CN101774886B - Method for preparing dichlorohydrin and reaction device - Google Patents
Method for preparing dichlorohydrin and reaction device Download PDFInfo
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- CN101774886B CN101774886B CN 200910028890 CN200910028890A CN101774886B CN 101774886 B CN101774886 B CN 101774886B CN 200910028890 CN200910028890 CN 200910028890 CN 200910028890 A CN200910028890 A CN 200910028890A CN 101774886 B CN101774886 B CN 101774886B
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Abstract
The invention relates to improvement on a method for preparing dichlorohydrin by chlorinating glycerin and a reaction device. The chlorinating reaction is the series reaction of a reaction kettle and a sprinkling reaction tower which is filled with filler. The sprinkling reaction tower is sequentially provided with a placing filter zone, a hollow built-in sprinkling device zone and a placing filter zone from top to bottom. After viscosity decrease by kettle type preaction, the sprinkling reaction is carried out, the reaction contact is sufficient, the reaction time is long, the reaction efficiency is greatly enhanced, the conversion rate of the glycerin achieves 100%, and the reaction time is short and only needs 6-8 hours. The dichlorohydrin yield can be enhanced to more than 96%, and the yield can be enhanced to more than 99.0% by adding kreatine and strong acid mixing catalyst. The invention has the advantages of simple process flow, convenient reaction operation and high reaction efficiency.
Description
Technical field
The invention relates to the improvement that glycerin chlorination is prepared epoxy chloropropane intermediate method for preparing dichlorohydrin and reaction unit, relate in particular to a kind of reaction efficiency and the dichlorohydrine yield is all high, method for preparing dichlorohydrin and reaction unit that the reaction times is short.
Background technology
Epoxy chloropropane has another name called Epicholorohydrin, is a kind of important Organic Chemicals and fine chemicals, and purposes is very extensive, is the important source material of preparation Resins, epoxy, synthetic elastomer, glue used in paper-making etc. such as it.Prior synthesizing method has propylene high-temperature chlorination process and allyl acetate method, after develop again preparing epoxy chloropropane by using glycerol method, its reaction process is as follows:
Reaction process in two steps, (1) formula; Glycerin chlorination prepare 1,3-dichlorohydrine and 1,2-dichlorohydrine (because the two further all generates epoxy chloropropane after the hydrolysis, thereby this patent is referred to as dichlorohydrine with 1,3-dichlorohydrine and 1,2-dichlorohydrine, lower with.); (2) formula: the reaction product dichlorohydrine is hydrolyzed cyclisation under alkaline condition, obtains epoxy chloropropane.In the two step reaction process, reaction (2) technique is simple, operation is ripe, reaction yield is high, thereby the key of preparing epoxy chloropropane by using glycerol method is that (1) step glycerin chlorination prepares dichlorohydrine.
Belgium Su Wei (SOLVAY) company is at EP1760060, EP1762556, WO2005/054167, WO2007/054505, CN1882522A, CN1974511A, CN100999443A, CN101003614A, CN10168761, disclosed by glycerine and HCl gas continuous production dichlorohydrine method among the CN101066909, by HCl bubbling in the reactor of one or more levels series connection, and and the glycerine countercurrent flow, and by azeotropic distillation except the water that generates in the dereaction, improve the yield of dichlorohydrine, product can make the high purity dichloropropanol product again through rectifying.The autoclave blistering reaction, HCl concentration is lower in the reaction system, add that reaction is gas-liquid reaction, initial reaction stage, glycerine viscosity is larger, and HCl gas and glycerine reaction are abundant not, although adopt many still series connection can increase the abundant contact reacts of HCl gas and glycerine, but cause the glycerine residence time long, the operation time needs 9～16h, has increased energy consumption of reaction; Secondly, solution-air still reaction HCl concentration is low, has also caused the yield of dichlorohydrine and selectivity not high, and the side reaction such as glycerine shrink occurs easily, and yield and selectivity only have respectively 76.6% and 77.3%.
Chinese patent CN101007751A discloses a kind of employing tubular reactor and bubbling reactor tandem process, from glycerine preparation dichlorohydrine method.At first glycerine is added mixing tank with HCl and carboxylic acid catalyst and mix, then be pressed into and carry out chlorination reaction in the tubular reactor, change into dichlorohydrine and glycerine monochlorohydrin through the reacted glycerine major part of tubular reactor; Then this mixture is entered blistering reaction still and HCl again and continue reaction, water, dichlorohydrine and unreacted HCl that reaction generates steam from blistering reaction still top azeotropic together, bottom still liquid then enters rectifying tower continuously to be separated, and high boiling glycerine monochlorohydrin is then sent to circulating reaction in the rectifying tower bottoms.This technique total reaction time 12～16h, the yield of dichlorohydrine＞90%, HCl utilization ratio＞70%, more above-mentioned pure autoclave blistering reaction has shortened the reaction times, has improved the yield of target product, and the HCl utilization ratio also is improved.But still for example have some deficiency: (1) for guarantee that glycerine can transform in a large number in tubular reactor, this reactor must be done very longly, and facility investment is larger; (2) water that generates in the tubular reactor can not in time be steamed, and has suppressed the carrying out of positive reaction, need to pass into a large amount of HCl and promote reaction, causes so a large amount of losses of HCl; (3) the gas-to-liquid contact area is little in the follow-up blistering reaction still, reacts insufficient, and residence time of material is short, and reaction efficiency is low; (4) HCl concentration is lower in the bubbling reactor, react insufficient, HCl loss seriously.
Secondly, catalyst system therefor in the existing chlorination reaction substantially all adopts single carboxylic-acid or organic nitrile compound.For example:
Belgium Su Wei (SOLVAY) company is in EP1760060, EP1762556, WO2005/054167, WO2007/054505, CN1882522A, CN1974511A, CN100999443A, CN101003614A, CN10168761, CN101066909 patent, disclosed glycerine and HCl gas continuous production dichlorohydrine method, its catalyzer of selecting is C
1～C
8Carboxylic acid, such as poly carboxylic acid such as the monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid or Succinic Acid, pentanedioic acid, hexanodioic acids, catalyst levels is usually greater than 1mol/kg (concentration of catalyzer in every kilogram of liquid).Because what adopt is single carboxylic-acid catalyzer, active relatively low, thereby the yield of dichlorohydrine and selectivity are lower, yield 76.6%, selectivity 77.3%; The operation time is longer, needs 9～16h.
Disclosedly among the Chinese patent CN101029000 prepare the method for dichlorohydrine by glycerin chlorination, adopt the organic nitrile compound to make catalyzer.The organic nitrile compound has: acetonitrile, propionitrile, vinyl cyanide, positive valeronitrile, isopropyl cyanide, hydroxyacetonitrile, chloro acetonitrile, succinonitrile, trimethylene cyanide, oxalic acid dinitrile and composition thereof or cyanobenzene, benzyl cyanide, the cyanobenzene of replacement, benzyl cyanide and composition thereof.Catalyzer needs the activation with 30%HCl before use, and the catalyzer usage quantity is 1～10% (accounting for the glycerine molar ratio), 1 to 10 hour this technological reaction time, and glycerol conversion yield 99%, the dichlorohydrine total recovery is greater than 90%.Because the organic nitrile compound catalyst needs to process with 30%HCl before use, has increased reaction process; Secondly, the catalyzer after HCl processes contains hypertoxic CN in reacted raffinate
-, environmental pollution is serious, the wastewater treatment difficulty.Simultaneously, these catalyzer are met acid still can be transformed into the carboxylic-acid catalyzer, so carboxylic-acid catalyzer defects still exists.
Therefore still having is worth improved place.
Summary of the invention:
The present invention's the first purpose is to overcome the deficiency of above-mentioned prior art, and the method for preparing dichlorohydrin that a kind of operation is convenient, reaction efficiency is high is provided.
Another purpose of the present invention is to provide a kind of aforesaid method used reaction unit.
The present invention's the first purpose realizes that main the improvement is: the glycerin chlorination reaction, and adopt reactor and fill Packed spray reaction tower cascade reaction technique, thereby overcome above-mentioned the deficiencies in the prior art, realize purpose of the present invention.Specifically, method for preparing dichlorohydrin of the present invention is characterized in that glycerine and the hydrogenchloride chlorination reaction under catalyst, for reactor with fill Packed spray reaction tower cascade reaction.
Because the glycerin chlorination reaction is gas-liquid reaction, initial reaction stage, glycerine viscosity is larger, by the first one-step chlorination of autoclave, after reaction proceeds to certain hour, is mainly a propylene chlorohydrin and dichlorohydrine in the system, and system viscosity reduces greatly; Material adopts spray to be vaporific importing spray reaction tower behind the viscosity reduction, with the HCl gas contact reacts that imports from tower bottom.The spray reaction tower of tower structure, filler all is equipped with in top and bottom, and the space is left at the middle part, be equipped with and import and sprinkling equipment, the spray reaction adds filler so that solution-air contact reacts area change, and the residence time prolongs, contact reacts is more abundant, thereby has improved reaction efficiency.And in the chlorination reaction later stage, reaction mainly is subjected to thermodynamic control, sprays tower reaction, can in time remove the water that reaction generates, and is conducive to the carrying out that reacts.Thereby can significantly improve reaction efficiency than still reaction.
Reactor is connected with filling Packed spray reaction tower, can be that a reactor is connected with a spray reaction tower, also can be that a plurality of reactors are connected with a plurality of spray reaction towers, for example still-still-Ta-Ta series connection, or omit one of them.The present invention tests comparison, and preferably connecting of 1～2 reactor and 1～2 spray reaction tower is both economical, and high reaction efficiency was arranged again.Said reactor is the popular response still, has no special requirements.
Glycerine and hydrogenchloride, catalyzer and each plant demand and remaining reaction condition are basic identical with prior art in the chlorination reaction of the present invention, and subsequent disposal is also basic identical.For example be pressed into continuously glycerine and catalyzer in the reactor first, be preheated to 60 ℃, pass into an amount of (being advisable not overflow) HCl and carry out chlorination, first one-step chlorination in reactor, after the reaction regular hour, to carry out degree of depth chlorination in second reactor of reaction mass importing, the amount of HCl still is advisable not overflow.Preliminary chlorination reaction is finished, and material is imported the spray reaction tower continue reaction, passes into HCl gas from spray reaction tower bottom, regulates HCl gaseous tension and flow, makes the glycerine complete reaction.The water that reaction process generates, HCl, part dichlorohydrine steam from spray reaction tower top azeotropic, and remaining dichlorohydrine, glycerine monochlorohydrin etc. flow out from the reaction tower bottom.Unnecessary HCl enters reactor from the top discharge of spray reaction tower and recycles after condensation, drying, pressurization.After chlorination reaction was finished, the azeotropic mixture that contains HCl, water, dichlorohydrine that cat head is distillated mixed with dichlorohydrine, the glycerine monochlorohydrin of generation, added for example Na of weak base or salt
2CO
3, CaCO
3, NaHCO
3Deng neutralization HCl wherein, filter, standing demix carries out respectively rectifying with lower floor's organic phase and upper strata water, gets final product to get the high purity dichlorohydrine.The glycerine monochlorohydrin that does not steam in the tower bottoms enters reactor and recycles.
In addition, for further improving reaction yield, Reaction time shorten, catalysts of the present invention, a kind of large organic carboxyl acid of catalytic activity and strong acid mixed catalyst of preferably adopting.Be the reaction of glycerine of the present invention and hydrogenchloride catalytic chlorination, catalyzer is organic carboxyl acid and strong acid mixed catalyst, and said organic carboxyl acid catalyzer is C
1～C
12Monocarboxylic acid or C
2～C
12Di-carboxylic acid, consumption are 0.5～5% of glycerine amount of substance; Said strong acid catalyst consumption is 0.5～15% of glycerine amount of substance; And organic carboxyl acid is 1: 1.0～8.0 with the ratio (mol ratio) of strong acid amount of substance.
Monocarboxylic acid or di-carboxylic acid are identical with existing carboxylic acid catalyst.Be generally C
1～C
12Aliphatic carboxylic acid and aromatic carboxylic acid, wherein the monobasic aliphatic carboxylic acid is preferably acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, sad, lauric acid; The monobasic aromatic carboxylic acid is generally F, Cl, the NO that the adjacency pair position is had sucting electronic effect
2Phenylformic acid Deng group replaces is preferably: phenylformic acid, Whitfield's ointment, 4-chloro-benzoic acid, 2,4 dichloro benzene formic acid, 4-nitrobenzoic acid, 4-fluorobenzoic acid; Di-carboxylic acid is C
2～C
12Dibasic aliphatic carboxylic acid or binary aromatic carboxylic acid.Wherein the dibasic aliphatic carboxylic acid has: such as but not limited to such as oxalic acid, Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid etc.; The binary aromatic carboxylic acid has: such as but not limited to phthalic acid and the terephthalic acid as there being a position to be replaced by F, Cl on phthalic acid, terephthalic acid, the phenyl ring, as: 2-chlorine terephthalic acid, 2-fluorine terephthalic acid etc.Di-carboxylic acid of the present invention is preferably: Succinic Acid, hexanodioic acid, nonane diacid, phthalic acid, terephthalic acid, 2-chlorine terephthalic acid.
Strong acid: a kind of commercially available general inorganic acid that can be the vitriol oil, phosphoric acid, concentrated nitric acid etc.; Also can be to be selected from sulfonic group polystyrene resin, sulfonic group polyvinyl resin, tosic acid, phosphorus heteropoly tungstic acid, and anhydrous AlCl
3, SnCl
4, TiCl
4, ZnCl
2, FeCl
3A kind of Deng in the Lewis acid.If when selecting Lewis acid, preferred anhydrous AlCl
3, TiCl
4, ZnCl
2
The ratio of the amount of the compounding substances of above-mentioned two class acid, be preferably 1: 1.0～5.0.
The present invention's the second purpose realizes that its still afterreaction device is the tower structure that three sheaf spaces are arranged, and is followed successively by from top to bottom and places packing area, built-in hollow spray equipment district, places the packing area.Through preliminary chlorination reaction thing, through spray and HCl gas countercurrent reaction in packing layer, greatly increased reaction contact area like this, prolonged both reaction times, thereby high reaction efficiency is arranged.
The present invention sprays reaction tower, and top packing layer Main Function is, and the one, reduce the HCl that passes into and overflow, the 2nd, be conducive to rectifying separation azeotropic component; Bottom packing layer Main Function is that the augmenting response contact area prolongs the reaction times, improves reaction efficiency.Therefore preferably packing area, top height accounts for tower total height 10-30%, and packing area, bottom height accounts for tower total height 60-80%, not increasing under the tower height degree prerequisite, higher reaction efficiency is arranged.
Filler in the spray column, effect is to increase the gas-liquid reaction contact area, prolong the reaction times, therefore conventional packing in the chemical filler tower, all can be used, such as but not limited to: the entity fillers such as Raschig ring, Pall ring, cascade ring, Berl saddle, square saddle screen filler, ripple packing also can be the dictyosome fillers such as saddle type net, θ net, ripple net.Be preferably Raschig ring, Pall ring, cascade ring, saddle type net, θ net, ripple net, ripple packing among the present invention.
Glycerin chlorination of the present invention prepares the dichlorohydrine method, owing to adopt autoclave pre-reaction and spray column reaction tandem process, the autoclave pre-reaction, make the reaction system viscosity degradation, for better condition has been created in follow-up spray reaction, spray reaction HCl gas contacts more abundant with the material that sprays after disperseing, long reaction time, and a unreacted propylene chlorohydrin and glycerine can continue the reaction with HCl in the packing layer of tower bottom, make the glycerin chlorination reaction more abundant, thereby have greatly improved reaction efficiency; Simultaneously, the packing section on tower top can play refinery distillation, has isolated unnecessary HCl and has discharged reaction tower, has also indirectly improved reaction efficiency, and glycerol conversion yield reaches 100%.Reaction times foreshortens to 6～8h by 12～16h of prior art, and the yield of dichlorohydrine is increased to more than 96%.Catalyzer adopts organic carboxyl acid and strong acid mixed catalyst, have than the prior art single catalyst: catalytic activity is high, further Reaction time shorten 1-2 hour, greatly improved industrial production efficient, the dichlorohydrine yield also can be increased to more than 99.0%; The advantages such as and the catalyzer raw material is easy to get, and preparation is simple, and use procedure is safe, pollution-free.Tank reactor of the present invention and spray reaction tower, equipment is simple, and it is less to increase cost of investment.Technical process is simple, and operation is convenient, and the reaction efficiency height is the maximum feature of present method.
Below in conjunction with five specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the technical scheme restriction total to the present invention, some do not depart from the unsubstantiality of the present invention's design and change In the view of the technician; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Description of drawings:
Fig. 1 is a kind of optimization embodiment of the present invention process flow sheet.
Fig. 2 is spray reaction tower structural representation in Fig. 1 technique.
Embodiment:
Embodiment 1: referring to Fig. 1,2,93% glycerine among the header tank E1 is passed into reactor E3, pass into simultaneously the acetate catalyst that accounts for glycerine amount of substance 5%, be heated to 65 ℃, pass into continuously HCl gas from steel cylinder E2 to E3, HCl passes into speed and is advisable not overflow.React after 1.5 hours, material is imported among the reactor E4 continue chlorination, the control temperature of reaction continues to pass into HCl reaction 1 hour at 90 ℃.
Material behind the initial action imports and is equipped with among the spray reaction tower E8 of ripple net filler, temperature is at 110 ℃ in the control tower, pass into continuously HCl by E7 to spray reaction tower E8 bottom, regulate the pressure 0.3～0.4MPa of HCl gas outlet, make the glycerine complete reaction, reaction is flowed out as terminal point without cut in condenser E9.Unnecessary HCl discharges from condenser E9, reenters spray reaction tower E8 after, E6 dry through E5 pressurizes and participates in reaction.
After chlorination reaction was finished, the azeotropic mixture that contains HCl, water, dichlorohydrine with the E8 cat head distillates mixed among the adding E10 with spray reaction tower bottoms, adds Na
2CO
3At neutralization HCl wherein, through E12 filtration, E13 standing demix, to tell dichlorohydrine and enter E15 rectifying, the upper strata water (steams gas through condenser E14 condensation income E17) behind the distillation dehydration in E13, again rectifying in E15, overhead product is collected among the E18 through condenser E16 condensation.Can get 99.3% dichlorohydrine from the E15 cat head, the high boiling point glycerine monochlorohydrin that does not steam in the rectifying tower enters reactor and recycles.This reaction process glycerol conversion yield 100%, dichlorohydrine yield 96.7%.
Spray reaction tower E8 is vertical tower body, and by being divided into three layers down, top accounts for total height 10-30% packing area 3, and the middle and lower part accounts for total height 60-80% packing area 4, is placed with respectively ripple net filler, is reaction solution spray district between two packing areas, built-in spray equipment 2.Spray reaction tower spray is distinguished the liquid opening for feed 8 that responds, and discharge port 1 is arranged at top, top, and tower reactor reuse liquid opening for feed 7, HCl inlet mouth 6, discharge port 5 are arranged at the bottom.
Embodiment 2: substantially with embodiment 1, just reduced by a reactor E4, and glycerol concentration 95%, catalyzer is the propionic acid that accounts for glycerine amount of substance 5%, is heated to 70 ℃, sustained reaction 2 hours.Spray reaction cat head can get 99.3% dichlorohydrine, this reaction process glycerol conversion yield 100%, dichlorohydrine yield 96.2%.
Embodiment 3: referring to Fig. 1,2,93% glycerine among the header tank E1 is passed in the reactor E3, pass into simultaneously the acetate catalyst that accounts for glycerine amount of substance 5%, the Catalyzed by p-Toluenesulfonic Acid agent of glycerine amount of substance 3%, be heated to 65 ℃, pass into continuously HCl gas from steel cylinder E2 to E3, the amount that passes into HCl is advisable not overflow.React after 1 hour, material is imported among the reactor E4 continue chlorination, the control temperature of reaction continues to pass into HCl reaction 1 hour at 90 ℃.
Material behind the initial action imports and is equipped with among the spray reaction tower E8 of ripple net filler, temperature is at 110 ℃ in the control tower, pass into continuously HCl by E7 to spray reaction tower E8 bottom, regulate the pressure 0.3～0.4MPa of HCl gas outlet, guarantee herein complete reaction of glycerine, reaction is flowed out as terminal point without cut in condenser E9.Unnecessary HCl discharges from condenser E9, reenters E8 after, E6 dry through E5 pressurizes and participates in reaction.
After chlorination reaction was finished, the azeotropic mixture that contains HCl, water, dichlorohydrine that the E8 cat head is distillated mixed with spray reaction tower bottoms and to add among the reactor E10 adding Na
2CO
3At neutralization HCl wherein, after filtering, E12 squeezes into standing demix among the E13, and tell dichlorohydrine and enter rectifying in the E15, the upper strata water distills dehydration in E13 after, again rectifying in E15.Can get 99.3% dichlorohydrine from the E15 cat head, the high boiling glycerine monochlorohydrin that does not steam in the rectifying tower enters among the E8 and recycles.This reaction process glycerol conversion yield 100%, dichlorohydrine yield 99.6%.
Embodiment 4: substantially with embodiment 4, just reduced by a reactor E4, glycerol concentration 95%, catalyzer are the propionic acid catalyzer that accounts for glycerine amount of substance 5%, and glycerine amount of substance 10% phosphoric acid catalyst is heated to 70 ℃, sustained reaction 2 hours.Follow-up spray inner-tower filling material is the triangle filler, regulates the pressure 0.4Mpa of HCl gas outlet.Can get 99.2% dichlorohydrine from the E15 cat head, this reaction process glycerol conversion yield 100%, dichlorohydrine yield 99.0%.
Comparative example: the glycerine with 95% is passed in the reactor, adds simultaneously the acetic acid that accounts for glycerine amount of substance 5% and makes catalyzer, is heated to 113 ℃, passes into HCl gas from the reactor bottom, and reaction is flowed out as terminal point without cut in condenser.Water and unreacted HCl that reaction generates, the part dichlorohydrine steams from the top azeotropic of reactor, and remaining dichlorohydrine, glycerine monochlorohydrin etc. flow out from the reactor bottom.Unnecessary HCl discharges from the top of reactor condenser, reenters reactor after vitriol oil drying, pressurization.
Reacted still liquid and overhead distillate are squeezed in the neutralization reaction still, add slightly excessive Na
2CO
3Neutralize, filter standing demix.Tell lower floor's organic phase, carry out rectifying.The upper strata water is stayed again rectifying after dehydration in the reactor, and the rectifying tower cat head can get dichlorohydrine.The glycerine monochlorohydrin byproduct that tower bottoms does not steam turns back to and continues reaction in the reactor.This reaction process glycerol conversion yield 95.8%, dichlorohydrine yield 76.2%.
To those skilled in the art; under this patent design and embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; the for example change of still-spray column array mode; the change of spray inner-tower filling material; the change of combination catalyst kind is at catalyst levels; change in the ratio range, etc. unsubstantiality change; can be employed equally; can both realize and the basic identical function of above-described embodiment and effect, no longer describe in detail for example one by one, all belong to this patent protection domain.
Claims (9)
1. method for preparing dichlorohydrin is characterized in that glycerine and the hydrogenchloride chlorination reaction under catalyst, for reactor with fill Packed spray reaction tower cascade reaction, catalyzer is the mixed catalyst of organic carboxyl acid and strong acid; Said organic carboxyl acid catalyzer is C
1～C
12Monocarboxylic acid or C
2～C
12Di-carboxylic acid, consumption are 0.5～5% of glycerine amount of substance; Said strong acid catalyst consumption is 0.5～15% of glycerine amount of substance, and the ratio of organic carboxyl acid and strong acid amount of substance is 1 ﹕ 1.0～8.0; Described strong acid is the vitriol oil, phosphoric acid, concentrated nitric acid, sulfonic group polystyrene resin, sulfonic group polyvinyl resin, tosic acid, phosphorus heteropoly tungstic acid, AlCl
3, TiCl
4, ZnCl
2In a kind of.
2. described method for preparing dichlorohydrin according to claim 1 is characterized in that reaction is that 1～2 reactor reacts with 1～2 spray reactors in series.
3. described method for preparing dichlorohydrin according to claim 1 is characterized in that organic carboxyl acid and the ratio of strong acid amount of substance are 1 ﹕ 1.0～5.0.
4. described method for preparing dichlorohydrin according to claim 1 is characterized in that monocarboxylic acid is acetic acid, a kind of in propionic acid, butyric acid, valeric acid, phenylformic acid, Whitfield's ointment, 4-chloro-benzoic acid, the 2,4 dichloro benzene formic acid.
5. described method for preparing dichlorohydrin according to claim 1 is characterized in that di-carboxylic acid is Succinic Acid, hexanodioic acid, nonane diacid, phthalic acid, a kind of in terephthalic acid, the 2-chlorine terephthalic acid.
6. according to the used spray reaction tower of above-mentioned arbitrary claim method reaction unit, it is characterized in that spraying reaction tower is three sheaf space tower structures, from and under be followed successively by and place packing area, built-in hollow spray equipment district, place the packing area.
7. described spray reaction tower reaction unit according to claim 6 is characterized in that packing area, top height accounts for tower total height 10-30%, and packing area, bottom height accounts for tower total height 60-80%.
8. according to claim 6 or 7 described spray reaction tower reaction units, it is characterized in that spraying the reaction tower filler is Raschig ring, Pall ring, cascade ring, saddle type net, θ net, ripple net.
9. according to claim 6 or 7 described spray reaction tower reaction units, it is characterized in that spraying the reaction tower filler is ripple packing.
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| CN102603481B (en) * | 2012-02-07 | 2014-05-28 | 江苏安邦电化有限公司 | Micro reaction system and method for chlorohydrination of chloropropene |
| CN105060263B (en) * | 2015-09-01 | 2017-06-13 | 青海盐湖工业股份有限公司 | A kind of neutralization reaction system |
| CN108863718A (en) * | 2018-07-11 | 2018-11-23 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dichlorohydrin |
| CN109516901A (en) * | 2018-12-28 | 2019-03-26 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of 2,2 '-dichloroether |
| CN111808049A (en) * | 2020-06-18 | 2020-10-23 | 浙江豪邦化工有限公司 | Device and method for preparing epoxy chloropropane by using glycerol method |
| CN114749121B (en) * | 2022-05-19 | 2022-09-09 | 北京化工大学 | System and process for preparing epichlorohydrin by glycerol method |
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