CN1993308A - Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and ester thereof in the presence of metal salt - Google Patents

Abstract

Process for producing a chlorohydrin by reaction between a multihydroxylated- aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof, and a chlorinating agent, according to which the multihydroxylated-aliphatic hydrocarbon, the ester of a multihydroxylated- aliphatic hydrocarbon, or the mixture thereof used contains at least one solid or dissolved metal salt, the process comprising a separation operation to remove at least part of the metal salt.

Description

The method that in the presence of metal-salt, is used to produce chloro-hydrin(e) by polyhydroxylated aliphatic hydrocarbons and/or its ester

Present patent application requires to enjoy in patent application FR05.05120 and the patent application EP 05104321.4 that submitted on May 20th, 2005, and U.S. Provisional Patent Application of submitting on November 8th, 2,005 60/734659,60/734627,60/734657,60/734658,60/734635,60/734634,60/734637 and 60/734636 right of priority, and the content of above-mentioned patent application is incorporated herein by reference.

The present invention relates to a kind of a kind of organic method that is used to produce, more specifically relate to a kind of method that is used to produce chloro-hydrin(e).

The known natural petrochemical industry resource that can obtain from the earth for example oil and gas is limited.These resources are used to produce fuel and are used to produce a large amount of useful organic compound as initial product at present, as be used to produce the monomer or the reactant of plastics, oxyethane for example, chloroethanol (referring to, K.Weissermel and H.-J.Arpe in IndustrialOrganic Chemistry for example, Third Completely Revised Edition, VCH Editor, 1997, page 149), a propylene oxide and a propylene chlorohydrin (referring to, K.Weissermel andH.-J.Arpe in Industrial Organic Chemistry for example, Third Completely RevisedEdition, VCH Editor, 1997, page 275), Epicholorohydrin or propylene dichloride (referring to, Ullmann ' s Encyclopedia of Industrial Chemistry for example, 5.ed., Vol.A9, p.539-540).Document Documents Chemistry and Industry, November 20,1931, Part III, pages 949 to 954, and November 27,1931, Part III, pages 970 to 975 have described a kind of method that is used for synthesizing dichloropropanol by glycerine and hydrochloric acid in the presence of the acetate as catalyzer.

According to the known method that is used to produce chloro-hydrin(e), product obtains with the aqueous solution form of the high dilution of titre with 5 to 15 weight % usually.Then the purifying to it is very expensive.And the main isomer that obtains according to such method is 2,3-dichloro third-1-alcohol.

Wish to find and to make the consumption that reduces natural petrochemical industry resource become possible purposes and method, purposes especially above-mentioned.

Also wish to find the method for the by product that is used for utilizing again other production process, make the total amount minimum of the by product that must eliminate or destroy.

Also wish to find the method for the cost minimization that is used to make the lock out operation that the aqueous solution with high dilution interrelates.

Therefore, the present invention relates to a kind of method that is used to produce chloro-hydrin(e) by the ester or the reaction between their mixture and the chlorizating agent of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, ester or their mixture according to the employed polyhydroxylated aliphatic hydrocarbons of this method, polyhydroxylated aliphatic hydrocarbons contain at least a solid or dissolved metal-salt, and this method comprises that a lock out operation is to remove part metals salt at least.

Term " polyhydroxylated aliphatic hydrocarbons " is meant a kind of at least two hydrocarbon that are connected to two oh groups on the different saturated carbon atoms that contain.This polyhydroxylated aliphatic hydrocarbons can contain but be not limited to 2 to 60 carbon atoms.

Each carbon atom that has a polyhydroxylated aliphatic hydrocarbons of hydroxy functional group (OH) can not have the OH group more than 1, and must have sp3 hydridization.The carbon atom that has the OH group can be primary carbon, secondary carbon or tertiary carbon.The polyhydroxylated aliphatic hydrocarbons of Shi Yonging must contain the carbon atom that respectively has an OH group of at least two sp3 hydridization in the present invention.This polyhydroxylated aliphatic hydrocarbons comprises any hydrocarbon that contains company's glycol (1, the 2-glycol) or connect triol (1,2, the 3-triol), comprises linking to each other or adjacent more high-grade ordering of these repeating units.It is for example one or more 1 that the definition of this polyhydroxylated aliphatic hydrocarbons also comprises, 3-, 1,4-, 1,5-and 1,6-functionalized with glycols group.This polyhydroxylated aliphatic hydrocarbons also can be polymkeric substance such as polyvinyl alcohol.Be to get rid of outside this class polyhydroxylated aliphatic hydrocarbons for example together with glycol.

Should be appreciated that this polyhydroxylated aliphatic hydrocarbons can contain aromatic portion or heteroatoms, comprise for example these heteroatomss of halogen, sulphur, phosphorus, nitrogen, oxygen, silicon and boron, and their mixture.

The polyhydroxylated aliphatic hydrocarbons that can use in the present invention comprises: as 1 (ethylene glycol), 1, and 2-propylene glycol (propylene glycol), 1, ammediol, 1-chloro-2, ammediol (propylene glycol of chlorine), glycerin (propylene glycol of chlorine), 1,4-butyleneglycol, 1,5-pentanediol, cyclohexanediol, 1,2-butyleneglycol, 1,2-cyclohexanedimethanol, 1,2,3-glycerol (being also referred to as " glycerine " or " glycerol "), and their mixture.Being used for preferred polyhydroxylated aliphatic hydrocarbons of the present invention comprises: 1,1 for example, 2-propylene glycol, 1, ammediol, 1,2,3-glycerol, and their mixture.More preferably, be used for polyhydroxylated aliphatic hydrocarbons of the present invention and comprise: 1,1 for example, 2-propylene glycol, propylene glycol of chlorine and 1,2,3-glycerol, and their any mixture.Most preferably 1,2, the 3-glycerol.

The ester of polyhydroxylated aliphatic hydrocarbons may reside in the polyhydroxylated aliphatic hydrocarbons, and/or can generate in the process of production chloro-hydrin(e) according to the present invention, and/or can produce before the process of producing chloro-hydrin(e).The example of the ester of polyhydroxylated aliphatic hydrocarbons comprises: ethylene glycol acetate, propylene glycol monoacetate, glyceryl monoacetate, Zerol, glyceryl diacetate and their mixture.

Term " chloro-hydrin(e) " is meant a kind of compound that contains at least one oh group of being connected on the different saturated carbon atoms and at least one chlorine atom.The chloro-hydrin(e) that contains at least two hydroxyls also is a kind of polyhydroxylated aliphatic hydrocarbons.Correspondingly, initial substance of the present invention and product can be respectively chloro-hydrin(e)s.In this case, the product chloro-hydrin(e) is a degree of depth chlorating more compared with the chloro-hydrin(e) of beginning, and in other words, the product chloro-hydrin(e) has more chlorine atom and oh group still less compared with the chloro-hydrin(e) of beginning.Preferred chloro-hydrin(e) is for example chloroethanol, propylene chlorohydrin, propylene glycol of chlorine and dichlorohydrine, and dichlorohydrine most preferably.Particularly preferred chloro-hydrin(e) is ethylene chlorhydrin, 1-chlorine propan-2-ol, 2-chlorine third-1-alcohol, 1-chlorine the third-2,3-glycol, 2-chlorine the third-1,3-glycol, 1,3-dichloro propan-2-ol, 2,3-dichloro third-1-alcohol and their mixture.

Polyhydroxylated aliphatic hydrocarbons that this polyhydroxylated aliphatic hydrocarbons can be the synthetic polyhydroxylated aliphatic hydrocarbons, obtained by renewable raw materials or their mixture.Preferably, polyhydroxylated aliphatic hydrocarbons to the small part of using is in the method according to the invention produced by renewable raw materials.Identical formulation (or Consideration) is applied to ester or the ester of polyhydroxylated aliphatic hydrocarbons and the mixture of polyhydroxylated aliphatic hydrocarbons of polyhydroxylated aliphatic hydrocarbons.

Statement " synthesizing " is meant that this polyhydroxylated aliphatic hydrocarbons is obtained by fossil feedstock.Fossil feedstock wherein, it is meant the material that is obtained by the so natural petrochemical material of for example oil, Sweet natural gas and coal.The organic compound that in these materials, preferably contains two and three carbon atoms.When this chloro-hydrin(e) was dichlorohydrine or propylene glycol of chlorine, chlorallylene, vinyl carbinol and " synthesizing " glycerine were preferred.Wherein " synthesize " glycerine, it is meant the glycerine that is obtained by petrochemical material.When this chloro-hydrin(e) was chloroethanol, ethene and " synthesizing " ethylene glycol were preferred.Wherein " synthesize " ethylene glycol, it is meant the ethylene glycol that is obtained by petrochemical material.When this chloro-hydrin(e) was propylene chlorohydrin, propylene and " synthesizing " propylene glycol were preferred.Wherein " synthesize " propylene glycol, it is meant the propylene glycol that petrochemical material obtains.Identical formulation (or Consideration) is applied to ester or the ester of polyhydroxylated aliphatic hydrocarbons and the mixture of polyhydroxylated aliphatic hydrocarbons of polyhydroxylated aliphatic hydrocarbons.

Renewable raw materials wherein, it is meant the material that is obtained by the processing renewable raw materials.Preferably natural ethylene glycol, natural polypropylene two pure and mild natural glycerins in these materials." natural " ethylene glycol, propylene glycol and glycerine can be by for example obtaining by thermochemical method Nulomoline, these sugar can be obtained by biomass processing, as at " Industrial Bioproducts:Todayand Tomorrow; Energetics; Incorporated for the U.S.Department ofEnergy; Office of Energy Efficiency and Renewable Energy; Office ofthe Biomass Program; July 2003, described among pages 49,52 to 56.One of them for example is for these methods, the sorbyl alcohol that catalytic hydrogenolysis obtains by the thermochemistry transforming glucose.The another one method for example is, the Xylitol that catalytic hydrogenolysis obtains by the wood sugar hydrogenation.This wood sugar can obtain by the hemicellulose that for example hydrolysis is present in the zein fiber.

Statement " glycerine that is obtained by renewable raw materials " or " natural glycerin " refer in particular to the glycerine that obtains in production biofuel process, perhaps usually as saponification, transesterification (or transesterify) effect or the hydrolysis reaction glycerine that transforms plant or animal tallow or obtain when oily.

In the oil that the application can use, it can mention the oil that all are existing, as Semen Maydis oil, sunflower (seed) oil, outmoded or new rapeseed oil, babassu oil, Oleum Cocois, wild cabbage tree oil, plam oil, Viscotrol C and cotton (seed) oil, peanut oil, soybean oil, oleum lini and Crambe oil, and all oil that obtain by Sunflower Receptacle crop that obtains by genetic modification or hybridization or vegetable seed crop.Even can use the old oil of frying, various animal oil are as the fat of fish oil, butter, lard even dismemberent.In the oil that uses, can also refer to for example by poly or oligomeric and partially modified oil, for example " linseed oil stand oil ", sunflower seed oil and flowering plant oil.

When transformed animal fat, can obtain a kind of specially suitable glycerine.Another specially suitable glycerine can obtain when the production biofuel.Another specially suitable glycerine can be in the presence of heterogeneous catalyst transforms the fat of plant or animal or obtains when oily by transesterification (or transesterify) effect, described at application documents FR 2752242, FR 2869612 and FR 2869613.More specifically, this heterogeneous catalyst is selected from the mixed oxide of aluminum and zinc, the mixed oxide of zinc and titanium, and the mixed oxide of zinc, titanium and aluminium, and the mixed oxide of bismuth and aluminium, and this heterogeneous catalyst is to use with the form of fixed bed.In the method according to the invention, glycerine can be as described in the application that is called " Process for preparing a chlorohydrinby chlorinating a polyhydroxylated aliphatic hydrocarbon " in the name of submitting to SOLVAY SA name on the same day with the application, and the content of above-mentioned application is incorporated herein by reference.

Especially mention a kind of method that is used to produce chloro-hydrin(e), wherein the total metal contents in soil of representing with element form is more than or equal to 0.1 μ g/kg and be less than or equal to the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons of 1000mg/kg or their mixture and chlorizating agent react.

In contrast, " synthetic polyhydroxylated aliphatic hydrocarbons " obtained by the petroleum chemicals resource usually.Identical formulation (or Consideration) is applied to ester or the ester of polyhydroxylated aliphatic hydrocarbons and the mixture of polyhydroxylated aliphatic hydrocarbons of polyhydroxylated aliphatic hydrocarbons.

In the method for epoxide produced according to the present invention, the polyhydroxylated aliphatic hydrocarbons of use can be the crude product of polyhydroxylated aliphatic hydrocarbons or the purified product of polyhydroxylated aliphatic hydrocarbons." slightly " product of polyhydroxylated aliphatic hydrocarbons is not carry out any processing after it is produced." purifying " product of polyhydroxylated aliphatic hydrocarbons is to carry out primary treatment at least after it is produced.When polyhydroxylated aliphatic hydrocarbons was the crude product that is obtained by renewable raw materials, it can contain for example water except that metal-salt.This metal-salt is metal chloride especially, and it preferentially is selected from NaCl and KCl.This metal-salt can also be selected from metal sulfate, as sodium sulfate and vitriolate of tartar.The polyhydroxylated aliphatic hydrocarbons that uses in according to the inventive method contains at least a solid or dissolved metal-salt, and it preferentially is selected from sodium-chlor, Repone K, sodium sulfate and vitriolate of tartar.The polyhydroxylated aliphatic hydrocarbons that uses in according to the inventive method contains the metal-salt content of at least 0.5 weight % usually, be preferably greater than or equal about 1 weight %, more preferably greater than or equal about 2 weight %, most preferably more than or equal to about 3 weight %.This metal-salt content is at most 15 weight % usually, preferably is less than or equal to about 10 weight %, is more preferably less than or equals about 7.5 weight %, most preferably is less than or equal to about 5 weight %.Identical formulation (or Consideration) is applied to ester or the ester of polyhydroxylated aliphatic hydrocarbons and the mixture of polyhydroxylated aliphatic hydrocarbons of polyhydroxylated aliphatic hydrocarbons.

In the method according to the invention, the crude product of polyhydroxylated aliphatic hydrocarbons can contain organic impurity such as carbonyl compound, especially the ester of the salt of aldehyde, lipid acid, lipid acid or lipid acid can be selected in monoesters or polynary ester in the composition with water as especially polyhydroxylated aliphatic hydrocarbons and lipid acid.When polyhydroxylated aliphatic hydrocarbons was glycerine, preferred lipid acid was the saturated and unsaturated fatty acids that contains more than 12 carbon courtyards, for example oleic acid, linoleic acid plus linolenic acid.These acid are for example to produce in the process by saponification, transesterification (transesterify) or hydrolysis reaction conversion rapeseed oil.Preferred fatty acid ester is a methyl ester.

In the method according to the invention, this crude product contains the organic impurity of 10 weight % at the most usually, often is 8% organic impurity.Frequently, this crude product contains the organic impurity of 6 weight % at the most.Preferably, it contains the organic impurity of 2 weight % at the most.Most preferably, it contains the organic impurity of 1 weight % at the most.Typically, this organic impurity is made up of lipid acid and its derivative basically.

In addition, the application also relates to a kind of method that is used to produce chloro-hydrin(e), according to this method the ester of the polyhydroxylated aliphatic hydrocarbons that contains the organic impurity of 8 weight % at the most, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent is reacted.

Astoundingly, discover to use to have high-load organic impurity for the reaction of carrying out the inventive method not influence basically.Optional by product from this organic impurity can be removed from reaction mixture at an easy rate, for example (if words applicatory) are realizing as the ratio of controlling the cleaning thing the 17th page of the 33rd row of patent application WO 2005/054167 of submitting to SOLVAY SA name passing through described in the 18th page of the 33rd row, 25 page of the 10th row of the 24th page of eighth row to the, and the content of above-mentioned application is incorporated herein by reference.

In the method according to the invention, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the polyhydroxylated aliphatic hydrocarbons of at least 40 weight % usually.Frequently, this crude product contains the polyhydroxylated aliphatic hydrocarbons of at least 50 weight %.Preferably, it contains the polyhydroxylated aliphatic hydrocarbons of at least 70 weight %.Frequently, this crude product contains the polyhydroxylated aliphatic hydrocarbons of 99 weight % at the most.Typically, it contains the polyhydroxylated aliphatic hydrocarbons of 95 weight % at the most.

In the method according to the invention, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the water of at least 5 weight % usually, perhaps contains the water of at least 1 weight % when not having other compound that is not water and polyhydroxylated aliphatic hydrocarbons.In the method according to the invention, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the water of 50 weight % at the most usually, perhaps contains the water of 60 weight % at the most when not having other compound that is not water and polyhydroxylated aliphatic hydrocarbons.Frequently, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the water of 30 weight % at the most, is preferably the water of 21 weight % at the most.

In another embodiment, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the polyhydroxylated aliphatic hydrocarbons of 89 weight % at the most.In this embodiment, the crude product of polyhydroxylated aliphatic hydrocarbons contains the polyhydroxylated aliphatic hydrocarbons of 85 weight % at the most.In this embodiment, the crude product of polyhydroxylated aliphatic hydrocarbons contains the water of at least 10 weight % usually, and often contains at least 14% water.

The crude product of this polyhydroxylated aliphatic hydrocarbons has the metal-salt content of at least 0.5 weight %, and be preferably more than or equal about 1%, and more preferably more than or equal to about 1.5%.The crude product of this polyhydroxylated aliphatic hydrocarbons has the metal-salt content of 15 weight % at the most, is preferably to be less than or equal to 12%, and more preferably is less than or equal to about 7.5%.

Especially be preferably applied to especially be applied in the production of chloro-hydrin(e) and epoxide in the production by the initial chlorinated compound of polyhydroxylated aliphatic hydrocarbons according to lock out operation of the present invention.Astoundingly, lock out operation of the present invention makes that obtaining these compounds economically by renewable raw materials becomes possibility.

Term " epoxide " is to be used for describing a kind of compound that contains the oxygen of at least one bridge joint on C-C.Usually, the carbon atom of this C-C is adjacent, and this compound can contain the atom except that carbon atom and Sauerstoffatom, for example hydrogen atom and halogen.Preferred epoxide is oxyethane, propylene oxide, Racemic glycidol and Epicholorohydrin.

Therefore, the present invention also relates in particular to a kind of method that is used to produce chloro organic cpd, use polyhydroxylated aliphatic hydrocarbons, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture that obtains by renewable raw materials according to this method, and the ester of employed polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture contain at least a solid or dissolved metal-salt, and this method comprises that a lock out operation is to remove the metal-salt to small part.

Should be appreciated that, production method described herein can also utilize the ester of common polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture to implement, and is not limited to polyhydroxylated aliphatic hydrocarbons, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture by the renewable raw materials acquisition of preferred use.

Below, statement " chlorinated compound " is construed as " chloro-hydrin(e) ".Preferred chloro-hydrin(e) is for example chloroethanol, propylene chlorohydrin, propylene glycol of chlorine and dichlorohydrine, and dichlorohydrine is most preferred.

Term " chloroethanol " is the mixture that is used for representing to comprise ethylene chlorhydrin.

Term " propylene chlorohydrin " is the mixture that is used for representing to comprise 1-chlorine propan-2-ol and 2-chlorine third-1-alcohol.

Term " propylene glycol of chlorine " is to be used for expression to comprise 1-chlorine the third-2, and 3-two is pure and mild 2, the mixture of 3-dichloro third-1-alcohol.

In the method for chloro-hydrin(e) produced according to the invention, this chlorizating agent can be as at page 4 the 30th row of the patent application WO 2005/054167 of SOLVAY SA hydrogenchloride and/or the hydrochloric acid described in the 6th page of the 2nd row.Especially the chlorizating agent of mentioning can be gas chlorination hydrogen, aqueous hydrochloric acid or the combination of the two.Hydrogenchloride can for example obtain from course of production of chloroethylene from the process of pyrolysis organic chloride, from producing 4, in 4-methylene radical dipropyl vulcabond (MDI) or toluenediisocyanate (TDI) process, from the metal cleaning process, or from as mineral acid sulfuric acid or the phosphoric acid and the reaction of the metal chloride as sodium-chlor, Repone K or calcium chloride, obtaining.

In the method for chloro-hydrin(e) produced according to the invention, this chlorizating agent can be hydrochloride aqueous solution or preferred anhydrous hydrogen chloride, derive from the device and/or chlorinolysis device and/or the high temperature oxidation device that are used to produce the device of chlorallylene and/or are used to produce methyl chloride, as being disclosed in the application that is called " Process formanufacturing a chlorohydrin by reaction between amulti-hydroxylated aliphatic hydrocarbon and a chlorinating agent " in the name of submitting to SOLVAY SA name on the same day with the application, and above-mentioned application content is incorporated herein by reference.

Mention a kind of ester or their mixture and chlorizating agent method of preparing chloro-hydrin(e) by polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons especially, this reagent contains at least a following compound: nitrogen (gas), oxygen (gas), hydrogen (gas), chlorine (gas), hydrocarbon polymer (or hydrocarbon), Organohalogen compounds, organic oxygen compound and metal.

Mention a kind of hydrocarbon polymer that is selected from aromatic hydrocarbon, saturated and unsaturated aliphatic hydrocarbon or their mixture especially.

Mention a kind of unsaturated aliphatic hydrocarbon that is selected from acetylene, ethene, propylene, butylene, propadiene, methylacetylene and their mixture especially, be selected from the aliphatic saturated hydrocarbon and the aromatic hydrocarbon benzene of methane, ethane, propane, butane and their mixture.

Mention a kind of organic halogen that is selected from the organic chloride of methyl chloride, monochloroethane, chloropropane, chlorobutane, vinylchlorid, vinylidene chloride, a propenyl chloride, tetrachloroethylene, trieline, chloroprene, chlorobenzene and their mixture especially.

Mention a kind of organic halogen that is selected from the organic fluoride of methyl fuoride, fluoroethane, vinyl fluoride, vinylidene and their mixture especially.

Mention a kind of organic oxygen compound that is selected from alcohol, chloropharin, chloro-ether and their mixture especially.

Mention the metal that is selected from basic metal, alkaline-earth metal, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminium, bismuth and their mixture especially.

Mention a kind of method more especially, wherein this chlorizating agent at least a portion is to obtain the process of oxidation chlorination thing from the process of producing chlorallylene and/or from the process of producing methyl chloride and/or from the process of chlorinolysis and/or when being greater than or equal to 800 ℃ in temperature.

In a preferred embodiment, this chlorizating agent does not contain gas chlorination hydrogen.

Can carry out as the 6th page of the 3rd row of the application WO 2005/054167 of SOLVAY SA reactor according to the method that is used for producing chloro-hydrin(e) of the present invention to the concrete disclosure of the 23rd row institute.

Mention a kind of material manufacturing or coated apparatus especially by anti-chlorizating agent under reaction conditions especially hydrogenchloride.The more special device of mentioning a kind of by Glassed Steel or tantalum manufacturing.The method that is used for producing chloro-hydrin(e) according to the present invention can undertaken by the material manufacturing or the coated apparatus of anti-chlorizating agent, as described in the patent application that is called " Process for manufacturing a chlorohydrin in equipmentsresisting to corrosion " in the name of submitting to SOLVAY SA name on the same day with the application, and the content of above-mentioned patent application is incorporated herein by reference.

Mention a kind of method that is used to produce chloro-hydrin(e) especially, this method comprises the step that the ester of a polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and the chlorizating agent that contains hydrogenchloride react, and another is the step of reacting in the equipment of the material manufacturing of anti-chlorizating agent under by the condition in these steps or coating (or covering) at least.More special what mention is metallic substance such as Glassed Steel, gold and tantalum, and the graphite of non-metallic material such as high density polyethylene(HDPE), polypropylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, PFA and poly-perfluoro propyl vinyl ether, polysulfones and polysulfide (or polysulphide), graphite and dipping.

According to the method that is used for producing chloro-hydrin(e) of the present invention can as carry out with reaction medium that name that the application submits to SOLVAY SA name on the same day is called described in the application of " Continuous process for themanufacture of chlorohydrins ", and the content of above-mentioned application is incorporated herein by reference.

Mention a kind of continuation method that is used to produce chloro-hydrin(e) especially, wherein the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture react with chlorizating agent and organic acid in liquid reaction medium, the stable state of this medium is formed the ester that (or stable state composition) comprises polyhydroxylated aliphatic hydrocarbons and polyhydroxylated aliphatic hydrocarbons, the total content of the polyhydroxylated aliphatic hydrocarbons of representing with the mole number of polyhydroxylated aliphatic hydrocarbons and the ester of polyhydroxylated aliphatic hydrocarbons is greater than 1.1mol% and be less than or equal to 30mol%, and this per-cent is to represent with the organic moiety with respect to this liquid reaction medium.

The organic moiety of this liquid medium is defined as the summation of the organic compound of this liquid medium, that is to say, described compound molecule contains at least one carbon atom.

In the method for chloro-hydrin(e) produced according to the invention, the reaction of the ester of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent can as the 6th page of the 28th row of the patent application WO 2005/054167 of SOLVAY SA in the 8th page of the 5th row carry out in the presence of the concrete catalyzer that discloses.Mention a kind of catalyzer that is greater than or equal to the derivative of 200 ℃ carboxylic acid or the catalyzer of carboxylic acid derivative, especially hexanodioic acid and hexanodioic acid based on atmospheric boiling point especially.

In the method for chloro-hydrin(e) produced according to the invention, the reaction of the ester of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent can as the 8th page of the 6th row of the patent application WO 2005/054167 of SOLVAY SA in the 10th page of the 10th row carry out under concrete temperature, pressure and the residence time that discloses.

What mention especially is that temperature is at least 20 ℃ 160 ℃ at the most, and pressure is at least 0.3 crust 100 crust at the most, and the residence time is the 50h at the most of 1h at least.

In the method for chloro-hydrin(e) produced according to the invention, the reaction of the ester of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent can be carried out in the presence of the solvent as the concrete disclosure of institute in the 36th row of the 11st page of the 12nd row of the patent application WO 2005/054167 of SOLVAY SA.

What mention especially is as chlorinated organic solvent, alcohol, ketone, ester or ether, as the mixture of chloroethanol, propylene chlorohydrin, propylene glycol of chlorine, dichlorohydrine, dioxane, phenol, cresols and propylene glycol of chlorine and dichlorohydrine with the immiscible anhydrous solvent of this polyhydroxylated aliphatic hydrocarbons, perhaps as the organic solvent of the heavy reaction product to the oligopolymer of small part chlorination and/or esterification of this polyhydroxylated aliphatic hydrocarbons.

In the method for chloro-hydrin(e) produced according to the invention, reaction between the ester of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and the chlorizating agent can as be called in the presence of the liquid phase that contains heavy compound described in the patent application of " Process for manufacturinga chlorohydrin in a liquid phase " with name that the application submits to SOLVAY SA name on the same day and carry out, and the content of above-mentioned application is incorporated herein by reference.

Mention a kind of method of producing chloro-hydrin(e) especially, wherein the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture react with chlorizating agent in the presence of the liquid phase that contains heavy compound, and the boiling temperature than this chloro-hydrin(e) under absolute pressure 1 crust is high 15 ℃ at least and this liquid phase is in the boiling temperature under absolute pressure 1 crust.

The method that is used to produce chloro-hydrin(e) according to the present invention can be carried out with intermittent mode or continuous mode.Especially preferred is continuous mode.

In the method for chloro-hydrin(e) produced according to the invention, the reaction between the ester of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and the chlorizating agent is preferably carried out in liquid reaction medium.This liquid reaction medium can be single-phase medium or multiphase medium.

This liquid reaction medium is made up of dissolvings all under temperature of reaction or dispersed solids compound, dissolving or dispersive gas and dissolving or dispersive liquid.

This reaction medium comprises reactant, catalyzer, and solvent is in reactant, in the catalyzer and the impurity, reaction intermediate, reaction product and the byproduct of reaction that exist in the solvent.

Reactant wherein, it is meant the ester and the chlorizating agent of this polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons.

Can mention carboxylic acid in the impurity that in polyhydroxylated aliphatic hydrocarbons, exists, carboxylate salt, the ester that the ester of lipid acid and polyhydroxylated aliphatic hydrocarbons, lipid acid and the alcohol that is used for the transesterification process form, and as the muriate (or hydrochloride) of basic metal or alkaline-earth metal and the inorganic salt the vitriol.

When this polyhydroxylated aliphatic hydrocarbons is glycerine, impurity in glycerine can be mentioned carboxylic acid, carboxylate salt, fatty acid ester as monoglyceride, Diglyceride and triglyceride, the ester of formation of lipid acid and the alcohol that is used for the transesterification process, and as the muriate of basic metal or alkaline-earth metal and the inorganic salt the vitriol.

In reaction intermediate, it can mention a chloro-hydrin(e) of this polyhydroxylated aliphatic hydrocarbons and their ester and/or polyester, the ester of the ester of this polyhydroxylated aliphatic hydrocarbons and/or polyester and these many chloro-hydrin(e)s.

When this chloro-hydrin(e) was dichlorohydrine, it can mention a chloro-hydrin(e) of glycerine and its ester and/or polyester, the ester of the ester of glycerine and/or polyester and dichlorohydrine in reaction intermediate.

Thereby the ester of this polyhydroxylated aliphatic hydrocarbons can be the impurity or the reaction intermediate of reactant, this polyhydroxylated aliphatic hydrocarbons.

Reaction product wherein, it is used to refer to the chloro alcohol and water.Water can be the water that forms in chlorination and/or be incorporated into water in this method.

In by product, it can mention for example part chlorination of this polyhydroxylated aliphatic hydrocarbons and/or the oligopolymer of esterification.

When this polyhydroxylated aliphatic hydrocarbons is glycerine, in by product, can mention the oligopolymer of chlorination of glycerine part and/or esterification.

In the different step of this method, can form this reaction intermediate and by product, for example in the production process of this chloro-hydrin(e) or in the separating step of this chloro-hydrin(e).

Thereby, this liquid reaction medium can contain this polyhydroxylated aliphatic hydrocarbons, the dissolving or with bubble form dispersive chlorizating agent, catalyzer, solvent, in reactant, in the catalyzer and the impurity that exists in the solvent, as dissolved or solid salt, for example reaction intermediate, reaction product and byproduct of reaction.

In the method according to the invention, from reaction medium, separate chloro-hydrin(e) and other compound can adopt with the 12nd page of the 1st row of the patent application WO 2005/054167 of SOLVAY SA to the 16th page of the 35th row and the 18th page of the 6th row to the 13rd the method disclosed in capable carry out.These other compounds are that those are mentioned in the above, and comprise the reactant that does not consume, the impurity that exists in reactant, catalyzer and solvent, catalyzer, solvent, reaction intermediate, the by product of water and reaction.

In the method according to the invention, separate and the processing reaction medium in other compound can as the 18th page of the 6th row of the patent application WO 2005/054167 of SOLVAY SA to the 13rd the method disclosed in capable carry out.

Mention especially be the mixture of water/chloro-hydrin(e)/chlorizating agent under the minimum condition of chlorizating agent loss by the separation of component distillation, this chloro-hydrin(e) then carries out precipitating (or decant) after separating.

In the method for chloro-hydrin(e) produced according to the invention, from reaction medium, chloro-hydrin(e) and other compound separation opened and to carry out as being called the identical method that discloses in the patent application of " Process for manufacturing a chlorohydrin ", and the content of above-mentioned application is incorporated herein by reference in the name of submitting to SOLVAY SA name on the same day with the application.

Mention a kind of method that is used to prepare chloro-hydrin(e) especially, comprising following steps: (a) make polyhydroxylated aliphatic hydrocarbons, thereby the ester of polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent and organic acid reaction obtain containing the mixture of the ester of this chloro-hydrin(e) and this chloro-hydrin(e), (b) compound of partial confounding at least that will obtain in step (a) carries out the one or many processing in step (a) step afterwards, and (c) in step (a) at least one step afterwards, add this polyhydroxylated aliphatic hydrocarbons, make in temperature during at least 20 ℃ and the reaction of chloro alcohol ester, so that form the ester of polyhydroxylated aliphatic hydrocarbons to small part.Mention a kind of method more especially, wherein this polyhydroxylated aliphatic hydrocarbons is a glycerine, and this chloro-hydrin(e) is a dichlorohydrine.

In the method for chloro-hydrin(e) produced according to the invention, from reaction medium, separate chloro-hydrin(e) and other compound and can adopt and carrying out, and the content of above-mentioned application is incorporated herein by reference with the identical method described in the application that is called " Process for manufacturing a chlorohydrin from amulti-hydroxylated aliphatic hydrocarbon " that the application submits to SOLVAY SA name on the same day.

Mention especially a kind of by polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons ester or their mixture and chlorizating agent between reaction in having the reactor that one or more liquid the flow to material method that is used to produce chloro-hydrin(e), for the gross weight of the whole liquid streams in introducing this reactor, this liquid stream contains the polyhydroxylated aliphatic hydrocarbons less than 50 weight %, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture.Mention a kind of method more especially, comprise the steps: that (a) makes polyhydroxylated aliphatic hydrocarbons, thereby the ester of polyhydroxylated aliphatic hydrocarbons or their mixture and chlorination reaction obtain containing chloro-hydrin(e), at least a medium of water and chlorizating agent, (b) take out at least a portion mixture that in reactions steps (a), obtains, and the part (or cut) that (c) will take out in step (b) is distilled and/or the stripping operation, wherein add this polyhydroxylated aliphatic hydrocarbons so that from the part (or cut) of step (b), taking out, isolate the mixture that contains water and chloro-hydrin(e), and it compares the chlorizating agent content that shows reduction with the cut that takes out in step (b).

In the method for chloro-hydrin(e) produced according to the invention, from reaction medium, separate chloro-hydrin(e) and other compound and can adopt and carrying out, and the content of above-mentioned application is incorporated herein by reference with the identical method described in the patent application that is called " Process for converting multi-hydroxylated aliphatichydrocarbons into chlrohydrins " that the application submits to SOLVAY SA name on the same day.

Mention a kind of method that comprises the steps to be used to produce chloro-hydrin(e) especially: may further comprise the steps: (a) make ester or their mixture and the chlorination reaction of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, thereby obtain containing the ester of chloro-hydrin(e), chloro-hydrin(e) and the mixture of water; (b) mixture that at least a portion (or cut) is obtained in step (a) distills and/or the stripping processing, thereby obtains the part that enrichment (or concentrating) has the ester of water, chloro-hydrin(e) and chloro-hydrin(e); And the part (or cut) that (c) at least a portion is obtained in step (b) exists under the condition of at least a additive and carrying out lock out operation, chloro-hydrin(e) and chloro alcohol ester arranged and contain part less than 40 weight % water thereby obtain enrichment (or concentrating).This lock out operation is precipitating (or decant) more particularly.

In the method according to the invention, from reaction medium, separate and handle other compound and can adopt and carrying out with the identical method described in name that the application submits to SOLVAY SA name on the same day is called the patent application of " Process for manufacturing a chlorohydrin by chlorination of amulti-hydroxylated aliphatic hydrocarbon ".Preferred treatment process can comprise that other product with a part carries out high temperature oxidation.

Mention a kind of method that is used to produce chloro-hydrin(e) that comprises the steps especially: (a) make basic metal and/or alkaline earth metal content be less than or equal to the polyhydroxylated aliphatic hydrocarbons of 5g/kg, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent and organic acid react, thereby the mixture that is contained chloro-hydrin(e) and ℃ by product at least, (b) carry out one or many in the step of mixture after step (a) that at least a portion is obtained and handle in step (a), and (c) at least one step after the step (a) is a oxygenizement when temperature is greater than or equal to 800 ℃.Mention a kind of method more especially, wherein in step subsequently, take out a part of mixture that in step (a), obtains, and this part is carried out oxidation in the taking-up process when temperature is greater than or equal to 800 ℃.Also mention a kind of method especially, wherein the processing of step (b) is to be selected from precipitating (being separated), filtration, centrifugal, extraction, washing, evaporation, stripping, distillation and adsorption operations, or the lock out operation of the combination of at least two kinds of these operations.

In the method that is used for producing chloro-hydrin(e) according to the present invention, can carry out the steam stripped of reaction medium, especially water vapour stripping (or wet distillation).Reaction medium as above defines.This medium is liquid reaction medium (liquid phase) as defined above preferably.When reaction medium was liquid phase, statement " reaction medium " also comprised the gas phase with liquid equilibrium.Thereby below, statement " reaction medium " will be used for referring to ambiguously the liquid phase that reacts between the polyhydroxylated aliphatic hydrocarbons and chlorizating agent therein and with the gas phase of this liquid equilibrium.When carrying out the steam stripped of reaction medium, can obtain to contain 1 to 5, be 2 to 3 to be preferably the stripping cut of 1.5 to 2.5mol/l chloro organic cpd (especially being chloro-hydrin(e)) sometimes.This stripping cut mainly is made up of water and chloro-hydrin(e).

In the method that is used for producing chloro-hydrin(e) according to the present invention, when chloro-hydrin(e) does not have to shift out fully by take off the fractions (or part), can shift out another cut of the reaction medium that contains chloro-hydrin(e) at least from reaction mixture.

Aspect this of the method that is used to produce chloro-hydrin(e) according to the present invention, reclaim usually and contain the chloro-hydrin(e) of 50 to 96 weight % and at least a cut of the water of 50 weight % at the most.Preferably, this cut contains the chloro-hydrin(e) of 75 to 99.9 weight % and the water of 0.01 to 25 weight %, often is the chloro-hydrin(e) of 75 to 99 weight % and the water of 1 to 25 weight %.

Reclaim preferably and undertaken by distillation or evaporation.In this step process, obtain contain intermediate for example, optionally other cut of polyhydroxylated aliphatic hydrocarbons and catalyzer can be recycled with chlorination reaction.As at the patent application WO of SOLVAY SA 2005/054167 page 1 the 32nd row described in the 11st page of the 34th row, can also separate at least a cut that contains the heavy by product that responds, especially the polymkeric substance of the polyhydroxylated aliphatic hydrocarbons of chloro, it can be destroyed or can be alternatively, for example by dehydrochlorination, be used for producing the process of the polymkeric substance of polyhydroxylated aliphatic hydrocarbons.

Distillation or evaporation are normally carried out under at least 20 ℃ temperature.This temperature often is at least 60 ℃.It is preferably at least 70 ℃.Distillation or evaporation are normally carried out under 180 ℃ temperature at the most.This temperature often is 140 ℃ at the most.

Distillation or evaporation are carried out under the pressure greater than 0.001 crust usually.This pressure is preferably greater than or equals about 0.003 and clings to.Distillation or evaporation are carried out under the pressure that is 15 crust to the maximum usually.This pressure often is to be 10 crust to the maximum.Preferably be 7 crust to the maximum, more preferably be 1 crust to the maximum, more very be preferably maximum 1 crust, and most preferably be maximum 0.1 crust.

Distillation or evaporation operation can utilize distillation tower utilize vaporizer, film evaporator or as an alternative the wall type thin-film evaporator of sweeping of scheme carry out.

The recyclable cut of residue can therefrom advantageously separate by the wall type thin-film evaporator of sweeping of being furnished with inside or external condensation device.The hydrolysis that an example of chemical operation is a residue is in order to reclaim for example catalyzer.

In a concrete variation scheme of method of the present invention, when chloro-hydrin(e) is dichlorohydrins, the method production that this dichlorohydrins basis comprises the following steps:

(a) first reactions steps wherein makes polyhydroxylated aliphatic hydrocarbons contact with chlorizating agent, thereby obtains to comprise at least a part of product (or a kind of cut of product) of a chloro-hydrin(e);

(b) the product cut (or portion of product) of optional near small part carries out drying operation;

(c) the optional exsiccant product cut (or portion of product) of near small part is incorporated in second reactions steps, wherein to a chloro-hydrin(e) and the chlorination reaction of small part.

Step (a) in this variation scheme and (c) preferably under certain condition, and carry out with the preferred value of the method that is used to produce chloro-hydrin(e) as described above according to the present invention.Yet, the preferably reaction of implementation step (a) in the presence of water, wherein the content of water is preferably 3～40 weight % of reaction medium gross weight.

For example, can be in step (a) or at least one reactor (c) by the stripping operation or utilize the vaporizer on the recirculation pipe that places the reactor outside or carry out step (b) by distillation.Preferably change scheme according to another, remove by membrane technique and anhydrate.

The method of chloro-hydrin(e) produced according to the invention can be for example at cascade reactor, carry out at least one tray column or in the associated plant of at least one bubble-plate column or these reactors.

Reactor can be by the inside stirring effectively or pass through the type that the recirculation pipe in the reactor outside stirs.

When reacting by heating medium in the method according to the invention, can for example heat by chuck or by inner heat exchanger.Also can heat by the heat exchanger on reactor external recirculation pipe.Alternatively, by being used in combination chuck and the heat exchanger on reactor external recirculation pipe heats.

Especially when the method according to this invention during with the operation of continuous or intermittent feeding pattern, secondary reaction can cause the accumulation of low-volatility byproducts in the reactor, wherein more or less be the chloride oligomer of polyhydroxylated aliphatic hydrocarbons.This accumulation can cause increasing progressively of reaction medium volume, causes increasing progressively of throughput loss, thereby needs continuously or cleaning reaction device discontinuously, volume is remained on enough levels.Wherein statement " cleaning ", it is to be used to refer to the cut (or part) that takes out reaction medium.

If suitable, the amount of the catalyzer of removing in this cleaning operation process can compensate by the catalyzer pure or purifying of introducing equivalent.

The catalyzer that comes to comprise in the cleaning thing of reaction mixture can recirculation in reactor after purification process economically.For example, the catalyzer that has low solubility in the water processing that can be hydrolyzed is preferably carried out being higher than under 30 ℃, preferred at least 50 ℃ the temperature, then be for example by decant (or being separated), filter or extract the separating step of (or extraction).Have been found that under the situation of hexanodioic acid the hydrolysis of cleaning thing causes reclaiming highly purified crystallization hexanodioic acid in cooling with after filtering with good yield.

Especially when the method according to this invention is operated with continuous or intermittent feeding pattern, metal-salt, especially NaCl (its optional starting material that are present in, for example in the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture, come from aforesaid renewable resources) can enrichment in reactor, in this reactor, carry out the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or the reaction between their mixture and the chlorizating agent.The increase of metal-salt content causes the crystalline accumulation of insoluble substance and causes the variety of issue relevant with solid matter, as on the reactor wall, on the agitator and on feeding line and the cleaning property management line and the settling on the valve form, this insoluble substance causes the increase of reaction mixture volume.Settling on reactor wall forms the energy that can reduce heat transfer efficiency and need increasing amount to keep temperature of reaction.Settling formation on pipeline and valve can cause blockage problem.The solid of the increasing amount in reaction mixture can reduce stirring efficiency and need more substantial energy to realize suitable stirring.And the increase of metal-salt content needs higher continuous or discrete cleaning frequency, thereby causes higher product loss.

Therefore yet it is acceptable surprisingly having metal-salt in the method according to the invention, and wishing can be from for example removing metal-salt, the especially NaCl of at least a portion the reactive system, thereby prevents any accumulation of metal-salt in reaction mixture.Removing like this can be handled (it comprises at least a lock out operation) by at least a portion (or a kind of cut) that makes the reaction mixture that contains solid or dissolved metal-salt aptly and be implemented in order to remove at least a portion metal-salt from described part (or cut).

This lock out operation can be selected from liquid/solid, liquid/liquid, liquid/gas and solid/gas to be separated.

Gu this liquid/lock out operation can be selected from decant (precipitating or be separated), centrifugal, filtration, absorption and spent ion exchange resin and handle.This liquid/liquid lock out operation can be selected from decant and centrifugal.This liquid/gas lock out operation can be selected from stripping, evaporation and distillation.

Gu liquid/lock out operation is preferred, filtration is preferred, is most preferred as the solid metal-salt wherein and remove by filter.

In the method according to the invention, reaction is preferably carried out in reaction mixture, and lock out operation is to carry out at least a portion of reaction mixture.It is not the composition of metal-salt that this partial reaction mixture can be handled to remove at least a before this lock out operation.This processing can be stripping or distillation procedure.

Carrying out the part (or cut) of the reaction mixture of lock out operation can directly take from the reaction mixture, particularly when reaction be when in liquid phase, carrying out.The part (or cut) of carrying out the reaction mixture of lock out operation can also be taken from the reaction mixture and carried out other processing before removing metal-salt.The example of suitable processing is that the liquid portion to reaction mixture carries out concentration operation, wherein volatile compound such as starting raw material and reaction product, it can reclaim and/or be recycled in the reaction mixture alternatively, for example separate, thereby obtain to have the enriched fraction (or part) of the solid that increases content or dissolved metal-salt and handle so that separating metal salt by stripping, distillation or evaporation.

Thereby, this separating step can walk to any step that being used for described in the 18th page of the 13rd row produce the method for chloro-hydrin(e) as the patent application WO 2005/054167 at SOLVAY SA for the 12nd page the 1st to carry out, for example after chlorination reaction, after the step of the mixture that from reaction mixture, shifts out the chloro alcohol and water, by distill the back evaporation shift out chloro-hydrin(e) after, after the cleaning at byproduct of reaction or be used for after the processing of cleaning thing recovery catalyzer, carrying out.

In a preferred embodiment, this part that contains the reaction mixture of metal-salt is to obtain from the cleaning thing that is reflected at the reactor that wherein takes place, and be fed at least one separating unit, in this separating unit, for example handle the separation of carrying out metal-salt by absorption, distillation, extraction, precipitating, centrifugal, filtration and spent ion exchange resin.Gu liquid/lock out operation is preferred, is preferred and filter.The preferred recirculation of separated liquid is got back in the reactor and metal-salt is stayed in the strainer.

Filtration step can be under usually more than or equal to 4 ℃ temperature, be preferably greater than or equal 20 ℃, more preferably greater than or equal 30 ℃, be preferably greater than again or equal 50 ℃, most preferably more than or equal to carrying out under 80 ℃ the temperature.This temperature is usually less than or equals 150 ℃, preferably is less than or equal to 140 ℃.

The kind of filtering system is noncritical and is conspicuous for knowing those skilled in the art.Can in " Perry ' sChemical Engineers ' Handbook, Sixth Edition, 1984, Sections 19-65 to19-103 ", find for the description of suitable filtering system.

For metal-salt gathering in filtering system, usually recommend the filtering unit of periodically regenerating by shifting out the salt that filters out.Regeneration can be passed through any way, for example shifts out solid especially mechanically or finishes regeneration by dissolved salt by shifting out.Alternatively, solid wash-out (or elution) processing can be integrated with in the reproducer.

In according to one embodiment of present invention, shift out metal-salt and need not any pre-treatment as solid from filtering system.

In the first variation scheme, need not further processing except that desalting in suitable mode.

In the second variation scheme, salt is stored in separating still and is used for further processing.Further processing can comprise with the solvent elution solid and use the dissolution with solvents solid.Described in such processing preferred specific embodiment hereinafter.

In a preferred embodiment according to the present invention, before from filtering system, shifting out metal-salt, this metal-salt is handled.

Alternatively, the product of absorption and reactant especially can especially be removed by wash-out with the suitable eluting solvent such as the mixture of water and chloro-hydrin(e) from NaCl from metal-salt as catalyzer and chloro-hydrin(e) and ester thereof.Any ratio between water and the chloro-hydrin(e) all suits.The at room temperature saturated chloro-hydrin(e) that water is arranged of preferred use.Preferred especially the use by being separated and the phase that obtains between the chloro alcohol and water.The water-content that is used as the chloro-hydrin(e) of eluting solvent is less than or equal to 20 weight % usually, preferably is less than or equal to 15 weight %, and most preferably is less than or equal to about 12 weight %.Water-content in the mixture of water and chloro-hydrin(e) is usually more than or equal to 1 weight %.

In another embodiment, eluting solvent is made up of chloro-hydrin(e) basically.In this embodiment, water-content less than 1 weight %, preferably is less than or equal to weight in 0.5% usually.

In another embodiment, eluting solvent is a water, for example fresh as defined above water.

Elution step can be carried out under being generally more than or equal to 20 ℃ temperature, preferably more than or equal to 50 ℃, most preferably carries out under more than or equal to 80 ℃ temperature.This temperature is less than or equal to 150 ℃ usually, and preferably is less than or equal to 140 ℃.

Behind wash-out, the solvent that is used for the wash-out metal-salt can be recycled to chlorination reactor.

Can implement several elution step.

Especially, after with the chloro-hydrin(e) wash-out, metal-salt can be followed alternatively with the further wash-out of the aqueous solution.This aqueous solution can come from any step of this method.The fresh as defined above water of preferred use.

Elution step can be carried out under being generally more than or equal to 20 ℃ temperature, preferably more than or equal to 50 ℃, most preferably carries out under more than or equal to 80 ℃ temperature.This temperature is less than or equal to 150 ℃ usually, and preferably is less than or equal to 140 ℃.

Behind wash-out, the aqueous solution that is used for the wash-out metal-salt can be fed in chlorination reactor, the dehydrochlorination unit, in the biological processing unit or in the oxide treatment unit.

In the first variation scheme, with after chloro-hydrin(e) and the water elution, salt is moved out of in suitable mode as solid and need not further processing.This salt is then disposed in suitable mode.

In the second variation scheme, after with chloro-hydrin(e) and water elution, salt has been dissolved with the aqueous solution.

This aqueous solution can come from any step of this method.The fresh as defined above water of preferred use.

Dissolving step can carry out under being generally more than or equal to 20 ℃ temperature, preferably more than or equal to 50 ℃, most preferably carries out under more than or equal to 80 ℃ temperature.This temperature is less than or equal to 150 ℃ usually, and preferably is less than or equal to 140 ℃.

The aqueous solution that contains the dissolved metal-salt can be disposed.Preferably, it can be fed in the dehydrochlorination unit, in the biological processing unit or in the oxide treatment unit.

In above-mentioned variation scheme, washing demetalization salt and water dissolved metal salt with water can be the part of single cell operation.

When metal-salt was sodium-chlor or Repone K or sodium sulfate or vitriolate of tartar or their any mixture, aforesaid operations was especially suitable, more specifically is applicable to sodium-chlor.

When cleaning is when carrying out in discontinuous mode, a filtering unit is normally enough, because filtering system can be regenerated in cleaning docking process.When cleaning is when carrying out in a continuous manner, preferably have at least two filtering unit alternations, one is in filtered model and another is in regeneration mode.

Filter operation can be carried out with intermittent mode or continuous mode.

When using anhydrous HCl, preferably contain the liquid flow of polyhydroxylated aliphatic hydrocarbons against the guide of flow of HCl logistics as chlorizating agent.When this process was carried out in several reactors, HCl was advantageously dry between two reactors, for example passes through with suitable solid such as molecular sieve adsorption, or carries out reverse osmosis by suitable membrane.

Can obtain spissated chloro-hydrin(e) especially economically according to this specific embodiment of the inventive method is feasible, wherein the content of chloro-hydrin(e) often is 90 weight % more than or equal to the chloro-hydrin(e) gross weight.When chloro-hydrin(e) is dichlorohydrine, by this method, can obtain 1,3-dichloro propan-2-ol is as main isomer, and this isomer purity is greater than 80%.

In the method according to the invention, mixture can contain with 1,3-dichloro propan-2-ol: 2, the mass ratio of 3-dichloro the third-1 alcohol represent 1,3-dichloro propan-2-ol and 2, the isomer of 3-dichloro the third-1 alcohol is usually more than or equal to 0.5, often more than or equal to 3, usually more than or equal to 7, especially more than or equal to 20.0.

The invention still further relates to a kind of method that is used to produce chloro-hydrin(e), according to this method:

(a) ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture are reacted in reaction medium with chlorizating agent,

(b) take out a part of reaction medium that contains water and chloro-hydrin(e) at least continuously or periodically,

(c) at least a portion of the reaction medium (or cut) that will obtain in step (b) is incorporated in the distilation steps,

(d) control the reflux ratio of this distilation steps by supplying water to described distilation steps.

Reaction medium is as defined above.

The water-content of the taking-up part (or cut) in step (b) is preferably with respect to taking out gross weight partly more than or equal to 12 weight %.

Taking-up part (or cut) in step (b) can also contain hydrogenchloride.Preferably, this part is taken out continuously with its component form.This part that obtains can be carried out precipitating (or being separated) operation subsequently after distilation steps.

The reaction medium of step (a) can be supplied with water, especially water vapour.This charging can or be used alternatively from the residuary water of other unit process or operation recovery and realize with the extraneous water that derives from suitable pipeline.

This charging is implemented usually by this way, so that the water-content in the reaction medium is maintained as in the 10th page of the 31st row of patent application WO 2005/054167 of SOLVAY SA name scope described in the 11st page of the 11st row.

Taking out continuously or periodically and can realize by introduce gas phase in distilation steps, particularly is to take out to be in the gas phase of equilibrium state with liquid phase and this gas phase is incorporated in the distilation steps.In the specific embodiment of the method according to this invention, step (a) to (d) is to carry out in the reactor of suitable distillation tower is equipped with at the top.Step (a) is carried out in this reactor.This embodiment is specially suitable when aqueous hydrochloric acid is used as chlorizating agent.It is not only when chlorizating agent does not contain gas chlorination hydrogen.In according to a further embodiment of the method according to the invention, can also distillation tower and reactor is arranged apart, the bottom liquid of reactor can be sent back in the reaction medium.This embodiment is suitable especially when for example gaseous state or substantially anhydrous hydrogenchloride are as chlorizating agent at hydrogenchloride.Anhydrous hydrogenchloride has the water-content that is less than or equal to 40 weight % usually, preferably is less than or equal to 30 weight %, and most preferably is less than or equal to 25 weight %.The water-content of anhydrous hydrogenchloride is usually more than or equal to 1ppm weight.

In one aspect, be introduced in the distillation tower that separates with reactor part (or cut) continuously or periodically, preferably from liquid reaction mixture, take out continuously, and water separates with chloro-hydrin(e) at least.In addition, contain the one or more parts (or cut) of organic product, specifically be that catalyzer and/or hydrogenchloride also can separate in this distilation steps, and be recycled in the reaction mixture usually as heavy by product.By selecting suitable reflux ratio, can be separated on the one hand at this and contain water less, do not contain the cut of hydrogenchloride substantially.

Reflux ratio can suitably be adjusted by supplying with water, and this water does not preferably contain hydrogenchloride substantially and enters in the distillation tower.In this embodiment, preferably supply water to the distillation cat head.Can for example supply with water by at least a portion isolating water in distillation procedure being recycled to the distillation cat head.Can also supply with water by fresh water being added to the distillation cat head.These the two kinds modes of supplying with water can be used in combination.Add fresh water and obtain especially good result.

" do not contain hydrogenchloride substantially " and be interpreted as that specifically the hydrogen chloride content in the watery distillate (or part) is equal to or less than 10 weight % of watery distillate gross weight.Often be that this content is equal to or less than 5 weight %, preferably be equal to or less than 1 weight %, more preferably be equal to or less than 0.3 weight %.If the hydrogenchloride that exists in cut is " not containing hydrogenchloride substantially ", its content is generally equal to respect to the gross weight of watery distillate or greater than 1mg/kg, often for being equal to or greater than 10mg/kg.

" fresh " water is interpreted as that glassware for drinking water has is not that other organic or inorganic components contents of water is less than or equal to 12 weight % with respect to the gross weight of water and other component, preferably is less than or equal to 10 weight %, most preferably is less than or equal to 1 weight %.Usually, " fresh " glassware for drinking water body be interpreted as other organic or inorganic components contents of non-water that glassware for drinking water has with respect to the gross weight of water and other component more than or equal to 0.001mg/kg, often more than or equal to 1mg/kg, usually more than or equal to 10mg/kg.The water that may the originating of fresh water can be the water that is used for the wash-out metal-salt for example described hereinafter, obtain by ion exchange resin, distilled water or from the water of water vapor condensation.

Wherein be not the component of water, it more specifically is meant chloro-hydrin(e).

Have been found that, liquid-balance of steam (vapor liquid equilibrium) feature of utilizing water-hydrogenchloride-chloro-hydrin(e) ternary to form makes can take out the reaction product that specifically comprises the chloro alcohol and water from produce reaction, make most of catalyzer and reactant (comprising hydrogenchloride) be recycled in the reactor simultaneously, especially when chloro-hydrin(e) is dichlorohydrine.

The invention still further relates to a kind of method that is used to produce chloro-hydrin(e), according to this method:

(a) ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture are reacted in reaction mixture with hydrogenchloride,

(b) take out a part of reaction mixture that contains water, chloro-hydrin(e) and hydrogenchloride at least continuously or periodically,

(c) at least a portion of the part (or cut) that will obtain in step (b) is incorporated in the distilation steps,

The ratio that wherein enters the hydrogen cloride concentration/water concentration in the cut of this distilation steps is less than under distillation temperature and pressure, the concentration ratio of the hydrogenchloride/water during hydrogenchloride/water binary azeotropic is formed.

This method is preferably carried out continuously.

In the method according to the invention, the preferred operational condition of the reactor that the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chloro-hydrin(e) are reacted therein, feeding rate, catalyst charge speed, temperature, reactor volume and pressure as reactant (specifically being the ester of hydrogenchloride and polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture) are regulated, the hydrogen cloride concentration during the binary azeotropic that makes the hydrogen cloride concentration that is incorporated into the mixture in the distilation steps be lower than hydrogenchloride/water under distillation temperature and pressure is formed.The effective ways of regulating this concentration are the supplies in liquid reaction medium of control hydrogenchloride.

For example can come hydrogen chloride content in the controlled step (b) by adding entry.This adding can for example be carried out in the employed distillation tower boiler by steam being injected in the distilation steps, or by carrying out to distilation steps recirculation water, the cut that described water can for example take out from the distillation tower top by decant (or being separated) obtains, perhaps undertaken, or the mixture of water by adding recirculation and fresh water carries out by the top that fresh water is joined distillation tower.

Maximum suitable hydrogen cloride concentration slightly descends when working pressure is higher, itself and liquid-vapor equilibrium (or vapor liquid equilibrium) data (J.Amer.Chem.Soc.52 of the azeotropic hydrogenchloride of announcing by Bonner and Titus, 633 (1930)) consistent, its partial data is replicated in the following table:

Pressure (Torr)	Temperature (℃)	HCl in the azeotropic mixture (%wt)
			50	48.74	23.42
250	85.21	21.88
			370	90.24	21.37
540	99.65	20.92
			760	108.58	20.22
1000	116.19	19.73
			1220	122.98	19.36

Under such condition, the cut that comprise water as defined above, is substantially free of hydrogenchloride can reclaim from reaction mixture or from the gas phase above liquid reaction mixture by distillation, for example takes from the material of described gas phase and the aqueous cut of bag that preferably obtains at the distillation tower top by distillation.

For example, under normal atmosphere (101.3kPa), if be lower than about 20.22 weight % with respect to total hydrogenchloride and water-content with the hydrogen chloride content in the gas phase that reaction medium contacts, then can obtain the binary azeotrope of water and dichlorohydrine by the distillation reactor gas phase, it contains the dichlorohydrine of 23 weight %.

In the method for chloro-hydrin(e) produced according to the invention, chloro-hydrin(e) can comprise the halogenation ketone that content increases, monochloroacetone particularly, as described in the patent application FR 05.05120 that is to submit to SOLVAY SA name on May 20th, 2005, and the content of above-mentioned patent application is incorporated herein by reference.In the method for chloro-hydrin(e) produced according to the invention, halogenated ketone content in the chloro-hydrin(e) can be by carrying out component distillation or this chloro-hydrin(e) carried out dehydrochlorination handle and reduce in the presence of water, as be described in the patent application FR 05.05120 of the SOLVAY SA that on May 20th, 2005 submitted to.Mention a kind of method that is used to produce epoxide especially, wherein halogenated ketone forms as by product, and this method comprises that at least one step is used to remove the processing of the formed halogenated ketone of at least a portion.Mention a kind of method that is used to produce epoxide by the chloro-hydrin(e) dehydrochlorination more especially, wherein at least a portion chloro-hydrin(e) is to produce by the ester of chlorination polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture, handle and be used to remove that halogenated ketone that at least a portion forms produces by component distillation treating water-halogenated ketone mixture by dehydrochlorination, and a kind of technology (or method) that is used to produce Epicholorohydrin, wherein halogenated ketone is a monochloroacetone.

In the method for chloro-hydrin(e) produced according to the invention, when chloro-hydrin(e) is dichlorohydrine, obtained for 1 the highly selective of 3-dichloro propan-2-ol astoundingly, 1,3-dichloro propan-2-ol is especially suitable to be used for dehydrochlorination to be used to produce Epicholorohydrin as initial product.

In the method according to the invention, chloro-hydrin(e) can carry out dehydrochlorination reaction producing epoxide, as with described in the patent application WO 2005/054167 of SOLVAY SA name and the FR 05.05120.

In the method according to the invention, chloro-hydrin(e) can carry out dehydrochlorination reaction, as described in the patent application that is called " Process formanufacturing an epoxide from a multi-hydroxylated aliphatichydrocarbon and a chlorinating agent " in the name of submitting to SOLVAY SA name on the same day with the application, its content is incorporated herein by reference.

Mention a kind of method that is used to produce epoxide especially, wherein from the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorination reaction, obtain reaction mixture, this reaction mixture contains the chloro-hydrin(e) of 10g/kg reaction mixture at least, and it carries out other chemical reaction and need not intermediate treatment.

Especially mention a kind of method that is used to produce epoxide, comprise the steps: that (a) reacts the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent and organic acid, thereby at the ester that contains polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, water, form the ester of chloro-hydrin(e) and chloro-hydrin(e) in this chlorizating agent and the organic acid reaction mixture, this reaction mixture contains 10g chloro-hydrin(e) at least in the reaction mixture of every kg; (b) at least a portion reaction mixture that will obtain in step (a) (this partial confounding compound has same composition with the reaction mixture that obtains in step (a)) carries out the one or many processing in step (a) step afterwards; And (c) in step (a) at least one step afterwards, add basic cpd, so that to the ester of small part and chloro-hydrin(e), chloro-hydrin(e), thereby chlorizating agent and organic acid reaction form a kind of epoxide and salt.

The method that is used to produce chloro-hydrin(e) according to the present invention can be incorporated into as the name of submitting to SOLVAY SA name on the same day with the application and be called among the whole design described in the patent application of " Process for manufacturing anepoxide from a chlorohydrin ", and the content of above-mentioned patent application is incorporated herein by reference.

Mention a kind of method that is used to produce epoxide especially, the step that comprises the epoxide that at least one purifying generates, this epoxide to small part is that the method by the chloro-hydrin(e) dehydrochlorination generates, and this chloro-hydrin(e) to small part is to produce by the method for the ester of chlorination polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture.

When this chloro-hydrin(e) is dichlorohydrine, method of the present invention can be then by the dichlorohydrine dehydrochlorination is produced Epicholorohydrin, and when this epoxide was Epicholorohydrin, this Epicholorohydrin can be used to produce Resins, epoxy usually.

Fig. 1 shows the especially preferred equipment flowsheet that can be used to implement chloro-hydrin(e) produced according to the invention.It is with continuous or intermittent mode, supply polyhydroxylated aliphatic hydrocarbons by pipeline (1) to reactor (4), the ester of polyhydroxylated aliphatic hydrocarbons or their mixture, by pipeline (2) supply catalyzer, the charging of chlorizating agent is carried out continuously or with intermittent mode by pipeline (3), the steam that distillation tower (6) is produced by reactor (4) by pipeline (5) supply, from tower (6), take out a fluid streams and be sent to condenser (8) by pipeline (7), fluid streams from condenser (8) is sent in the decanting vessel (or phase separator) (10) by pipeline (9), and water and organic phase are separated in decanting vessel.The part of the water after the separation is optional to be recycled to cat head by pipeline (11) and to be used to keep backflow (ratio).Fresh water can join cat head by pipeline (12) and be used to keep backflow (ratio).The chloro-hydrin(e) that generates distributes between organic phase of taking out by pipeline (14) and the water by pipeline (13) taking-up.Residue from tower (6) can be recycled to reactor by pipeline (15).Heavy by product can shift out from reactor by the cleaning thing (16) that is arranged in reactor bottom liquid alternatively.One liquid of taking-up flows and is sent in the vaporizer (18) by pipeline (17) from clean thing (16), carry out the part evaporation operation there, for example by heating or pass through with nitrogen or steam purging, the gas phase that comprises most of chlorizating agent from liquid stream (17) is recycled to tower (6) by pipeline (19) or is recycled in the reactor (4) by pipeline (20), the liquid phase that distillation tower or stripping tower (22) come flash-pot (18) by pipeline (21) supply, the main fraction of chloro-hydrin(e) supplies to filtering unit (25) from the top of tower (22) and the residue of tower by pipeline (24) through pipeline (23) collection, solid and liquid phase are separated there opens, and liquid phase is recirculated to reactor (4) by pipeline (26).Solid can pass through pipeline (27) and take out from filtering unit (25) as solid or as solution.Solvent can join by pipeline (28) and (29) and be used for washing and/or solid dissolving in the filtering unit (25) and take out from pipeline (27).Alternatively, one liquid of taking-up flows and supplies in the filtering unit (25) by pipeline (30) from clean thing (16).Stripping tower (18) and distillation tower (22) are then by bypass.

According to this is last (stripping tower (18) and (distillation) tower (22) by bypass) result that schema obtains in an embodiment by detail record.

When this polyhydroxylated aliphatic hydrocarbons is ethylene glycol, propylene glycol and glycerine, chloro-hydrin(e) is chloroethanol, propylene chlorohydrin, propylene glycol of chlorine and dichlorohydrine, epoxide is oxyethane, propylene oxide, Racemic glycidol and Epicholorohydrin and chlorizating agent when being anhydrous hydrogen chloride or hydrochloride aqueous solution, and above-described method is very suitable.When polyhydroxylated aliphatic hydrocarbons is that glycerine, chloro-hydrin(e) are dichlorohydrine and epoxide when being Epicholorohydrin, this method is especially easily.

When polyhydroxylated aliphatic hydrocarbons is glycerine, this variation scheme of this method allow by azeotropy shift out on (tower) top almost all come self-reacting, from water starting raw material and/or that may supply with at reactor or tower bottom, thereby obtain the mixture of the dichlorohydrine of extreme high purity, summation for two kinds of isomer is to surpass 99.5 weight % (it has the selectivity that is higher than 99 weight % with respect to hydrocarbon chain and hydrogenchloride), and shifts out the metal-salt that can accumulate in when using crude glycerol in reactor in the reactor.

The following examples are to be used for illustrating the present invention rather than to be used for limiting of the present invention.

Embodiment 1

Numeral in the bracket is with reference to Fig. 1.The optional equipment that has stripping tower (18) and (distillation) tower (22) in Fig. 1 flow process does not use in this example.

Reactor (4) 2.06 has been supplied with the aqueous hydrochloric acid of crude glycerol and 33 weight % continuously with the relative discharge mass ratio.This crude glycerol is the by product of production biofuel, and contains 85% glycerine, 6% NaCl and 0.5% organic impurity (lipid acid and derivative).The residence time is 16h, and the concentration of the hexanodioic acid in reaction medium is 2.5mol acid functional group/kg.Reactor is in normal atmosphere and 115 ℃ of operations down.Reaction mixture passes through pipeline (5) in distillation tower (6) processed (Fig. 1) with the vapor phase of nitrogen stripping and generation.The gas phase that shifts out from tower (6) is condensed (8) and decant (or being separated) in decanting vessel (10) at 25 ℃.Regulate reflux ratio in order to take out whole dichlorohydrines of being produced from the water of the appropriate amount of decanting vessel and at top of tower by recirculation.The organic phase (14) that contains the water (13) of 15.0% dichlorohydrine and contain 88% dichlorohydrine is reclaimed in exit at decanting vessel.Organic impurity measuring result in this two-phase does not demonstrate with to use pure glycerine to have in the method different.

In the future the mashing pump of autoreactor is delivered on 115 microns the PTFE film filter in filtration tank (25).Salt-cake in strainer has the dichlorohydrine of water to wash with saturated down at 20 ℃.Shift out liquid phase and discharging solid, salt is water-soluble and discard the salt water.Washing and salt dissolved time length are about 2 hours.Follow the slurry of autoreactor to carry out new filtration cycle.The recirculation of dichlorohydrine washings is returned in the reactor by continuously feeding.The water analysis revealed dichlorohydrine that has salt: the mass ratio of NaCl is 1.44 and a spot of catalyzer (less than 10g/kg).The amount of the dichlorohydrine in salt solution shows as 1.6% of dichlorohydrine total product.

Overall yield with dichlorohydrine (expression) is 93%.

Claims (26)

1. the method that is used to produce chloro-hydrin(e) of ester or the reaction between their mixture and the chlorizating agent by polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons, contain at least a solid or dissolved metal-salt according to the described polyhydroxylated aliphatic hydrocarbons of described method use, the ester or their mixture of polyhydroxylated aliphatic hydrocarbons, described method comprises that a lock out operation is to remove to the described metal-salt of small part.

2. method according to claim 1, the ester of use therein described polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture to small part is obtained by renewable raw materials.

3. method according to claim 1 and 2, wherein said metal-salt is selected from sodium-chlor, Repone K, sodium sulfate and vitriolate of tartar.

4. according to each described method in the claim 1 to 3, the ester of wherein said polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture contain the metal-salt of 0.5 to 15 weight %.

5. according to each described method in the claim 1 to 4, wherein said chlorizating agent is the combination or the hydrochloride aqueous solution of gas chlorination hydrogen and hydrochloride aqueous solution.

6. according to each described method in the claim 1 to 5, wherein said reaction is carried out in the presence of catalyzer.

7. method according to claim 6, wherein said catalyzer are carboxylic acid or carboxylic acid derivative.

8. method according to claim 7, wherein said carboxylic acid has the atmospheric boiling point that is greater than or equal to 200 ℃, preferably the derivative of hexanodioic acid or hexanodioic acid.

9. according to each described method in the claim 1 to 8, wherein said lock out operation is selected from liquid/solid, liquid/liquid, liquid/gas and solid/gas to be separated.

10. method according to claim 9, Gu wherein said liquid/lock out operation is selected from decant, centrifugal, filtration, absorption and spent ion exchange resin and handles, described liquid/liquid lock out operation is selected from decant and centrifugal, and described liquid/gas lock out operation is selected from stripping, evaporation and distillation.

11. method according to claim 10, Gu wherein said liquid/lock out operation is to filter, and wherein said metal-salt is removed as solid.

12. according to each described method in the claim 1 to 11, wherein said reaction is carried out in reaction mixture, and described lock out operation is to carry out at least a portion of described reaction mixture.

13. method according to claim 12 is wherein handled at least a composition that is not described metal-salt to remove before described lock out operation to the part of described reaction mixture.

14. method according to claim 13, wherein said processing are stripping or distillation procedure.

15. according to each described method in the claim 1 to 14, described method is carried out continuously.

16. be used to produce the method for chloro-hydrin(e), the ester of the polyhydroxylated aliphatic hydrocarbons that contains 10 weight % organic impuritys at the most, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent reacted according to described method.

17. be used to produce the method for chloro-hydrin(e), according to described method

(a) ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent are reacted in reaction medium;

(b) from described reaction medium, take out the part that contains water and described chloro-hydrin(e) at least continuously or off and on;

(c) will be incorporated in the distilation steps at least partially in the described part that obtains in the step (b); And

(d) by supplying with the splitting ratio that water is controlled described distilation steps to described distilation steps.

18. method according to claim 17, wherein described in step (b) taken out part and has water-content more than or equal to 21 weight % with respect to described gross weight of taking out part.

19. be used to produce the method for chloro-hydrin(e), according to described method

(a) ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and hydrogenchloride are reacted in reaction medium;

(b) from described reaction medium, take out the part that contains water, described chloro-hydrin(e) and hydrogenchloride at least continuously or off and on;

(c) will be incorporated in the distilation steps at least partially in the described part that obtains in the step (b);

Wherein be incorporated into the ratio that the described hydrogen chloride content of the described part in the described distilation steps and the ratio between the described water-content are lower than binary azeotropic under described distillation temperature and the pressure hydrogenchloride/water in forming.

20. according to each described method in the claim 1 to 19, wherein said polyhydroxylated aliphatic hydrocarbons is selected from ethylene glycol, propylene glycol, propylene glycol of chlorine, glycerine and composition thereof.

21. according to each described method in the claim 1 to 20, wherein said chloro-hydrin(e) is chloroethanol, propylene chlorohydrin, propylene glycol of chlorine, dichlorohydrine and composition thereof.

22. according to claim 20 or 21 described methods, wherein said polyhydroxylated aliphatic hydrocarbons is a glycerine, and described chloro-hydrin(e) is a dichlorohydrine.

23. method according to claim 22 is produced Epicholorohydrin by the dichlorohydrine dehydrochlorination subsequently.

24. method according to claim 23, wherein said Epicholorohydrin is used to produce Resins, epoxy.

25. method according to claim 22, a use therein described glycerine part is to obtain in the process of production biofuel, or in the fatty or oily conversion process of plant or animal-origin, obtain, described conversion is selected from saponification, transesterification or hydrolysis reaction.

26. method according to claim 25, wherein said oil or fat are selected from Semen Maydis oil, sunflower seed oil, outmoded or new rapeseed oil, babassu oil, Oleum Cocois, wild cabbage tree oil, plam oil, Viscotrol C and Oleum Gossypii semen, peanut oil, soybean oil, oleum lini and Crambe oil, fat, " linseed oil stand oil ", part poly or the oligomeric sunflower seed oil and the flowering plant oil of the oil that is obtained by Sunflower Receptacle crop that obtains by genetic modification or hybridization or vegetable seed crop, the old oil of frying, fish oil, butter, lard, dismemberent.