WO2005097722A1 - Process for preparing 1,3-dichloroacetone - Google Patents
Process for preparing 1,3-dichloroacetone Download PDFInfo
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- WO2005097722A1 WO2005097722A1 PCT/US2005/009767 US2005009767W WO2005097722A1 WO 2005097722 A1 WO2005097722 A1 WO 2005097722A1 US 2005009767 W US2005009767 W US 2005009767W WO 2005097722 A1 WO2005097722 A1 WO 2005097722A1
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- WO
- WIPO (PCT)
- Prior art keywords
- dichloroacetone
- catalyst
- monochloroacetone
- produce
- acetone
- Prior art date
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- SUNMBRGCANLOEG-UHFFFAOYSA-N 1,3-dichloroacetone Chemical compound ClCC(=O)CCl SUNMBRGCANLOEG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims abstract description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 alkali metal salt Chemical class 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 150000002496 iodine Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 238000007138 Deacon process reaction Methods 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
Epichlorohydrin is produced from acetone by (1) chlorinating acetone to form monochloroacetone; (2) disproportionating the monochloroacetone in the presence of a platinum catalyst, a strong acid and preferably a chloride source (for example, added as a salt or from hydrolysis of monochloroacetone) and some water to produce acetone and 1,3-dichloroacetone; (3) hydrogenating the 1,3-dichloroacetone in the presence of a catalyst to produce 1,3-dichlorohydrin; and (4) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin.
Description
PROCESS FOR PREPARING 1,3-DICHLOROACETONE
Background of the Invention The present invention relates to a process for preparing 1,3-dichloroacetone and epichlorohydrin. It is known to prepare 1,3-dichloroacetone by the direct chlorination of acetone with chlorine. See, for example, U.S. Patent 4,251,467. The process involves the use of iodine or iodine salts in greater than catalytic amounts. Iodine is very expensive ($13/kilo according to the 9/23/02 issue of The Chemical Marketing Reporter) . For this reason, it is very important to recover and recycle the iodine or iodine salts in the process . The extra steps of recovering and recycling the iodine or iodine salts add significant complexity for building a commercially viable process for a commodity-type product. Another method for directly chlorinating acetone involves using ethanol instead of iodine or an iodine salt. However, the major product of this process is the ketal of the chlorinated species . To get the 1, 3-dichloroketone, one must hydrolyze the ketal which is not a trivial process. It would be desirable to provide a process for preparing 1,3-dichloroacetone which would eliminate the need for using iodine and all the associated complexity of recovering and recycling it, as well as eliminate the need for hydrolyzing the ketal in the case of the latter method.
SUMMARY OF THE INVENTION In a first aspect, the present invention is a process for preparing 1,3-dichloroacetone which comprises (1) chlorinating acetone to form monochloroacetone, and (2) disproportionating the monochloroacetone in the presence of a platinum catalyst to produce acetone and 1,3-dichloroacetone.
Additionally, a strong acid and, preferably, a chloride source (for example, added as a salt or from hydrolysis of monochloroacetone) and some water may be added to help initiate the reaction. In a second aspect, the present invention is a process for preparing epichlorohydrin which comprises (1) chlorinating acetone to form monochloroacetone; (2) disproportionating the monochloroacetone in the presence of a platinum catalyst, optionally, a strong acid and, preferably, a chloride source (for example, added as a salt or from hydrolysis of monochloroacetone) and some water to produce acetone and 1,3-dichloroacetone; (3) hydrogenating the 1,3-dichloroacetone in the presence of a catalyst to produce 1,3-dichlorohydrin; and (4) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin. Other aspects of the present invention will become apparent from the following detailed description and claims.
DETAILED DESCRIPTION OF THE INVENTION The process of the present invention comprises the following steps: (1) Chlorination Chlorination of acetone to produce monochloroacetone (MCA) is a well known process. See, for example, U.S. Patent 4,439,623 and U.S. Patent 3,397,240. (2) Disproportiona ion The monochloroacetone produced in step (1) is subjected to a disproportionation reaction to produce both acetone and 1,3-dichloroacetone, in the presence of a platinum catalyst, optionally a strong acid and, preferably, a chloride source (for example, added as a salt or from
hydrolysis of monochloroacetone) and some water. The products may be recovered by known methods, such as extraction or distillation. Surprisingly, it has been found that heating monochloroacetone with a specific type of catalyst, which is a platinum catalyst, produces acetone and 1,3-dichloroacetone simultaneously, without producing any significant amount of 1, 1-dichloroacetone or higher chlorinated by-products. The platinum catalysts useful in the present invention include any platinum +2 and/or +4 catalysts. Such catalysts are described in U.S. Patent 6,262,280. Examples of suitable catalysts include PtCl2 and its hydrate, or an alkali metal salt (or its hydrate) of the PtCl4 "2, Pt02, chloroplatinic acid, ammonium chloroplatinate, polyamine platinum salts . It is not necessary for the catalysts to be complexed with ligands such as, for example, siloxane complexes . Preferably, the catalysts employed in the practice of the present invention, are platinum salts. The platinum catalyst is present in a homogeneous form regardless of whether or not it is added as an insoluble salt. If some of the platinum catalyst is leached into the reaction mixture a reaction takes place. If no platinum is leached into the reaction mixture (based on Pt analyses of the liquid phase of the reaction mixture), no reaction takes place. While not wishing to be bound by theory, it is believed that this reaction is related to what goes on in the Shilov-type reaction, described in Luinstra, G.A.; Wang, L.; Stahl, S.S.; Labinger, J.A. ; Bercaw, J.E. J". Organometallic Chem 1995, 504, 75-91, "C-H activation by aqueous platinum complexes: A mechanistic study."
(3) Hydrogenation A key feature of the present invention is to hydrogenate the 1,3-dichloroacetone without removing a chlorine atom through the formation of HC1. Such hydrogenation process is described in US Patents 5,744,655, and 6,350,922. The hydrogenation catalysts can be homogeneous or heterogeneous with heterogeneous being most preferred. Use of a heterogeneous catalyst minimizes or eliminates the need to isolate the catalyst for continued use . The 1,3-dichloroacetone produced in Step (2) is hydrogenated by reaction with a hydrogenating agent to produce 1 , 3-dichlorohydrin. The hydrogenating agent useful in the present invention may be, for example, molecular hydrogen, an alcohol, or a combination thereof. The hydrogenating agent is preferably molecular hydrogen. Examples of suitable alcohols useful in the present invention can be primary or secondary alcohols such as methanol, ethanol and C3-C10 primary and secondary alcohols.
Preferably, the alcohol is methanol. Examples of other secondary alcohols useful in the present invention are described in U.S. Patent No. 2,860,146. The maximum quantity of hydrogenating agent source is not critical and is governed by practical considerations such as pressure, reactor efficiency, and safety. When the hydrogenating agent source is gaseous, then the quantity of hydrogenating agent is preferably at least enough to provide the desired pressure. However, in most cases, the reactor preferably contains no more than 1,000 moles of molecular hydrogen per mole of α-chloroketone and more preferably contains no more than 100 moles of molecular hydrogen per
mole of α-chloroketone. Gaseous hydrogenating agent sources, such as molecular hydrogen, are preferably used according to known methods for mixing a gaseous reagent with a liquid reaction mixture, such as bubbling the gas through the mixture with agitation or solubilizing the hydrogen under pressure. The hydrogenation reaction of the present invention takes place in the presence of a heterogeneous transition metal-containing catalyst. The transition metal useful as the heterogeneous catalyst of the present invention may be one or more metals selected from any of Groups IB, IIB or IIIA-VI IA on the periodic table of elements, as currently adopted by the International Union of Pure and Applied Chemistry (IUPAC) . The catalyst metal is preferably selected from Group VIIIA of the IUPAC periodic table, including for example, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof. The catalyst metal is most preferably platinum. The temperature of the reaction is not critical, provided that all of the reagents, aside from the hydrogen, remain liquid and in contact with each other. However, low temperatures require longer reaction times and lead to increased levels of impurities. The reaction temperature is preferably at least -10°C, more preferably at least 20°C and most preferably at least 50°C. The reaction temperature is preferably less than 250°C, more preferably no more than 100°C and, most preferably no more than 85°C. The reaction pressure is not critical as long as there is sufficient hydrogen to run the reaction in the reaction mixture. The pressure is preferably at least 14 psi (97 kPa, 1 atmosphere) and more preferably at least 50 psi (340 kPa, 3.4 atmospheres). The pressure is preferably no
more than 3,000 psi (21 MPa, 220 atmospheres). Higher pressures lead to shorter reaction times. (4) Ring-Forming or Cyclizing Step The 1,3-dichlorohydrin produced in step (3) is cyclized to produce epichlorohydrin by contacting it with a strong base, such as an aqueous alkali metal hydroxide, including, for example, sodium hydroxide. This step is well known in the art of manufacturing epihalohydrin. See, for example, U.S. Patent 2,860,146. The process of the present invention can be represented by the following general equation:
(1) [chlorination]
(2) [disproportionation]
catalyst OH
(3) [hydrogenati iion]
+ H2 1,3-dichlorohydrin (1,3-DCH)
OH + ring forming) *--l- ^^1 ^/Cl "*■ C1^-^ j + NaCl
(4) ( epichlorohydrin (1,3-DCH) The Deacon Process comprises producing chlorine by direct oxidation of. gaseous HCl with 0 in the presence of a
CuCl2 catalyst. This process is described by the overall chemical equation: HCl(g)+1 θ2 (g)→ V2H20(g)+ VaCls (g) . (1)
Reaction (1) in the presence of a CuCl catalyst is a fast overall exothermic process, which is expected to reach equilibrium under normal industrial operating conditions of 700°K to 750° . The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight . EXAMPLES 1 to 4 GC Conditions GC: HP 5890 II with FID and 6890 auto-injectors (Front detector)
Column: Rtx-35, Restek Corp., Cat # 10453, serf 441628
Column type: 35 percent diphenyl - 65 percent dimethyl polysi1oxane
Column dimensions: 30m x 0.25 mm x 1.0 u Head pressure: 25 psi
Split vent flow: 50 mL/min
Purge gas flow: 4 mL/min
Air flow: -300 mL/min
Hydrogen flow: 30 mL/min Make-up flow: 30 mL/min (column flow ~4 mL/min)
Temperature ramp: 55°C for 4 min hold, +15°C/min to 250°C for 10 min.
Run time: 27 minutes
Injector volume: 0.5 uL (5 uL syringe) Injector temp: 200°C
Detector temp: 290°C
Solvent washes: A= acetonitrile, B= 50/50 acetonitrile/water
Integrator: HP ChemStation The disproportionation reactor was a 4-dram vial equipped with a magnetic stir bar. Monochloroacetone was added to the reactor which contains water, a catalyst as shown in Table I and a strong acid and preferably a chloride ■salt. The relative amounts of the materials are shown in Tables I-IV. The mixture was stirred and then heated at 95 to 100°C for 17 hours. The product was cooled to room temperature. Ten drops of the filtrate was diluted to 1 L with acetonitrile, then filtered through a disposable syringe filter and analyzed by gas chromatography. The amounts of products produced are reported by GC area percentages as shown in Tables I to IV (EXAMPLES 1 to 4, respectively) .
TABLE I: Results for MCA with Different Non-supported Catalysts (NOTE: All samples contain MCA and catalyst. Water added to all reaction mixtures.)
TABLE π. Results for MCA with PtO2 (with and without HCl) vs Time (NOTE: All samples contain MCA (2g). 5 wt percent HCl was used with Pt02 and 11 wt percent HCl was used with Pt/carbon)
The data in Table II indicate that adding HCl to the reaction mixture in the presence of a platinum catalyst early in the reaction (6.5 hours after start of reaction) helps get the reaction started sooner.
TABLE m. Results for MCA with Different Acids (NOTE: All samples contain MCA (2g), 5 wt percent Pt on carbon (0.2 g), acid and water)
The data in Table III indicate that HCl performs better than the other strong acids for running the disproportionation reaction.
TABLE IV: Results for MCA with 5 wt percent Pt on carbon catalyst and LiCl (NOTE: All samples contain MCA (2g) and 5 wt percent Pt on carbon (0.2g))
*p-TSA = para-toluenesulfonic acid dihydrate
The data in Table IV indicate that a chloride salt helps generate the disproportionation reaction.
Claims
WHAT IS CLAIMED IS 1. A process for producing 1,3-dichloroacetone which comprises (1) chlorinating acetone to form monochloroacetone, and (2) disproportionating the monochloroacetone in the presence of a platinum catalyst, a chloride source, water and, optionally, a strong acid to produce acetone and 1,3- dichloroacetone . 2. The process of Claim 1 wherein the platinum catalyst is selected from the group consisting of PtCl4 ~2,
Pt0 , chloroplatinic acid, ammonium chloroplatinate, and polyamine platinum salts. 3. The process of Claim 1 wherein the strong acid is hydrochloric acid. 4. A process for producing epichlorohydrin which comprises (1) chlorinating acetone to form monochloroacetone; (2) disproportionating the monochloroacetone in the presence of a platinum catalyst, a chloride source, water and, optionally, a strong acid to produce acetone and 1,3- dichloroacetone; (3) hydrogenating the 1,3-dichloroacetone in the presence of a catalyst to produce 1,3-dichlorohydrin; and (4) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin . 6. The process of Claim 5 wherein the hydrogenating agent is molecular hydrogen, an alcohol, or a combination thereof. 7. The process of Claim 5 wherein the catalyst is a heterogeneous transition metal-containing catalyst. 8. The process of Claim 5 wherein the hydrogenating agent is molecular hydrogen.
9. The process of Claim 5 wherein the 1,3- dichloroacetone produced in step (2) is hydrogenated without removing a chlorine atom through the formation of HCl. 10. The process of Claim 5 wherein the 1,3- dichlorohydrin produced in step (3) is cyclized to produce epichlorohydrin by contacting it with a strong base. 11. The process of Claim 5 wherein the strong base is an aqueous alkali metal hydroxide.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002559522A CA2559522A1 (en) | 2004-03-31 | 2005-03-24 | Process for preparing 1,3-dichloroacetone |
| AT05729166T ATE467612T1 (en) | 2004-03-31 | 2005-03-24 | METHOD FOR PRODUCING 1,3-DICHLOROACETONE |
| DE602005021209T DE602005021209D1 (en) | 2004-03-31 | 2005-03-24 | PROCESS FOR THE PREPARATION OF 1,3-DICHLORACETONE |
| US10/588,623 US7361790B2 (en) | 2004-03-31 | 2005-03-24 | Process for preparing 1,3-dichloroacetone |
| JP2007506260A JP4638482B2 (en) | 2004-03-31 | 2005-03-24 | Method for producing 1,3-dichloroacetone |
| EP05729166A EP1732873B1 (en) | 2004-03-31 | 2005-03-24 | Process for preparing 1,3-dichloroacetone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55821404P | 2004-03-31 | 2004-03-31 | |
| US60/558,214 | 2004-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005097722A1 true WO2005097722A1 (en) | 2005-10-20 |
Family
ID=34963647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/009767 WO2005097722A1 (en) | 2004-03-31 | 2005-03-24 | Process for preparing 1,3-dichloroacetone |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7361790B2 (en) |
| EP (1) | EP1732873B1 (en) |
| JP (1) | JP4638482B2 (en) |
| CN (1) | CN100494147C (en) |
| AT (1) | ATE467612T1 (en) |
| CA (1) | CA2559522A1 (en) |
| DE (1) | DE602005021209D1 (en) |
| WO (1) | WO2005097722A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2669308A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669306A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669305A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669247A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing dichloropropanol |
| EP2669307A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxide |
| WO2015074684A1 (en) | 2013-11-20 | 2015-05-28 | Solvay Sa | Process for manufacturing an epoxy resin |
| US9309209B2 (en) | 2010-09-30 | 2016-04-12 | Solvay Sa | Derivative of epichlorohydrin of natural origin |
| US9663427B2 (en) | 2003-11-20 | 2017-05-30 | Solvay (Société Anonyme) | Process for producing epichlorohydrin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100032617A1 (en) | 2007-02-20 | 2010-02-11 | Solvay (Societe Anonyme) | Process for manufacturing epichlorohydrin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251467A (en) * | 1976-09-02 | 1981-02-17 | Chevron Research Company | Continuous preparation of chloroacetone |
| US6262280B1 (en) * | 1999-01-20 | 2001-07-17 | E. I. Du Pont De Nemours And Company | Shilov-type reactions |
| WO2003064357A1 (en) * | 2002-01-29 | 2003-08-07 | Dow Global Technologies Inc. | PROCESS FOR REDUCING α-HALOKETONES TO SECONDARY α-HALOALCOHOLS |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2860146A (en) * | 1955-04-14 | 1958-11-11 | Shell Dev | Manufacture of epihalohydrins |
| US3397240A (en) * | 1962-07-24 | 1968-08-13 | Merck & Co Inc | Process for the monohalogenation of acetone |
| US4439623A (en) * | 1981-10-05 | 1984-03-27 | Merck & Co., Inc. | Process for the preparation of monochloroacetone |
| US5744655A (en) * | 1996-06-19 | 1998-04-28 | The Dow Chemical Company | Process to make 2,3-dihalopropanols |
| EP1140751B1 (en) * | 1998-12-18 | 2004-03-24 | Dow Global Technologies Inc. | Process for making 2,3-dihalopropanols |
-
2005
- 2005-03-24 DE DE602005021209T patent/DE602005021209D1/en active Active
- 2005-03-24 CA CA002559522A patent/CA2559522A1/en not_active Abandoned
- 2005-03-24 EP EP05729166A patent/EP1732873B1/en not_active Not-in-force
- 2005-03-24 WO PCT/US2005/009767 patent/WO2005097722A1/en active Application Filing
- 2005-03-24 JP JP2007506260A patent/JP4638482B2/en not_active Expired - Fee Related
- 2005-03-24 CN CN200580010765.2A patent/CN100494147C/en not_active Expired - Fee Related
- 2005-03-24 AT AT05729166T patent/ATE467612T1/en not_active IP Right Cessation
- 2005-03-24 US US10/588,623 patent/US7361790B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251467A (en) * | 1976-09-02 | 1981-02-17 | Chevron Research Company | Continuous preparation of chloroacetone |
| US6262280B1 (en) * | 1999-01-20 | 2001-07-17 | E. I. Du Pont De Nemours And Company | Shilov-type reactions |
| WO2003064357A1 (en) * | 2002-01-29 | 2003-08-07 | Dow Global Technologies Inc. | PROCESS FOR REDUCING α-HALOKETONES TO SECONDARY α-HALOALCOHOLS |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663427B2 (en) | 2003-11-20 | 2017-05-30 | Solvay (Société Anonyme) | Process for producing epichlorohydrin |
| US9309209B2 (en) | 2010-09-30 | 2016-04-12 | Solvay Sa | Derivative of epichlorohydrin of natural origin |
| EP2669308A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669306A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669305A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxy resin |
| EP2669247A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing dichloropropanol |
| EP2669307A1 (en) | 2012-06-01 | 2013-12-04 | Solvay Sa | Process for manufacturing an epoxide |
| WO2015074684A1 (en) | 2013-11-20 | 2015-05-28 | Solvay Sa | Process for manufacturing an epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| US7361790B2 (en) | 2008-04-22 |
| US20070129556A1 (en) | 2007-06-07 |
| DE602005021209D1 (en) | 2010-06-24 |
| CA2559522A1 (en) | 2005-10-20 |
| JP2007530686A (en) | 2007-11-01 |
| EP1732873A1 (en) | 2006-12-20 |
| CN1938252A (en) | 2007-03-28 |
| CN100494147C (en) | 2009-06-03 |
| EP1732873B1 (en) | 2010-05-12 |
| ATE467612T1 (en) | 2010-05-15 |
| JP4638482B2 (en) | 2011-02-23 |
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