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Production of allyl chloride

Abstract
CA2004312C
A process is provided for the production of allyl chloride from three carbon atom hydrocarbons
CA Grant
(propane and/or propylene) using hydrogen chloride or hydrogen chloride/chlorine mixtures as the
chlorinating agent. The process includes reaction steps operated in tandem in separate zones rst
comprising the reaction of perchloroethylene with hydrogen chloride and oxygen in the presence of Find Prior Art Similar
an oxychlorination catalyst to give hexachloroethane and water, second comprising the vapor phase
reaction of hexachloroethane with propane/propylene feedstock to produce allyl chloride, Other languages: French
perchloroethylene, and hydrogen chloride, and third isolating the products of the second step and
Inventor: John E. Stauffer
repeating the rst step using as starting materials the thus isolated perchloroethylene and hydrogen
chloride. Original Assignee: John E. Stauffer

Priority date : 1989-01-27

Classi cations
Family: US (1) EP (1) JP (1) CA (1) DE (2) ES (1) WO (1)
C07C21/067 Allyl chloride; Methallyl chloride
Date App/Pub Number Status
View 3 more classi cations
1989-11-30 CA 2004312 Expired - Fee
Related

1990-07-27 CA2004312A1 Application

1996-04-30 CA2004312C Grant

Info: Patent citations (3), Cited by (30), Legal events, Similar

documents, Priority and Related Applications

External links: Espacenet, Global Dossier, CIPO, Discuss

Claims (8)

1. A process for the production of allyl chloride using reaction steps operated in tandem:
rst, subjecting perchloroethylene to oxychlorination with hydrogen chloride and oxygen in the presence of an oxychlorination catalyst to give reaction products consisting
essentially of hexachloroethane and water;
second, isolating and reacting said hexachloroethane with a hydrocarbon containing three carbon atoms and optionally added chlorine in the vapor phase to produce products
comprising allyl chloride, perchloroethylene and hydrogen chloride, and third, isolating said products of the second step and repeating the rst step using as starting materials
the perchloroethylene and hydrogen chloride thus isolated whereby chlorination using regenerated hexachloroethane is accomplished, the process being operated with total
utilization of hydrogen chloride and net production of hydrogen chloride and hexachloroethane is avoided.

2. A process according to claim 1 wherein the hydrocarbon containing three carbon atoms that is reacted in the second step comprises propane.

3. A process according to claim 1 wherein the hydrocarbon containing three carbon atoms that is reacted in the second step comprises propylene.

4. A process according to claim 1 in which chlorine is added such that the second step comprises the reaction of chlorine with a hydrocarbon containing three carbon
atoms to produce allyl chloride and hydrogen chloride.

5. A process according to claim 1 in which the catalyst in step 1 comprises copper chloride.

6. A process to claim 5 where the catalyst comprises an admixture of copper chloride with one or more salts selected from the group consisting of potassium chloride,
ferric chloride, and lead chloride.

7. A process according to claim 1 in which the oxychlorination reaction with perchloroethylene is carried out at temperatures in the range from about 200° C. to about
375°
C.

8. A process according to claim 1 in which the vapor phase reaction is carried out at temperatures in the range from about 400° C. to about 700° C.

Description

- a~(}O43~2 _, PRODUCTION OF ALLYL CHLORIDE

This invention relates to a novel method of producing allyl chloride (CH2= CHCH2CI ) from hydrocarbons containing three carbon atoms, i.e., propane and propylene,
using hydrogen chloride or chlorine as the chlorinating agent. An important feature of the process is that any proportion of hydrogen 5 chloride to chlorine can be used
and the net production of hydrogen chloride can be avoided. A further advantage of the process is that high yields of allyl chloride can be obtained based on the
hydrocarbon and the chlorine values used.

Historically, allyl chloride has been made by the addition chlorination of propylene with chlorine followed by the pyrolysis of 1,2 - dichloropropane at high temperatures.
The resulting product mix from the dehydrochlorination reaction consists of about 55 to 70 pe~cent allyl chloride and approximately 30 to 40 percent 1-chloropropene.
Because of the relatively low yield of allyl 15 chloride this process is not used industrially at the present time.
The newer method of producing allyl chloride involves the high-temperature substitution chlorination of propylene with chlorine to produce the product directly in one
step. High yields of allyl chloride, up to 96 percent, have been reported for the reaction. Minor quantities of 2 - chloropronene - 1 and 1-20 chloropropene -1 are obtained.
20~43~2 The above method of making allyl chloride commercially has several disadvantages. First, it requires chlorine as the chlorinating agent. This raw material,
which is produced by an electrochemical process, has been vulnerable to the escalating cost of electric power. Second, less than half of the chlorine consumed is used to
produce allyl chloride. The rest of the chlorine iswasted, mostly as byproduct hydrogen chloride.
The object of the present invention, therefore, is to be able to produce allyl chloride by substituting hydrogen chloride for all or part of the chlorinerequirements. Thereby
dependence on an expensive raw material, which on lo occasion has been in short supply, is avoided.
A further object of the present invention is the production of allyl chloride whithout producing byproduct hydrogen chloride. Added exibility and improved economics
thus can be realized.
Still another object is to manufacture allyl chloride in high yields from propane and/or propylene. Several bene ts accrue from this result. The consumption of
hydrocarbon is minimized. Processing costs of purifying the product are reduced. Finally, the disposal of unwanted and environmentally-damaging byproduct
chlorohydrocarbons can be simpli ed.

Figure 1 is a diagrammatic representation of a preferred means for operating the present chlorination method. A shell and tube catalytic reactor isillustrated in series with
a thermal reactor with means for separating allyl chloride and for isolating and recycling hydrogen chloride and 20043~

perchloroethylene to the catalytic reactor.

Summary and Detailed Description The invention, in one preferred embodiment, concerns a process for the chlorination of a hydrocarbon containing three carbon atoms
using hydrogen 5 chloride as a source of chlorine. The process includes reaction steps operated in tandem in separate reaction zones; rst, comprising the reaction of
perchloroethylene with hydrogen chloride and oxygen in the presence of an oxychlorination catalyst to give hexachloroethane and water, and second, comprising the
vapor phase reaction of hexachloroethane with a hydrocarbon o containing three carbon atoms to produce allyl chloride as the principal product along with hydrogen
chloride and perchloroethylene.
The invention, in another preferred embodiment, concerns a process for the chlorination of a hydrocarbon containing three carbon atoms using hydrogen chloride as a
source of chlorine, said process including reaction steps15 operated in tandem; rst, subjecting perchloroethylene to oxychlorination with hydrogen chloride and oxygen
in the presence oS an oxychlorination catalyst to give reaction products consisting essentially of hexachloroethane and water;
second, isolating and reacting said hexachloroethane with a hydrocarbon containing three carbon atoms in the vapor phase to produce predominantly 20 allyl chloride,
perchloroethylene and hydrogen chloride; and third, isolating said products of the second step and repeating the rst step using as starting materials the
perchloroethylene and hydrogen chloride thus isolated whereby chlorination using regenerated hexachloroethane is accomplished; the process being operated with total
utilization of hydrogen chloride and net production ofhydrogen chloride and hexachloroethane being avoided.
Problems encountered by the conventional methods are circumvented by the method of the present invention. In the present method, according to a 5 preferred
embodiment, two separate reactions are carried out in tandem, as indicated. First, perchloroethylene is reacted with hydrogen chloride and air oroxygen to produce
hexachloroethane and water. In the second reaction the hexachloroethane is reacted with a hydrocarbon containing three carbon atoms, i.e. propane, propylene or any
proportion of these compounds, to give the desired allyl chloride plus hydrogen chloride. The latter is recycled to the~
- ~ rst reaction so that there is no net production of hydrogen chloride.
The reactions in the present invention may be illustrated by the following equations using propylene as the hydrocarbon feedstock:

1. CCI2 = CCI2 + 2 HCI+--2 cat. ~ CCI3CCI3 +H20 2a. CCI3CCI3 + C3H6 ~ > CCI2=CCI2 +CH2= CHCH2CI + HCI

Therefore the net reaction is:

3. C3H6 + HCI + 2 2 > CH2 = CHCH2CI + H2O

If, in a preferred embodiment, chlorine is added in the second step, the following reaction will occur:

Z0043~Z
--2b. Cl2+ C3H6 ~ > CH2= CHCH2CI + HCI

The rst reaction, in which perchloroethylene is oxychlorinated to hexachloroethane employing an oxychlorination catalyst, may typically be carried out in a molten salt
reactor, uidized bed reactor, or in a shell and tube reactor. Such reactor designs assist in the control of the reaction temperature.This temperature is maintained
preferably in the range from about 200C. to about 375C. The catalyst of choice is copper chloride which may be deposited on an inert support. This is the well-known
Deacon catalyst which has been used in experimental processes to produce chlorine from hydrogen chloride and air. Various salts may be mixed with the copper chloride
in order to promote its effectiveness, e.g., potassium chloride, ferric chloride, and lead chloride.
The second reaction is conducted in the vapor phase of an elevated temperature prefereably in the range from about 400C. to about 700 C. The probable mechanism by
which propylene is chlorinated in this temperature range is a series of free radical reactions. In the event that insu cient hydrogen~
chloride is available to produce the required hexachloroethane, chlorine can be added to supplement the hexachloroethane. Thus, various predetermined proportions of
hydrogen chloride and chlorine, depend!ng on requirements, can be used in the overall process.
As a feature of the invention, temperature control of the second reaction is facilitated when using hexachloroethane instead of chlorine as the chlorinating agent.
Substitution chlorination, such as the formation of allyl chloride from propylene and chlorine, releases considerable heat. By contrast, dissociation reactions, such the the
instant decomposition of hexachloroethane to perchloroethylene and chlorine, absorb a substantial quantity of heaat. Thus,according to the present invention, when
these two reactions, substitution chlorination and dissociation, are conducted in an intimate manner, the heat requirements can be closely balanced.
Operation of the process is illustrated in the attached drawing. Air, hydrogen chloride and perchloroethylene are fed to the shell and tube reactor which contains the
copper chloride catalyst. The e uent is cooled su ciently to condense the liquids. The inert gases are vented to a scrubber while a separator decants the water from the
chlorinated organics. After being dried, hexachloroethane dissolved in unreacted perchloroethylene is pumped to the thermal reactor where it chlorinates propylene. The
hot vapors from the reactor are quenched, and the hydrogen chloride is separated for recycle to the catalytic reactor. Unreacted hydrocarbon is recycled to the thermal
reactor. Thechlorinated organic compounds are fractionated in a distillation column. Allyl chloride is removed overhead and the higher boiling perchloroethylene is
recovered in the still bottoms and returned to the oxychlorination step.
Although the process seems rather straightforward, successful operation depends on the strict adherence to the following nules:
1. Hexachloroethane produced via oxychlorination must be isolated from all impurities with the exception of perchloroethylene before being fed to the thermal reactor.
This separation is necessary to avoid the formation of byproducts and the loss of hydrogen chloride e ciency. The thermal reactor 20~312 _ -- 7 must be kept anhydrous
or above the dew point to prevent severe corrosion problems. ~ll oxygen has to be excluded from the thermal reactor to avoid burning and the formation of water.

2. Hydrogen chloride, before being recycled to the oxychlorination 5 reactor, must be freed of all hydrocarbons to prevent combustion reactions and to avoid pollution
problems caused by their escape in the vent gases.

3. Perchloroethylene that is reformed in the thermal reactor must be isolated from the product stream before being recycled to the oxychlorination reactor. Any saturated
hydrocarbons which are fed to the oxychlorination 10 reactor will partially burn. Unsaturated hydrocarbons, other than perchloroethylene, will be chlorinated in the
oxychlorination reactor and eventually lead to unwanted byproducts.
The allyl chloride produced by the method of the present invention is a valuable itèm of commerce. It is an intermediate in the production of allyl 15 alcohol,
epichlorohydrin, and synthetic glycerol. End use markets include pharmaceuticals, resins, plastics and food products. Recent market research data indicate that
epichlorohydrin accounts for 5.7 percent of chlorine consumption in the United States and is the second fastest growing outlet for chlorine.
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Industries by an oxychlorination step
Inc

DE1282637B * 1967-01-19 1968-11-14 Hoechst Ag A process for the production of allyl chloride or methallyl chloride

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Cited By (30)

Publication number Priority date Publication date Assignee Title

Family To Family Citations

CA1322769C * 1988-12-30 1993-10-05 John E. Stauffer Process for the chlorination of ethane

US6909024B1 * 1999-11-22 2005-06-21 The Dow Chemical Process for the conversion of ethylene to vinyl chloride and novel catalyst
Company compositions useful for such process

US6797845B1 1999-11-22 2004-09-28 Dow Global Process for vinyl chloride manufacture from ethane and ethylene with immediate
Technologies Inc. HCl recovery from reactor e uent

US6933417B1 1999-11-22 2005-08-23 Dow Global Process for vinyl chloride manufacture from ethane and ethylene with partial CHl
Technologies Inc. recovery from reactor e uent

US6680415B1 1999-11-22 2004-01-20 Dow Global Oxyhalogenation process using catalyst having porous rare earth halide support
Technologies Inc.

US20040152929A1 * 2002-05-08 2004-08-05 Clarke William D Process for vinyl chloride manufacture from ethane and ethylene with air feed and
alternative hcl processing methods

US6984763B2 * 2001-05-23 2006-01-10 Dow Global Oxidative halogenation and optional dehydrogenation of c3+hydrocarbons
Technologies Inc.

US7838708B2 * 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements

EP1682465A1 * 2003-07-15 2006-07-26 GRT, Inc. Hydrocarbon synthesis

US20050171393A1 * 2003-07-15 2005-08-04 Lorkovic Ivan M. Hydrocarbon synthesis

US20080275284A1 2004-04-16 2008-11-06 Marathon Oil Process for converting gaseous alkanes to liquid hydrocarbons
Company

US7244867B2 2004-04-16 2007-07-17 Marathon Oil Process for converting gaseous alkanes to liquid hydrocarbons
Company

US20060100469A1 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to ole ns and liquid hydrocarbons

US7674941B2 * 2004-04-16 2010-03-09 Marathon Gtf Processes for converting gaseous alkanes to liquid hydrocarbons
Technology, Ltd.

US8642822B2 2004-04-16 2014-02-04 Marathon Gtf Processes for converting gaseous alkanes to liquid hydrocarbons using
Technology, Ltd. microchannel reactor

US8173851B2 2004-04-16 2012-05-08 Marathon Gtf Processes for converting gaseous alkanes to liquid hydrocarbons
Technology, Ltd.

EP1993979A4 2006-02-03 2011-07-06 Grt Inc Continuous process for converting natural gas to liquid hydrocarbons

CA2730934C * 2008-07-18 2017-07-04 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons

CA2641426C * 2006-02-03 2015-06-09 Grt, Inc. Separation of light gases from halogens

JP2010527358A * 2007-05-14 2010-08-12 ジーアールティー イ Process for converting a hydrocarbon feedstock with electrolytic recovery of silver
ンコーポレイテッド

CN101765574A * 2007-05-24 2010-06-30 Grt公司 Zone reactor incorporating reversible hydrogen halide capture and release

US8282810B2 2008-06-13 2012-10-09 Marathon Gtf Bromine-based method and system for converting gaseous alkanes to liquid
Technology, Ltd. hydrocarbons using electrolysis for bromine recovery

US20100270167A1 * 2009-04-22 2010-10-28 Mcfarland Eric Process for converting hydrocarbon feedstocks with electrolytic and
photoelectrocatalytic recovery of halogens

US8367884B2 2010-03-02 2013-02-05 Marathon Gtf Processes and systems for the staged synthesis of alkyl bromides
Technology, Ltd.

US8198495B2 2010-03-02 2012-06-12 Marathon Gtf Processes and systems for the staged synthesis of alkyl bromides
Technology, Ltd.
 US8815050B2 2011-03-22 2014-08-26 Marathon Gtf Processes and systems for drying liquid bromine
Technology, Ltd.

US8436220B2 2011-06-10 2013-05-07 Marathon Gtf Processes and systems for demethanization of brominated hydrocarbons
Technology, Ltd.

US8829256B2 2011-06-30 2014-09-09 Gtc Technology Us, Processes and systems for fractionation of brominated hydrocarbons in the
Llc conversion of natural gas to liquid hydrocarbons

US8802908B2 2011-10-21 2014-08-12 Marathon Gtf Processes and systems for separate, parallel methane and higher alkanes'
Technology, Ltd. bromination

US9193641B2 2011-12-16 2015-11-24 Gtc Technology Us, Processes and systems for conversion of alkyl bromides to higher molecular weight
Llc hydrocarbons in circulating catalyst reactor-regenerator systems

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Priority And Related Applications

Priority Applications (2)

Application Priority date Filing date Title

US07303498 1989-01-27 1989-01-27 Production of allyl chloride

US303,498 1989-01-27

Legal Events
Date Code Title Description

1990-12-21 EEER Examination request

1998-11-30 MKLA Lapsed

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