CN101481364B - Continuous production method of epoxy chloropropane by hydrogen peroxide process - Google Patents
Continuous production method of epoxy chloropropane by hydrogen peroxide process Download PDFInfo
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Abstract
The invention provides a preparation method of chloroepoxy propane by chloropropene epoxidation. Chloropropene, a solvent and titanium silicalite molecular sieve catalyst fine particles are put in a reaction kettle for reaction at the temperature of 10-80 DEG C. The method is characterized in that the reaction kettle is a single kettle or multistage slurry bed reaction kettles with same or different volumes which are connected in series; the reaction solution needs not to be homogeneous phase, slurry particles of the chloropropene, the solvent and the titanium silicalite molecular sieve catalyst are added to a first stage reaction kettle by a metering pump, hydrogen peroxide is dropwise added to the first stage reaction kettle or each stage of the reaction kettles, the reaction occurs in a weakly acidic condition, materials are subject to oil-water delamination after the reaction to be divided into oil-phase slurry and water-phase slurry; the catalyst is suspended in the water phase, and the oil phase is sent to a rectification tower to separate the chloropropene, the epichlorohydrin and trace methanol; the water phase slurry is filtered, a catalyst filter cake or concentrated slurry is directly beaten by the solvent, and pumped to a first stage epoxidation reaction kettle, the water phase slurry contains the methanol, trace epichlorohydrin and the water which is generated by the reaction and the water which is taken by the hydrogen peroxide, the trace methanol and the epichlorohydrin are separated out by negative pressure rectification, and the recovered methanol is used for preparation of the catalyst slurry. The method has the advantages of simple process, little solvent consumption and high product separation yield, and is available for industrialized production.
Description
Technical field
The invention relates to the production method of epoxy chloropropane, specifically, relating to a kind of is catalyzer with the HTS, with the hydrogen peroxide is oxygenant, carry out the slurry bed continuous reaction, the method that the direct epoxidation of catalyzed oxidation propenyl chloride is produced epoxy chloropropane, genus organic chemical industry's technical field.
Background technology
Epoxy chloropropane (ECH) is a kind of important large Organic Chemicals and fine chemical product, is the third-largest epoxide that output is only second to oxyethane and propylene oxide.Be widely used in synthetic epoxy resin, glycerine, chlorohydrin rubber etc.
At present, epoxy chloropropane is raw material production with the propylene, and production method mainly is a chlorohydrination, and it is that synthetic route is longer from the method for the indirect synthesizing epoxy chloropropane of propenyl chloride (AC).At first be the hydrolysis of chlorine, hydrolysate hypochlorous acid and propenyl chloride carry out addition reaction, are that adduct is under alkaline condition, as at Ca (OH) at last
2Effect closed loop down makes epoxy chloropropane.Chlorohydrination is a classical way synthetic and the production epoxy chloropropane, though the status that it has overwhelming superiority in the production of epoxy chloropropane, because some shortcomings of self, as the material consumption height, equipment corrosion is serious, and by product is many, produce a large amount of sewage in the production process, environmental pollution is serious.For overcoming this defective, chemists study with the direct epoxidation system epoxy chloropropane of propenyl chloride.
1993, people such as Clerici MG found that the TS-1 molecular sieve is to H
2O
2The catalytic capability of solution epoxidation light alkene.With the propenyl chloride is raw material, and (MA) makes solvent with methyl alcohol, and hydrogen peroxide is an oxygenant, reacts 30 minutes down at 45 ℃, and the transformation efficiency of hydrogen peroxide is 98%, and selectivity is 92%, and productive rate is 90%.The epoxidation reaction heat release is bigger, if move heat untimely, exceed controlled temperature easily, increase the invalid rate of decomposition of hydrogen peroxide, therefore, CN1219536A slows down reaction by add solid inert diluents in catalyzer, be beneficial to controlled temperature, but the useful volume of reactor descends obviously.
EP0659473A1 discloses a kind of trickle-bed reactor and production technique thereof that is used for chloro propylene epoxidation.This reactor structure complexity, the working pressure height, temperature control relies on the systemic circulation material and realizes that granules of catalyst is too big, has increased diffusional resistance, has reduced the effective rate of utilization of catalyzer.Though adopt fixed bed or trickle-bed reactor to realize the material serialization, because propenyl chloride and hydrogen peroxide do not dissolve each other, need to add a large amount of solvents such as methyl alcohol, making propenyl chloride and hydrogen peroxide form homogeneous phase in this solvent could the initial ring oxidizing reaction.In the epoxidation reaction product that obtains after the HTS solid-liquid separation, usually contain excessive propenyl chloride, a large amount of solvent methanol, epoxy chloropropane, hydrogen peroxide chargings water that bring into and that react generation, and a spot of Racemic glycidol methyl ether, glycerine monomethyl ether and 3-chloro-1,2-propylene glycol by product.Therefore the separation of subsequent products need be reclaimed a large amount of solvent methanols, excessive propenyl chloride, water, sepn process energy consumption height, and by-product increases, and yield is low.
CN1534030A discloses a kind of epichlorohydrin production process, and propenyl chloride, hydrogen peroxide, solvent and titanium-silicon molecular sieve catalyst fine particle carry out epoxidation reaction in tank reactor.Though this technical process is simple, realized kettle-type continuous, hydrogen peroxide utilization ratio height, (mol ratio of solvent and propenyl chloride is 8～20: 1), the reaction liquid phase is a homogeneous phase, utilizes reacting heat evaporation to separate remaining reactants and solvent after reaction finishes but this process methanol solvent load is big, reaction solution is in the rectifying separation process, a large amount of first alcohol and waters can continue reaction, particularly by product such as etherificate and hydrolysis with epoxy chloropropane (ECH) to be increased, and separation yield is low.
CN1769277 discloses a kind of epichlorohydrin production process, liquid phase propenyl chloride and titanium-silicon molecular sieve catalyst are configured back adding rotating bed with helix channel or rotating packed bed supergravity reactor, add liquid phase or gas phase propenyl chloride and hydrogen peroxide simultaneously continuously, propenyl chloride and hydrogen peroxide directly carry out epoxidation reaction under katalysis.A small amount of gas of unreacted propenyl chloride and generation returns material-compound tank through condensation to be continued to use, slurries in the reactor flow into material-compound tank, partial material pressurization back circulation enters reactor, partial material is sent separator, thick epoxy chloropropane after the separation is sent to refining, and the slurries that contain catalyzer return material-compound tank to be continued to use.Because solubilizing agent not, catalyst activity reduction is very fast, and the life-span is short, is unfavorable for the recycled of catalyzer, also increases catalyst regeneration frequency and cost simultaneously.
In sum, existing serialization prepares the method existence of epoxy chloropropane and 1. adopts fixed bed or trickle-bed reactor to realize the material serialization, must make the reaction solution phase materials be homogeneous phase, therefore solvent load is big, separating energy consumption is high, propenyl chloride, epoxy chloropropane separate with a large amount of direct atmospheric distillation of first alcohol and water, will cause by-product to increase more than 50 ℃, the epoxy chloropropane separation yield is low; If use the negative pressure rectifying separation, the propenyl chloride loss is big, and the rate of recovery is low, and cost increases; If the use extraction agent will be introduced new component, increase the complicacy of technical process.2. still formula or hypergravity continuous reaction do not use novel solvent, directly with propenyl chloride both as reaction raw materials, can cause as reaction solvent again: do not use alcohol, ketone etc. to make solvent on the one hand, catalyzer surface tension in liquid phase (propenyl chloride and hydrogen peroxide) is big, dispersing property is poor, is unfavorable for that on the other hand reaction product spreads in the catalyzer duct, and catalyst activity reduction is very fast, life-span is short, and catalyst regeneration frequency and use cost increase.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of flow process is simple, solvent load is few, separating energy consumption is low, the epoxy chloropropane yield is high slurry bed serialization to prepare the method for epoxy chloropropane.
Method provided by the invention, by still formula/slurry bed continuous reaction, do not need to make oil phase and water to be homogeneous phase, only need to add a small amount of alcohol and make solvent, under well-beaten condition, micron order catalyzer high dispersing is at oil phase and aqueous phase, propenyl chloride and hydrogen peroxide are under catalyst action, three contact carries out epoxidation reaction and generates epoxy chloropropane, and the epoxidation reaction time is at 1～2hr, hydrogen peroxide transformation efficiency height, the epoxy chloropropane selectivity is good, because the alcoholic solvent consumption is few, in being soluble in the aqueous phase, a large amount of epoxy chloropropane are distributed in the oil phase, easily there is by-product to generate when having avoided pure and mild epoxy chloropropane to separate, oil phase is by atmospheric distillation, and water is by negative pressure rectifying, epoxy chloropropane separation yield height.Catalyst slurry filters and adopts ceramic membrane filter simultaneously, and catalyst recovery yield is up to more than 99.99%, and the consumption of catalyzer is low.
Method provided by the invention comprises: reactor types is single still, or the series connection of the slurry-bed reaction still of multistage equal volume or different volumes.The pulpous state particle of propenyl chloride, solvent and titanium-silicon molecular sieve catalyst adds in the first step reactor with volume pump, catalyzer in solvent pulpous state concentration 5～50%, preferred 8～30%, more preferably 8～25%.Drip hydrogen peroxide in first step reactor or each order reaction still, temperature of reaction is at 10～80 ℃, and preferred 20～60 ℃, more preferably 35～55 ℃.The control of multi-stage reacting kettle temperature of reaction is identical or different.The concentration of hydrogen peroxide is 10%～70%, and is preferred 25～60%, more preferably 27.5～50%.Suitable reaction solvent is organic nitrile, alcohols, ethers, ketone, ester class etc.The alcohol that is fit to comprises C
1～C
4The Fatty Alcohol(C12-C14 and C12-C18) of straight or branched is as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, the trimethyl carbinol etc.Particular methanol.
The mol ratio of propenyl chloride and hydrogen peroxide is 1～20: 1, preferred 1～10: 1, more preferably 1～4: 1.The mol ratio of solvent and propenyl chloride is 0.5～8: 1, preferred 0.5～4: 1, more preferably 0.5～2: 1.It is characterized in that reacting rear material carries out the profit layering through tundish, be divided into oil phase and water slurries, catalyzer is suspended in aqueous phase.The epoxy chloropropane that the methyl alcohol of excessive propenyl chloride, trace, reaction generate more than 85% in oil reservoir, send into rectifying tower and separate propenyl chloride and ECH and Trace Methanol by oil phase; The water slurries are through after filtering, catalyzer filter cake or concentrated slurry are directly squeezed into first step epoxidation reaction still with solvent making beating back with pump, filter the back water and contain methyl alcohol, a small amount of epoxy chloropropane and reaction generates and hydrogen peroxide is brought into water, adopt the negative pressure rectifying separation to go out a spot of methyl alcohol and epoxy chloropropane, reclaim the preparation that methyl alcohol is used for catalyst slurry.
Technical scheme of the present invention is further characterized in that, catalyst slurry filters and adopts the ceramic membrane filter device, carry out solid-liquid separation by microporous membrane, the pore size filter of microfiltration membrane or ultra-filtration membrane is 0.01～1 micron, material is the organic or inorganic material, working pressure is 0.2～1.0 MPa, and service temperature is 5～90 ℃.Through ceramic membrane filter, catalyst recovery yield reaches more than 99.99%.
Technical scheme of the present invention is further characterized in that the mol ratio of propenyl chloride and hydrogen peroxide is 1～4: 1, and propenyl chloride can be suitably excessive, reacts completely to guarantee hydrogen peroxide, and reaction finishes the back hydrogen peroxide does not have remnants or micro residue, and temperature of reaction is 35～55 ℃.
Technical scheme of the present invention is further characterized in that, has realized epoxidation list still or many stills continuous reaction, does not need the picture rhythmic reaction to exist and heats up or temperature-fall period, makes things convenient for quiet run control, helps realization of industrialization.Reaction is thermopositive reaction, needs logical cooling fluid chuck cooling or inner coil pipe or pump circulation cooling.
Technical scheme of the present invention is further characterized in that, the concentration of hydrogen peroxide is 27.5%, 35% or 50%, HTS is a molecular sieve after the TS-1 modification, catalyst particle size 1～3um, solvent is a methyl alcohol, and catalyst consumption is 5～15g/1mol hydrogen peroxide, and the reaction solution that contains a small amount of solvent fully contacts with granules of catalyst under whipped state, can guarantee to react and carry out fast, not need reaction solution to be homogeneous phase.
The present invention has following good result: (1) methanol usage of the present invention is few, can reduce the energy consumption of a large amount of solvents of Separation and Recovery, reaction solution is heterogeneous, reaction finishes back oil phase and the layering of water layer slurries, the epoxy chloropropane that excessive propenyl chloride, a spot of methyl alcohol, reaction generate more than 85% in oil reservoir, directly atmospheric distillation separates, have only less epoxy chloropropane (below 15% of growing amount) in water layer, to pass through the negative pressure rectifying separation, epoxy chloropropane has been avoided direct high temperature (＞50 ℃) the Contact Pair reaction with methyl alcohol, water, separation yield height; (2) the present invention has realized epoxidation list still or many stills continuous reaction, makes things convenient for quiet run control, compares with batch reactor, improves the unit production capacity of reactor; (3) nanometer of the present invention or micron order catalyst slurry are through ceramic membrane filter, and catalyst loss is few, rate of recovery height; (4) slurry bed continuous reaction of the present invention is through running more than month, and activity of such catalysts and epoxidation selectivity are well kept.
Description of drawings
The continuous production method process frame chart of Fig. 1 epoxy chloropropane by hydrogen peroxide method.
Two still continuous production method process flow diagrams of Fig. 2 epoxy chloropropane by hydrogen peroxide method.
Embodiment
Embodiment 1:
The series connection of three stills, every still effective volume: 130mL, 270mL, 230mL, effective volume 630mL. temperature of reaction is 41-49 ℃ altogether, reacts to be thermopositive reaction, by the chuck heat exchange.Catalyzer and 27.5%H
2O
2Mass ratio 1: 12.Propenyl chloride (AC) and H
2O
2Throw first step reactor simultaneously into peristaltic pump, flow is respectively V
AC=167.1mL/hr, V
H2O2=87.0mL/hr, methyl alcohol and catalyst mix evenly making beating are controlled charging with peristaltic pump, V
MA=165.9mL/hr.Mixing speed 350rpm, three stills stop about 1.5hr, and feed rate=420mL/h per hour, reaction mass overflow on the reactor enters the next stage reactor.
After reaction finished, after the aqueous phase catalyst slurries separated through membrane filtration, catalyzer filter cake or concentrated slurry were directly with after the solvent making beating, with being pumped into first step epoxidation reaction still.
Reaction charge ratio: n methyl alcohol: n propenyl chloride: nH
2O
2=5.2: 2.6: 1 (mol ratio of material)
Embodiment 2:
Three stills series connection, every still effective volume: 130mL, 270mL, 230mL, amount to effective volume 630mL, temperature of reaction 41-49 ℃, react and be thermopositive reaction, by the chuck heat exchange.Catalyzer and 35%H
2O
2Mass ratio 1: 10.AC and H
2O
2Throw first step reactor with certain flow simultaneously into peristaltic pump, flow is respectively V
AC=167.1mL/hr, V
H2O2=87.0mL/hr, methyl alcohol and catalyst mix evenly making beating are controlled charging with peristaltic pump, V
MA=165.9mL/hr.Three stills stop about 1.5hr, feed rate=420mL/h per hour, and mixing speed 350rpm, reaction mass overflow on the reactor enters the next stage reactor.
After reaction finished, after the aqueous phase catalyst slurries separated through membrane filtration, catalyzer filter cake or concentrated slurry were directly with after the solvent making beating, with being pumped into first step epoxidation reaction still.
Reaction charge ratio: n methyl alcohol: n propenyl chloride: nH
2O
2=4: 2: 1 (mol ratio of material)
Embodiment 3:
Single still serialization, the effective volume of still: 500mL.Methyl alcohol and catalyst mix slurries, AC and H
2O
2With certain flow with peristaltic pump simultaneously from the Polycondensation Reactor and Esterification Reactor charging, flow 90mL/hr, propenyl chloride and the 50%H of catalyzer and methanol mixed slurries
2O
2Flow be respectively: 187mL/hr, 56mL/hr, catalyzer and 50%H
2O
2Mass ratio 1: 8.5, mixing speed 350rpm, temperature of reaction 41-49 ℃, react and be thermopositive reaction, by the chuck heat exchange, residence time 1.5hr, reaction mass enters filtration unit from reactor upper end overflow.After the aqueous phase catalyst slurries separated through membrane filtration, catalyzer filter cake or concentrated slurry were directly with after the solvent making beating, with being pumped into the epoxidation reaction still.
Reaction charge ratio: n methyl alcohol: n propenyl chloride: nH
2O
2=2: 2: 1 (mol ratio of material)
Embodiment 4
The series connection of two stills, every still effective volume: 2.5L, 12.5L, 15 liters of the total effective volumes of reactor.Methyl alcohol and catalyst mix slurries, AC and H
2O
2Throw first step reactor with certain flow simultaneously into volume pump, catalyzer and methanol mixed slurries, propenyl chloride, 50%H
2O
2Flow be respectively: 2.7,5.6,1.66 (L/hr), catalyzer and 50%H
2O
2Mass ratio 1: 8.5, mixing speed 350rpm, temperature of reaction 41-49 ℃, residence time 1.5hr reacts and is thermopositive reaction, by the chuck heat exchange, reaction mass enters the next stage reactor from reactor upper end overflow.
The reaction mass (epoxidation reaction end) of second stage reactor upper end overflow enters membrane filter appts, catalyzer filter cake after the filtration or concentrated slurry are directly with after the solvent making beating, with pumping first step epoxidation reaction still, water layer and the oil reservoir that does not contain catalyzer leaves standstill at settling vessel, layering, the direct rectifying separation of epoxidation oil reservoir of settling vessel lower end extraction, the water layer of settling vessel upper end extraction are carried out negative pressure rectifying and are reclaimed methyl alcohol and a small amount of epoxy chloropropane.See diagram 2.
Reaction charge ratio: n methyl alcohol: n propenyl chloride: nH
2O
2=2: 2: 1 (mol ratio of material)
Quality/theory reaction that epoxidation yield=separation obtains epoxy chloropropane generates the quality of epoxy chloropropane
Theoretical reaction generates quality * 50% * 92.5/34 of the quality=hydrogen peroxide of epoxy chloropropane
Claims (6)
1. the continuous production method of an epoxy chloropropane by hydrogen peroxide method, propenyl chloride, methyl alcohol and titanium-silicon molecular sieve catalyst fine particle are put into reactor, 10～80 ℃ of temperature of reaction, it is characterized in that, reactor types is single still, or the series connection of the slurry-bed reaction still of multistage equal volume or different volumes; Reaction solution does not need to be homogeneous phase, the pulpous state particle of propenyl chloride, solvent methanol and titanium-silicon molecular sieve catalyst adds in the first step reactor with volume pump, drip hydrogen peroxide in each order reaction still, reacting rear material carries out the profit layering through tundish, is divided into oil phase and water slurries; Catalyzer is suspended in aqueous phase, and oil phase is sent into rectifying tower and separated propenyl chloride and epoxy chloropropane and Trace Methanol; The water slurries obtain catalyzer filter cake or concentrated slurry after filtering, concentrated slurry is directly squeezed into first step epoxidation reaction still with solvent methanol making beating back with pump, filter the back water and contain the water of methyl alcohol, a small amount of epoxy chloropropane and reaction generation and the water that hydrogen peroxide is brought into, adopt the negative pressure rectifying separation to go out a spot of methyl alcohol and epoxy chloropropane, the methyl alcohol of Separation and Recovery is used for the preparation of catalyst slurry;
The mol ratio of described propenyl chloride and hydrogen peroxide is 1～20: 1, and the mol ratio of methyl alcohol and propenyl chloride is 0.5～4: 1, and catalyst consumption is 5～15g/1mol hydrogen peroxide;
Particle diameter 1～the 3um of described molecular sieve catalyst.
2. the continuous production method of epoxy chloropropane by hydrogen peroxide method according to claim 1 is characterized in that, described catalyst slurry filters and adopts the ceramic membrane filter device, carries out solid-liquid separation by microporous membrane.
3. the continuous production method of epoxy chloropropane by hydrogen peroxide method according to claim 1 is characterized in that, described being reflected under 35～55 ℃ carried out.
4. the continuous production method of epoxy chloropropane by hydrogen peroxide method according to claim 1 is characterized in that, the mol ratio of described propenyl chloride and hydrogen peroxide is 1～4: 1, and the mol ratio of methyl alcohol and propenyl chloride is 0.5～2: 1.
5. the continuous production method of epoxy chloropropane by hydrogen peroxide method according to claim 1 is characterized in that, the concentration of described hydrogen peroxide is 27.5%, 35% or 50%.
6. the continuous production method of epoxy chloropropane by hydrogen peroxide method according to claim 1, it is characterized in that, described reaction is a strong exothermal reaction, need in reactor, be provided with the cooling of cooling fluid chuck cooling or inner coil pipe or outside the pump circulation cooling system.
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