CN104591967A - Crude glycerin treatment and applications of the same in epichlorohydrin production - Google Patents
Crude glycerin treatment and applications of the same in epichlorohydrin production Download PDFInfo
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- CN104591967A CN104591967A CN201310746633.2A CN201310746633A CN104591967A CN 104591967 A CN104591967 A CN 104591967A CN 201310746633 A CN201310746633 A CN 201310746633A CN 104591967 A CN104591967 A CN 104591967A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
The present invention relates to a crude glycerin treatment and applications of the same in epichlorohydrin production. The present invention relates to a crude glycerin treatment method, which comprises: (a) adding hydrogen chloride gas to crude glycerin to precipitate insoluble solids; and (b) filtering to remove the precipitated solids to obtain the treated glycerin.
Description
Technical field
The present invention relates to a kind for the treatment of process of raw glycerine, and utilize the method for the rear glycerol production epoxy chloropropane of process.
Background technology
Epoxy chloropropane is the important source material of producing the products such as epoxy resin, chlorohydrin rubber, stablizer, tensio-active agent, fire retardant and oil field chemical, and dichlorohydrine is the key intermediate of its synthesis.At present, the method for industrial production dichlorohydrine, being mainly with propylene is propylene high-temperature chlorination process and the acetate propylene ester process of raw material.Propylene high-temperature chlorination process exists that energy consumption is high, propylene utilization ratio is low, by product mainly with and the problem such as chlorine-contained wastewater quantity discharged is too large; Acetate propylene ester process exists that operational path is long, investment is large, expensive catalyst and the problem such as the life-span is short.Generally speaking, above-mentioned two kinds of commercial runs consume Nonrenewable resources all in a large number, but also consume chlorine in a large number, cause serious environmental pollution.Since entering 21st century, because biofuel is greatly developed in countries in the world, thereupon can a large amount of glycerine of by-product, cause glycerol market superfluous, glycerine price is slumped, and under this background, it is the novel process of raw material production epoxy chloropropane that many countries have developed with glycerine.
The technique of glycerine method synthesizing epoxy chloropropane relates to two committed steps: (1) glycerine and hydrogenchloride react and generates dichlorohydrine under catalyst action; (2) dichlorohydrine carries out cyclization and obtains epoxy chloropropane in the basic solution such as sodium hydroxide or milk of lime.Due to cyclization process similar, relative maturity, so people mainly concentrate on the method for research glycerine and hcl reaction synthesizing dichloropropanol.
Existing many patent literatures are by the method for glycerine and hcl reaction synthesizing dichloropropanol.Can find that glycerine used in these patents mainly refers to the glycerine of content more than 95%, if China Forestry Science Research Institute (CN 101003523 A) catalytic chlorination glycerine is the industry glycerol of 95%, Spolek of Czech (CN 1845888 A, WO 2005021476) use 97.5% glycerine, Yanzhou Tian Cheng Chemical Co., Ltd. (CN 101704722A) 99.5% smart glycerine, Ah Purcell Co., Ltd. of Italy (CN 101184715A, WO2006111810) uses 99.9% anhydrous glycerol.Above these patent literatures be all adopt high-purity glycerol and do not adopt raw glycerine be the major cause of raw material have following some: (1) is in the continuous chlorination production process of glycerine, the raffinate that inorganic salt in raw glycerine can produce with chlorination mixes, easy caking, cause the blocking of pipeline, need regularly to carry out pipe-dredging, not only consuming time but also effort, and reduce production capacity, normal operation is produced in impact; (2) inorganic salt in raw glycerine can enter the dichlorohydrine underpressure distillation stage, cause distillation system to bubble, and impact steams the quality of dichlorohydrine.If process and purifying raw glycerine, obtain the glycerine that can carry out chlorination reaction, can reduce costs, additional income.
The method of conventional purifying crude glycerol is distillation under vacuum, and pretreated raw glycerine, in the process of purifying crude glycerol, is carried out underpressure distillation by U.S. patent documents US 4655879 in thin layer evaporator.This needs careful control condition, because when Heating temperature reaches 170-180 DEG C, glycerine can decompose or be polymerized, and causes the formation of impurity and reduces the rate of recovery of glycerine.
In order to stable still-process, and the qualities of glycerin can improved after underpressure distillation, Russ P RU2210560 adds the auxiliary agent Fenozean28 of 0.2-0.3% content in the forward direction glycerine of underpressure distillation, effect improves, but keep away unavoidable expensive distillation plant by distillation under vacuum purifying crude glycerol, cause higher production cost.
Ion exchange method also has important application in sweet oil handling.(CN 101475444A) carries out purifying by ion-exchange-resin process to raw glycerine in Jiangmen City Hongjie Fine Chemical Co., Ltd, and method carries out evaporative removal moisture and methyl alcohol after being filtered by raw glycerine; Carried out ion-exchange again and removed inorganic salt; Finally by the glycerine that thin film distillation acquisition purity is greater than 95%.
Method described in patent WO 2008156612 comprises continuous two or more nanofiltration system or reverse osmosis filter filters raw glycerine mixture, and at least one filter membrane comprises the filtration medium that contact angle is about 44-56 degree.
France sieve ground sub-(CN 102596871 A, WO 2011030204) carries out purifying by chemical treatment to raw glycerine, is divided into four steps: (1) is by raw glycerine and low-grade carboxylic acid or anhydride reaction; (2) by glyceryl ester that fractionation by distillation is formed; (3) ester formed and at least one alkyl alcohol or cycloalkyl alcohol are reacted; (4) be separated the smart glycerine of formation, high purity 99%, but the method complex steps, be difficult to industrialization.
France sieve ground sub-(CN 103097327, WO 2012034904) also disclosed the method by organic solvent extraction purifying crude glycerine, is divided into four steps: (1) is by raw glycerine and suitable immiscible organic solvent; (2) soluble phase and liquid phase is separated; (3) solvent in the rear liquid phase of separation and moisture is removed; (4) reclaim glycerine, the raw glycerine of glycerol content 79.3%, water-content 15.8% and salts contg 1.61% is purified to the smart glycerine that glycerol content is 97.5%.But it is large to there is consumption of organic solvent in the method, and the shortcomings such as energy consumption is large, are not suitable for industrial application.
Solvay of Belgium (CN 101066909 A, WO 2007144335) discloses a kind of purification process containing glycerine alkyl oxide raw glycerine, and utilizes the method for glycerine synthesizing dichloropropanol after purifying.This raw glycerine can pass through evaporation concentration, evaporative crystallization, distillation, fractionation, and at least one method process in air lift or liquid-liquid extraction, these treatment processs make the production method of dichlorohydrine complicated.
In view of existing raw glycerine treatment technology, need to develop that a kind of operation steps is few, expense is relatively low, the raw glycerine treatment process of temperature and pressure condition milder, especially from the raw glycerine of by-product a large amount of in production of biodiesel process, can be used as the cheap raw material of synthesizing epoxy chloropropane after treatment.
Summary of the invention
the problem that invention will solve
The object of this invention is to provide a kind of simple raw glycerine treatment process, and after utilizing process, the method for epoxy chloropropane prepared by glycerine.
The raw material of current glycerin chlorination production epoxy chloropropane is the glycerine of more than 95% purity, and the glycerine of 95% purity is all by raw glycerine pyrogenic distillation being obtained, wherein derive from the raw glycerine of biodiesel byproduct, except containing except glycerine, also containing water, metal-salt and other organism on a small quantity, partial glycerol polymerization, decomposition etc. will certainly be had when it is distilled and make glycerine yield lower, and bottom distillation tower, glycerine and the polyglycerine of a large amount of saliferous that by-product color is comparatively dark and utility value is lower.If directly raw glycerine is applied to glycerin chlorination to produce dichlorohydrine, the above-mentioned listed impurity in raw glycerine can produce a very large impact raw glycerine chlorination.The particularly existence of sodium-chlor, to the line clogging of glycerin chlorination production unit, cannot normally can produce, and therefore needs to process raw glycerine before chlorination.
for the scheme of dealing with problems
[1] the present invention relates to a kind of raw glycerine treatment process, the method comprises the steps:
A raw glycerine contacts with hydrogen chloride gas by (), separate out insoluble solid;
B () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
[2] the present invention relates to a kind of raw glycerine treatment process, it is characterized in that, the method comprises the steps:
A raw glycerine is removed water at least partially by (), raw glycerine after obtaining dewatering;
B raw glycerine after described dewatering contacts with hydrogen chloride gas by (), separate out insoluble solid;
C () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
[3] according to [1] or the raw glycerine treatment process described in [2], the raw glycerine wherein in step (a) comprises the glycerine of 5 % by weight to 95 % by weight, the water of 1 % by weight to 80 % by weight, and the metal-salt of 1 % by weight to 30 % by weight.
[4] the raw glycerine treatment process Gen Ju [1], wherein comprise the glycerine of 5 % by weight to 90 % by weight after the described process that obtains of step (b) in glycerine, the hydrogenchloride of 5 % by weight to 40 % by weight, the water of 0.5 % by weight to 60 % by weight, and the metal-salt being less than 1 % by weight.
[5] the raw glycerine treatment process Gen Ju [2], wherein step (a) obtain described in dewater after comprise in raw glycerine 30 % by weight to 99 % by weight glycerine, the water of 0.1 % by weight to 10 % by weight, and the metal-salt of 1 % by weight to 55 % by weight.
[6] the raw glycerine treatment process Gen Ju [1], when wherein passing into hydrogen chloride gas, the gauge pressure of system is that-0.1MPa is to 1MPa, the described amount passing into hydrogenchloride is 5% to 70% of raw glycerine weight, the initial temperature of the described raw glycerine contacted with hydrogen chloride gas is 20 DEG C to 200 DEG C, and when solid-liquid separation, raw glycerine temperature is 20 DEG C to 200 DEG C.
[7] the raw glycerine treatment process Gen Ju [2], when wherein passing into hydrogen chloride gas, the gauge pressure of system is that-0.1MPa is to 1MPa, the described amount passing into hydrogenchloride is 5% to 70% of raw glycerine weight after dewatering, described contact with hydrogen chloride gas dewater after the initial temperature of raw glycerine be 20 DEG C to 200 DEG C, after dewatering when solid-liquid separation, raw glycerine temperature is 20 DEG C to 200 DEG C.
[8] the raw glycerine treatment process Gen Ju [2], wherein comprise the glycerine of 50 % by weight to 95 % by weight after the described process that obtains of step (c) in glycerine, the hydrogenchloride of 1 % by weight to 30 % by weight, the water of 0.1 % by weight to 20 % by weight, and the metal-salt being less than 1 % by weight.
[9] preparation method for epoxy chloropropane, is characterized in that, the method comprises the steps:
A () adopts the method described in any one of [1-8] to obtain processing rear glycerine;
B (), under the existence of carboxylic-acid catalyzer, after described process step (a) obtained, glycerine or its mixture and hydrogen chloride gas precursor reactant, prepare dichlorohydrine;
C dichlorohydrine and cyclizing agent carry out removing hcl reaction by (), prepare epoxy chloropropane.
The preparation method of the epoxy chloropropane [10] Gen Ju [9], wherein, described carboxylic-acid catalyzer is the combination of one or more in acetic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid and sebacic acid.
The preparation method of the epoxy chloropropane [11] Gen Ju [9], wherein, the consumption of described carboxylic-acid catalyzer is 0.1% to 10% of glycerine molar weight after process, preferably 1% to 6%.
The preparation method of the epoxy chloropropane [12] Gen Ju [9], wherein, the temperature of reaction of step (b) is 80 DEG C to 130 DEG C, preferably 100 DEG C to 120 DEG C.
The preparation method of the epoxy chloropropane [13] Gen Ju [9], wherein, the reaction times of step (b) is 1h to 20h, preferred 5h to 15h.
The preparation method of the epoxy chloropropane [14] Gen Ju [9], wherein, in step (b), after process, the mol ratio of glycerine and hydrogenchloride is 1:2 to 1:5, preferred 1:2 to 1:3.
The preparation method of the epoxy chloropropane [15] Gen Ju [9], wherein, the false ternary azeotrope of the water formed in step (b), hydrogenchloride and dichlorohydrine shifts out and obtains carry-over from reaction system, after the reaction of step (b) terminates, by underpressure distillation dichlorohydrine steamed and obtain steaming thing.
The preparation method of the epoxy chloropropane [16] Gen Ju [9], wherein, by described carry-over with steam thing and be mixed to get dichloropropanol mixture, and prepare epoxy chloropropane for cyclization.
The preparation method of the epoxy chloropropane [17] Gen Ju [9], wherein, the dichlorohydrine that step (b) obtains comprises 1,3-dichlorohydrine and 2,3-dichlorohydrine.
The preparation method of the epoxy chloropropane [18] Gen Ju [9], wherein, the concentration of described dichlorohydrine, based on dichloropropanol mixture total weight, is 10 % by weight to 95 % by weight, preferably 60 % by weight to 90 % by weight.
The preparation method of the epoxy chloropropane [19] Gen Ju [9], wherein, the cyclizing agent of step (c) is sodium hydroxide solution or milk of lime, preferred sodium hydroxide solution.
The preparation method of the epoxy chloropropane [20] Gen Ju [9], wherein, the cyclizing agent concentration of step (c), be 1 % by weight to 75 % by weight, preferably 10 % by weight to 55 % by weight, more preferably 20 % by weight to 40 % by weight, particularly preferably 20 % by weight to 30 % by weight.
The preparation method of the epoxy chloropropane [21] Gen Ju [9], wherein, the mol ratio of described dichlorohydrine and cyclizing agent is 1:1 to 1:3, preferred 1:1 to 1:1.5.
The preparation method of the epoxy chloropropane [22] Gen Ju [9], wherein, described cyclization temperature is 20 DEG C to 100 DEG C, preferably 50 DEG C to 90 DEG C.
[23] a kind of glycerin compositions, wherein comprise the glycerine of 5 % by weight to 90 % by weight, the hydrogenchloride of 5 % by weight to 40 % by weight, the water of 0.5 % by weight to 60 % by weight, with the metal-salt being less than 1 % by weight, preferred glycerin compositions contains the glycerine of 50 % by weight to 90 % by weight, the hydrogenchloride of 5 % by weight to 30 % by weight, the water of 1 % by weight to 20 % by weight, is greater than 0.02 % by weight metal-salt being less than 1 % by weight.
[24] prepare a method for epoxy compounds and derivative thereof, wherein, the glycerine adopting the method process of claim 1 and claim 2 to obtain is prepared as starting raw material.
the effect of invention
Compared with the method applied in epoxy chloropropane is produced with existing raw glycerine treatment process and glycerine, tool of the present invention has the following advantages:
(1) cost of raw glycerine raw material is far below glycerine more than 95% content, significantly reduces the production cost of epoxy chloropropane;
(2) be directly used in production epoxy chloropropane after raw glycerine process, carry out producing for epoxy chloropropane by distillation acquisition 95% glycerine compared to raw glycerine, produce without polyglycerine, the utilization ratio of glycerine improves further, reduces production cost further again;
(3) operation is simple in the process of raw glycerine, and processing condition comprise temperature, pressure milder;
(4) the process energy consumption of raw glycerine is little, processing cost is low, be easy to realize industrialization;
(5) hydrogenchloride after process in glycerine can be used for chlorination reaction as raw material, realizes recycling, energy-conserving and environment-protective;
(6) after process, the chlorination effect of glycerine is suitable with the chlorination effect of content more than 95% glycerine.
Embodiment
The invention provides a kind of raw glycerine treatment process, the method comprises the steps:
A raw glycerine contacts with hydrogen chloride gas by (), separate out insoluble solid;
B () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
The invention provides a kind of raw glycerine treatment process, the method comprises the steps:
A raw glycerine is removed water at least partially by (), raw glycerine after obtaining dewatering;
B raw glycerine after described dewatering contacts with hydrogen chloride gas by (), separate out insoluble solid;
C () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
Wherein said raw glycerine comprise with the way of contact of hydrogenchloride spray, adverse current, vapour-liquid mix, in raw glycerine, pass into the modes such as hydrogen chloride gas, what those skilled in the art understood can carry out well-mixed embodiment by raw glycerine and hydrogen chloride gas and all can be applied in the present invention.
Wherein said insoluble solid comprises the solid existed with particle or suspended state, comprises metal-salt.In an embodiment of the invention, described insoluble solid refers to solid metal salt, and metal-salt is selected from an alkali metal salt or alkaline earth salt.
Wherein the mode removing water at least partially in raw glycerine is comprised the modes such as underpressure distillation, air distillation, drying, adsorbent.In the understandable deglycerizin of those skilled in that art, the mode of moisture all can be applicable in the present invention.
Present invention also offers a kind of glycerin compositions, wherein contain the glycerine of 50 % by weight to 90 % by weight, the hydrogenchloride of 5 % by weight to 30 % by weight, the water of 1 % by weight to 60 % by weight, is greater than 0.02 % by weight metal-salt being less than 1 % by weight.This glycerine can be directly used in prepares dichlorohydrine, and does not need further process.Due in the glycerine that obtains after process containing partial oxidation hydrogen, therefore can pass into hydrogenchloride less in the process preparing dichlorohydrine.
Present invention also offers a kind of method preparing epoxy compounds and derivative thereof, wherein, the glycerine that employing aforesaid method obtains is as starting raw material.
In the method according to the invention, epoxy compounds comprises epoxy chloropropane etc., epoxy derivative refers to and further to react on the basis of epoxy compounds, the organism adopting the conventional method of the replacement, grafting, polymerization etc. of functional group to obtain, comprise epoxy compounds the compound that can directly or indirectly be obtained by reacting.
Epoxy derivative is normally selected from epoxy resin, Racemic glycidol ethers, glycidyl ester class, glycidyl amides, glycidyl imides, Racemic glycidol amine.Described epoxy derivative also comprises and carries out the various modified alternate compounds obtained to these compounds.Described epoxy derivative can be used as condensing agent class, wet strengthening resin class, cationics class, fire retardant class, product for the composition of sanitising agent, epichlorohydrin elastomer class, the polyether-polyols of halogenation.The method preparing above-mentioned epoxy compounds and epoxy derivative is known all as is known to those skilled in the art, can with reference to corresponding reference book or textbook.
In an embodiment of the invention, wherein said method comprises the steps: to pass into hydrogen chloride gas in raw glycerine (A), precipitating metal salt gradually, removes the metal-salt of separating out, obtains processing rear glycerine (C1) finally by Filter Press.
In yet another embodiment of the present invention, wherein said method comprises the steps: raw glycerine (A) to carry out underpressure distillation and removes most of moisture wherein and low-boiling-point organic compound, raw glycerine (B) after obtaining dewatering, then in raw glycerine (B) after dewatering, hydrogen chloride gas is passed into, precipitating metal salt gradually, remove the metal-salt of separating out finally by Filter Press, obtain processing rear glycerine (C2).
In the present invention, the embodiment of raw glycerine treatment process can be periodical operation or operate continuously, preferred operate continuously.
Periodical operation refers in the treating processes of raw glycerine, raw glycerine batch treatment, and every a collection of raw glycerine all obtains processing rear glycerine respectively by the operation such as hydrogen chloride gas, press filtration desalination that dewaters, passes into.
Operate continuously refers to that raw glycerine processes continuously in the treating processes of raw glycerine, and continuous print passes into raw glycerine, and continuously across dewatering, passing into, the operation such as hydrogen chloride gas, press filtration desalination obtains processing rear glycerine.
Wherein, described metal-salt is metal chloride or metal sulfate, preferably from sodium-chlor, Repone K or sodium sulfate, potassium sulfate.Described hydrogen chloride gas derives from combustion method or prepares the by product produced in organism, and the hydrogen chloride gas of originating in the industrial production all can be used in the present invention.Described hydrogen chloride gas can comprise the water vapor of less than 5%, preferably the water vapor of less than 3%.
Wherein, described raw glycerine (A) refers to natural fats and oils commercial run, such as saponification, highly pressured hydrolysis or the glycerine obtained with the transesterification reaction of alcohol, especially preferably produces from vegetables oil and animal tallow the raw glycerine obtained biodiesel process.The raw glycerine used in the application by commercially available, as bought in Wilmar Trading Pte Ltd company.
In the present invention, term " solid-liquid separation " refer to adopt leave standstill, press filtration, suction filtration, or the solid-liquid separation means such as centrifugation makes solid be separated with liquid phase.
Wherein, described raw glycerine (A) comprises the glycerine of 5 % by weight to 95 % by weight, preferably the glycerine of 40 % by weight to 90 % by weight, more preferably the glycerine of 70 % by weight to 90 % by weight.Described raw glycerine (A) comprises the water of 1 % by weight to 80 % by weight, preferably the water of 5 % by weight to 30 % by weight, more preferably the water of 5 % by weight to 20 % by weight.
Wherein, based on raw glycerine total amount, the ash content of described raw glycerine (A), for being less than 35 % by weight, being preferably less than 15 % by weight, being more preferably less than 5 % by weight.The ash content of described raw glycerine (A) is mainly from metal-salt.Described raw glycerine (A) comprises the metal-salt of 1 % by weight to 30 % by weight, preferably the metal-salt of 1 % by weight to 15 % by weight, more preferably the metal-salt of 1 % by weight to 5 % by weight.
Wherein, the temperature of described raw glycerine (A) when passing into hydrogen chloride gas is 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more preferably 40 DEG C to 100 DEG C.The amount passing into hydrogen chloride gas in described raw glycerine (A) is 5% to 70% of raw glycerine (A) weight, preferably 8% to 50%, more preferably 10% to 37%.Described raw glycerine (A) when passing into hydrogen chloride gas, the gauge pressure of system be-0.1MPa to 1MPa, preferred 0.01MPa to 0.5MPa, more preferably 0.01MPa to 0.1MPa.
Wherein, during described press filtration, the filter cloth aperture of pressure filter is 40 order to 1250 orders, preferably 100 order to 800 orders, more preferably 500 order to 800 orders.After process during described solid-liquid separation, glycerine temperature is 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more preferably 40 DEG C to 100 DEG C.
Wherein, the glycerine of 5 % by weight to 90 % by weight is comprised after described process in glycerine (C1), the preferably glycerine of 40 % by weight to 80 % by weight, the more preferably glycerine of 60 % by weight to 80 % by weight.The hydrogenchloride of 5 % by weight to 40 % by weight is comprised in glycerine (C1), the preferably hydrogenchloride of 5 % by weight to 30 % by weight, the more preferably hydrogenchloride of 10 % by weight to 20 % by weight after described process.The water of 1 % by weight to 60 % by weight is comprised in glycerine (C1), the preferably water of 5 % by weight to 30 % by weight, the more preferably water of 5 % by weight to 15 % by weight after described process.
Wherein, based on glycerine total amount after process, after described process, the ash content of glycerine (C1) is for being less than 2 % by weight, is preferably less than 1 % by weight, is more preferably less than 0.5 % by weight.After described process, the ash content of glycerine (C1) is mainly from metal-salt.After described process, in glycerine (C1), the content of metal-salt, for being less than 1 % by weight, being preferably less than 0.5 % by weight, being more preferably less than 0.3 % by weight.
In yet another embodiment of the present invention, wherein, described in dewater after comprise in raw glycerine (B) 30 % by weight to 99 % by weight glycerine, the preferably glycerine of 60 % by weight to 95 % by weight.Described dewater after comprise in raw glycerine (B) 0.1 % by weight to 20 % by weight water, the preferably water of 0.5 % by weight to 10 % by weight, the more preferably water of 0.5 % by weight to 5 % by weight.Described dewater after raw glycerine (B) comprise 0.5 % by weight to 55 % by weight metal-salt, the preferably metal-salt of 1 % by weight to 30 % by weight, the more preferably metal-salt of 1 % by weight to 15 % by weight.
Wherein, when passing into hydrogen chloride gas, described in dewater after the initial temperature of raw glycerine (B) be 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more preferably 40 DEG C to 100 DEG C.The amount passing into hydrogen chloride gas after described dewatering in raw glycerine (B) is 5% to 70% of raw glycerine (B) weight after dewatering, preferably 8% to 50%, more preferably 10% to 37%.When passing into hydrogen chloride gas in raw glycerine (B) after described dewatering, system gauge pressure be-0.1MPa to 1MPa, preferred 0.01MPa to 0.5MPa, more preferably 0.01MPa to 0.1MPa.
Wherein, during described press filtration, the filter cloth aperture of pressure filter is 40 order to 1250 orders, preferably 100 order to 800 orders, more preferably 500 order to 800 orders.After process during described solid-liquid separation, glycerine temperature is 20 DEG C to 200 DEG C, preferably 30 DEG C to 150 DEG C, more preferably 40 DEG C to 100 DEG C.
Wherein, the glycerine of 50 % by weight to 95 % by weight is comprised after described process in glycerine (C2), the preferably glycerine of 70 % by weight to 95 % by weight, the more preferably glycerine of 70 % by weight to 85 % by weight.The hydrogenchloride of 1 % by weight to 30 % by weight is comprised in glycerine (C2), the preferably hydrogenchloride of 5 % by weight to 20 % by weight, the more preferably hydrogenchloride of 5 % by weight to 15 % by weight after described process.The water of 0.1 % by weight to 20 % by weight is comprised in glycerine (C2), the preferably water of 0.3 % by weight to 8 % by weight, the more preferably water of 0.5 % by weight to 5 % by weight after described process.Based on glycerine total amount after process, after described process, the ash content of glycerine (C2) is for being less than 2 % by weight, is preferably less than 1 % by weight, is more preferably less than 0.5 % by weight.
Wherein, after described process the ash content of glycerine (C2) mainly from metal-salt.After described process, in glycerine (C2), the content of metal-salt is less than 1%, is preferably less than 0.5%, is more preferably and is less than 0.3%.
On the other hand, the invention provides a kind of method preparing epoxy chloropropane, it is characterized in that, glycerine (C1) or (C2) after the process that described method adopts above-mentioned raw glycerine treatment process to obtain, or the composition production epoxy chloropropane of glycerine (C1) and (C2) after the process of arbitrary proportion, the method comprises the steps:
(1) under the existence of carboxylic-acid catalyzer, glycerine (C1) or (C2) after processing, or after the process of arbitrary proportion, the composition of glycerine (C1) and (C2) and hydrogen chloride gas react, and prepare dichlorohydrine;
(2) dichlorohydrine and cyclizing agent are carried out removing hcl reaction, prepare epoxy chloropropane.
Wherein, glycerine (C1) or (C2) after described process, or after the process of arbitrary proportion glycerine (C1) and (C2) composition in the hydrogenchloride that contains can participate in reacting as raw material in dichlorohydrine preparation process.
Wherein, described carboxylic-acid catalyzer is comprise the combination of one or more in the organic carboxyl acids such as acetic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid.Wherein, the consumption of described carboxylic-acid catalyzer is 0.1% to 10% of glycerine molar weight after process, preferably 1% to 6%.
Wherein, the temperature of reaction of described step (1) is 80 DEG C to 130 DEG C, preferably 100 DEG C to 120 DEG C.Wherein, the reaction times of described step (1) is 1h to 20h, preferred 5h to 15h.Wherein, after described process, the mol ratio of glycerine and hydrogenchloride is 1:2 to 1:5, preferred 1:2 to 1:3.Wherein, described hydrogenchloride is dry hydrogen chloride gas.
Wherein, false to the water of formation, hydrogenchloride and dichlorohydrine ternary azeotrope is shifted out from reaction system and is called carry-over, by underpressure distillation dichlorohydrine steamed after step (1) reaction terminates and be called and steam thing.
Wherein, by described carry-over with steam thing and be mixed to get dichloropropanol mixture, and prepare epoxy chloropropane for cyclization.Wherein, the product dichlorohydrine obtained comprises 1,3-dichlorohydrine and 2,3-dichlorohydrine.The concentration of described dichlorohydrine, based on dichloropropanol mixture total weight, is 10 % by weight to 95 % by weight, preferably 50 % by weight to 90 % by weight.
Wherein, cyclizing agent described in step (2) is sodium hydroxide solution or milk of lime (calcium hydroxide), and preferred cyclizing agent is sodium hydroxide solution.Wherein, the concentration of described cyclizing agent is 1 % by weight to 75 % by weight, preferably 10 % by weight to 55 % by weight, more preferably 20 % by weight to 40 % by weight, particularly preferably 20 % by weight to 30 % by weight.Wherein, the mol ratio of described dichlorohydrine and cyclizing agent is 1:1 to 1:3, preferred 1:1 to 1:1.5.Described cyclisation temperature is 20 DEG C to 100 DEG C, preferably 50 DEG C to 90 DEG C.
In the present invention, described term " raw glycerine " is for deriving from the raw glycerine of biodiesel byproduct, and it is except containing except glycerine, also containing water, metal-salt and other organism on a small quantity.The existence of these materials can produce a very large impact raw glycerine chlorination, therefore needs to process raw glycerine before chlorination.
In the present invention, the fluid indicator pressure that described term " gauge pressure " is is benchmark with the ambient atmosphere pressure of locality, available pressure measures, and is called gauge pressure.That is: gauge pressure=absolute pressure-ambient atmosphere pressure.Gauge pressure is that negative value represents lower than ambient atmosphere pressure, and gauge pressure is higher than ambient atmosphere pressure on the occasion of expression.
Embodiment
The following examples are to further elaboration of the present invention, and its object only for explaining and illustrating, content of the present invention is not limited to this.Embodiment in specification sheets of the present invention is only for the present invention will be described, and it does not play restriction effect to protection scope of the present invention.Protection scope of the present invention is only defined by the claims, and any interpolation that those skilled in the art make on the basis of embodiment disclosed by the invention, replacement or amendment all will fall into protection scope of the present invention.
Wherein, unless otherwise indicated, " % " expression " % by weight " in embodiment.
The measuring method of raw glycerine index is: GB/T 13216-2008 is shown in content, moisture and determination of ash, and salts contg is shown in QB/T 2623.6-2003.
The measuring method of epoxy chloropropane leading indicator is: GB/T13097-2007 is shown in color and luster, content, moisture and density measurement.
Dichloropropanol content is detected by GC method, detailed process reference Jia Chaohui etc., gas-chromatography Simultaneously test epoxy chloropropane and intermediate thereof, fine-chemical intermediate, the 38th phase in volume year the 3rd, in June, 2008, the method for 68-70 page.
Embodiment 1
The process of raw glycerine
Raw material raw glycerine is made up of following: 80.6% glycerine, 14.3% water, 3.6% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount, ash oontent is 4.1%.
Above-mentioned raw glycerine (A) 600g is added in the four neck flasks of 1000mL, at room temperature, pass into hydrogen chloride gas 128g, in system, have the solid salt of fine particle to separate out gradually; At 60 DEG C, the glycerine having led to hydrogen chloride gas being transferred to filter cloth aperture is 800 object pressure filters carry out filter the metal-salt removed and separate out, and obtains processing rear glycerine (C1) 706g(68.5% glycerine, 18.1% hydrogenchloride, 12.2% water, 0.06% sodium-chlor, and the impurity of surplus.Wherein, based on glycerine total amount after process, ash oontent is 0.23%).
The preparation of epoxy chloropropane
Glycerine (C1) after above-mentioned process is transferred in another 2000mL tetra-neck flask, add 38.3g hexanodioic acid (99%, W/W), heating content to temperature passes into hydrogen chloride gas under stirring when being 100 DEG C, hydrogen chloride gas 20h is passed in 110 DEG C, common enter hydrogen chloride gas 387g, wherein false to the water of formation, hydrogenchloride and dichlorohydrine ternary azeotrope is constantly shifted out from reaction system and obtain carry-over, by underpressure distillation dichlorohydrine steamed after reaction terminates and obtain steaming thing.React complete, by carry-over with steam thing and be mixed to get dichlorohydrine mixed solution 967g, wherein dichloropropanol content is 54.8%, and yield is that 78.2%(calculates with amounts of glycerol).
Dichlorohydrine mixed solution obtained above is transferred in 3000mL tetra-neck flask, heating content to 100 DEG C, 30% sodium hydroxide solution 602g is dripped in system, after carrying out cyclization, obtain epoxy chloropropane 286g through fractional column, yield is that 75.4%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.57%, moisture 0.06%, colourity 14(APHA), density 1.181g/cm
3.
Embodiment 2
The process of raw glycerine
The composition of raw material raw glycerine is with embodiment 1.
Being joined by above-mentioned raw glycerine (A) 600g in the four neck flasks of 1000mL, is-98.2KPa in gauge pressure, carries out underpressure distillation and remove moisture at temperature 75 DEG C, raw glycerine (B) 560g(86.3% glycerine after obtaining dewatering, 8.2% water, 3.9% sodium-chlor, surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 4.2%); In raw glycerine (B) after dewatering, pass into hydrogen chloride gas 114g, in system, have the solid salt of fine particle to separate out gradually; At 60 DEG C, the glycerine having led to hydrogen chloride gas being transferred to filter cloth aperture is 800 object pressure filters carry out filter the metal-salt removed and separate out, and obtains processing rear glycerine (C2) 653g(74.0% glycerine, 17.5% hydrogenchloride, 7.0% water, 0.07% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.32%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Obtain dichlorohydrine mixed solution 946g through chlorination, wherein dichloropropanol content 59.9%, yield is that 83.7%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 645g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 322g, yield is that 79.2%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.25%, moisture 0.07%, colourity 10(APHA), density 1.182g/cm
3.
Embodiment 3
The process of raw glycerine
The composition of raw material raw glycerine, charging capacity and treatment process are with embodiment 2.
Difference is, obtain dewater after raw glycerine (B) 538g(89.8% glycerine, 4.5% water, 4% sodium-chlor, surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 4.3%), pass into 106g hydrogen chloride gas during desalination, obtain processing rear glycerine (C2) 624g(77.5% glycerine, 17.1% hydrogenchloride, 3.9% water, 0.07% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.3%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Obtain dichlorohydrine mixed solution 943g through chlorination, wherein dichloropropanol content 63.4%, yield is that 88.3%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 680g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 359g, yield is that 83.7%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.40%, moisture 0.06%, colourity 8(APHA), density 1.182g/cm
3.
Embodiment 4
The process of raw glycerine
The composition of raw material raw glycerine, charging capacity and treatment process are with embodiment 2.
Difference is, obtain dewater after raw glycerine (B) 520g(93.0% glycerine, 1.1% water, 4.2% sodium-chlor, surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 4.4%), pass into 99g hydrogen chloride gas during desalination, obtain processing rear glycerine (C2) 598g(80.9% glycerine, 16.6% hydrogenchloride, 0.9% water, 0.08% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.34%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Obtain dichlorohydrine mixed solution 942g through chlorination, wherein dichloropropanol content 66.6%, yield is that 92.6%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 713g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 395g, yield is that 87.8%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.50%, moisture 0.07%, colourity 12(APHA), density 1.181g/cm
3.
Embodiment 5
The process of raw glycerine
Raw material raw glycerine is made up of following: 10.3% glycerine, 77.6% water, 11.4% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount, ash oontent is 11.9%.
The charging capacity of raw glycerine and treatment process are with embodiment 2.
Difference is, raw glycerine (B) 136g(45.4% glycerine after obtaining dewatering, 1.3% water, 50.23% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 50.5%), pass into 15g hydrogen chloride gas during desalination, obtain processing rear glycerine (C2) 83.0g(74.5% glycerine, 18.3% hydrogenchloride, 2.1% water, 0.08% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.45%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Difference is, adds hexanodioic acid 4.9g, passes into hydrogen chloride gas 49g, obtains dichlorohydrine mixed solution 125g, wherein dichloropropanol content 62.1% through chlorination, and yield is that 89.4%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 88g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 46g, yield is that 82.5%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.3%, moisture 0.05%, colourity 11(APHA), density 1.182g/cm
3.
Embodiment 6
The process of raw glycerine
Raw material raw glycerine is made up of following: 46.7% glycerine, 45.7% water, 6.8% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount, ash oontent is 7.1%.
The charging capacity of raw glycerine and treatment process are with embodiment 2.
Difference is, raw glycerine (B) 331g(84.7% glycerine after obtaining dewatering, 1.5% water, 12.3% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 12.7%), pass into 59g hydrogen chloride gas during desalination, obtain processing rear glycerine (C2) 350g(80.2% glycerine, 17.0% hydrogenchloride, 1.4% water, 0.09% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.39%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Difference is, adds hexanodioic acid 22.2g, passes into hydrogen chloride gas 224g, obtains dichlorohydrine mixed solution 543g, wherein dichloropropanol content 65.6% through chlorination, and yield is that 90.7%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 405g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 215g, yield is that 84.3%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.5%, moisture 0.07%, colourity 9(APHA), density 1.182g/cm
3.
Embodiment 7
The process of raw glycerine
Raw material raw glycerine is made up of following: 92.5% glycerine, 4.6% water, 1.7% sodium-chlor, and surplus is impurity; Wherein, based on raw glycerine total amount, ash oontent is 2.1%.
The charging capacity of raw glycerine and treatment process are with embodiment 2.
By dehydration, raw glycerine (B) 579g(95.8% glycerine after obtaining dewatering, 1.2% water, 1.8% sodium-chlor, surplus is impurity; Wherein, based on raw glycerine total amount after dewatering, ash oontent is 2.5%), pass into 114g hydrogen chloride gas during desalination, obtain processing rear glycerine (C2) 683g(81.3% glycerine, 16.6% hydrogenchloride, 1.0% water, 0.05% sodium-chlor, surplus is impurity; Wherein, based on glycerine total amount after process, ash oontent is 0.48%).
The preparation of epoxy chloropropane
The preparation method of epoxy chloropropane is with embodiment 1.
Difference is, adds hexanodioic acid 44g, passes into hydrogen chloride gas 444g, obtains dichlorohydrine mixed solution 1082g, wherein dichloropropanol content 67.0% through chlorination, and yield is that 93.2%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 824g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 459g, yield is that 88.3%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.6%, moisture 0.03%, colourity 7(APHA), density 1.182g/cm
3.
Comparative example 1.
The untreated preparation being directly used in epoxy chloropropane of raw glycerine.
The composition of raw material raw glycerine, charging capacity and epoxy chloropropane preparation method are with embodiment 1.
Difference is, when passing into hydrogenchloride chlorination, has a large amount of salt particle to separate out in system, affects normally carrying out of chlorination reaction.Pass into hydrogen chloride gas 484g, obtain dichlorohydrine mixed solution 882g, wherein dichloropropanol content 50.0% through chlorination, yield is that 65.2%(calculates with amounts of glycerol), the amount obtaining solid salt particles is 21g.
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 502g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 213g, yield is that 67.3%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.53%, moisture 0.08%, colourity 11(APHA), density 1.182g/cm
3.
Comparative example 2
Epoxy chloropropane is prepared with 99.5% smart glycerine.
The preparation method of epoxy chloropropane is with embodiment 1.
Difference is, adds hexanodioic acid 47.3g, passes into hydrogen chloride gas 597g, obtains dichlorohydrine mixed solution 1020g, wherein dichloropropanol content 76.2% through chlorination, and yield is that 92.9%(calculates with amounts of glycerol).
Obtain dichlorohydrine mixed solution and 30% sodium hydroxide solution 883g carries out cyclisation by above-mentioned, obtain epoxy chloropropane 480g, yield is that 86.3%(calculates with dichlorohydrine gauge), the content of epoxy chloropropane is 99.49%, moisture 0.06%, colourity 9(APHA), density 1.181g/cm
3.
By above embodiment and comparative example known, when untreated raw glycerine is directly used in chlorination, have a large amount of inorganic salt separate out, easily cause line clogging aborning, impact reaction normally carry out; The moisture contained in glycerine after process is more, and chlorination efficiency is lower, and epoxy chloropropane productive rate is lower; The chlorination efficiency of the raw glycerine of different content glycerine after processing the process obtained and epoxy chloropropane productive rate and 99.5% smart glycerine suitable.
utilizability in industry
As mentioned above, the treatment process of raw glycerine of the present invention, and after utilizing process the method for glycerol production epoxy chloropropane in industry with industrial there is utilizability and practicality.
Claims (10)
1. a raw glycerine treatment process, is characterized in that, the method comprises the steps:
A raw glycerine contacts with hydrogen chloride gas by (), separate out insoluble solid;
B () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
2. a raw glycerine treatment process, is characterized in that, the method comprises the steps:
A raw glycerine is removed water at least partially by (), raw glycerine after obtaining dewatering;
B raw glycerine after described dewatering contacts with hydrogen chloride gas by (), separate out insoluble solid;
C () removes the described solid of separating out by solid-liquid separation, obtain processing rear glycerine.
3. raw glycerine treatment process according to claim 1 and 2, the raw glycerine wherein in step (a) comprises the glycerine of 5 % by weight to 95 % by weight, the water of 1 % by weight to 80 % by weight, and the metal-salt of 1 % by weight to 30 % by weight.
4. raw glycerine treatment process according to claim 1, wherein comprise the glycerine of 5 % by weight to 90 % by weight after the described process that obtains of step (b) in glycerine, the hydrogenchloride of 5 % by weight to 40 % by weight, the water of 0.5 % by weight to 60 % by weight, and the metal-salt being less than 1 % by weight.
5. raw glycerine treatment process according to claim 2, wherein step (a) obtain described in dewater after comprise in raw glycerine 30 % by weight to 99 % by weight glycerine, the water of 0.1 % by weight to 10 % by weight, and the metal-salt of 1 % by weight to 55 % by weight.
6. raw glycerine treatment process according to claim 1 and 2, when wherein passing into hydrogen chloride gas, the gauge pressure of system is that-0.1MPa is to 1MPa, the described amount passing into hydrogenchloride is 5% to 70% of raw glycerine weight, the described raw glycerine that contacts with hydrogen chloride gas or after dewatering the initial temperature of raw glycerine be 20 DEG C to 200 DEG C, when solid-liquid separation raw glycerine or after dewatering raw glycerine temperature be 20 DEG C to 200 DEG C.
7. raw glycerine treatment process according to claim 2, wherein comprise the glycerine of 50 % by weight to 95 % by weight after the described process that obtains of step (c) in glycerine, the hydrogenchloride of 1 % by weight to 30 % by weight, the water of 0.1 % by weight to 20 % by weight, and the metal-salt being less than 1 % by weight.
8. a preparation method for epoxy chloropropane, is characterized in that, the method comprises the steps:
A () adopts the method described in any one of claim 1-7 to obtain processing rear glycerine;
B (), under the existence of carboxylic-acid catalyzer, after described process step (a) obtained, glycerine or its mixture and hydrogen chloride gas precursor reactant, prepare dichlorohydrine;
C dichlorohydrine and cyclizing agent carry out removing hcl reaction by (), prepare epoxy chloropropane;
Preferably, described carboxylic-acid catalyzer is the combination of one or more in acetic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid and sebacic acid; And/or the consumption of described carboxylic-acid catalyzer is 0.1% to 10% of glycerine molar weight after process, preferably 1% to 6%; And/or the temperature of reaction of step (b) is 80 DEG C to 130 DEG C, preferably 100 DEG C to 120 DEG C; And/or the reaction times of step (b) is 1h to 20h, preferred 5h to 15h; And/or in step (b), after process, the mol ratio of glycerine and hydrogenchloride is 1:2 to 1:5, preferred 1:2 to 1:3.
9. a glycerin compositions, wherein containing the glycerine comprising 5 % by weight to 90 % by weight, the hydrogenchloride of 5 % by weight to 40 % by weight, the water of 0.5 % by weight to 60 % by weight, and the metal-salt being less than 1 % by weight, preferably, described glycerin compositions comprises the glycerine of 50 % by weight to 90 % by weight, the hydrogenchloride of 5 % by weight to 30 % by weight, the water of 1 % by weight to 20 % by weight, is greater than 0.02 % by weight metal-salt being less than 1 % by weight.
10. prepare a method for epoxy compounds and derivative thereof, wherein, the glycerine adopting the method process of claim 1 or claim 2 to obtain is prepared as starting raw material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699511A (en) * | 2016-12-28 | 2017-05-24 | 江苏扬农化工集团有限公司 | Method for recycling inorganic/organic matters from glycerin chlorination distillate |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113999190A (en) * | 2021-11-19 | 2022-02-01 | 江苏瑞祥化工有限公司 | Method for decoloring microchannel continuous flow epichlorohydrin and hydrogen peroxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054167A1 (en) * | 2003-11-20 | 2005-06-16 | Solvay (Société Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| WO2006020234A1 (en) * | 2004-07-21 | 2006-02-23 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| CN101195607A (en) * | 2006-12-09 | 2008-06-11 | 中国石化集团巴陵石油化工有限责任公司 | Epoxychloropropane and production method of midbody dichlorohydrin |
| CN101265160A (en) * | 2008-04-30 | 2008-09-17 | 上海三瑞高分子材料有限公司 | Method for purifying biological diesel oil byproduct glycerin |
-
2013
- 2013-12-30 CN CN201310746633.2A patent/CN104591967B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054167A1 (en) * | 2003-11-20 | 2005-06-16 | Solvay (Société Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| WO2006020234A1 (en) * | 2004-07-21 | 2006-02-23 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| CN101195607A (en) * | 2006-12-09 | 2008-06-11 | 中国石化集团巴陵石油化工有限责任公司 | Epoxychloropropane and production method of midbody dichlorohydrin |
| CN101265160A (en) * | 2008-04-30 | 2008-09-17 | 上海三瑞高分子材料有限公司 | Method for purifying biological diesel oil byproduct glycerin |
Non-Patent Citations (1)
| Title |
|---|
| 刘蕾 等: "以生物甘油为原料制备环氧氯丙烷的研究", 《化学与生物工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699511A (en) * | 2016-12-28 | 2017-05-24 | 江苏扬农化工集团有限公司 | Method for recycling inorganic/organic matters from glycerin chlorination distillate |
| CN106699511B (en) * | 2016-12-28 | 2020-04-17 | 江苏扬农化工集团有限公司 | Method for recycling organic/inorganic matters in glycerol chlorination distillate |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113234041B (en) * | 2021-04-07 | 2023-03-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113999190A (en) * | 2021-11-19 | 2022-02-01 | 江苏瑞祥化工有限公司 | Method for decoloring microchannel continuous flow epichlorohydrin and hydrogen peroxide |
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