WO1994013611A1 - Process for the production of dichlorohydrin - Google Patents
Process for the production of dichlorohydrin Download PDFInfo
- Publication number
- WO1994013611A1 WO1994013611A1 PCT/EP1993/003546 EP9303546W WO9413611A1 WO 1994013611 A1 WO1994013611 A1 WO 1994013611A1 EP 9303546 W EP9303546 W EP 9303546W WO 9413611 A1 WO9413611 A1 WO 9413611A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hexadiene
- allyl chloride
- process according
- reaction
- chloride feed
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
- C07C29/66—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens by addition of hypohalogenous acids, which may be formed in situ, to carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/36—Halogenated alcohols the halogen not being fluorine
-
- 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
-
- 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
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- 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
Definitions
- the present invention relates to a process for the production of dichlorohydrin and to dichlorohydrin prepared by such process.
- dichlorohydrin as employed herein covers both isomers 1,2-dichloro-3-hydroxypropane and 1,3-dichloro-2-hydroxypropane.
- dichlorohydrin It is known to prepare dichlorohydrin by reacting an allyl chloride feed with water and chlorine in a dilute aqueous phase. Allyl chloride is commercially prepared by the high-temperature chlorination of propene.
- the main use of dichlorohydrin is for preparing epichlorohydrin (1,2-epoxy-3-chloropropane) , by dehydrochlorination in the presence of a base.
- the subject reactions may be carried out batchwise, semi-continuously or continuously.
- the voluminous aqueous effluent emerging from the epichlorohydrin plant contains appreciable amounts of other chlorinated organic compounds (Extractable Organic Chlorine, E0C1, up to about 100 mg Cl/1) , mainly chloroaliphatic ethers and chloroaliphatic alkanes. Since these chlorinated organic by-products are toxic, their concentration in the waste water should be reduced as much as possible before the waste water is fit for being passed to receiving bodies such as rivers and lakes. Since the removal of the chlorinated organic by-products from the epichlorohydrin plant effluent by conventional methods, such as fractional distillation is very expensive, there exists a need for an alternative method for reducing their level.
- E0C1 Extractable Organic Chlorine
- the present applicant's EP-A-0 359 331 is directed to a method of reducing the level of chlorinated organic by-products in the above-described reaction effluent by extracting the aqueous product of the reaction of allyl chloride with water and chlorine, with a water-immiscible solvent having an atmospheric boiling point of from 40 °C to 105 °C.
- the present applicant's EP-A-0 537 846 discloses a similar method wherein the extracting water-immiscible solvent is 1,2,3-trichloropropane.
- the present invention now presents a different approach to reducing the level of chlorinated organic by-products in the above-described reaction effluent.
- chlorinated organic by-products are mainly chloroaliphatic ethers and chloroaliphatic alkanes. These are already present in the conventionally-prepared dichlorohydrin, and they are carried to the effluent of the epichlorohydrin plant. In particular, they were found to be mainly chloroaliphatic ethers having 9 and 12 carbon atoms (C q and C X , the level of the C. chloroaliphatic ethers being much lower.
- the present inventors investigated the source of these chlorinated organic by-products. Theoretically, they would be expected to originate from oligomerisation reactions of reactive intermediates formed from allyl chloride and chlorine with water and/or dichlorohydrin. However, the present inventors found their main source to be hexadienes (C,H n ⁇ V isomers, in particular o iU).
- 1,5-hexadiene, 1,4-hexadiene and 2-methyl-l,4-pentadiene) which 0 are by-products of the high temperature chlorination of propene to allyl chloride.
- this hexadiene also reacts with chlorine, water and dichlorohydrin to form the chloroaliphatic ethers found in the - > reaction effluent.
- allyl chloride is at least 97.5 wt% pure and contains hexadiene as an impurity (Ullman's Encyclopaedia of Industrial Chemistry, 5th Edition, vol. A 1985, page 431). Normally, 0.3-1.0 wt%, of hexadiene is present. It has now been 0 found that when an allyl chloride feed containing less than
- the present invention therefore is directed to a process for the preparation of dichlorohydrin by reacting an allyl chloride feed with water and chlorine, characterized in that an allyl chloride feed is used which contains less than 0.30 wt% of hexadiene .
- the allyl chloride feed contains less than 0.20 wt%, more preferably less than 0.10 wt% of hexadiene.
- allyl chloride feed according to the invention will contain no (0) hexadiene, and that practical and economical considerations will play an important role in determining the actual reduction employed.
- allyl chloride feed containing less than 0.30 wt% of hexadiene will generally involve a step of removing excess hexadiene from such commercially available allyl chloride. This may be performed by selective distillation of the hexadiene, or alternatively by reacting the hexadiene to form compounds which are more easily removable.
- the reactor according to the present applicant's EP-B-0 107 215 is expected to effect a more efficient chlorination of propene to allyl chloride and less production of by-products, including hexadiene. Furthermore, beside the high temperature chlorination of propene, different reactions for the production of allyl chloride are also feasible, which will also produce allyl chloride having a lower content of hexadiene .
- Selective distillation is a preferred method of removing hexadiene from commercially available allyl chloride feed.
- considerably more intensive distillation is required in order to separate the hexadienes from the allyl chloride, in particular when the hexadienes are predominantly present as their low-boiling isomers, as is generally the case in crude, untreated allyl chloride.
- the boiling point at atmospheric pressure of allyl chloride is 45 °C and that of 2-methyl-l,4-penta- diene, 1-5-hexadiene and 1,4-hexadiene is 55 °C, 59,5 °C and 65 °C respectively.
- a considerably lower strain is placed on the distillation step by first isomerising the lower-boiling hexadienes which form the greater part of the hexadienes in untreated allyl chloride to the higher boiling hexadiene isomers.
- the higher boiling 1,3-hexadiene and 2,4-hexadiene having a boiling point at atmospheric pressure of 73 °C and 80 °C respectively, are not normally present in untreated allyl chloride.
- the isomerisation step can be performed by using known acid catalysts, preferably solid acid catalysts, such as ion exchange resins. Strong acid catalysts are preferred. Particularly preferred are the macroporous ion exchange resins, such as Amberlist 15 (H ) , trade mark of Rohm & Haas. Homogenous acid catalysts can also be used in principle.
- the isomerisation reaction can be performed continuously, or batchwise.
- the effective amount of macroporous ion exchange catalyst for the continuous treatment of a given flow of hexadiene-containing allyl chloride will depend on the reaction temperature.
- the temperature range within which the ion exchange resin can effectively be used is 0 - 150 °C and preferably 20 - 120 °C.
- the catalyst amount required to effectively treat 1 kg/h of hexadiene-containing allyl chloride is 0.1 - 100 equivalents of H (typically corresponding to 0.05 - 50 L of catalyst bed volume) and preferably 0.2 - 50 equivalents.
- the lower amounts of catalyst are typically used at the higher reaction temperatures and vice versa.
- the pressure is preferably selected such that the system is operated in the liquid phase, by keeping it (slightly) above the vapour pressure, at the reaction temperature used, of the allyl chloride.
- This isomerisation of the hexadienes can be performed selectively, without concurrently modifying the allyl chloride (to 1-chloro-propene) in any appreciable amount.
- An alternative to the step of isomerising the low-boiling hexadienes in allyl chloride to higher-boiling hexadienes prior to distillation, is the step of converting the hexadienes by hydro- chlorination to chlorohexenes and dichlorohexanes.
- this hydrochlorination of the hexadienes can be performed selectively, without concurrently modifying the allyl chloride (to 1, 2-dichloropropane) in any appreciable amount.
- Lewis acids examples include FeCl_, ReCl ZnCl. and SbCl .
- a preferred Lewis acid catalyst was found to be MoCl In order to treat 1 kg/h of allyl chloride feed, an amount of the Lewis acid generally ranging from 0.01 to 100 mmol, preferably from 0.1 to 10 mmole, is effective.
- the catalyst can be immobilised in a manner known in the art, for example on graphite or on a sulphonated polystyrene resin.
- the concentration of HCl used to hydrochlorinate the hexadienes is preferably kept within the range of 0.1 to 5.0 wt% , based on the total amount of the allyl chloride containing feed, since much higher concentrations of HCl will tend to hydrochlorinate the allyl chloride as well.
- the pressure is preferably selected such that the system is operated in the liquid phase, by keeping it (slightly) above the vapour pressure, at the reaction temperature used, of the allyl chloride.
- the organic phase was analysed for chloroaliphatic ethers (C q +C_. ⁇ +C ) , using gas chromatography, equipped with a chlorine-selective detector having a linear response (HALL) .
- Table 1 presents the results of Experiment 1.1 and Comparative Experiment 1.2, wherein the > 99% allyl chloride feed used respectively contained 0.032 wt% and 0.5 wt% of hexadiene (Hex/AC) . Therein, the chloroaliphatic ethers contents are expressed in mg Cl per litre of the aqueous reaction mixture.
- the feed flow was 70 ml/h (LHSV 0,5), the pressure 400 kPa and the temperature 90 °C.
- the outflow stream from the reactor also contained a total of 0.4 wt% hexadienes but only 12.5% of this (0.05 wt%) was 1,5-hexadiene and about 75% was 2,4-hexadiene.
- This outflow stream was subjected to distillation in an OLDERSHAW-type distillation column as in Example 2, the differences being that the mass reflux over distillation ratio (R/D ratio) was 0.8, the number of trays 40 (the feed tray being the 20th) and the mass top flow rate 90% of the feed.
- the top distillate stream contained 0.04 wt% of total hexadiene, most of which was 1,5-hexadiene.
- 1,5-hexadiene was fed to a 140 ml pressurised and thermostatically controlled reactor, containing a fixed bed of 86 gram (dry) Amberlite 15 (H + ) ion exchanger.
- the feed flow was 30 ml/h (LHSV 0.2), the pressure 400 kPa and the temperature 70 °C.
- the outflow stream from the reactor also contained a total of 0.4 wt% hexadienes but only 7.5% of this (0.03 wt%) was 1,5-hexadiene and about 85% was 2,4-hexadiene.
- This outflow stream was subjected to distillation in an OLDERSHAW-type distillation column as in Example 2, the differences being that the mass reflux over distillation ratio (R/D ratio) was 1.8, the number of trays 60 (the feed tray being the 20th from the top) and the mass top flow rate 99% of the feed.
- the top distillate stream contained 0.02 wt% of total hexadiene, most of which was 1,5-hexadiene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69311369T DE69311369T2 (en) | 1992-12-11 | 1993-12-09 | METHOD FOR PRODUCING DICHLORHYDRINE |
KR1019950702366A KR100281797B1 (en) | 1992-12-11 | 1993-12-09 | Method of producing dichlorohydrin |
JP51379794A JP3415841B2 (en) | 1992-12-11 | 1993-12-09 | Method for producing dichlorohydrin |
EP94902773A EP0675866B1 (en) | 1992-12-11 | 1993-12-09 | Process for the production of dichlorohydrin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US98962192A | 1992-12-11 | 1992-12-11 | |
US989,621 | 1992-12-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994013611A1 true WO1994013611A1 (en) | 1994-06-23 |
Family
ID=25535293
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/003546 WO1994013611A1 (en) | 1992-12-11 | 1993-12-09 | Process for the production of dichlorohydrin |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0675866B1 (en) |
JP (1) | JP3415841B2 (en) |
KR (1) | KR100281797B1 (en) |
CN (1) | CN1046259C (en) |
CA (1) | CA2151269A1 (en) |
DE (1) | DE69311369T2 (en) |
ES (1) | ES2104338T3 (en) |
SG (1) | SG66243A1 (en) |
TW (1) | TW283140B (en) |
WO (1) | WO1994013611A1 (en) |
ZA (1) | ZA939237B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996003362A1 (en) | 1994-07-22 | 1996-02-08 | Shell Internationale Research Maatschappij B.V. | Purification of allyl chloride |
CZ296880B6 (en) * | 2002-12-23 | 2006-07-12 | Spolek Pro Chemickou A Hutní Výrobu, Akciová Spolecnost | Method for removing alkadienes and alkenes from a mixture of unsaturated chlorinated hydrocarbons |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5482045B2 (en) * | 2008-09-25 | 2014-04-23 | 東ソー株式会社 | Method for producing dichlorobutene |
JP2011105637A (en) * | 2009-11-17 | 2011-06-02 | Sumitomo Chemical Co Ltd | Method for producing allyl chloride and dichlorohydrin |
CN110183305A (en) * | 2019-06-04 | 2019-08-30 | 山东凯泰科技股份有限公司 | A kind of raw material chloropropene pretreating process of direct oxidation method production epoxychloropropane |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0228118A2 (en) * | 1985-12-27 | 1987-07-08 | Shell Internationale Researchmaatschappij B.V. | Process for the production of dichlorohydrin |
EP0359331A1 (en) * | 1988-09-09 | 1990-03-21 | Shell Internationale Researchmaatschappij B.V. | A continuous process for the production of dichlorohydrin |
EP0537846A1 (en) * | 1991-10-10 | 1993-04-21 | Shell Internationale Researchmaatschappij B.V. | Production of dichlorohydrin |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1014524B (en) * | 1983-12-23 | 1991-10-30 | 卡伯特公司 | Process for producing carbon black |
JPH108747A (en) * | 1996-06-19 | 1998-01-13 | Inax Corp | Toilet room assembly unit and execution method using the same |
-
1993
- 1993-11-17 TW TW082109613A patent/TW283140B/zh not_active IP Right Cessation
- 1993-12-09 DE DE69311369T patent/DE69311369T2/en not_active Expired - Lifetime
- 1993-12-09 CA CA002151269A patent/CA2151269A1/en not_active Abandoned
- 1993-12-09 SG SG1996003416A patent/SG66243A1/en unknown
- 1993-12-09 KR KR1019950702366A patent/KR100281797B1/en not_active IP Right Cessation
- 1993-12-09 ZA ZA939237A patent/ZA939237B/en unknown
- 1993-12-09 EP EP94902773A patent/EP0675866B1/en not_active Expired - Lifetime
- 1993-12-09 ES ES94902773T patent/ES2104338T3/en not_active Expired - Lifetime
- 1993-12-09 WO PCT/EP1993/003546 patent/WO1994013611A1/en active IP Right Grant
- 1993-12-09 JP JP51379794A patent/JP3415841B2/en not_active Expired - Lifetime
- 1993-12-10 CN CN93120854A patent/CN1046259C/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0228118A2 (en) * | 1985-12-27 | 1987-07-08 | Shell Internationale Researchmaatschappij B.V. | Process for the production of dichlorohydrin |
EP0359331A1 (en) * | 1988-09-09 | 1990-03-21 | Shell Internationale Researchmaatschappij B.V. | A continuous process for the production of dichlorohydrin |
EP0537846A1 (en) * | 1991-10-10 | 1993-04-21 | Shell Internationale Researchmaatschappij B.V. | Production of dichlorohydrin |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996003362A1 (en) | 1994-07-22 | 1996-02-08 | Shell Internationale Research Maatschappij B.V. | Purification of allyl chloride |
US5723703A (en) * | 1994-07-22 | 1998-03-03 | Shell Oil Company | Purification of allyl chloride |
CZ296880B6 (en) * | 2002-12-23 | 2006-07-12 | Spolek Pro Chemickou A Hutní Výrobu, Akciová Spolecnost | Method for removing alkadienes and alkenes from a mixture of unsaturated chlorinated hydrocarbons |
Also Published As
Publication number | Publication date |
---|---|
CA2151269A1 (en) | 1994-06-23 |
JPH08504422A (en) | 1996-05-14 |
ZA939237B (en) | 1994-08-05 |
TW283140B (en) | 1996-08-11 |
SG66243A1 (en) | 1999-07-20 |
DE69311369D1 (en) | 1997-07-10 |
EP0675866A1 (en) | 1995-10-11 |
KR100281797B1 (en) | 2001-02-15 |
CN1094023A (en) | 1994-10-26 |
ES2104338T3 (en) | 1997-10-01 |
JP3415841B2 (en) | 2003-06-09 |
EP0675866B1 (en) | 1997-06-04 |
KR950704220A (en) | 1995-11-17 |
DE69311369T2 (en) | 1997-09-18 |
CN1046259C (en) | 1999-11-10 |
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