WO1996007626A1 - Process for the chlorination of hydrocarbons - Google Patents
Process for the chlorination of hydrocarbons Download PDFInfo
- Publication number
- WO1996007626A1 WO1996007626A1 PCT/US1995/010925 US9510925W WO9607626A1 WO 1996007626 A1 WO1996007626 A1 WO 1996007626A1 US 9510925 W US9510925 W US 9510925W WO 9607626 A1 WO9607626 A1 WO 9607626A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chloride
- process according
- hydrogen chloride
- unsaturated aliphatic
- perchlorofluorocarbon
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/158—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/03—Chloromethanes
Definitions
- This invention relates to a novel method of chlorinating aliphatic hydrocarbons containing 1 to 4 carbon atoms using hydrogen chloride as the source of chlorine.
- the principal products are monochlorinated compounds such as methyl chloride and allyl chloride as well as polychlorinated compounds, for example chloroform and ethylene dichloride.
- the process has a distinct advantage of providing high yields of chlorinated hydrocarbons. In addition, it offers significant cost savings over existing technology.
- Hexachloroethane sublimes at about 187°C, which requires that it must be heated above this temperature to transport it, or a solvent such as perchloroethylene is needed. Furthermore, even though the hexachloroethane is sealed within the system, its relative toxicity is a potential hazard.
- the equilibrium between the dehalogenation of hexachloroethane and its regeneration from perchloroethylene may constrain the operating conditions of the process.
- the oxychlorination reaction temperature must be maintained sufficiently low in order to favor the formation of hexachloroethane. At higher temperatures, the hexachloroethane will decompose to perchloroethylene and chlorine.
- Figure 1 is a diagrammatic representation of a preferred means for operating the present chlorination method, including a shell and tube catalytic reactor in series with a thermal reactor with means for recycling and for withdrawal of chlorinated product and fractionation.
- two separate reaction steps are carried out in tandem.
- an unsaturated aliphatic fluorocarbon selected from the group consisting of perchlorofluorocarbons and perfluorocarbons
- hydrogen chloride and oxygen in the presence of a catalyst to produce the corresponding saturated perchlorofluorocarbon and water.
- the perchlorofluorocarbon so produced is isolated from the reaction products of the first step, and it is reacted in the vapor phase with an aliphatic hydrocarbon containing from one to four carbon atoms, thereby producing the desired chlorinated hydrocarbon plus hydrogen chloride and the original unsaturated aliphatic fluorocarbon.
- Both the hydrogen chloride and fluorocarbon produced in the second step are separated from the chlorinated hydrocarbon product and are recycled to the first step, which is conventionally known as oxychlorination.
- the fluorocarbon serves as a chlorine carrier.
- air is substituted for all or part of the oxygen requirement.
- chlorine is used to supplement or replace entirely the supply of hydrogen chloride by introducing chlorine along with the saturated perchlorofluorocarbon to the second reaction zone.
- CFC1 CC1 2 + 2HC1 + 1/2 0 2 - ⁇ CFC1 2 CC1 3 + H 2 0
- Trichlorofluoroethylene has a boiling point of 71°C and melting point of -119°C.
- Pentachlorofluoroethane boils at approximately 173°C and melts at close to 100°C. Furthermore, the solubilities of these compounds in water are low.
- the chemical properties of the selected fluorocarbons are conducive to the success of the process. These compounds are comparatively nontoxic. Being stable compounds, they resist oxidation and are slow to hydrolyze. Pentachlorofluoroethane dehalogenates less readily than hexachloroethane but not to such a degree that it loses its effectiveness as a chlorinating agent.
- fluorocarbons are candidates for use in the process.
- one isomer of C 3 C1 5 F boils at 171°C and melts at -77°C.
- the corresponding paraffin C 3 C1 7 F boils at 105°C under 14 mm pressure and melts at 8°C.
- Tetrafluoroethylene has a boiling point of -76°C.
- dichlorotetrafluoroethane has a boiling point of 3.6°C.
- the first reaction in which trichlorofluoroethylene was shown to be oxychlorinated to pentachlorofluoroethane employing a catalyst, may typically be carried out in a molten salt reactor, fluidized bed reactor or shell and tube reactor. These reactor types are planned to remove heat from the reaction and to minimize side reactions. The stability of perchlorofluorocarbons allows greater latitude in reactor design, thereby achieving savings in investment cost.
- the temperature of the oxychlorination reaction is maintained preferably in the range from about 200° to about 395°C.
- the use of perchlorofluorocarbons will permit operation within this higher than normal temperature range.
- the catalyst of choice is copper chloride deposited on an inert support. This is the well-known Deacon catalyst which has been used experimentally to produce chlorine from hydrogen chloride and air.
- Various salts may be mixed with the copper chloride to promote its effectiveness, e.g., potassium chloride, ferric chloride, and lead chloride.
- the second reaction is conducted in the vapor phase at an elevated temperature, preferably in the range from about 400° to about 700°C. Because of the lower reactivity of fluorocarbons as opposed to hexachloroethane, the actual temperature used will exceed what would normally be the case for hexachloroethane.
- the probable mechanism by which the methane is chlorinated is a series of free-radical reactions. Chlorine is released from the pentachlorofluoroethane and reacts with the methane to form methyl chloride. The dehalogenation of pentachlorofluoroethane is endothermic, whereas the chlorination of methane is exothermic. Thus, some degree of temperature control is obtained with the heat given off by one reaction being absorbed by the other.
- methane is the hydrocarbon or some other feed is used, such as butane
- methane chlorination the following products are formed: methyl chloride, methylene chloride, chloroform and carbon tetrachloride. Under certain conditions, i.e., an excess of chlorinating agent and high temperatures, some perchloroethylene may also be produced.
- the mix of products will depend, as already noted, on certain variables. One is temperature. Another is the ratio of pentachlorofluoroethane to methane feed. The use of an excess of methane will maximize the production of methyl chloride.
- the reactor design can also be a factor. By incorporating a static mixer into a tubular reactor, back- mixing can be reduced in order to control polychlorination. Finally, in the literature catalysts have been reported which can provide some degree of selectivity.
- Figure 1 is a schematic view of the operation of a preferred embodiment of the present invention.
- Air, hydrogen chloride and trichlorofluoroethylene are fed to the shell and tube catalytic reactor 10 which contains copper chloride catalyst.
- the oxychlorination reaction is carried out in this catalytic reactor.
- the effluent stream from reactor 10 is cooled in condenser 20 to condense the vapors.
- the inert gases are vented while the water is decanted from the chlorinated organics in separator 30.
- Pentachlorofluoroethane dissolved in an excess of trichlorofluoroethylene is transferred to thermal reactor 40 where it is reacted in the vapor phase with methane feedstock.
- Hot vapors from the thermal reactor are quenched, as for example, by a stream of cold trichlorofluoroethylene in order to minimize the formation of heavy ends and tars.
- Unreacted methane and hydrogen chloride are separated from the liquid organics which are pumped to distillation column 50. In this column the product methyl chloride is fractionated from trichlorofluoroethylene, which is recycled back to catalytic reactor 10.
- absorber 60 hydrogen gas is separated from the unreacted methane by absorption in weak hydrochloric acid.
- the concentrated acid exiting from the absorber is pumped to a stripper column 70 where hydrogen chloride is desorbed. Hydrogen chloride from the stripper is recycled back to catalytic reactor 10.
- Methane from the top of the absorber is recycled to thermal reactor 40.
- a purge stream is taken from the recycled methane stream in order to remove inert gases.
- methyl chloride is unavoidably further chlorinated to methylene chloride, chloroform and carbon tetrachloride. These byproducts are separated in additional facilities (not shown) .
- the proportion of methyl chloride produced compared with the total chlorinated organics can be controlled by adjusting the methane feed rate and consequently the methane recycle stream.
- Chlorinated hydrocarbons which can be produced by the process are valuable items of commerce.
- methyl chloride is used in the manufacture of silicone polymers. It has also been proposed as an intermediate in the production of methyl alcohol.
- Ethylene dichloride is a raw material for producing vinyl chloride resins. Allyl chloride is a reactant used in the manufacture of pharmaceuticals, resins and plastics.
- Butyl chloride is used in organic synthesis, e.g., in the manufacture of butyl cellulose.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95930989A EP0779882A4 (en) | 1994-09-07 | 1995-08-29 | Process for the chlorination of hydrocarbons |
AU34181/95A AU3418195A (en) | 1994-09-07 | 1995-08-29 | Process for the chlorination of hydrocarbons |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US30311494A | 1994-09-07 | 1994-09-07 | |
US08/303,114 | 1994-09-07 | ||
US50029995A | 1995-07-10 | 1995-07-10 | |
US08/500,299 | 1995-07-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996007626A1 true WO1996007626A1 (en) | 1996-03-14 |
Family
ID=26973268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/010925 WO1996007626A1 (en) | 1994-09-07 | 1995-08-29 | Process for the chlorination of hydrocarbons |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0779882A4 (en) |
AU (1) | AU3418195A (en) |
WO (1) | WO1996007626A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7812201B2 (en) | 2008-10-01 | 2010-10-12 | Targa Resources, Inc. | Process and catalyst for converting alkanes |
CN111102584A (en) * | 2019-12-20 | 2020-05-05 | 浙江巨化技术中心有限公司 | Polychlorinated hydrocarbon waste treatment device and method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5099084A (en) * | 1985-10-31 | 1992-03-24 | Stauffer John E | Process for the chlorination of methane |
-
1995
- 1995-08-29 AU AU34181/95A patent/AU3418195A/en not_active Abandoned
- 1995-08-29 WO PCT/US1995/010925 patent/WO1996007626A1/en not_active Application Discontinuation
- 1995-08-29 EP EP95930989A patent/EP0779882A4/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5099084A (en) * | 1985-10-31 | 1992-03-24 | Stauffer John E | Process for the chlorination of methane |
Non-Patent Citations (1)
Title |
---|
See also references of EP0779882A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7812201B2 (en) | 2008-10-01 | 2010-10-12 | Targa Resources, Inc. | Process and catalyst for converting alkanes |
US7968755B2 (en) | 2008-10-01 | 2011-06-28 | Sajet Development Llc | Process and catalyst for converting alkanes |
CN111102584A (en) * | 2019-12-20 | 2020-05-05 | 浙江巨化技术中心有限公司 | Polychlorinated hydrocarbon waste treatment device and method |
Also Published As
Publication number | Publication date |
---|---|
EP0779882A1 (en) | 1997-06-25 |
AU3418195A (en) | 1996-03-27 |
EP0779882A4 (en) | 1997-12-29 |
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