CN1993308B

CN1993308B - Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and ester thereof in the presence of metal salt

Info

Publication number: CN1993308B
Application number: CN2006800005668A
Authority: CN
Inventors: 帕特里克·吉尔博; 伊万·德安多伦科; 菲利普·克拉夫特; 弗雷迪·吉伦
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2005-05-20
Filing date: 2006-05-19
Publication date: 2013-04-03
Anticipated expiration: 2026-05-19
Also published as: FR2885903B1; FR2885903A1; AR094376A2; CN1993308A

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

In the presence of metal-salt by polyhydroxylated aliphatic hydrocarbons and/or its ester method for the production of chloro-hydrin(e)

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 the U.S. Provisional Patent Application 60/734659,60/734627,60/734657,60/734658,60/734635,60/734634 of submitting on November 8th, 2005,60/734637 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 ofly for the production of a kind of organic method, more specifically relate to a kind of method for the production of chloro-hydrin(e).

The known natural petrochemical industry resource that can obtain from the earth for example oil and gas is limited.At present these resources be used to produce fuel and as initial product for the production of a large amount of useful organic compound, such as monomer or the reactant for the production 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), 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 by glycerine and the hydrochloric acid method for the synthesis of dichlorohydrine in the presence of as the acetic acid of catalyzer.

According to the known method for the production of chloro-hydrin(e), product obtains with the aqueous solution form of the high dilution of titre with 5 to 15 % by weight usually.Very expensive to its purifying then.And the main isomer that obtains according to such method is 2,3-dichloro, third-1-alcohol.

Wishing to find can become possible purposes and method so that reduce the consumption of natural petrochemical industry resource, purposes especially above-mentioned.

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

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

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

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

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: such as 1，2-ethandiol (ethylene glycol), 1,2-PD (propylene glycol), 1, ammediol, 1-chloro-2, ammediol (propylene glycol of chlorine), glycerinβ-chlorohydrin (propylene glycol of chlorine), BDO, 1,5-pentanediol, cyclohexanediol, 1,2-butyleneglycol, 1,2-CHDM, 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: for example 1，2-ethandiol, 1,2-PD, 1,3-PD, Glycerin, and their mixture.More preferably, be used for polyhydroxylated aliphatic hydrocarbons of the present invention and comprise: for example 1，2-ethandiol, 1,2-PD, propylene glycol of chlorine and Glycerin, and their any mixture.Glycerin most preferably.

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) " refers to 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 more degree of depth chlorination compared with the chloro-hydrin(e) that begins, and in other words, the product chloro-hydrin(e) has more chlorine atom and oh group still less compared with the chloro-hydrin(e) that begins.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.

The polyhydroxylated aliphatic hydrocarbons that this polyhydroxylated aliphatic hydrocarbons can be the polyhydroxylated aliphatic hydrocarbons that synthesizes, obtained by renewable raw materials or their mixture.Preferably, the polyhydroxylated aliphatic hydrocarbons that uses in the method according to the invention is at least part of to be 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 " refers to that this polyhydroxylated aliphatic hydrocarbons is obtained by fossil feedstock.Fossil feedstock wherein, it refers to the material that 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 refers to the glycerine that obtained by petrochemical material.When this chloro-hydrin(e) was chloroethanol, ethene and " synthesizing " ethylene glycol were preferred.Wherein " synthesize " ethylene glycol, it refers to the ethylene glycol that obtained by petrochemical material.When this chloro-hydrin(e) was propylene chlorohydrin, propylene and " synthesizing " propylene glycol were preferred.Wherein " synthesize " propylene glycol, it refers to 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 refers to the material that 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 hydrolysis reaction conversion of plant or animal tallow or the glycerine that obtains when oily.

In the oil that the application can use, it can mention the oil that all are existing, such 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 obtained by the 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 such 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 blown vegetable 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 obtains by the fat of transesterification (or transesterify) effect conversion of plant or animal or when oily, 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 for the production of chloro-hydrin(e), the total metal contents in soil that wherein represents 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 processing at least one times 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 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, such as sodium sulfate and vitriolate of tartar.The polyhydroxylated aliphatic hydrocarbons that uses in according to the inventive method contains the metal-salt of at least a solid or dissolving, 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 % by weight usually, preferably greater than or equal to about 1 % by weight, more preferably greater than or equal about 2 % by weight, most preferably more than or equal to about 3 % by weight.This metal-salt content is at most 15 % by weight usually, preferably is less than or equal to about 10 % by weight, is more preferably less than or equals about 7.5 % by weight, most preferably is less than or equal to about 5 % by 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 such 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 methyl ester.

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

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

Astoundingly, research finds to use the crude product of the organic impurity with high-content to there is no impact for the reaction of carrying out the inventive method.Optional by product from this organic impurity can be removed from reaction mixture at an easy rate, for example (if words applicatory) are realizing such as the ratio that passing through the control cleaning materials described at 18 page of the 33rd row of the 17th page of the 33rd row to the of patent application WO 2005/054167 of submitting to SOLVAY SA name, 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 % by weight usually.Frequently, this crude product contains the polyhydroxylated aliphatic hydrocarbons of at least 50 % by weight.Preferably, it contains the polyhydroxylated aliphatic hydrocarbons of at least 70 % by weight.Frequently, this crude product contains the at the most polyhydroxylated aliphatic hydrocarbons of 99 % by weight.Typically, it contains the at the most polyhydroxylated aliphatic hydrocarbons of 95 % by weight.

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

In another embodiment, the crude product of this polyhydroxylated aliphatic hydrocarbons contains the at the most polyhydroxylated aliphatic hydrocarbons of 89 % by weight.In this embodiment, the crude product of polyhydroxylated aliphatic hydrocarbons contains the at the most polyhydroxylated aliphatic hydrocarbons of 85 % by weight.In this embodiment, the crude product of polyhydroxylated aliphatic hydrocarbons contains the water of at least 10 % by 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 % by 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 at the most metal-salt content of 15 % by weight, 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 chloro-hydrin(e) and the epoxidation the production of material 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 becomes possibility so that obtain economically these compounds by renewable raw materials.

Term " epoxide " is to describe 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 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 for the production of chloro organic cpd, use polyhydroxylated aliphatic hydrocarbons, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture that is obtained by renewable raw materials according to the method, and the ester of employed polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture contain the metal-salt of at least a solid or dissolving, and the method comprises that a lock out operation is to remove at least part of metal-salt.

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 represents to comprise ethylene chlorhydrin.

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

Term " propylene glycol of chlorine " is that expression comprises 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 such as hydrogenchloride and/or hydrochloric acid described at 6 page of the 2nd row of page 4 the 30th row to the of the patent application WO 2005/054167 of SOLVAY SA.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 the 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 for the production of the device of chlorallylene and/or for the production of device and/or chlorinolysis device and/or the high temperature oxidation device of 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 especially the method that a kind of ester by polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorizating agent prepare chloro-hydrin(e), 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 especially a kind of hydrocarbon polymer that is selected from aromatic hydrocarbon, saturated and unsaturated aliphatic hydrocarbon or their mixture.

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

Mention especially 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.

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

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

Mention especially 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.

Mention more especially a kind of method, wherein this chlorizating agent at least a portion is to obtain the process of chlorine monoxide compound 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.

According to the method for the production of chloro-hydrin(e) of the present invention can as the 6th page of the 3rd row to the 23 row of the application WO 2005/054167 of SOLVAY SA carry out in the concrete reactor that discloses.

Mention especially a kind of material manufacturing by anti-chlorizating agent under reaction conditions especially hydrogenchloride or the device of coating.Mention more especially a kind of device of being made by Glassed Steel or tantalum.Can in the device by the material manufacturing of anti-chlorizating agent or coating, carry out according to the method for the production of chloro-hydrin(e) of the present invention, 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 especially a kind of method for the production of chloro-hydrin(e), the 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.What mention more especially 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 for the production of chloro-hydrin(e) of the present invention can as be called in the reaction medium described in the application of " Continuous process for themanufacture of chlorohydrins " 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 especially a kind of continuation method for the production of chloro-hydrin(e), 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 forms the ester that (or stable state composition) comprises polyhydroxylated aliphatic hydrocarbons and polyhydroxylated aliphatic hydrocarbons, the total content of the polyhydroxylated aliphatic hydrocarbons that represents 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 be in such as 8 page of the 5th row of the 6th page of the 28th row to the of the patent application WO 2005/054167 of SOLVAY SA carry out in the presence of the concrete catalyzer that discloses.Mention especially 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.

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 in such as 10 page of the 10th row of the 8th page of the 6th row to the of the patent application WO 2005/054167 of SOLVAY SA 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 bar 100 bar 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 in such as the 11st page of the 12nd row to the 36 row of the patent application WO 2005/054167 of SOLVAY SA carry out in the presence of the concrete solvent that discloses.

What mention especially is such 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, the perhaps organic solvent of the heavy reaction product as the oligopolymer of at least part of chlorination of this polyhydroxylated aliphatic hydrocarbons and/or esterification.

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 especially a kind of method of producing chloro-hydrin(e), 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 bar is high 15 ℃ at least and this liquid phase is in the boiling temperature under absolute pressure 1 bar.

Method according to the present invention for the production of chloro-hydrin(e) 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 comprised of the liquid of the gas of solid chemical compound, dissolving or the dispersion of dissolvings all under temperature of reaction or dispersion and dissolving or dispersion.

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 refers to 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 such 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 such as monoglyceride, Diglyceride and triglyceride, the ester of lipid acid and the formation of the alcohol that is used for the transesterification process, and such 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 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 the method.

In by product, it for example can mention the partial oxidation 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 glycerine partial oxidation and/or esterification.

In the different step of the 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, dissolving or the chlorizating agent that disperses with bubble form, catalyzer, solvent, in reactant, in the catalyzer and the impurity that exists in the solvent, such as salt dissolving or solid, for example reaction intermediate, reaction product and byproduct of reaction.

In the method according to the invention, separating chloro-hydrin(e) and other compound from reaction medium can adopt and carry out in the method disclosed in 16 page of the 35th row of the 12nd page of the 1st row to the of the patent application WO 2005/054167 of SOLVAY SA and the 18th page of the 6th row to the 13 row.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, catalysts and solvents, 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 be as carrying out in the method disclosed in the 18th page of the 6th row to the 13 row of the patent application WO 2005/054167 of SOLVAY SA.

What mention especially is the separation by component distillation under the condition of chlorizating agent loss reduction of the mixture of water/chloro-hydrin(e)/chlorizating agent, then carries out precipitating (or decant) after this chloro-hydrin(e) separates.

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 " 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.

Mention especially a kind of method for the preparation of chloro-hydrin(e), 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), at least part of mixture that (b) will obtain in step (a) carries out one or many in step (a) step afterwards processes, and (c) in step (a) at least one step afterwards, add this polyhydroxylated aliphatic hydrocarbons, so that in temperature during at least 20 ℃ and the reaction of chloro alcohol ester, so that the ester of at least part of formation polyhydroxylated aliphatic hydrocarbons.Mention more especially a kind of method, wherein this polyhydroxylated aliphatic hydrocarbons is glycerine, and this chloro-hydrin(e) is dichlorohydrine.

In the method for chloro-hydrin(e) produced according to the invention, pure and mild other compound 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 application of " Process for manufacturing a chlorohydrin from amulti-hydroxylated aliphatic hydrocarbon " separating chlorine generation from reaction medium, and the content of above-mentioned application is incorporated herein by reference.

Mention that especially the reaction in the reactor that flows to material with one or more liquid is for the production of the method for chloro-hydrin(e) between a kind of ester by polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and the chlorizating agent, for the gross weight of the whole liquid streams in introducing this reactor, this liquid stream contains the polyhydroxylated aliphatic hydrocarbons less than 50 % by weight, the ester of polyhydroxylated aliphatic hydrocarbons or their mixture.Mention more especially a kind of method, 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 in order to 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, pure and mild other compound 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 converting multi-hydroxylated aliphatichydrocarbons into chlrohydrins " separating chlorine generation from reaction medium, and the content of above-mentioned application is incorporated herein by reference.

Mention especially a kind of method for the production of chloro-hydrin(e) that comprises the steps: 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 stripping is processed, thereby obtains the part that enrichment (or concentrated) 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 % by weight water thereby obtain enrichment (or concentrated).This lock out operation is precipitating (or decant) more particularly.

In the method according to the invention, from reaction medium, separate and process 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 especially a kind of method for the production of chloro-hydrin(e) that comprises the steps: (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 at least chloro-hydrin(e) and ℃ by product, (b) carry out one or many in the step of mixture after step (a) that at least a portion is obtained and process in step (a), and (c) at least one step after the step (a) is oxygenizement when temperature is greater than or equal to 800 ℃.Mention more especially a kind of method, 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 especially a kind of method, 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 for the production of 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 comprised of water and chloro-hydrin(e).

In the method for the production of 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 at least another cut of the reaction medium that contains chloro-hydrin(e) from reaction mixture.

According to the present invention for the production of aspect this of the method for chloro-hydrin(e), usually reclaim and contain the chloro-hydrin(e) of 50 to 96 % by weight and at least a cut of the water of 50 % by weight at the most.Preferably, this cut contains the chloro-hydrin(e) of 75 to 99.9 % by weight and the water of 0.01 to 25 % by weight, often is the chloro-hydrin(e) of 75 to 99 % by weight and the water of 1 to 25 % by weight.

Reclaim preferably and undertaken by distillation or evaporation.Other cut that contains intermediate for example, optional polyhydroxylated aliphatic hydrocarbons and catalyzer that in this step process, obtains can be recycled with chlorination reaction.As described at 11 page of the 34th row of the patent application WO of SOLVAY SA 2005/054167 page 1 the 32nd row to the, 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, in the process for the production 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 greater than the pressure of 0.001 bar usually.This pressure is preferably greater than or equal to about 0.003 bar.Distillation or evaporation are carried out under the pressure that is 15 bar to the maximum usually.This pressure often is to be 10 bar to the maximum.Preferably be 7 bar to the maximum, more preferably be 1 bar to the maximum, more very be preferably maximum 1 bar, and most preferably be maximum 0.1 bar.

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 residue is in order to reclaim for example catalyzer.

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

(a) the 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) optional at least part of product cut (or portion of product) is carried out drying operation;

(c) the product cut (or portion of product) with at least part of optional drying is incorporated in the second reactions steps, wherein an at least part of chloro-hydrin(e) and chlorination reaction.

Step in this change programme (a) and (c) preferably under certain condition, and with as described above according to the present invention the preferred value for the production of the method for chloro-hydrin(e) carry out.Yet, the preferably reaction of implementation step (a) in the presence of water, wherein the content of water is preferably 3～40 % by 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.According to another preferred change programme, by membrane technique except anhydrating.

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 materials of reaction mixture can economically recirculation in reactor after purification process.For example, the catalyzer that in water, has the low solubility processing that can be hydrolyzed, preferably carry 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 in the situation that hexanodioic acid, the hydrolysis of cleaning materials causes reclaiming highly purified crystallization hexanodioic acid in cooling with after filtering with good yield.

Especially when the method according to this invention operates 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 cause insoluble substance crystallization accumulation and cause the variety of issue relevant with solid matter, as on the reactor wall, on the agitator and on feeding line and the cleaning materials pipeline 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 in the method according to the invention metal-salt, 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.Like this remove can be aptly at least a portion (or a kind of cut) of reaction mixture by making the metal-salt that contains solid or dissolving process (it comprises at least a lock out operation) and implement in order to from described part (or cut), to remove at least a portion metal-salt.

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 process.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, and the metal-salt that removes by filter wherein as solid is most preferred.

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 processed 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 by stripping, distillation or evaporation, thus obtain to have the solid that increases content or dissolving metal-salt enriched fraction (or part) and process so that separating metal salt.

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

In a preferred embodiment, this part that contains the reaction mixture of metal-salt is to obtain from the cleaning materials of reacting the reactor that occurs therein, and be fed at least one separating unit, in this separating unit, for example process to carry out the separation of 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, preferably greater than or equal to 20 ℃, more preferably greater than or equal 30 ℃, again preferably greater than or equal to 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 apparent 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 by any mode, for example be shifted out solid or finish regeneration by dissolved salt by shifting out especially mechanically.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 change programme, need not further processing in suitable mode except desalting.

In the second change programme, 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 processed.

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

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

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

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 the method.Preferably use fresh as defined above water.

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 change programme, 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 change programme, 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 the method.Preferably use fresh as defined above water.

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 metal-salt of dissolving 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 change programme, washing metal-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 especially suited, and 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 as chlorizating agent, preferably contain the liquid stream of polyhydroxylated aliphatic hydrocarbons against the guide of flow of HCl logistics.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.

So that can obtain especially economically the chloro-hydrin(e) that concentrates, wherein the content of chloro-hydrin(e) often is 90 % by weight more than or equal to the chloro-hydrin(e) gross weight according to this specific embodiment of the inventive method.When chloro-hydrin(e) is dichlorohydrine, by the method, can obtain 1,3-dichloro propan-2-ol 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, the isomer of 3-dichloro propan-2-ol and 2,3-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 for the production of chloro-hydrin(e), according to the method:

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

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

At least a portion of the reaction medium (or cut) that (c) 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 % by weight.

Taking-up part (or cut) in step (b) can also contain hydrogenchloride.Preferably, this part is taken out continuously with its chemical species.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 for feedwater, 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, in order to the water-content in the reaction medium is maintained as in the scope described in 11 page of the 11st row of the 10th page of the 31st row to the of patent application WO 2005/054167 of SOLVAY SA name.

Take out continuously or periodically and can realize by introduce gas phase in distilation steps, specifically taking-up is 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 % by weight usually, preferably is less than or equal to 30 % by weight, and most preferably is less than or equal to 25 % by 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 organic product such as one or more parts (or cut) of heavy by product, specifically catalyzer and/or hydrogenchloride also can separate in this distilation steps, and usually are recycled in the reaction mixture.By selecting suitable reflux ratio, can be separated on the one hand at this and contain less water, the basic cut of containing hydrogen chloride not.

Reflux ratio can be by for feedwater and suitably be adjusted, and this water is basic containing hydrogen chloride and entering in the distillation tower not preferably.In this embodiment, preferably supply water to the distillation cat head.Can for example supply feedwater by the water recycle that at least a portion is separated to distilling cat head in distillation procedure.Can also supply feedwater by fresh water being added to the distillation cat head.These the two kinds modes for feedwater can be combined with.Add fresh water and obtain especially good result.

" substantially not containing hydrogen chloride " is interpreted as that specifically the hydrogen chloride content in the watery distillate (or part) is equal to or less than 10 % by weight of watery distillate gross weight.Often be that this content is equal to or less than 5 % by weight, preferably be equal to or less than 1 % by weight, more preferably be equal to or less than 0.3 % by weight.If the hydrogenchloride that exists in cut is " substantially not containing hydrogen chloride ", 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 the content of other organic or inorganic component of water is less than or equal to 12 % by weight with respect to the gross weight of water and other component, preferably is less than or equal to 10 % by weight, most preferably is less than or equal to 1 % by weight.Usually, " fresh " glassware for drinking water body content of being interpreted as other organic or inorganic component 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.May originating of fresh water can be the water that is used for the wash-out metal-salt of for example describing hereinafter: the softening water that obtains by ion exchange resin, distilled water or from the water of water vapor condensation.

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

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

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

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

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

Wherein enter the ratio of the hydrogen cloride concentration/water concentration in the cut of this distilation steps less than under distillation temperature and pressure, the concentration ratio of the hydrogenchloride/water during hydrogenchloride/water binary azeotropic forms.

The method is preferably carried out continuously.

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

For example can control hydrogen chloride content in the step (b) by adding entry.This adding can be for example by steam injection is carried out in the employed distillation tower boiler 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 by the top that fresh water is joined distillation tower, or the mixture of the water by adding recirculation and fresh water carries out.

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 being announced 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 as defined above water, 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 cut that comprises water that preferably obtains at the distillation tower top by distillation.

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

In the method for chloro-hydrin(e) produced according to the invention, chloro-hydrin(e) can comprise the halogenation ketone of increased content, 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 process to 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 especially a kind of method for the production of epoxide, wherein halogenated ketone forms as by product, and the method comprises that at least one step is for the processing of removing the formed halogenated ketone of at least a portion.Mention more especially a kind of by the method for chloro-hydrin(e) dehydrochlorination for the production of epoxide, 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, process and produce for the halogenated ketone of removing at least a portion formation by component distillation processing water-halogenated ketone mixture by dehydrochlorination, and a kind of technique for the production of Epicholorohydrin (or method), wherein halogenated ketone is monochloroacetone.

In the method for chloro-hydrin(e) produced according to the invention, when chloro-hydrin(e) is dichlorohydrine, obtained astoundingly the highly selective for 1,3-dichloro propan-2-ol, 1,3-dichloro propan-2-ol is especially suitable to be used for dehydrochlorination with for the production of 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 especially a kind of method for the production of epoxide, wherein from the ester of polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or their mixture and chlorination reaction, obtain reaction mixture, this reaction mixture contains at least chloro-hydrin(e) of 10g/kg reaction mixture, and it carries out other chemical reaction and need not intermediate treatment.

Especially mention a kind of method for the production of 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 at least 10g chloro-hydrin(e) in the reaction mixture of every kg; At least a portion reaction mixture that (b) will obtain in step (a) (this partially mixed thing has same composition with the reaction mixture that obtains in step (a)) carries out one or many in step (a) step afterwards processes; And (c) in step (a) at least one step afterwards, add basic cpd, so that ester at least part of and chloro-hydrin(e), chloro-hydrin(e), thereby chlorizating agent and organic acid reaction form a kind of epoxide and salt.

Can be incorporated into such as the name of submitting to SOLVAY SA name on the same day with the application for the production of the method for chloro-hydrin(e) according to the present invention and to 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 especially a kind of method for the production of epoxide, the step that comprises the epoxide that at least one purifying generates, this epoxide is at least part of to be that method by the chloro-hydrin(e) dehydrochlorination generates, and this chloro-hydrin(e) is at least part of to be to produce by the ester of chlorination polyhydroxylated aliphatic hydrocarbons, polyhydroxylated aliphatic hydrocarbons or the method for 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 usually can be for the production of Resins, epoxy.

Fig. 1 shows the especially preferred equipment flowsheet that can be used for implementing 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 for keeping backflow (ratio) by pipeline (11).Fresh water can join cat head by pipeline (12) and be used for keeping backflow (ratio).The chloro-hydrin(e) that generates distributes between the 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 materials that is arranged in reactor bottom liquid (16) alternatively.One liquid of taking-up flows and is sent in the vaporizer (18) by pipeline (17) from cleaning materials (16), carry out there the part evaporation operation, 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), distillation tower or stripping tower (22) come the liquid phase of 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 in the filtering unit (25) by pipeline (28) and (29) and be used for washing and/or dissolution of solid and take out from pipeline (27).Alternatively, one liquid of taking-up flows and supplies in the filtering unit (25) by pipeline (30) from cleaning materials (16).Stripping tower (18) and distillation tower (22) then are bypassed.

The result who obtains according to this last (stripping tower (18) and (distillation) tower (22) are bypassed) schema by detail record in an embodiment.

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 suits very much.When polyhydroxylated aliphatic hydrocarbons is that glycerine, chloro-hydrin(e) are dichlorohydrine and epoxide when being Epicholorohydrin, the method is especially easily.

When polyhydroxylated aliphatic hydrocarbons is glycerine, this change programme of the 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 % by weight (it has the selectivity that is higher than 99 % by 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 the present invention to be described 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) is take the relative discharge mass ratio as 2.06 by the aqueous hydrochloric acid of continuous supplying to crude glycerol and 33 % by weight.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 lower operations.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 producing 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 to use in the method pure glycerine to have different.

The slurry pumping of autoreactor arrives on 115 microns the PTFE film filter in filtration tank (25) in the future.Salt-cake in strainer is lower to the saturated dichlorohydrine washing that water is arranged at 20 ℃.Shift out liquid phase and discharging solid, salt is water-soluble and discard the salt water.The time length of washing and salt dissolving is approximately 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.Water with salt the analysis showed that dichlorohydrine: the mass ratio of NaCl is 1.44 and a small amount of catalyzer (less than 10g/kg).The amount of the dichlorohydrine in salt solution shows as 1.6% of dichlorohydrine total product.

Take the overall yield of dichlorohydrine (expression) as 93%.

Claims

1. for the production of the method for chloro-hydrin(e), make according to described method and to contain at the most that polyhydroxylated aliphatic hydrocarbons and the chlorizating agent of the organic impurity of 8 % by weight react, wherein said organic impurity is the ester of lipid acid or lipid acid, and wherein said polyhydroxylated aliphatic hydrocarbons is glycerine, and described chloro-hydrin(e) is dichlorohydrine.

2. method according to claim 1, the content of wherein said organic impurity is at most 6 % by weight.

3. method according to claim 2, the content of wherein said organic impurity is at most 1 % by weight.

4. method according to claim 1, wherein said lipid acid is selected from the saturated and unsaturated fatty acids that contains more than 12 carbon.

5. method according to claim 1, wherein said lipid acid is selected from oleic acid, linoleic acid plus linolenic acid.

6. method according to claim 1, the ester of wherein said lipid acid is methyl ester.

7. method according to claim 1, the ester of wherein said lipid acid is monoesters or the polyester of described polyhydroxylated aliphatic hydrocarbons and lipid acid.

8. each described method in 7 is according to claim 1 produced Epicholorohydrin by the dichlorohydrine dehydrochlorination subsequently.

9. method according to claim 8, wherein said Epicholorohydrin is for the production of Resins, epoxy.

10. each described method in 7 according to claim 1, wherein said chlorizating agent is gas chlorination hydrogen.

11. each described method in 7 according to claim 1, wherein said reaction is carried out in the presence of catalyzer.

12. method according to claim 11, wherein said catalyzer is carboxylic acid.

13. having, method according to claim 12, wherein said carboxylic acid be greater than or equal to 200 ℃ atmospheric boiling point.

14. method according to claim 13, wherein said carboxylic acid is hexanodioic acid.

15. each described method in 7 according to claim 1, described method is carried out in a continuous manner.

16. each described method in 7 according to claim 1, 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.