CN101337950A - Method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation - Google Patents
Method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation Download PDFInfo
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Abstract
The invention relates to a method for preparing epoxy chloropropane which is obtained through successive reaction and distillation coupling technology after glycerine that is the by-product of biological diesel oil reacts with chlorine hydride through substitution reaction under homogeneous multielement catalysis and further performs saponification cyclization reaction. The method comprises the following steps: (1) chlorine hydride is pumped in glycerine that is the by-product of biological diesel oil for reaction under homogeneous multielement catalysis, and the mixture composed of 1, 3-dichloro-2-propanol and 2, 3-dichloro-1-propanol is prepared through the technologies of continuous feeding, continuous catalyzed chlorination and continuous rectification; (2) the isomeride mixture solution of 1, 3-dichloro-2-propanol and 2, 3-dichloro-1-propanol performs the saponification cyclization to generate a product of epoxy chloropropane in alkaline solution. The method has the advantages of mild reaction condition is mild, high catalyst activity, dedicated catalytic performance, high product selectivity, process 'cleaning', easy separation, continuous operation, environment-friendliness, etc.
Description
Technical field
The present invention relates to a kind of production technique of epoxy chloropropane, specifically, relate to the method for preparing epoxy chloropropane by biological diesel oil byproduct glycerin through continuous catalysis chlorination, reactive distillation, saponification.
Background technology
Biofuel is rich in the green of potentiality, " petroleum plant " of clean alternative fuel as 21st century, with its recyclability and good environmental friendliness characteristic, demonstrate powerful developing state in fossil fuel oil substitute field, be subjected to the extensive concern of countries in the world.Current, along with the rise that with the renewable biomass is the new round biodiesel technology of raw material, the Sustainable development of its downstream industry becomes the focus of research gradually, and the deep process technology research of biological diesel oil byproduct glycerin is in the ascendant in the whole world.
The a large amount of glycerine of by-product in the production of biodiesel process, 10 tons of biofuel of every production promptly produce 1 ton of glycerine, and this produces great impact to traditional glycerine manufacturing enterprise.Surging along with international oil price in recent years, the biofuel of the energy extensively is subjected to favor and is in fashion in the world as an alternative, will cause the excessive of glycerine supply, it is the growth requirement of the chemical industry of raw material with glycerine that the increase of cheap glycerine supply has excited new.
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemical product, is used for synthetic epoxy resin in a large number.It is strong to be with it that Resins, epoxy that raw material makes has cohesiveness, characteristics such as resistant to chemical media burn into shrinking percentage is low, chemical stability good, excellent in cushion effect and dielectric properties excellence have widely in industries such as coating, tackiness agent, strongthener, cast material and electronic shell stampings and to use.In addition, epoxy chloropropane also can be used for multiple products such as synthetic nitroglycerine explosive, electrical isolation product, tensio-active agent, medicine, agricultural chemicals, coating, sizing material, ion exchange resin, softening agent, (contracting) glycerol derivative, chlorohydrin rubber, solvent as cellulose ester, resin, ether of cellulose is used to produce chemical stabilizer, chemical dyestuff and water conditioner etc.
In the industrial production of epoxy chloropropane, the normally used technology in the whole world is two kinds of propylene high-temperature chlorination process and allyl acetate methods, and based on the former.The propylene high-temperature chlorination process is meant that propylene excites the replacement chlorination to prepare propenyl chloride through high temperature, and addition prepares dichlorohydrine to chlorallylene by hypochlorous acid, and dichlorohydrine generates epoxy chloropropane with alkaline aqueous solution cyclization dehydrochlorination then.The allyl acetate method is meant that propylene generates propylene acetate with the via palladium-catalyzed oxidation of acetic acid, generates vinyl carbinol through the catex-catalytic hydrolysis again, and vinyl carbinol is generating dichlorohydrine through catalytic chlorination, generates epoxy chloropropane through alkaline dehydrochlorination again.In these two kinds of methods, described basic starting raw material is propylene, chlorine and such as the alkali of sodium hydroxide or calcium hydroxide.
All mention the propylene high-temperature chlorination process among patent US5011980, US5227541, US4634784, CN1534030A and the CN1462265A to some extent, basic and the most important characteristic of this technology is: the equipment corrosion that raw material chlorine causes is serious, material to purified propylene and reactor requires high, energy consumption is big, chlorine consumption height, by product is many, and product yield is low.Production process produces contains calcium chloride and the organic chloride sewage quantity is big, the processing costs height, and coke cleaning period is short.
It is catalyzer with the HTS that US4833260 discloses a kind of, directly alkene (comprising haloolefin) is carried out epoxidation with hydrogen peroxide and produces the epoxide method.Because have strong polar compound such as water or alcohol in the reaction, the catalysis ring-opening reaction will partly take place in the epoxide of generation, reduce the yield of epoxide.For this reason, patent disclosures such as US4824976, CN1319099, CN1131152A and CN1219536A some improve the assist measure of epoxide yields, as add alkaline organic or inorganic compound etc., reduce the invalid rate of decomposition of hydrogen peroxide, add solid inert diluents in addition and slow down reaction, be beneficial to temperature control, but the useful volume of reactor can descend.
EP0659473A1 discloses a kind of trickle-bed reactor and method thereof that is used for chloro propylene epoxidation, catalyzer divides four sections to be filled in the trickle-bed reactor with oarse-grained form, intersegmental riser and the liquid collecting plate of being provided with, first three section of lathe bed is the main reaction section, and indirect cooler of every section peripheral hardware is with heat-obtaining.Epoxidation reaction with propylene is an example, under the above reaction pressure of 1.25MPa, the mode that reaction mass is gas-liquid two-phase and stream is flowed downward and is reacted by the bed top, on the main reaction section, reaction mixture is carried out extraction, heat exchange, returned and replenish reinforced process, be that the reacted reaction of each section does not have after an indirect cooler cooling, a part loops back this section, and another part and fresh feed are mixed into next section.In order to improve transformation efficiency, the feed liquid that enters the 4th section does not add fresh feed, product and tail gas by bed at the bottom of extraction.This reactor structure complexity, the working pressure height, temperature control is relied on the systemic circulation material and is realized, also needs after reaction finishes solvent is evaporated separation to realize recycle, and energy consumption is very high.In addition, granules of catalyst is too big, has increased diffusional resistance, has reduced the availability of catalyzer.
CN2581060A discloses a kind of structural shape of reactor, i.e. the rotating bed with helix channel supergravity reactor.CN1059105A has reported a kind of rotating packed bed supergravity reactor, two-phase or multiphase logistics can be in these two kinds of supergravity reactors the adverse current stream contact of fighting carry out mass transfer or mass transfer-reaction, these two kinds of supergravity reactors can both reinforcing mass transfer process or mass transfer-reaction process.No. 2144612, United States Patent (USP) can make various inert that the water in the described reaction removes as acid overhead product and water go on foot the blended solvent to remove water in the described reaction fully such as n-butyl ether, ethylene dichloride, dichloropropylene or chlorobenzene by using under suitable temperature.This patent is mentioned the resistates that has only formed minute quantity, can be easy to finish this reaction, and the solution of the glycerin dichlorohydrin that obtains as reaction product is substantially devoid of water, and in being difficult to isolating acidic aqueous solution the loss of glycerin dichlorohydrin is minimized.
The method of producing dichlorohydrine from glycerine of WO2005054167 patent report Belgium Solvay exploitation, glycerine are finally from the conversion of animal tallow in the production of biodiesel.This patent has also been mentioned " deriving from the glycerine of renewable raw materials " and specifically be meant the glycerine that obtains in the process of production biofuel, perhaps is generally the glycerine that obtains in the fat of plant or animal-origin or oily conversion such as saponification, transesterify or the hydrolysis reaction.This method makes glycerine through with the prepared in reaction of chlorizating agent, it is characterized in that except the reaction of carrying out in the presence of the acetate or derivatives thereof.
Patent DE1973081906 discloses the possible synthetic route of a kind of Epicholorohydrin, and its principle is for being 1 with anhydrous hydrogen chloride with the glycerin catalytic hydrochlorinate, 3-two chloro-2-third alcohol and water.Described reaction is about 100 ℃, realizes in described liquid phase.In order to increase the solubleness of HCl gas at this reaction mixture, pressure can be normal atmosphere or increase.The optimum concn of the acetate catalyst of described homogeneous is approximately 1～2% weight part; When higher concentration, undesirable by product can be formed, yield can be reduced like this with bigger degree.Except that acetic acid, also mention other carboxylic acid in the patent, tested propionic acid.Recomputating of control, not with water sepn, the yield of disclosed described batch control amounts to and is approximately 75%.
The WO2005021476 patent disclosure hydrochlorination of glycerine and/or glycerine monochlorohydrin is prepared dichlorohydrine, 1,3-two chloro-2-propyl alcohol and 2, the method of 3-two trimethylewne chlorohydrin 3-s, this invention relates to gasiform hydrogenchloride and carboxylic acid catalyst, under 70～140 ℃ temperature of reaction and remove water in the described reaction continuously, add and contain the glycerine of at least 50% weight ratio and/or the described liquid of glycerine monochlorohydrin, at least one successive reaction zone, finish.Described method can be finished in one step of operate continuously recirculation reactor or in the liquid-gaseous type continuous flow reactor in cascade.
In patent separately disclosed all aforesaid methods basically can be intermittently or continuous production carry out, be feasible in industrial-scale production.But the difference of described method is the high yield of the high conversion of described starting raw material, described product and the highly selective of described reactive system.
Summary of the invention
The present invention relates to a kind of biological diesel oil byproduct glycerin and under the effect of homogeneous phase multiple catalyzing, carry out substitution reaction earlier, and then carry out the saponification cyclization reaction, produce the method for epoxy chloropropane by successive reaction and separating technology with hydrogenchloride.
Prepare the method for epoxy chloropropane, it comprises:
1. biological diesel oil byproduct glycerin feeds chlorizating agent and reacts under the effect of homogeneous phase multiple catalyzing, and by continuous or intermittent feeding, the catalytic chlorination technology of continuous rectification produces 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s.
2. 1,3-two chloro-2-propyl alcohol and 2, the mixing solutions of 3-two trimethylewne chlorohydrin 3-isomerss saponification cyclization under basic solution generates the epoxy chloropropane product.
Wherein being used for chlorizating agent of the present invention can be C1
2, HCl, HClO or its combination, be preferably HCl.
Be meant that as multiple catalyzing system of the present invention Primary Catalysts is that atmospheric boiling point is preferably greater than or equals in 180 ℃ monobasic or di-carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, carboxylate salt, the carboxylicesters one or more.Primary Catalysts consumption (is benchmark with the biological glycerol quality) is 1～3%, is preferably 2%.
Promotor is meant one or more among the Lewis hydrochlorate AB, wherein A=H
+, Al
3+, Zn
2+, Fe
3+, Cu
+, P
3+, P
5+, K
+, Ti
4+, Sn
4+, B=Cl
-, Br
-, F
-, SO
4 2-, CH
3COO
-, ClO
-Promotor consumption (is benchmark with the biological glycerol quality) is 1～2%, is preferably 1.5%.
The continuous chlorination temperature of reaction should be controlled at 80～150 ℃, is preferably 100～110 ℃.
The required concentration of lye of saponification reaction is 10～40%, is preferably 20～30%.
Preparation method of the present invention comprises two kinds of interrupter method and continuous processings.Wherein the mode of limit charging, limit discharging is all adopted in charging of continuous processing device and discharging, and product index detects by the gas-chromatography on-line tracing.
Wherein remove the water that dereaction generates continuously by adding hydrophobic solvent in this chlorination reaction process, at least one successive reaction zone, finish described hydrochlorination.Wherein hydrophobic solvent is one or more in hexanaphthene, normal hexane, n-butyl ether, toluene, the chlorobenzene.
This reaction system has also been introduced the chlorination initiator, as light, benzoyl peroxide, azo-bis-isobutyl cyanide, 1-hydroxyl-cyclohexyl-phenyl ketone, isopropyl thioxanthone etc.Chlorination initiator amount (is benchmark with the biological glycerol quality) is 1～3 ‰, is preferably 2 ‰.
This reaction system also adds stopper, as Resorcinol, N, and N-diethyl hydroxylamine, 2-sec-butyl-4,6-dinitrophenol(DNP) etc.Stopper consumption (is benchmark with the biological glycerol quality) is 1～2 ‰, is preferably 1.5 ‰.
Dichlorohydrine that this method is related and described mixture of products also comprise water and a spot of polynary homogeneous catalyst and the unreacted hydrogen chloride in the described reaction, and the mixture of this reaction need not any processing and still can be used for described next reactions steps smoothly continuously in epoxy chloropropane synthetic.
Among the present invention through 1 of catalytic chlorination, 3-two chloro-2-propyl alcohol and 2, the solution of 3-two trimethylewne chlorohydrin 3-s is incorporated into degassing tower so that discharge hydrogenchloride, making hydrogenchloride turn back to reactor uses for chlorination, it is characterized in that this method is included in the device that is provided for absorbing tail chlorine in the reactor that is right after before the degassing tower, the hci flow of the control reactor that is introduced into makes the pressure of hydrogenchloride can remain on 0.01～0.04MPa.
Reaction equation is as follows:
Chlorination reaction mechanism of the present invention:
1. the nucleophilic substitution reaction of glycerine and catalyst acid generates a part water.
The first step is a nucleophilic substitution reaction, and organic acid discharges H
+Combine with the hydroxyl on the glycerine, generate a part water.This is a classical acid-catalyzed esterification reaction of a step.
2. alkyl oxygen splitting of chain forms oxonium ion with closing on hydroxyl, discharges acid catalyst.
Second step formed the oxonium ion of three former subrings, discharged organic acid catalyst simultaneously, and catalyst recirculation is used, and continued to combine with another oh group on the glycerine.
3. chlorion attack forms chlorination glycerine
The 3rd step was the S of nucleophilic substitution
2The N reaction, chlorion attack carbon atom, the oxonium ion open loop of triatomic ring generates chlorination glycerine.
Advantage of the present invention is mainly reflected in following several respects:
1. the present invention adopts reaction rectification method, has realized that product and the effective of by product separate, and have guaranteed purity 〉=99.5% of product.
2. this process using homogeneous phase multiple catalyzing system is a Primary Catalysts with di-carboxylic acid and series derivates thereof, and Lewis acid is the composite catalyst system of promotor, and katalysis had both taken place, and has produced solvent effect again, and intermediates quality height does not stay residue.
3. employed raw material biological glycerol is from the by product of biofuel among the present invention, and purity is low, the water content height, and impurity is many, and biological glycerol concentration is low, without concentrating, can directly use, and saves energy consumption.
4. in the continuous chlorination process, the cl content of different substitution products also is one of core technology of technology of the present invention in the balancing control of second order reaction.Adopt continuous chlorination reaction tower, chlorination sparger, chlorine substituent is induced attack to poly-hydroxy group in the glycerol molecule in chlorination reaction process, increase the content of two substitution products, thereby be implemented in the equilibrium state of each component concentration in the different chlorination degree of depth, reduce the side reaction odds.
5. in rectifying, effectively realized the continuous lock out operation of different light, heavy constituent by the rectifier unit of two-stage tandem, the glycerin chlorohydrin and the part catalyzer that remove can be back to use chloride process after simple distillation, improved the utilization ratio of device.
6. pollution is lower, and wastewater discharge is few, and part waste water can be realized the recycle with the chlor-alkali device.
The present invention has the reaction conditions gentleness, the catalyst activity height, and catalytic performance is single-minded, product selectivity height, process " cleaning " and easily separated, advantages of environment protection.
Description of drawings
Fig. 1 is a technological process of production block diagram of the present invention
1.HCl jar 2. blower fans, 3. chlorination reaction towers, 4,9,14. condensers, 5,11. water-and-oil separators, 6. degassing vessels, 7,12. rectifying tower, 8,13. reboilers, 10. saponification reaction towers
A. hydrogenchloride B. glycerine, catalyzer C. water D. air E. hydrogen chloride tail gas F, K. raffinate G, L vacuum H. dichlorohydrine I. alkaline solution J. salts solution M. epoxy chloropropane
Hydrogen chloride passes into the chlorination reaction tower bottom after buffering, biological glycerol, major catalyst and co-catalyst 1～3 are from cat head Add, carry out the chlorination reaction of glycerine in tower, reaction heat is taken away by overhead condenser and tower body cooler; Reaction produces Water steams from cat head and part dichlorohydrin azeotropic, and through condensation, unreacted hydrogen chloride is circulated to the hydrogen chloride buffering through blower fan and establishes Standby applying mechanically, solidifying through water-oil separating, water is discharged, and oil phase removes the dissolving hydrogen chloride tail gas and removes to be absorbed as hydrochloric acid, and rectifying gets two The chloropropyl alcohol sterling. Dichlorohydrin and aqueous slkali carry out ring-closure reaction in the saponification tower, generate epoxychloropropane crude product and salt, Salting liquid is removed in layering, and crude product rectifying gets the epoxychloropropane finished product.
Embodiment
The following examples will be further specified the present invention, but not thereby limiting the invention.
Embodiment comprises a plurality of operations such as chloride process, rectification working process, cyclization operation, and concrete steps are:
1. chloride process
1. interrupter method
In the chlorination reaction tower with the long 1000mm*30mm of biological glycerol input, pack into the successively Primary Catalysts of 2% (is benchmark with the biological glycerol quality) and 1.5% promotor, connect prolong then, plug thermometer, feeding steam heats up, and when temperature rises to 80 ℃, begins to feed HCl gas, blistering reaction distributes by chlorination sparger adjustments of gas.When cat head has backflow, begin insulation, continue to feed HCl gas.Liquid color is converted into Vandyke brown by redness, continues reaction, adds 1% catalyzer, continues reaction, begins to follow the tracks of detection reaction.Sampling analysis is observed the content of a chlorine, glycerin dichlorohydrin and the situation of side reaction.When glycerin dichlorohydrin content reaches 75～80%, during about 10% left and right sides of a glycerin chlorohydrin content, begin at the bottom of post, to collect chlorination glycerine.
2. continuous processing
Carry out the glycerin chlorination reaction according to above-mentioned batch process, glycerin dichlorohydrin content reaches 75～80% in reactor, during about 10% left and right sides of one glycerin chlorohydrin content, begin to collect chlorination glycerine at the bottom of post, capital begins to drip biological glycerol (containing catalyzer), regulate input and output material speed, and strengthen the HCl air flow, reaction is normally carried out, the holding device liquid level stabilizing, keep the input and output material balance, the chlorination glycerine of collecting is treated rectification working process usefulness.
2. rectification working process
Get chlorination glycerine and put in the four-hole boiling flask, insert thermometer, kapillary.Rectifying column length 600mm,
29mm, capital install thermometer, prolong, receiving bottle, and connect vacuum pump and carry out rectification under vacuum (vacuum tightness-0.098MPa).Regulate heater voltage with voltate regulator, control vacuum tightness well.After the trim the top of column, be 52～56 ℃ in tower top temperature and begin to collect light constituent, data analysis: main component is water, a small amount of dichlorohydrine 1,3-two chloro-2-propyl alcohol, 2,3-two trimethylewne chlorohydrin 3-s and hydrochloric acid.Tower still effluent through placed in-line second depressurized rectifying (vacuum tightness-0.098MPa), be 110～116 ℃ in tower top temperature is collected heavy constituent, and data analysis: main component is 1,3-two chloro-2-propyl alcohol and 2,3-two trimethylewne chlorohydrin 3-s, glycerin dichlorohydrin purity is more than 95%.Tower still material is collected overhead product through simple distillation, and data analysis: main component is a propylene chlorohydrin and a spot of glycerine, waits until chloride process and applies mechanically.
3. cyclization operation
Dichlorohydrine is put in the cyclization four-hole bottle, stirring, thermometer, constant pressure funnel, prolong, receiving bottle, vacuum pump are installed.Be that to drip concentration at 1: 1.1 be 30% sodium hydroxide by the mol ratio of glycerin dichlorohydrin and sodium hydroxide in constant pressure funnel, start vacuum pump, regulating vacuum tightness is 0.06MPa, and the beginning dripping alkali liquid has oil droplet to produce at the still head afterbody.When reacting liquid temperature surpasses 80 ℃, and till no longer including oil droplet and producing, collecting liquid is water oil two-phase, pours that separating funnel shakes, leaves standstill, layering into.Lower floor is an oil reservoir, and the upper strata is a water layer, divides oil-yielding stratum, and promptly epoxy chloropropane product crude product is waited until the secondary rectification working process and used.
In the successive reaction rectification cell, adopt the chlorination reaction tower, can realize the carrying out of gas liquid reaction effectively, glycerine, homogeneous catalyst, solvent and various auxiliary agent with intermittently or the successive mode in Ta Nei and hydrogenchloride counter current contact, under the effect of homogeneous phase multicomponent catalyst, react, ensured the gas-liquid mass transfer effect.
Adopt the reactive distillation coupling technique in the present invention, realized 1 effectively, 3-two chloro-2-propyl alcohol and 2, the reaction of 3-two trimethylewne chlorohydrin 3-s is docked with separating process, has guaranteed the quality product of intermediate product.
The chlorated liquid of continuous chlorination in the stage outgases in degassing vessel in the technology of the present invention, to remove wherein dissolved hydrogen chloride gas.This unit has produced the purging air tail gas that contains hydrogen chloride gas, carries out two-stage pump circulation water with the hydrogen chloride tail gas absorption system and absorbs.
Contain the dichlorohydrine, a propylene chlorohydrin, hydrogenchloride of minimal amounts of dissolved etc. in the water that the chlorination reaction stage produces in the technology of the present invention, adopt the ClO 2 catalyzed oxidation degrading waste water to handle.But the elementary salt solution of chlor-alkali is made in the treated reuse of the brine waste of saponification cell processing.
[embodiment 1]
With 300g glycerine, 3g oxalic acid and 1.5gZnCl
2, 0.75gFeCl
20.75gCuCl, 0.3g benzoyl peroxide, 0.3g the mixture of Resorcinol intermittently or continuously adds from the chlorination reaction top of tower, at the bottom of tower, feed the 450g hydrogenchloride that drying is crossed, control reaction temperature is at 105 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 450gNaOH solution of 10% mass concentration again and gets epoxy chloropropane product 216g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
[embodiment 2]
With 300g glycerine, 4.5g propanedioic acid and 2gZnCl
2, 0.5gFeCl
3, 0.5gTiCl
4, 0.45g benzoyl peroxide, 0.45g Resorcinol mixture intermittently or continuously add from the chlorination reaction top of tower, at the bottom of tower, feed the hydrogenchloride 462g that drying is crossed, control reaction temperature is at 108 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 430gNaOH solution of 15% mass concentration again and gets epoxy chloropropane product 220g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
[embodiment 3]
With 500g glycerine, 10g Succinic Acid and 5gZnCl
2, 1.25gFeCl
21.25gKCl, 0.75g benzoyl peroxide, 0.75g the mixture of Resorcinol intermittently or continuously adds from the chlorination reaction top of tower, at the bottom of tower, feed the 450g hydrogenchloride that drying is crossed, control reaction temperature is at 105 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 550g NaOH solution of 20% mass concentration again and gets epoxy chloropropane product 360g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
[embodiment 4]
With 500g glycerine, 12.5g hexanodioic acid and 6.25gZnCl
2, 1.25gFeCl
3, 1.25gSnCl
41.0g azo-bis-isobutyl cyanide, 0.75gN, the mixture of N-diethyl hydroxylamine intermittently or continuously adds from the chlorination reaction top of tower, at the bottom of tower, feed the 750g hydrogenchloride that drying is crossed, control reaction temperature is at 108 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 410gNaOH solution of 30% mass concentration again and gets epoxy chloropropane product 347g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
[embodiment 5]
With 1000g glycerine, 20g oxalic acid and 10gMgCl
2, 2.5gFeCl
22.5gCuCl, 2.0g azo-bis-isobutyl cyanide, 1.0g N, the mixture chlorination reaction top of tower of N-diethyl hydroxylamine intermittently or continuously adds, at the bottom of tower, feed the 450g hydrogenchloride that drying is crossed, control reaction temperature is at 108 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 1000gNaOH solution of 34% mass concentration again and gets epoxy chloropropane product 716g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
[embodiment 6]
With 1000g glycerine, 25g hexanodioic acid and 12.5gPCl
3, 2.5gFeCl
2, 2.5gPCl
53.0g azo-bis-isobutyl cyanide, 1.0g N, the mixture of N-diethyl hydroxylamine intermittently or continuously adds from the chlorination reaction top of tower, at the bottom of tower, feed the 450g hydrogenchloride that drying is crossed, control reaction temperature is at 110 ℃, the chlorination mixed solution to degassing tower so that discharge hydrogenchloride, rectification under vacuum, follow the tracks of detection with gas-chromatography, the cut of collecting 68～75 ℃ (1.87KPa) is 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s carries out saponification cyclization with the 960gNaOH solution of 40% mass concentration again and gets epoxy chloropropane product 705g in the saponification reaction tower.Demonstrate described basic parameter and result in the following table:
Claims (8)
1. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation is characterized in that comprising two steps:
1. biological diesel oil byproduct glycerin feeds hydrogenchloride and reacts under the effect of homogeneous phase multiple catalyzing, and by continuous or intermittent feeding, the catalytic chlorination technology of continuous rectification produces 1,3-two chloro-2-propyl alcohol and 2, the mixture of 3-two trimethylewne chlorohydrin 3-s;
2. 1,3-two chloro-2-propyl alcohol and 2, the mixing solutions of 3-two trimethylewne chlorohydrin 3-isomerss saponification cyclization under basic solution generates the epoxy chloropropane product:
Wherein said chlorizating agent is Cl
2, HCl, HClO or its combination;
Described multiple catalyzing system is meant that Primary Catalysts is an atmospheric boiling point more than or equal in 180 ℃ monobasic or di-carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, carboxylate salt, the carboxylicesters one or more; Primary Catalysts consumption (is benchmark with the biological glycerol quality) is 1～3%, is preferably 2%.
Promotor is meant one or more among the Lewis hydrochlorate AB, wherein A=H
+, Al
3+, Zn
2+, Fe
3+, Cu
+, P
3+, P
5+, K
+, Ti
4+, Sn
4+, B=Cl
-, Br
-, F
-, SO
4 2-, CH
3COO
-, ClO
-Promotor consumption (is benchmark with the biological glycerol quality) is 1～2%, is preferably 1.5%;
Remove the water that produces in the dereaction by adding dewatering agent in the wherein said chlorination reaction process.
2. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 1 is characterized in that described chlorizating agent is HCl.
3. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 1 is characterized in that the continuous chlorination temperature of reaction is controlled at 100～110 ℃.
4. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 1 is characterized in that described two steps comprise the chloride process chloride process of interrupter method and continuous processing, rectification working process, cyclization operation, are specially:
(1) chloride process of interrupter method
Biological glycerol is dropped in the chlorination reaction tower, and pack into successively 1% Primary Catalysts and 1.5% promotor connect prolong then, plug thermometer, feed steam and heat up, and when temperature rises to 80 ℃, begin to feed HCl gas, blistering reaction; When cat head has backflow, begin insulation, continue to feed HCl gas; Liquid color is converted into Vandyke brown by redness, continues reaction, adds 1% Primary Catalysts, continues reaction, begins to follow the tracks of detection reaction, and when glycerin dichlorohydrin content reaches 75～80%, about 10% o'clock of a glycerin chlorohydrin content begins to collect chlorination glycerine at the bottom of post;
(2) rectification working process
Get chlorination glycerine and put in the four-hole boiling flask, insert thermometer, kapillary.Rectifying column length 600mm,
Capital is installed thermometer, prolong, receiving bottle, and the connection vacuum pump carries out rectification under vacuum, vacuum tightness-0.098MPa; Regulate heater voltage with voltate regulator, control vacuum tightness well; After the trim the top of column, be 52～56 ℃ in tower top temperature and begin to collect light constituent, data analysis: main component is water, a small amount of dichlorohydrine 1,3-two chloro-2-propyl alcohol, 2,3-two trimethylewne chlorohydrin 3-s and hydrochloric acid; Tower still effluent is through placed in-line second depressurized rectifying, and vacuum tightness-0.098MPa is 110～116 ℃ in tower top temperature, collects heavy constituent, promptly 1,3-two chloro-2-propyl alcohol and 2,3-two trimethylewne chlorohydrin 3-s, tower still material is collected overhead product through simple distillation, waits until chloride process and applies mechanically;
(3) cyclization operation
The dichlorohydrine of collecting is put in the cyclization four-hole bottle, stirring, thermometer, constant pressure funnel, prolong, receiving bottle, vacuum pump are installed; Be that to drip concentration at 1: 1.1 be 30% sodium hydroxide by the mol ratio of glycerin dichlorohydrin and sodium hydroxide in constant pressure funnel, start vacuum pump, regulating vacuum tightness is 0.06MPa, and the beginning dripping alkali liquid has oil droplet to produce at the still head afterbody; When reacting liquid temperature surpasses 80 ℃, and till no longer including oil droplet and producing, collecting liquid is water oil two-phase, pour that separating funnel shakes, leaves standstill, layering into, lower floor is an oil reservoir, and the upper strata is a water layer, divide oil-yielding stratum, promptly epoxy chloropropane product crude product is waited until the secondary rectification working process and is used.
5. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 4, the chloride process that it is characterized in that described continuous processing is for carrying out the glycerin chlorination reaction according to described batch process, glycerin dichlorohydrin content reaches 75～80% in reactor, during about 10% left and right sides of one glycerin chlorohydrin content, begin at the bottom of post, to collect chlorination glycerine, capital begins to drip the biological glycerol that contains catalyzer, regulate input and output material speed, and increasing HCl air flow, reaction is normally carried out, the holding device liquid level stabilizing keeps the input and output material balance, and the chlorination glycerine of collecting is treated rectification working process usefulness.
6. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 4 is characterized in that adopting the chlorination reaction tower in the successive reaction rectification cell.
7. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 4 is characterized in that rectifying and cyclization operation carry out in the coupling integrated device of reactive distillation.
8. the method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation according to claim 4 is provided with the device that is used to absorb tail chlorine in the reactor that it is characterized in that being right after before degassing tower.
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| CN101704722B (en) * | 2009-12-02 | 2011-05-11 | 兖州市天成化工有限公司 | Method for synthesizing dichloropropanol by catalyzing glycerol for chlorination under existence of dicarboxylic acid-rare earth chloride and reaction device |
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| CN101704722B (en) * | 2009-12-02 | 2011-05-11 | 兖州市天成化工有限公司 | Method for synthesizing dichloropropanol by catalyzing glycerol for chlorination under existence of dicarboxylic acid-rare earth chloride and reaction device |
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| CN102372684A (en) * | 2011-11-07 | 2012-03-14 | 常州大学 | Method for preparing epoxy chloropropane by micro-channel reactor |
| CN102491958A (en) * | 2011-11-14 | 2012-06-13 | 烟台恒邦化工有限公司 | Production process using chloroacetic acid tail gas to produce epoxy chloropropane |
| CN103044358A (en) * | 2013-01-30 | 2013-04-17 | 淄博永大化工有限公司 | Method for co-producing epoxypropane and epoxy chloropropane |
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