CN106518611B

CN106518611B - A method of preparing halogen ethyl alcohol and ethylene oxide

Info

Publication number: CN106518611B
Application number: CN201610142778.5A
Authority: CN
Inventors: 林民; 廖维林; 舒兴田
Original assignee: JIANGXI SUKEER NEW MATERIAL CO Ltd
Current assignee: JIANGXI SUKEER NEW MATERIAL CO Ltd
Priority date: 2016-03-14
Filing date: 2016-03-14
Publication date: 2019-09-20
Anticipated expiration: 2036-03-14
Also published as: CN106518611A

Abstract

There is provided a kind of method for preparing halogen ethyl alcohol, comprising the following steps: (1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；(2) hydrogen halides, H halogen alcoholization: are added in reaction unit₂O₂, ethylene and through step (1) processed catalyst, carry out halogen alcoholization reaction and obtain halogen ethyl alcohol；Optionally, (3) are saponified: the hydroxide of the halogen ethyl alcohol of step (2) and alkali metal being carried out saponification, separates and obtains ethylene oxide and halogenated alkali metal salt；Optionally, (4) electrodialysis: the halogenated alkali metal salt that step (2) are obtained passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.Method of the invention prepares halogen ethyl alcohol with high selectivity and yield, and considerably reduces the discharge of waste water, waste residue.

Description

A method of preparing halogen ethyl alcohol and ethylene oxide

Technical field

The present invention relates to a kind of preparation methods of halogen ethyl alcohol, and the method for preparing ethylene oxide by halogen ethyl alcohol；More specifically A kind of method for using new halogenohydrin method to prepare halogen ethyl alcohol as raw material using ethylene is provided, and ethylene oxide is prepared using new halogenohydrin method Method.

Background technique

Ethylene chlorhydrin (being also " chloroethanes ") is important organic solvent and organic synthesis raw material.For manufacturing epoxy second Alkane, synthetic rubber, dyestuff, medicine and pesticide etc., also serve as organic solvent.For manufacturing ethylene glycol, ethylene oxide, and medicine, Dyestuff, synthesis of pesticide etc..

Ethylene oxide (hereinafter referred to as " EO ") is a kind of important Organic Chemicals.It is a kind of organic compound, is changed Formula is C2H4O, is a kind of toxic carcinogen, is used to manufacture fungicide in the past.It is widely used in washing, is made Medicine, the industries such as printing and dyeing.It can be used as the initiator of detergent in chemical industry related industry.Ethylene oxide is a kind of simplest cyclic ethers, Belong to heterocycle compound, is important petroleum chemicals.Ethylene oxide mainly for the manufacture of ethylene glycol (polyester fiber raw materials processed), Synthetic detergent, nonionic surfactant, antifreeze, emulsifier and condensed ethandiol class product, be also used for production plasticizer, Lubricant, rubber and plastics etc..It is widely used in washing dye, electronics, medicine, pesticide, weaving, papermaking, automobile, oil exploitation and refining The various fields such as system.

In the prior art, the preparation method of ethylene oxide: one, chlorohydrination: reacting in two steps, and the first step is by ethylene and chlorine Gas is passed through in water, generates ethylene chlorhydrin.Second step is to be reacted with alkali (usually milk of lime) with ethylene chlorhydrin, generates epoxy second Alkane.Two, air method and two kinds of oxygen method oxidizing process: can be divided into., using air as oxidant, the latter is greater than 95% with concentration for the former The oxygen of (volume) is as oxidant.

Chlorohydrination production history is long, and the main processes of chlorohydrination are ethylene chlorohydrination, milk of lime saponification and product Purification, its main feature is that mature production technology, operational load elasticity are big, selectivity is good, it is not high to the purity requirement of feed ethylene, from And the safety of production can be improved, construction investment is few.Since fixed assets investment is few, product cost is lower, product have compared with Strong cost competitiveness.

The chlorohydrination of the prior art prepares ethylene oxide and is primarily present following problems: 1. addition occurs for raw material chlorine and ethylene Side reaction generates dichloroethanes.Dichloroethanes is difficult to be utilized, and wastes a large amount of raw material.In addition, chlorine and ethylene reaction, A large amount of heat is released, heat is concentrated in the reaction vessel, causes to produce dangerous row very big.2. raw material chlorine is in process of production not The evitable a small amount of oxygen of entrainment, with the progress of reaction, chlorine constantly participates in reaction, it is therefore desirable to chlorine is constantly supplemented, And oxygen cannot participate in reacting, in reaction unit, with the progress of reaction, oxygen concentration is constantly increased, and anti-for constantly accumulation Heat should be released, oxygen, chlorine, ethylene exist simultaneously, and are easy to cause explosion under high temperature.3. reaction generates hydrochloric acid, need to consume A large amount of alkali (such as calcium hydroxide) carrys out the product hydrochloric acid of neutralization reaction, can just be conducive to react.4. reaction generates a large amount of chlorine Change calcium, calcium chloride causes the waste water COD generated higher, pollutes environment.5. water resources consumption is big, a large amount of waste water and waste residue are generated, Chlorohydrination produces waste water, the 2.1t calcium chloride waste residue that 1t ethylene oxide generates 40-50t chloride, the waste water have temperature it is high, " five is high " feature that pH value is high, chloride content is high, COD content is high and suspension content is high, it is difficult to handle, seriously pollute environment. 6. the hypochlorous acid generated in production process is to the corrosion of equipment also than more serious.

Ethylene oxide is produced with chlorohydrination technique, if waste water, waste residue problem, enterprise's process units cannot be efficiently solved Ability is bigger, and the burden of environmental protection is bigger；Output is higher, deeper to the injury of environment.Thus, environmental protection has become system The about primary factor of ethylene oxide industrial development.It is earliest that U.S.'s development and application chlorohydrination prepares epoxides, using initial stage, chlorine Alcohol method technique is widely developed and produces.2000, since the waste water of chlorohydrination technique generation, the U.S. cannot be effectively treated It is forbidden to use chlorohydrination technique production epoxides.

Summary of the invention

The inventor of the present application found through research that using ethylene, hydrogen halides and H₂O₂Halogen ethyl alcohol is prepared, is then saponified, energy It is enough that ethylene oxide is prepared with high selectivity and yield, and considerably reduce the discharge of waste water, waste residue.

According to the first embodiment of the present invention, a kind of method for preparing halogen ethyl alcohol is provided, this method includes following step It is rapid:

(1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；

(2) hydrogen halides, H halogen alcoholization: are added in reaction unit₂O₂, ethylene and through step (1) processed catalyst, into The reaction of row halogen alcoholization obtains halogen ethyl alcohol.

In the present invention, in step (1) acid be organic and or inorganic acids, preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, One of carbonic acid, chloric acid, acetic acid are a variety of.The concentration of acid is not required, concentrated acid is can be, is also possible to olefin(e) acid.It can be with It is mixed acid.

Preferably, catalyst described in step (1) is hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecule One of sieve is a variety of.

In the present invention, it is washed in step (1) with distilled water or deionized water.

In the present invention, hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.

In the present invention, ethylene and H in step (2)₂O₂Molar ratio be 1:0.1-100, preferably 1:0.5-50, more preferably 1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.

In the present invention, the H₂O₂Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more Preferably 10-70%, more preferably 15-60%, more preferable 20-50%.

In the present invention, in step (2) molar ratio of ethylene and hydrogen halides be 1:0.1-100, preferably 1:0.5-50, it is more excellent Select 1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.

In the present invention, the reaction temperature in step (2) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.

In the present invention, there is no limit the purpose of immersion is the leaching for allowing catalyst first to pass in and out acid to soaking time in step (1) Bubble, improves catalytic performance and the shelf life of catalyst.General soaking time be 0.1-72h, preferably 0.2-48h, more preferably For 0.3-24h, such as 0.5h, 1h, 2h, 6h.

In the present invention, the purpose of washing catalyst is the acid on washing immersion rear catalyst.Generally with distilled water or go Ionized water, or can also be washed with weak base.

In the present invention, the purpose dried in step (1) is the moisture on removal washing rear catalyst.Do not damaging catalysis Agent structure and in the case where not influencing catalyst performance, the temperature of drying can be controlled arbitrarily.If high temperature is dried, when drying Between it is shorter.If low temperature drying, drying time is appropriately extended.Achieve the purpose that moisture removal.Generally, drying temperature 5- 90 DEG C, drying time 0.1-48h；It is preferred that 10-60 DEG C of drying temperature, drying time 0.2-24h；More preferably drying temperature 20-50 DEG C, drying time is such as 30 DEG C of drying temperature of 0.5-12h., drying time 10h；40 DEG C of drying temperature, when drying Between be 6h；45 DEG C of drying temperature, drying time 2h.

In the present invention, the concentration range of the acid of step (1) is unrestricted, can be weak acid, can be strong acid, can also be with It is mixed acid.It can be low concentration acid, be also possible to high concentrated acid.In general, the concentration range of hydrochloric acid is 2-38%, preferably 10-35%.The concentration range 2-98% of sulfuric acid, preferably 5-80%.The concentration range 10-98% of nitric acid, preferably 20-80%.

According to the second embodiment of the present invention, a kind of method that halogenohydrin method prepares ethylene oxide, this method packet are provided Include following steps:

(3) it is saponified: the hydroxide of the halogen ethyl alcohol of step (2) and alkali metal being subjected to saponification, separates and obtains ring Oxidative ethane and halogenated alkali metal salt.

Preferably, the method also includes: (4) electrodialysis: the halogenated alkali metal salt that step (3) are obtained is by bipolar Membrane electrodialysis obtains the hydroxide and hydrogen halides of alkali metal.

Preferably, the method also includes: the purification (such as distillation or rectifying) of (5) epoxides: by step (3) acquisition Ethylene oxide by distillation and/or rectifying, the ethylene oxide refined.

(2) halogen alcoholization: being passed through hydrogen halides in reaction unit, adds H₂O₂, ethylene and processed through step (1) is added Catalyst carries out halogen alcoholization reaction and obtains halogen ethyl alcohol.

In the present invention, in step (3) molar ratio of halogen ethyl alcohol and alkali metal hydroxide be 1:0.1-50, preferably 1: 0.5-30, more preferably 1:0.8-20, more preferable 1:1.0-10, more preferable 1:1.1-5.

In the present invention, the reaction temperature in step (3) is 0-100 DEG C, preferably 5-90 DEG C, preferably 10-80 DEG C, more preferably 20-60℃。

Preferably, the hydroxide of the alkali metal is sodium hydroxide or one of potassium hydroxide or lithium hydroxide Or it is a variety of.

Preferably, the halogenated alkali metal salt be sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, One of sodium iodide, potassium iodide, lithium iodide are a variety of.

In the present invention, the concentration of hydrogen halides can be any concentration in step (1), when using low concentration hydrogen halides, It can be very good the carry out speed of control reaction；When using high concentration hydrogen halides, it can promote to react to production halogen ethyl alcohol Direction quickly carries out.As long as there is the presence of hydrogen halides in reaction system, regardless of the concentration of hydrogen halides is how many, reacting can be into Row, can obtain halogen ethyl alcohol.Preferably, the concentration of hydrogen halides is 1-40%, further preferred 2-30%, in preferred 3- 20%, more preferable 5-10%.

It is preferred that according in any method of first embodiment or second embodiment, the step (2) In reaction unit be single reactor, concatenated multiple reactors, tubular reactor or micro passage reaction.

Preferably, the reaction in step (2) is carried out according to intermittent, semi continuous or continuous mode.

When step (2) carries out in single reactor according to intermittent mode, in step (1) when addition catalyst, second The weight ratio of alkene and catalyst be 1:0.001-0.4, preferably 1:0.005-0.3, more preferably 1:0.01-0.2, more preferable 1: 0.015-0.1.When carrying out in step (1) according to continuously or semi-continuously mode, catalyst can be with fixed catalyst bed Mode be arranged in the continuously or semi-continuously reactor of mode, such as concatenated multiple reactors, tubular reactor or microchannel In reactor.At this point, the dosage of catalyst is then more.In catalyst bed, the weight of olefinic unsaturated compound and catalyst Than for 1:0.001-0.99, preferably 1:0.005-0.8, more preferably 1:0.01-0.6, more preferable 1:0.015-0.4.

In the present invention, hetero-atom molecular-sieve containing Ti is including TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 etc..

TS-1 is a kind of Titanium Sieve Molecular Sieve, belongs to Pentasil type hetero-atom molecular-sieve, rhombic system, synthetic method reference CN201410812216.8。

TS-2 molecular sieve has MEL topological structure, has good catalytic oxidation performance.Synthetic method reference CN200910013070.X。

Ti-MWW shows more excellent catalysis oxidation in the epoxidation reaction to linear alpha-olefin and cyclic olefin Performance, and very high trans selective is shown in alkene asymmetric epoxidation reaction.Synthetic method reference CN200710037012.1。

Ti-Beta molecular sieve has the twelve-ring channel design and stronger acidity of three-dimensional staggered, anti-in heterogeneous catalysis The good catalytic performance of Ying Zhongyou.Specific synthesis is referring to " synthesis of Beta molecular sieve and its research of catalytic performance ", author: Liu Set duckweed, East China Normal University.

Ti-SBA-15 belongs to one kind of mesopore molecular sieve, and Ti-SBA-15 has two-dimentional six side's through-hole structures.Synthetic method Referring to CN201110211854.0.

In the present invention, HTS molecular sieve refers to containing Ti, has multi-stage porous, MFI structure molecular sieve, including HTS-1, HTS- 2, HTS-3 molecular sieve.HTS molecular sieve has unique hollow tunnel structure, and the Ti content of framework of molecular sieve is high, makes it have Good thermal stability, antianaphylaxis and higher catalytic activity and selectivity.

HTS molecular sieve includes HTS-1 molecular sieve, HTS-2 molecular sieve, HTS-3 molecular sieve.

HTS-1 molecular sieve surface acid site catalytic activity with higher, her diffusion and solvent polarity is to reaction Active influence is very big.Specific synthesized reference " the probe reaction research of HTS-1 molecular sieve surface acidification catalysis ", author: Liu Xuan Gorgeous, Yin Dulin, Zhu Huayuan, Shen Gang, " catalysis journal ".

Titanium Sieve Molecular Sieve HTS-2, with the identical catalytic oxidation activity of Titanium Sieve Molecular Sieve HTS, selectivity and general Physicochemical property.Specific synthesized reference " synthesis of Titanium Sieve Molecular Sieve HTS-2 ", author: Zhu Bin, Lin Min, Shu Xingtian, Wang Xieqing.

Monocrystalline Multihollow titanium-silicon molecular sieve catalyst HTS-3, molecular sieve surface titanium is uniformly distributed, when shortening crystallization Between, improve synthesising stability and repeatability.HTS-3 molecular sieve catalyst has more activated centres, better catalytic Can, it is more advantageous to reactant molecule diffusion.Specific synthesized reference " development of monocrystalline Multihollow HTS-3 molecular sieve catalyst ", " stone Oil refining and chemical industry ".

In the present invention, Zr-MFI molecular sieve refers to hetero atom containing Zr, has MFI structure molecular sieve.Zr-MFI molecular sieve It is a kind of typical solid Lewis acid catalyst, reacts (Meerwein-Ponndorf-Verley reactions) in MPV In show good catalytic activity.There is hetero atom containing Zr MFI structure molecular sieve to be metalloid element zirconium incorporation In MFI structure (orthogonal system, mesh straight hole) molecule, ZSM-5, Silicalite-1 etc. common are.

ZSM-5 molecular sieve is prepared referring to the method for patent CN200510029462.7.

Silicalite-1 molecular sieve is prepared referring to the method for patent CN201010220796.3.

It is preferred that halogen alcoholization reaction carries out in the bubble tower type or turbulent flow tubular reactor of no internal component, reaction pressure It can be for higher than normal pressure, or normal pressure or close to normal pressure.Such as temperature is 0~60 DEG C, the conversion ratio of ethylene reaches 97%, Hydrogen peroxide substantially completely converts.

Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam enters from tower bottom and makes to give birth to At thick ethylene oxide from tower top blow out.At 0~100 DEG C, tower top pressure is normal pressure or negative pressure for saponification temperature control.Saponification Device designs and the key problem in technology of operation is to be sufficiently mixed and control pH with lye into the halogen ethanol water before saponification column, Flow out the ethylene oxide generated from tower top as early as possible.

Since traditional chlorohydrination technique is saponified using lime, all chlorine is finally with CaCl₂Form consumption, generate a large amount of Containing CaCl₂With the sewage of organic chloride.Calculation shows that every production 1t ethylene oxide, about generation 2.1t CaCl₂Waste residue and extremely Few 43t waste water.The present invention uses the hydroxide (such as sodium hydroxide, potassium hydroxide, lithium hydroxide) of alkali metal, saponification process The salt applied afterwards can be reduced into the hydroxide and hydrogen halides of alkali metal, fully achieve circulation by bipolar membrane electrodialysis It utilizes.

(1) reaction system combined using tubular reactor with tower reactor mitigates the load of chlorohydrination tower.

(2) saponification column decompression operation, steam consumption are few.

(3) tower and rectifying column are evaporated before rectification working process setting, ethylene oxide and the production of production ethylene glycol is made in 2 towers respectively The ethylene oxide of polyethers.

(4) the dichloro diisopropyl ether in the waste water that saponification process generates, drop are separated by the scattered tower with special tower tray Biological oxygen content, chemical oxygen content in low waste liquid.

In the prior art, halogenohydrin method prepares the process (by taking chlorine as an example) of ethylene oxide:

CH₂=CH₂+Cl₂+H₂O——ClCH₂CH₂OH+HCl

ClCH₂CH₂OH+Ca(OH)₂——EO+CaCl₂+H₂O

The present invention provides the process (by taking hydrogen chloride as an example) that a kind of novel halogenohydrin method prepares ethylene oxide:

CH=CH₂+HCl+H₂O₂——CH(Cl)-CH₂(OH)+H₂(catalyst is added) in O

CH(Cl)-CH₂(OH)+NaOH(KOH、LiOH)——EO+H₂O+NaCl (KaCl or LiCl)

NaCl (KaCl or LiCl) becomes NaOH (KOH, LiOH) and HCl by bipolar membrane electrodialysis.

The hydroxide and hydrogen halides of alkali metal after bipolar membrane electrodialysis can be recycled.

Bipolar Membrane is a kind of novel ion-exchange composite membranes, it is usually hydrophilic by cation exchange layer (N-type film), interface Layer (Catalytic Layer) and anion exchange layer (p-type film) are combined, and are reaction films truly.It is acted in DC electric field Under, hydrolytic dissociation can be respectively obtained hydrogen ion and hydroxide ion in film two sides by Bipolar Membrane.Using this feature, by Bipolar Membrane The bipolar membrane electrodialysis system being combined into other anion and cation exchange membranes, can will be water-soluble in the case where not introducing new component Salt in liquid is converted into corresponding bronsted lowry acids and bases bronsted lowry, and this method is known as bipolar membrane electrodialysis method.

It is not particularly limited for the bipolar membrane electrodialysis equipment in the application.It is preferable, however, that using such a Bipolar membrane electrodialysis equipment, it includes: the 1) film being made of Bipolar Membrane, cavity block, anode membrane, partition, pole plate as core component Heap and 2) ancillary equipment, the ancillary equipment include water pot, flowmeter, pump, pipeline etc..Ancillary equipment includes rectifier cabinet.Core The frame of stainless steel structure is used in component.The quantity of film and partition can according to specific treating capacity (volume of salting liquid) and It is fixed.

Bipolar membrane, one kind of electric drive film, main function are that H+ ion and OH-ion are provided under electric field force, film Side is the back, and the other side is sunny side, and the middle layer of the back and sunny side is water layer, under the action of applying direct current electric field power, water H in layer₂O splits into H+ ion and OH-ion, and is migrated respectively by sunny side and the back to two sides theme solution, so double The effect of Polar Crystal Slab is to provide H+ ion and OH-ion source under electric field force effect.

When in the present invention, using bipolar membrane electrodialysis treatment brine waste, corresponding bronsted lowry acids and bases bronsted lowry is obtained.

Advantages of the present invention:

In the prior art, ethylene oxide is produced using halogenohydrin method, generates a large amount of chloride containing calcium (or sodium chloride) waste water, given up It is also thorough containing not separating also containing the raw material organic matter or intermediate product organic matter not reacted completely in reaction process in water Ethylene oxide, these debirs are difficult to degrade, and deal with extremely difficult, and never find effective processing side Method.The main reason for disabling chlorohydrination technique of U.S. 2000 is exactly calcium chloride (or the chlorine containing the organic matter waste for being difficult to degrade Change sodium) waste water is difficult to handle.The waste water that someone is generated using electrolysis method processing chlorohydrination technique, due to containing organic waste in waste water Object, deals with extremely difficult, and the debirs in waste water are very sensitive to electrolysis with ion-exchange film system, damage electrolysis installation It is larger；Meanwhile electrolysis wastewater needs to consume a large amount of energy, the benefit of acquisition is little；The biggest problems are that: electrolysis wastewater produces Raw chlorine and hydrogen, organic matter there are the case where, it is abnormally dangerous, be easy explosion.

The present invention uses bipolar membrane electrodialysis technology, and bipolar membrane electrodialysis technology is the technology of a processing salt, and salt passes through Bipolar membrane electrodialysis generates bronsted lowry acids and bases bronsted lowry.Someone is by bipolar membrane electrodialysis treatment sodium chloride-containing waste water before, but never There is the production technology that bipolar membrane electrodialysis is applied to ethylene oxide.Intrinsic prejudice, halogenohydrin method prepare the useless of ethylene oxide Containing the debirs for being difficult to degrade in water, common debirs are very sensitive to ionic membrane, and treatment effect is very poor.Inventor's warp It crosses and explores and test many times, discovery bipolar membrane electrodialysis treatment halogenohydrin method prepares the waste water excellent of ethylene oxide, halogenohydrin The waste water containing debirs that method prepares ethylene oxide generation does not influence the technique of bipolar membrane electrodialysis, can be very good to locate Manage the salt in waste water.The present invention cleverly prepares the characteristics of ethylene oxide generates useless Organic substance in water using halogenohydrin method, can be very The good preparation applied bipolar membrane electrodialysis technology with ethylene oxide, may be implemented clean manufacturing, solves halogenohydrin method and prepare ring The reluctant problem of waste water that oxidative ethane generates.Waste water handling problem is captured, halogenohydrin method prepares the advantage of ethylene oxide just Quite obvious, less investment, high conversion rate is easy to control.Therefore, present invention introduces bipolar membrane electrodialysis technologies to have overturned traditional halogen The method that alcohol method prepares ethylene oxide the problem of completely solving containing organic runoff water, makes halogenohydrin method efficiently prepare epoxy While ethane, clean manufacturing is realized.

Bronsted lowry acids and bases bronsted lowry is the raw material of this programme, and the bronsted lowry acids and bases bronsted lowry that bipolar membrane electrodialysis generates just can be used as raw material again and be applicable in, So as to form circulation, realizes cleaning, circulation, produced without waste.Original waste is become into present raw material, saves material While, the discharge of waste is reduced, environment is protected.

Compared with electrolysis process, the energy of bipolar membrane electrodialysis consumption greatly reduces, and effect gets a promotion instead.Together When, bipolar membrane electrodialysis produces bronsted lowry acids and bases bronsted lowry, and dangerous property is not present, and overcomes electrolysis process danger, is easy the problem of explosion.Most Importantly, electrolysis process handles waste water, the foreign organic matter in waste water can not be handled, can only be discharged, and this kind of organic Waste is difficult to degrade, and greatly pollutes environment；And bipolar membrane electrodialysis treatment waste water, the foreign organic matter in waste water can restore At raw material or product is directly obtained, so that the debirs in waste water have also been handled while handling salt in waste water, by organic waste Object becomes raw material or product, takes full advantage of material, while waste zero-emission may be implemented, and protects environment well.

Compared with prior art, technical solution of the present invention has following advantageous effects:

1, overcome the problems, such as the by-product (chlorine, calcium chloride, side reaction product) of the prior art: 1. without using Cl₂For raw material, It avoids because of Cl₂Lasting consumption the trace oxygen in chlorine can be made constantly to accumulate caused by explosion danger；2. without Cl₂It participates in Reaction greatly reduces intermediate addition side reaction, reduces the generation of organic by-products；3. in saponification process, base amount is big Big reduction, only 1/2 or so of original process.

2, the prior art is to reduce the generation of side reaction, prepare halogen ethyl alcohol concentration can only generally control 4.5% with Under；And new halogenohydrin method technique of the invention, since side reaction is few, the concentration of halogen ethyl alcohol is unrestricted.1) saponification process is saved Energy consumption, only 1/10 or so of original process；2) saving water resource, the 1/10 of water consumption deficiency original process；Meanwhile it greatly reducing The discharge of wastewater flow rate, and the waste water is easily handled.

3, using bipolar membrane electrodialysis technology, handle while containing organic wastewater, the NaOH (KOH, LiOH) of generation and HCl is reusable.

4, catalyst of the invention first passes through sour processing, improves the catalytic performance of catalyst and improves the suitable of catalyst Use the service life.

Detailed description of the invention

Fig. 1 is bipolar membrane electrodialysis artwork of the present invention；

Fig. 2 is bipolar membrane working principle diagram of the present invention.

Appended drawing reference: 1,2,3: mixing vessel.

Specific embodiment

Below by embodiment, the present invention will be further described, but content not thereby limiting the invention.

Qualitative analysis is carried out to product using Agilent 7890/5975C-GC/MSD type gas chromatography-mass spectrometry, Quantitative analysis is carried out to product using Agilent 6890N type gas chromatograph and external standard method.

According to detection and analysis as a result, defining following objective function as inspection target.

Conversion of ethylene:

Halogen ethanol selectivity:

Halogen ethanol yield: Y_{Halogen ethyl alcohol}=C_Ethylene×S_{Halogen ethyl alcohol}

Ethylene oxide output:

In formula, C is conversion ratio, and S is selectivity, and Y is yield, and n is the amount of substance after reaction, n₀For the amount of parent material.

Bipolar membrane electrodialysis equipment is as depicted in figs. 1 and 2.

Bipolar membrane electrodialysis equipment, it includes: 1) as core component by Bipolar Membrane, cavity block, anode membrane, partition, pole plate The membrane stack of composition and 2) ancillary equipment, the ancillary equipment include water pot, flowmeter, pump, pipeline etc..Ancillary equipment includes whole Flow cabinet.The frame of stainless steel structure is used in core component.The quantity of film and partition can according to specific treating capacity (salting liquid Volume) depending on.

Bipolar membrane, one kind of electric drive film, main function are that H+ ion and OH-ion are provided under electric field force, film Side is the back, and the other side is sunny side, and the middle layer of the back and sunny side is water layer, under the action of applying direct current electric field power, water H2O in layer splits into H+ ion and OH-ion, and is migrated respectively by sunny side and the back to two sides theme solution, so double The effect of Polar Crystal Slab is to provide H+ ion and OH-ion source under electric field force effect.

The performance indicator of Bipolar Membrane is as follows:

* in 0.5Mol Na₂SO₄In solution, at 25 DEG C, 10-100mA/cm²It is measured under current density

Embodiment 1

1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 1h, then use Catalyst is dried 6h in the environment of 40 DEG C by distilled water washing catalyst；

2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe) The oxydol H of 70wt% concentration₂O₂, 35wt% concentration HCl solution (hydrochloric acid) and ethylene, 45 DEG C at a temperature of carry out chloropharin Change reaction, the wherein oxydol H of 70wt% concentration₂O₂, the HCl solution of 35wt% concentration and the flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- alcohol of 2- chloro second -1- Mixture.

Comparative example 1

1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 1h, then use Catalyst is dried 6h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1 The embodiment 1 of CN201410812216.8.

2) water halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe) H₂O, chlorine and ethylene, 45 DEG C at a temperature of carry out chlorohydrin action, wherein water H₂O, chlorine and the flow of ethylene three should make Obtain H₂The molar ratio of O and chlorine and ethylene is about 80:3.6:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- of 2- chloro second -1- The mixture of alcohol.

Embodiment 2

1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 25%, is impregnated 2h, then use Catalyst is dried 2h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1 The embodiment 1 of CN201410812216.8.

2) oxydol H of TS-1 molecular sieve, 35wt% concentration halogen alcoholization: is added in tower reactor₂O₂, 20wt% it is dense The HCl solution (hydrochloric acid) and ethylene of degree, 35 DEG C at a temperature of carry out chlorohydrin action, the wherein matter of TS-1 molecular sieve and ethylene Amount is than being 0.05:1, the oxydol H of 35wt% concentration₂O₂, the HCl solution of 20wt% concentration and the additional amount of ethylene three should make Obtain H₂O₂Molar ratio with HCl and ethylene is about 1.5:1.1:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- of 2- chloro second -1- The mixture of alcohol.

Comparative example 2

2) TS-1 molecular sieve, water H halogen alcoholization: are added in tower reactor₂O, chlorine and ethylene, 35 DEG C at a temperature of Chlorohydrin action is carried out, wherein TS-1 molecular sieve and the mass ratio of ethylene are 0.05:1, water H₂O, chlorine and ethylene three plus H should be made by entering amount₂The molar ratio of O and chlorine and ethylene is about 70:3.3:1:1.Halogenohydrin is obtained, i.e. 2- chloro second -1- is pure and mild The mixture of 1- chloro second -2- alcohol.

Comparative example 3

1) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe) The oxydol H of 70wt% concentration₂O₂, 35wt% concentration HCl solution (hydrochloric acid) and ethylene, 45 DEG C at a temperature of carry out chloropharin Change reaction, wherein the oxydol H of 70wt% concentration₂O₂, the HCl solution of 35wt% concentration and the flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- alcohol of 2- chloro second -1- Mixture.Wherein, embodiment 1 of the synthetic method of TS-1 referring to CN201410812216.8.

Comparative example 4

1) oxydol H of 70wt% concentration halogen alcoholization: is added in tubular reactor₂O₂, 35wt% concentration HCl solution (hydrochloric acid) and ethylene, 45 DEG C at a temperature of carry out chlorohydrin action, the wherein oxydol H of 70wt% concentration₂O₂, 35wt% it is dense The HCl solution of degree and the flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 1.2:1.2:1.Obtain halogen The mixture of the pure and mild 1- chloro second -2- alcohol of alcohol, i.e. 2- chloro second -1-.

Comparative example 5

1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 2h, then use Catalyst is dried 2h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1 The embodiment 1 of CN201410812216.8.

2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe) The HCl solution (hydrochloric acid) and ethylene of 35wt% concentration, 45 DEG C at a temperature of carry out chlorohydrin action, wherein 35wt% concentration The flow of both HCl solution and ethylene should make the molar ratio of HCl and ethylene be about 1.2:1.

Embodiment 3

2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe) The oxydol H of 70wt% concentration₂O₂, 35wt% concentration HCl solution (hydrochloric acid) and ethylene, 45 DEG C at a temperature of carry out chloropharin Change reaction, wherein the oxydol H of 70wt% concentration₂O₂, the HCl solution of 35wt% concentration and the flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- alcohol of 2- chloro second -1- Mixture.

3) be saponified: the halogenohydrin and sodium hydroxide that step 2) is obtained carry out saponification, separate and obtaining ethylene oxide has Machine phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from tower bottom Into make generate thick ethylene oxide from tower top blow out.Saponification temperature is controlled at 60~70 DEG C.

4) electrodialysis: the sodium chloride solution that step 3) is obtained passes through bipolar membrane electrodialysis (I type of TRPB8040-, Beijing Ting Run membrane technology development corporation, Ltd. produces and sells, and the transmembrane voltage of application is 1.3V, and operating temperature is 20-30 DEG C), it obtains Sodium hydroxide and HCl.

5) purification of ethylene oxide:

The ethylene oxide crude product obtained in step 3) is subjected to rectifying, obtains the epoxy second of high-purity (99.9wt%) Alkane.

Embodiment 4

1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 15%, is impregnated 2h, then use Catalyst is dried 2h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1 The embodiment 1 of CN201410812216.8.

3) be saponified: the halogenohydrin and sodium hydroxide that step 2) is obtained carry out saponification, separate and obtaining ethylene oxide has Machine phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from tower bottom Into make generate thick ethylene oxide from tower top blow out.Saponification temperature is controlled at 40~50 DEG C.

4) electrodialysis: the sodium chloride solution that step 3) is obtained passes through bipolar membrane electrodialysis, obtains sodium hydroxide and HCl.

5) purification of ethylene oxide:

Embodiment 5

Embodiment 3 is repeated, catalyst soak is only impregnated into 12h in the hydrochloric acid that mass fraction is 60%, uses deionization Water washing dries 5h at 60 DEG C.

Embodiment 6

Embodiment 3 is repeated, only replaces HCl solution with HBr solution.

Embodiment 7

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of TS-2.TS-2 synthetic method reference The specific embodiment (only one embodiment) of CN200910013070.X

Embodiment 8

Embodiment 3 is repeated, fixed Ti-MWW catalyst bed substitution TS- has only been loaded in the pipe of tubular reactor 1 molecular sieve.Embodiment 1 of the Ti-MWW synthetic method referring to CN200710037012.1.

Embodiment 9

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Ti-Beta.

Embodiment 10

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Ti-SBA-15.The synthesis side Ti-SBA-15 Embodiment 1 of the method referring to CN201110211854.0.

Embodiment 11

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-1 molecular sieve.

Embodiment 12

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-2 molecular sieve.

Embodiment 13

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-3 molecular sieve.

Embodiment 14

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of ZSM-5 molecular sieve.ZSM-5 molecular sieve ginseng According to the method preparation of embodiment 1-3 in patent 200510029462.7.

Embodiment 15

Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Silicalite-1 molecular sieve. Method preparation of the Silicalite-1 molecular sieve referring to embodiment 1 in patent 201010220796.3.

Embodiment 16

Embodiment 3 is repeated, only the sodium hydroxide in step (2) is substituted with potassium hydroxide.

Embodiment 17

Repeat embodiment 3, only in step (1) 65wt% concentration oxydol H₂O₂, 35wt% concentration HCl solution and The flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 0.8:0.3:1.

Embodiment 18

Repeat embodiment 3, only in step (1) 65wt% concentration oxydol H₂O₂, 35wt% concentration HCl solution and The flow of ethylene three should make H₂O₂Molar ratio with HCl and ethylene is about 0.9:1.1:1.

Embodiment 19

Embodiment 3 is repeated, only the reaction temperature in step (1) is 20 DEG C, and the residence time is 2 minutes.

Embodiment 20

Embodiment 3 is repeated, only the temperature in step (2) is controlled at 50 DEG C.

1 embodiment 1-20 of table and comparative example 1-4 reaction condition and reaction result

Catalyst amount is that " bed " refers to that catalyst is arranged in the reactor, such as in a manner of fixed catalyst bed Concatenated multiple reactors, in tubular reactor or micro passage reaction.In catalyst bed, olefinic unsaturated compound with urge The weight ratio of agent is 1:0.001-0.99, preferably 1:0.3.

Claims

1. a kind of method for preparing halogen ethyl alcohol, comprising the following steps:

(2) hydrogen halides, H halogen alcoholization: are added in reaction unit₂O₂, ethylene and through step (1) processed catalyst, carry out halogen Alcoholization reaction and obtain halogen ethyl alcohol；

Wherein: the catalyst is one of hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecular sieve or a variety of； The hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or a variety of；It is described HTS molecular sieve is one of HTS-1, HTS-2, HTS-3 or a variety of；The Zr-MFI molecular sieve be ZSM-5 and/or Silicalite-1；Reaction temperature in step (2) is 10-50 DEG C.

2. a kind of method that halogenohydrin method prepares ethylene oxide, comprising the following steps:

(3) it is saponified: the hydroxide of the halogen ethyl alcohol of step (2) and alkali metal being subjected to saponification, separates and obtains epoxy second Alkane and halogenated alkali metal salt；

3. according to the method described in claim 2, it is characterized by: the method also includes: (4) electrodialysis: step (3) is obtained The halogenated alkali metal salt obtained passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.

4. according to the method in claim 2 or 3, it is characterised in that: the method also includes: the purification of (5) epoxides: The ethylene oxide that step (3) are obtained is by distillation and/or rectifying, the ethylene oxide refined.

5. method according to any one of claim 1-3, it is characterised in that: acid is organic acid and/or nothing in step (1) Machine acid.

6. according to the method described in claim 4, it is characterized by: acid is organic and or inorganic acids in step (1).

7. according to the method described in claim 5, it is characterized by: acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carbon in step (1) One of acid, chloric acid, acetic acid are a variety of.

8. according to the method described in claim 6, it is characterized by: acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carbon in step (1) One of acid, chloric acid, acetic acid are a variety of.

9. according to claim 1-3, method described in any one of 6-8, it is characterised in that: soaking time is in step (1) 0.1-72h is washed with distilled water or deionized water, drying time 0.1-48h, and/or

Hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.

10. according to the method described in claim 4, it is characterized by: in step (1) soaking time be 0.1-72h, use distilled water Or deionized water washing, drying time 0.1-48h, and/or

11. according to the method described in claim 5, it is characterized by: in step (1) soaking time be 0.1-72h, use distilled water Or deionized water washing, drying time 0.1-48h, and/or

12. according to claim 1-3, method described in any one of 6-8,10-11, it is characterised in that: in step (2) ethylene with H₂O₂Molar ratio be 1:0.1-100；And/or

The H₂O₂Concentration (wt%) be 5-90%.

13. according to the method described in claim 4, it is characterized by: ethylene and H in step (2)₂O₂Molar ratio be 1:0.1- 100；And/or

The H₂O₂Concentration (wt%) be 5-90%.

14. according to the method for claim 12, it is characterised in that: ethylene and H in step (2)₂O₂Molar ratio be 1:0.5- 50；And/or

The H₂O₂Concentration (wt%) be 8-80%.

15. according to the method for claim 13, it is characterised in that: ethylene and H in step (2)₂O₂Molar ratio be 1:0.5- 50；And/or

The H₂O₂Concentration (wt%) be 8-80%.

16. method according to claim 14 or 15, it is characterised in that: ethylene and H in step (2)₂O₂Molar ratio be 1: 0.8-30；And/or

The H₂O₂Concentration (wt%) be 10-70%.

17. according to claim 1-3, method described in any one of 6-8,10-11,13-15, it is characterised in that: in step (2) The molar ratio of ethylene and hydrogen halides is 1:0.1-100.

18. according to the method described in claim 4, it is characterized by: the molar ratio of ethylene and hydrogen halides is 1 in step (2): 0.1-100。

19. according to the method for claim 17, it is characterised in that: the molar ratio of ethylene and hydrogen halides is 1 in step (2): 0.5-50；And/or

Reaction temperature in step (2) is 20-45 DEG C.

20. according to the method for claim 18, it is characterised in that: the molar ratio of ethylene and hydrogen halides is 1 in step (2): 0.5-50；And/or

Reaction temperature in step (2) is 20-45 DEG C.

21. method described in 9 or 20 according to claim 1, it is characterised in that: the molar ratio of ethylene and hydrogen halides in step (2) For 1:0.8-30.

22. the method according to any one of claim 2,3,6,8,10,13,15,18,20, it is characterised in that: step (3) molar ratio of halogen ethyl alcohol and alkali metal hydroxide is 1:0.1-50 in, and/or

Reaction temperature in step (3) is 0-100 DEG C.

23. according to the method described in claim 4, it is characterized by: halogen ethyl alcohol and alkali metal hydroxide rub in step (3) Your ratio is 1:0.1-50, and/or

Reaction temperature in step (3) is 0-100 DEG C.

24. according to the method for claim 22, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (3) Molar ratio is 1:0.5-30, and/or

Reaction temperature in step (3) is 5-90 DEG C.

25. according to the method for claim 23, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (3) Molar ratio is 1:0.5-30, and/or

Reaction temperature in step (3) is 5-90 DEG C.

26. the method according to claim 24 or 25, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (3) The molar ratio of object is 1:0.8-20, and/or

Reaction temperature in step (3) is 10-80 DEG C.

27. the method according to any one of claim 2,3,6,8,10,13,15,18,20,23-25, it is characterised in that: The hydroxide of the alkali metal be sodium hydroxide or one of potassium hydroxide or lithium hydroxide or a variety of,

And/or

The halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, sodium iodide, iodate One of potassium, lithium iodide are a variety of.

28. according to the method described in claim 4, it is characterized by: the hydroxide of the alkali metal is sodium hydroxide or hydrogen One of potassium oxide or lithium hydroxide are a variety of,

And/or

29. according to claim 1-3, method described in any one of 6-8,10-11,13-15,18-20,23-25,28, special Sign is: the reaction unit in the step (2) is single reactor, concatenated multiple reactors, tubular reactor or micro- logical One of road reactor is a variety of；And/or

Wherein the reaction in step (2) is carried out according to intermittent, semi continuous or continuous mode.

30. according to the method described in claim 4, it is characterized by: the reaction unit in the step (2) is single reaction One of device, concatenated multiple reactors, tubular reactor or micro passage reaction are a variety of；And/or