CN106518622B - A method of preparing halogen ethyl alcohol and ethylene oxide - Google Patents
A method of preparing halogen ethyl alcohol and ethylene oxide Download PDFInfo
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- CN106518622B CN106518622B CN201610142806.3A CN201610142806A CN106518622B CN 106518622 B CN106518622 B CN 106518622B CN 201610142806 A CN201610142806 A CN 201610142806A CN 106518622 B CN106518622 B CN 106518622B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
It provides a kind of method for preparing halogen ethyl alcohol, comprising the following steps: (1) halogen alcoholization: hydrogen halides, H being added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, carry out halogen alcoholization reaction and obtain halogen ethyl alcohol.A kind of method that halogenohydrin method prepares ethylene oxide, including (1) halogen alcoholization are also provided: hydrogen halides, H being added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, carry out halogen alcoholization reaction and obtain halogen ethyl alcohol；(2) it is saponified: the hydroxide of the halogen ethyl alcohol of step (1) and alkali metal being subjected to saponification, separates and obtains ethylene oxide and halogenated alkali metal salt；Optionally, (3) 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 or ethylene oxide with high selectivity and yield, and considerably reduces the discharge of waste water, waste residue.
Description
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) that hydrogen halides, H halogen alcoholization: being added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, carry out halogen alcoholization reaction
And obtain halogen ethyl alcohol.
Preferably, hetero-atom molecular-sieve containing Ti described in step (1) is TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-
One of SBA-15 or a variety of.
In the present invention, hydrogen halides described in step (1) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
In the present invention, ethylene and H in step (1)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 (1) 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 (1) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.
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:
(1) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, carry out halogenohydrin
Change reaction and obtains halogen ethyl alcohol；
(2) it is saponified: the hydroxide of the halogen ethyl alcohol of step (1) and alkali metal being subjected to saponification, separates and obtains ring
Oxidative ethane and halogenated alkali metal salt.
Preferably, the method also includes: (3) electrodialysis: the halogenated alkali metal salt that step (2) 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 (4) epoxides: by step (2) acquisition
Ethylene oxide by distillation and/or rectifying, the ethylene oxide refined.
Preferably, hetero-atom molecular-sieve containing Ti described in step (1) is TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-
One of SBA-15 or a variety of.
In the present invention, hydrogen halides described in step (1) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
In the present invention, ethylene and H in step (1)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 (1) 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 (1) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.
In the present invention, in step (2) 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 (2) 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 (1)
In reaction unit be single reactor, concatenated multiple reactors, tubular reactor or micro passage reaction.
Preferably, the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
When step (1) 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.
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.
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.
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: YHalogen ethyl alcohol=CEthylene×SHalogen 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) 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 H2O
Molar ratio with HCl and ethylene is about 1.2:1.2:1.Obtain halogenohydrin, i.e. the pure and mild 1- chloro second -2- alcohol of 2- chloro second -1-
Mixture.
Comparative example 1
1) 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 81:3.6:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro second -2- of 2- chloro second -1-
The mixture of alcohol.
Embodiment 2
1) 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, wherein TS-1 molecular sieve and ethylene rub
You are 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 H2O2Mass 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.Wherein, embodiment 1 of the synthetic method of TS-1 referring to CN201410812216.8.
Comparative example 2
1) 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 53:3.3:1.Obtain halogenohydrin, the i.e. pure and mild 1- of 2- chloro second -1-
The mixture of chloro second -2- alcohol.
Comparative example 3
Halogen alcoholization: the oxydol H of 70wt% concentration is added in tubular reactor2O2, 35wt% concentration HCl solution (salt
Acid) and ethylene, 45 DEG C at a temperature of carry out chlorohydrin action, the wherein oxydol H of 70wt% concentration2O2, 35wt% concentration
HCl solution and the flow of ethylene three should make H2O2Molar ratio with HCl and ethylene is about 1.2:1.2:1.Halogenohydrin is obtained,
That is the mixture of the pure and mild 1- chloro second -2- alcohol of 2- chloro second -1-.
Comparative example 4
Halogen alcoholization: 35wt% is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
The HCl solution (hydrochloric acid) and ethylene of concentration, 45 DEG C at a temperature of carry out chlorohydrin action, wherein the HCl of 35wt% concentration is molten
The flow of liquid and ethylene should make the molar ratio of HCl and ethylene be about 1.2:1.
Embodiment 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.
2) be saponified: the halogenohydrin and sodium hydroxide that step 1) 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.
3) electrodialysis: the sodium chloride solution that step 2) 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.
4) purification of ethylene oxide:
The ethylene oxide crude product obtained in step 2 is subjected to rectifying, obtains the ethylene oxide of high-purity (99.9wt%).
Embodiment 4
1) 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 residence time in tubular reactor
Be 10 minutes, wherein TS-1 molecular sieve and the mass ratio of ethylene be 0.05:1, the oxydol H of 35wt% concentration2O2, 20wt% it is dense
The HCl solution of degree and the additional amount of ethylene three should make H2O2Molar ratio with HCl and ethylene is about 1.5:1.1:1.It obtains
The mixture of the pure and mild 1- chloro second -2- alcohol of halogenohydrin, i.e. 2- chloro second -1-.
2) be saponified: the halogenohydrin and sodium hydroxide that step 1) 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.
3) electrodialysis: the sodium chloride solution that step 2) is obtained passes through bipolar membrane electrodialysis, obtains sodium hydroxide and HCl.
4) purification of ethylene oxide:
The ethylene oxide crude product obtained in step 2 is subjected to rectifying, obtains the ethylene oxide of high-purity (99.9wt%).
Embodiment 5
Embodiment 3 is repeated, only replaces HCl solution with HBr solution.
Embodiment 6
Embodiment 3 is repeated, the catalyst bed of TS-2 is only used.TS-2 synthetic method is referring to CN200910013070.X's
Specific embodiment (only one embodiment).
Embodiment 7
Embodiment 3 is repeated, fixed Ti-MWW catalyst bed has only been loaded in the pipe of tubular reactor.Ti-MWW
Embodiment 1 of the synthetic method referring to CN200710037012.1.
Embodiment 8
Embodiment 3 is repeated, the catalyst bed of Ti-Beta is only used.
Embodiment 9
Embodiment 3 is repeated, the catalyst bed of Ti-SBA-15 is only used.Ti-SBA-15 synthetic method reference
The embodiment 1 of CN201110211854.0.
Embodiment 10
Embodiment 3 is repeated, only the sodium hydroxide in step (2) is substituted with potassium hydroxide.
Embodiment 11
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 12
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 13
Embodiment 3 is repeated, only the reaction temperature in step (1) is 20 DEG C, and the residence time is 2 minutes.
Embodiment 14
Embodiment 3 is repeated, only the temperature in step (2) is controlled at 50 DEG C.
1 embodiment 1-14 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 1:0.3.
Claims (25)
1. a kind of method for preparing halogen ethyl alcohol, comprising the following steps:
(1) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, it is anti-to carry out halogen alcoholization
It answers and obtains halogen ethyl alcohol；
Wherein: the hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or more
Kind；Reaction temperature in step (1) is 10-50 DEG C.
2. a kind of method that halogenohydrin method prepares ethylene oxide, comprising the following steps:
(1) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, ethylene and hetero-atom molecular-sieve containing Ti, it is anti-to carry out halogen alcoholization
It answers and obtains halogen ethyl alcohol；With
(2) it is saponified: the hydroxide of the halogen ethyl alcohol of step (1) and alkali metal being subjected to saponification, separates and obtains epoxy second
Alkane and halogenated alkali metal salt；
Wherein: the hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or more
Kind；Reaction temperature in step (1) is 10-50 DEG C.
3. according to the method described in claim 2, it is characterized by: the method also includes: (3) electrodialysis: step (2) 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 described in claim 3, it is characterized by: the method also includes the purifications of (4) epoxides: will
The ethylene oxide that step (2) obtains is by distillation and/or rectifying, the ethylene oxide refined.
5. method according to any of claims 1-4, it is characterised in that: hydrogen halides described in step (1) is chlorination
One of hydrogen, hydrogen bromide or hydrogen iodide are a variety of.
6. method according to any of claims 1-4, it is characterised in that: ethylene and H in step (1)2O2Molar ratio
For 1:0.1-100, and/or
The H2O2Concentration (wt%) be 5-90%.
7. according to the method described in claim 5, it is characterized by: ethylene and H in step (1)2O2Molar ratio be 1:0.1-
100, and/or
The H2O2Concentration (wt%) be 5-90%.
8. according to the method described in claim 6, it is characterized by: ethylene and H in step (1)2O2Molar ratio be 1:0.5-
50, and/or
The H2O2Concentration (wt%) be 8-80%.
9. according to the method described in claim 7, it is characterized by: ethylene and H in step (1)2O2Molar ratio be 1:0.5-
50, and/or
The H2O2Concentration (wt%) be 8-80%.
10. method according to claim 8 or claim 9, it is characterised in that: ethylene and H in step (1)2O2Molar ratio be 1:
0.8-30, and/or
The H2O2Concentration (wt%) be 10-70%.
11. according to claim 1-4, method described in any one of 7-9, it is characterised in that: ethylene and hydrogen halides in step (1)
Molar ratio be 1:0.1-100.
12. according to the method described in claim 5, it is characterized by: the molar ratio of ethylene and hydrogen halides is 1 in step (1):
0.1-100。
13. according to the method described in claim 6, it is characterized by: the molar ratio of ethylene and hydrogen halides is 1 in step (1):
0.1-100。
14. according to the method for claim 11, it is characterised in that: the molar ratio of ethylene and hydrogen halides is 1 in step (1):
0.5-50, and/or
Reaction temperature in step (1) is 20-45 DEG C.
15. method according to claim 12 or 13, it is characterised in that: the molar ratio of ethylene and hydrogen halides in step (1)
For 1:0.5-50, and/or
Reaction temperature in step (1) is 20-45 DEG C.
16. according to the method for claim 14, it is characterised in that: the molar ratio of ethylene and hydrogen halides is 1 in step (1):
0.8-30。
17. according to the method for claim 15, it is characterised in that: the molar ratio of ethylene and hydrogen halides is 1 in step (1):
0.8-30。
18. the method according to any one of claim 2-4, it is characterised in that: halogen ethyl alcohol and alkali metal hydrogen in step (2)
The molar ratio of oxide is 1:0.1-50, and/or
Reaction temperature in step (2) is 0-100 DEG C.
19. according to the method for claim 18, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
Molar ratio is 1:0.5-30, and/or
Reaction temperature in step (2) is 5-90 DEG C.
20. according to the method for claim 19, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
Molar ratio is 1:0.8-20, and/or
Reaction temperature in step (2) is 10-80 DEG C.
21. the method according to any one of claim 2-4,19-20, it is characterised in that: the hydroxide of the alkali metal
Object 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.
22. according to the method for claim 18, it is characterised in that: the hydroxide of the alkali metal be sodium hydroxide or
One of potassium hydroxide or lithium hydroxide are 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.
23. according to claim 1-4, method described in any one of 7-9,12-14,16-17,19-20,22, it is characterised in that:
Reaction unit in the step (1) is single reactor, concatenated multiple reactors, tubular reactor or micro passage reaction
One of or it is a variety of；And/or
Wherein the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
24. according to the method described in claim 5, it is characterized by: the reaction unit in the step (1) is single reaction
One of device, concatenated multiple reactors, tubular reactor or micro passage reaction are a variety of；And/or
Wherein the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
25. according to the method described in claim 6, it is characterized by: the reaction unit in the step (1) is single reaction
One of device, concatenated multiple reactors, tubular reactor or micro passage reaction are a variety of；And/or
Wherein the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
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| CN109721467B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Process for preparing halohydrins |
| CN115724719A (en) * | 2021-08-30 | 2023-03-03 | 中国石油化工股份有限公司 | Method for preparing halohydrin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414976A (en) * | 1971-12-07 | 1975-11-26 | Degussa | Production of chloro-and bromo-hydrins |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414976A (en) * | 1971-12-07 | 1975-11-26 | Degussa | Production of chloro-and bromo-hydrins |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
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