

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US730703A (en) * 1902-01-27 1903-06-09 Alexander Sydney Ramage Process of producing lactose from whey.
FR358146A (fr) * 1905-04-28 1906-01-29 Alby Carbidfabriks Aktiebolag Procédé de production de composés ou combinaisons entre l'acétylène et le chlore, et produits ainsi obtenus
US1418882A (en) * 1922-02-03 1922-06-06 Firm Method for the chlorination of acetylene
US1516350A (en) * 1922-09-01 1924-11-18 Firm Of Holzverkohlungs Ind Ak Method of chlorinating acetylene
US1895086A (en) * 1927-04-27 1933-01-24 Continental Oil Co Apparatus for the manufacture of benzol and valuable by-products from a gas containing either butane, propane, or ethane, or portions of each
US2178622A (en) * 1937-02-22 1939-11-07 Wacker Chemie Gmbh Process for producing tetrachlorethylene
US2160574A (en) * 1937-05-10 1939-05-30 Ig Farbenindustrie Ag Manufacture of carbon tetrachloride
US2255752A (en) * 1937-06-19 1941-09-16 Wacker Chemie Gmbh Process for producing tetrachlorethylene
US2140551A (en) * 1938-02-11 1938-12-20 Dow Chemical Co Chlorination of acetylene
CH224640A (de) * 1940-08-06 1942-12-15 Donau Chemie Ag Verfahren zur Herstellung von Perchloräthylen.
US2442324A (en) * 1945-01-22 1948-05-25 Dow Chemical Co Process of making carbon tetrachloride and perchlorethylene

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734926A (en) * 1956-02-14 Agitation of hflloqenffteo liquid
US2960543A (en) * 1953-09-28 1960-11-15 Wyandotte Chemicals Corp Total chlorination of c4 and higher aliphatic hydrocarbons
US2858347A (en) * 1954-08-26 1958-10-28 Pure Oil Co Process for manufacturing aliphatic chlorides
US2843638A (en) * 1954-11-15 1958-07-15 Columbia Southern Chem Corp Dehydrochlorination of tetrachloroethane
US2895999A (en) * 1955-12-01 1959-07-21 Allied Chem Production of carbon tetrafluoride
US2919296A (en) * 1956-04-17 1959-12-29 Electro Chimie Metal Method of obtaining tetrachlorethylene and tetrachloride of carbon
US2938931A (en) * 1957-02-19 1960-05-31 Electro Chimie Metal Manufacture of tri-and tetrachlorethylene
US3065279A (en) * 1960-08-24 1962-11-20 Pittsburgh Plate Giass Company Resolution of trichloroethylene from reaction products

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