US2569923A - Halogenated unsaturated hydrocarbon production - Google Patents

Halogenated unsaturated hydrocarbon production Download PDF

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Publication number
US2569923A
US2569923A US764551A US76455147A US2569923A US 2569923 A US2569923 A US 2569923A US 764551 A US764551 A US 764551A US 76455147 A US76455147 A US 76455147A US 2569923 A US2569923 A US 2569923A
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porous
reaction zone
vinyl chloride
packing material
reaction
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US764551A
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Harry A Cheney
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Shell Development Co
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Shell Development Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • This invention relates to the production of halogenated unsaturated hydrocarbons.
  • the invention relates more particularly to an improved process for the more eflicient pyrolytic dehydrochlorination of alkyl chlorides to chlorinated unsaturated hydrocarbons. Still more particularly the invention relates to an improved process for the more efiicient pyrolysis of ethylene dichloride to vinyl chloride.
  • porous packing material such as, for example, clays, pumice, chamotte. charcoal, carbon, etc. may be resorted to aid in controlling the heat input into the reaction zone.
  • the use 2 of such porous materials it has been found, however, entails distinct disadvantages militating against efiicient large scale operation of the process.
  • the use of such porous packing material although facilitating the control of the reaction temperature within the reaction zone, not only does not obviate the formation and deposition of carbonaceous deposits but generally materially aggravates these difliculties thereby increasing the rate at which fouling and clogging of the tubes is encountered.
  • the carbonaceous deposit formed upon the porous packing material generally may be removed therefrom by the passage therethrough of oxygen-containing gases at relatively high temperatures, the frequency of the regenerative operation necessitated by the relatively rapid fouling of the porous packing materially increases to an inordinate degree the cost of the process.
  • the considerable amount of carbonaceousdeposit encountered when using a porous packing medium generally precludes the use of regeneration gases containing substantial amounts of oxygen. Not only is each regeneration period thereby considerably prolonged but readily available oxygen-containing gases, such as air can therefore not be employed. Because of the presence of hydrogen halide in the system, the restort to the use of steam to aid in efifecting the regeneration of the porous packing material can generally not be desorted to.
  • a particular disadvantage of processes employing porous packing material in the reaction zone resides in the fact that the inherent difficulties, such as formation of carbonaceous deposit, product, contamination, reduction in yields, etc. become progressively more severe after each regeneration of the packing material.
  • the rate of formation of carbonaceous deposits and consequent fouling of the reactor was such as to necessitate regeneration of the packing material after each twenty-four hours of operation.
  • the crude vinyl chloride obtained contained only 89% vinyl chloride and the following Since the suitability of the vinyl chloride product as a starting or intermediate material in many processes is often dependent upon a relatively high degree of purity, its production in processes utilizing porous packing material in the reaction zone would of necessity entail the discarding of the packing material after an operation of only relatively short duration, or the resort to additional complex and costly purifying steps.
  • an alkyl halide is passed in the vapor phase, at pyrolytic dehydrohalogenating conditions, through an externally heated reaction zone containing a non-porous packing material, thereby convertin the alkyl halide to reaction products consisting essentially of ahalogenated unsaturated hydrocarbon and hydrogen halide in the absence of any substantial formation of by-products and of any substantial deposition of carbonaceous material within the reaction zone.
  • Suitable non-porous packing materials employed in the process of the invention comprise any of the available non-porous or smooth-surfaced, thermally stable packing materials which are inert under the conditions of execution of the reaction.
  • the non-porous packing material employed may be of natural or synthetic origin.
  • non-porous packing materials substantially devoid of micropores are the non-metallic, smooth-surfaced or non-porous, naturally occurring stony materials as, for example, gravel, pebbles, crushed rock, granite, and the like; manufactued smooth-surfaced, or non-porous, materials such as granules, particles, fragments, chunks, pieces, or the like of ceramic material, glass, porcelain, etc.; examples of such manufactured non-porous packing materials are Raschig rings, porcelain tubes, porcelain saddles, porcelain disks, glass marbles, rock wool; glass wool, glass beads, and the like.
  • a particularly desirable and preferred non-porous packing material comprises pebbles, or gravel.
  • non-porous packing mate rial may vary widely within the scope of the invention.
  • a particularly suitable noneporous packing material for use in reaction zones of restricted cross-sectional areas are pebbles, or gravel, having a particle size of from about 1 to about 3 cm.
  • the process of the invention is applied broadly to the pyrolytic dehydrohalogenation of alkyl halides containing at least two halogen atoms in the molecule to a corresponding halogenated unsaturated hydrocarbon.
  • the halogen substituent of the alkyl halide charged may consist, for example, of chlorine, bromine or iodide.
  • the process of the invention lends itself with advantage to the treatment of the diand tri-halosubstituted hydrocarbons.
  • alkyl halides pyrolytically dehydrohalogenated in accordance with the process of the invention are 1,1-dichloroethane, 1,2-dichloroethane, trichloroethanes, dichloropropanes, trichloropropanes, dichlorobutanes, trichlorobutanes, dibromoethanes, dibromopropanes, tribromopropanes, dibromobutanes, tribromobutanes, and higher boiling saturated alkyl chlorides and bromides having at least two halogen atoms in the molecule.
  • the charge to the system need not necessarily consist of a single alkyl halide but may comprise two or more alkyl halides.
  • Gaseous materials, inert under the conditions of execution of the reaction such as, for example, nitrogen, may be introduced into the system together with the charge or may be introduced in part or entirety into the reaction zone at a plurality of spaced points along the length thereof.
  • the reaction zone may comprise a reaction chamber or a tubular reactor, or a plurality of such chambers or tubular reactors arranged in series or in parallel with one another, provided with means for maintaining the dehydrohalogenating conditions of temperature therein and for containing the non-porous packing.
  • a particularly preferred type of reactor comprises an externally heated reaction zone of restricted cross-sectional area such as, for example, reaction tubes or coils positioned in a suitable furnace structure.
  • Other suitable types of reactors comprise furnace-type structures containing one or more beds of non-porous packing material, means for the passage of the alkyl halide charge through said bed or beds, and means for maintaining said beds at pyrolytic dehydrohalogenating temperatures.
  • the alkyl halide charge to the system such as. for example, ethylene dichloride is passed into the reaction zone through an inlet positioned at one end thereof, or may be introduced in part through such inlet and the remainder through a plurality of inlets spaced along the length of said reaction zone.
  • the reaction zone is maintained at a sufliciently high temperature to eiiect the dehydrohalogenation of the alkyl halide charged with the formation of reaction products consisting essentially of the corresponding halogenated unsaturated hydrocarbon and halogen halide.
  • the reaction zone is maintained at a temperature of from about 425 C. to about 675 0., and preferably from about 475 C.
  • Subatmospheric, atmospheric, or superatmospheric pressures may be maintained within the reaction zone. Suitable pressures comprise the pressures in the range oi! from substantially about 1 to about 10 atmospheres. Higher or lower pressures may, however, be employed within the scope of the invention.
  • Eiiluence from the reaction zone comprising unsaturated alkyl halide, hydrogen halide and unconverted alkyl halide is passed to suitable separating means to effect the separation of unsaturated alkyl halide therein.
  • Unconverted 'alkyl halide separated from the reaction products is preferably recycled to the reaction zone, optionally aiter separating therefrom any higher boiling reaction products which may have been formed in the process.
  • any carbon or carbonaceous products deposited upon the non-porous support after a prolonged period of operation are readily removed therefrom by the passage of an oxygen containing 8 ment and clogging of the apparatus, but often makes possible the attainment of these advantages together with a substantial increase in the yield of the desired halogenated unsaturated hydrocarbon.
  • a further significant advantage inherent in the use of non-porous packing material resides in the ability to eifect the removal of the lesser amount of carbonaceous deposits eiiiciently and in exceedingly short time in situ with gaseous media having a relatively high oxygen content, thereb enabling resort to the economically advantageous expedient of utilizing air as the regenerating medium.
  • the non-porous packing material possesses the still further advantage of being able to be regenerated, even after relatively long periods of operation, without sufiering the adverse eiiects peculiar to porous materials which upon regeneration progressively increase the initial difllculties at an inordinately rapid rate.
  • the substantial improvement obtained in the production of vinyl chloride by the pyrolytic dehydrochlorination of ethylene dichloride in accordance with the process of the invention utilizing a reaction zone packed with non-porous packing material as compared with processes employing reactors containing no packing, or containing packing of a porous character. is evidenced by the following examples:
  • EXAMPLE I In twelve separate operations ethylene dichloride was dehydrohalogenated to vinyl chloride and hydrogen chloride by passage through an externally heated, stainless steel, tubular reactor at a pressure of 100 lbs. The charge was passed through the reactor at the rate of 621 lbs. of ethylene dichloride per hour in all of the operations except in runs 2 and 3 wherein the throughput rate was reduced to 42 lbs. and 2'! lbs., respectively, in an eifort to increase the conversion.
  • the packing employed in the reactor, reaction temperature, total ethylene dichloride conversion. duration of the run, and the reason for stopping the run are indicated in the following gas such as, for example, air, flue gas, etc. there- 45 table for each individual operation.
  • reaction zone temperature of for example, from about 500 C. to about 700 C.
  • the tubular reactor was packed with a porous fire clay of 10 to 15mm. grain size. After each run the packing was regenerated by passage therethrough of an oxygen-containing stream at a temperature of about 500 C. and at the rate of 3000 liters of oxygen containing gas per hour. The thus regenerated packing was then employed in the subsequent run.
  • the yield of vinyl chloride obtained in mole per cent of the theoretical yield and the length of operation for each run are indicated in column A of the following Table III.
  • Ethylene dichloride was dehydrochlorinated in a separate series of operation under substantially identical conditions with the exception that the tubular reactor was packed with porous gravel of 15 to 2 mm. particle size. The yield of vinyl chloride obtained in mole per cent of theoretical The signal advantages of the process of the ample: EXAMPLE III In a plurality of separate operations ethylene dichloride was dehydrochlorinated to vinyl chloride and hydrogen chloride by passage through an externally heated tubular reactor at a presyield and the duration of the operation for each A particular advantage of the invention attributable to the use of non-porous packing material is the elimination of the need for the use of reactors constructed of relatively costly alloy materials.
  • the process may be executed in iron or ferrous metal reactors without substantial contamination of the crude vinyl chloride product, even after repeated regenerations of the packing material. This is attributable, as indicated above, to the absence for the need of steam to temper the regeneration and the absence of any excessive temperature rise during regenerations due to the low rate of carbon deposition, which obviate to at least a substantial degree the corrosion of reactor walls and the deposition upon the packing of metal compounds conducive to product contamination.
  • the crude vinyl chloride product obtained in run 1A of Example III after only 24 hours of operation with a fresh porous packing contained 97.1% by weight of vinyl chloride
  • the crude vinyl chloride product obtained from run 10 employing the non-porous packing material used for 108 hours of total operation and which had been subjected to two regeneration operations still contained 98.4% vinyl chloride.
  • the process for the chloride which comprises production of vinyl passing 1,1-dich1oro- 10 ethane in the vapor phase at a temperature of from about 425 C. to about 675 C. through a bed of inert gravel consisting of smooth surfaced rounded fragments of rock positioned in a reaction zone of restricted cross-sectional area.
  • the process for the production of vinyl chloride which comprises passing dichloroethane in the vapor phase at a temperature of from about 425 C. to about 675 C. through a bed of inert gravel consisting of smooth surfaced rounded fragments of rock positioned in a'reaction zone of restricted cross-sectional area.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US764551A 1946-12-17 1947-07-29 Halogenated unsaturated hydrocarbon production Expired - Lifetime US2569923A (en)

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GB (1) GB633211A (en(2012))
NL (1) NL68138C (en(2012))

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2681372A (en) * 1951-01-16 1954-06-15 Ethyl Corp Manufacture of ethyl chloride and vinyl chloride
US2724006A (en) * 1950-12-27 1955-11-15 Hoechst Ag Process of preparing vinyl chloride
US2803677A (en) * 1954-06-28 1957-08-20 Ethyl Corp Dehydrochlorination of 1, 1,-dichlkoroethane and 1, 1, 1-trichloroethane
US2838577A (en) * 1955-01-03 1958-06-10 Ethyl Corp Process of making ethyl chloride and vinyl chloride
US2896000A (en) * 1955-05-09 1959-07-21 Nat Distillers Chem Corp Process for the manufacture of vinyl chloride
US3476955A (en) * 1965-09-11 1969-11-04 Knapsack Ag Process for the manufacture of vinyl chloride from contaminated 1,2-dichloroethane
US3896182A (en) * 1971-07-06 1975-07-22 Bp Chem Int Ltd Process for preparing vinyl chloride by the pyrolysis of 1,2-dichloro-ethane
EP0000847A1 (en) * 1977-08-16 1979-02-21 BP Chemicals Limited Vinyl chloride monomer production
US4665243A (en) * 1982-12-08 1987-05-12 Stauffer Chemical Company Process for preparing vinyl chloride monomer
HRP930942A2 (en) * 1993-05-31 1995-02-28 Inos D O O Process for the production of vinyl chloride
CN110405949A (zh) * 2019-08-05 2019-11-05 恩欣格工程塑料（上海）有限公司 一种使用化学试剂对有机玻璃制品进行表面抛光的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290399A (en) * 1961-05-05 1966-12-06 Belge Produits Chimiques Sa Process for preparing vinyl chloride

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1986876A (en) * 1930-09-19 1935-01-08 Ici Ltd Production of unsaturated compounds
GB501071A (en) * 1937-09-01 1939-02-21 Ig Farbenindustrie Ag Improvements in the manufacture of butadiene
US2183036A (en) * 1936-12-24 1939-12-12 Dow Chemical Co Process of forming an aldehyde and an olefin monohalide
US2310523A (en) * 1938-12-19 1943-02-09 Shell Dev Process for the production of diolefins
US2474206A (en) * 1943-10-05 1949-06-28 Shell Dev Production of vinyl chloride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1986876A (en) * 1930-09-19 1935-01-08 Ici Ltd Production of unsaturated compounds
US2183036A (en) * 1936-12-24 1939-12-12 Dow Chemical Co Process of forming an aldehyde and an olefin monohalide
GB501071A (en) * 1937-09-01 1939-02-21 Ig Farbenindustrie Ag Improvements in the manufacture of butadiene
US2310523A (en) * 1938-12-19 1943-02-09 Shell Dev Process for the production of diolefins
US2474206A (en) * 1943-10-05 1949-06-28 Shell Dev Production of vinyl chloride

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2724006A (en) * 1950-12-27 1955-11-15 Hoechst Ag Process of preparing vinyl chloride
US2681372A (en) * 1951-01-16 1954-06-15 Ethyl Corp Manufacture of ethyl chloride and vinyl chloride
US2803677A (en) * 1954-06-28 1957-08-20 Ethyl Corp Dehydrochlorination of 1, 1,-dichlkoroethane and 1, 1, 1-trichloroethane
US2838577A (en) * 1955-01-03 1958-06-10 Ethyl Corp Process of making ethyl chloride and vinyl chloride
US2896000A (en) * 1955-05-09 1959-07-21 Nat Distillers Chem Corp Process for the manufacture of vinyl chloride
US3476955A (en) * 1965-09-11 1969-11-04 Knapsack Ag Process for the manufacture of vinyl chloride from contaminated 1,2-dichloroethane
US3896182A (en) * 1971-07-06 1975-07-22 Bp Chem Int Ltd Process for preparing vinyl chloride by the pyrolysis of 1,2-dichloro-ethane
EP0000847A1 (en) * 1977-08-16 1979-02-21 BP Chemicals Limited Vinyl chloride monomer production
US4665243A (en) * 1982-12-08 1987-05-12 Stauffer Chemical Company Process for preparing vinyl chloride monomer
HRP930942A2 (en) * 1993-05-31 1995-02-28 Inos D O O Process for the production of vinyl chloride
CN110405949A (zh) * 2019-08-05 2019-11-05 恩欣格工程塑料（上海）有限公司 一种使用化学试剂对有机玻璃制品进行表面抛光的方法

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DE835142C (de) 1952-03-27
GB633211A (en) 1949-12-12
FR957327A (en(2012)) 1950-02-18
NL68138C (en(2012))
BE478259A (en(2012))

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