CN106518615B - A kind of method that dry gas prepares halogen ethyl alcohol and ethylene oxide - Google Patents
A kind of method that dry gas prepares halogen ethyl alcohol and ethylene oxide Download PDFInfo
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- CN106518615B CN106518615B CN201610784079.0A CN201610784079A CN106518615B CN 106518615 B CN106518615 B CN 106518615B CN 201610784079 A CN201610784079 A CN 201610784079A CN 106518615 B CN106518615 B CN 106518615B
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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
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps: (1) halogen alcoholization: H being added in reaction unit2O2, halogen simple substance, dry gas, carry out halogen alcoholization reaction and obtain halogen ethyl alcohol.A kind of method that dry gas prepares ethylene oxide, comprising the following steps: (1) H halogen alcoholization: is added in reaction unit2O2, halogen simple substance, dry gas, 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.Using dry gas, halogen simple substance and H2O2Halogen ethyl alcohol is prepared, is then saponified, ethylene oxide can be prepared using the ethylene ingredient in dry gas with high selectivity and yield, and considerably reduce 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 dry gas；More specifically mention
For a kind of method for using new halogenohydrin method to prepare halogen ethyl alcohol as raw material using dry gas, and the side for using new alcohol method to prepare ethylene oxide
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..
Epoxides contains epoxy group, and chemical property is active, easy ring-opening polymerisation, is a kind of important Organic Chemicals.
Ethylene oxide is a kind of important Organic Chemicals.It is a kind of organic compound, and chemical formula is C2H4O is a kind of toxic
Carcinogen is used to manufacture fungicide in the past.It is widely used in washing, pharmacy, the industries such as printing and dyeing.It is produced in chemical industry correlation
Industry can be used as the initiator of detergent.Ethylene oxide (referred to as " EO ") is a kind of simplest cyclic ethers, belongs to heterocycle compound,
It is important petroleum chemicals.Ethylene oxide is mainly for the manufacture of ethylene glycol (polyester fiber raw materials processed), synthetic detergent, nonionic
Surfactant, antifreeze, emulsifier and condensed ethandiol class product are also used for production plasticizer, lubricant, rubber and plastics
Deng.It is widely used in washing the various fields such as dye, electronics, medicine, pesticide, weaving, papermaking, automobile, oil exploitation and refining.
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.
Epoxides is prepared, halogenohydrin method production history is long, and the main processes of chlorohydrination are alkene halogen alcoholization, lime
Cream saponification and product purification, its main feature is that mature production technology, operational load elasticity are big, selectivity is good, to the pure of raw material olefin
Spend of less demanding, so that the safety of production can be improved, construction investment is few.Since fixed assets investment is few, product cost is lower,
Its product has stronger cost competitiveness.
The chlorohydrination of the prior art prepares epoxides and is primarily present following problems: 1. chlorine is passed through in water, reacts pole
Slow and solubility very little, the reaction of chlorine and water are reversible reactions, the hypochlorous acid ratio very little for causing reaction to generate, thus are caused
The yield for reacting halogen alcoholization is very low, generally only 3-4%.2. reaction generates hydrochloric acid, need to consume a large amount of alkali (such as hydrogen-oxygen
Change calcium) the product hydrochloric acid that carrys out neutralization reaction, it can just be conducive to react.3. reaction generates a large amount of calcium chloride, calcium chloride causes to produce
Raw waste water COD is higher, pollutes environment.4. the shortcomings that chlorohydrination is that water resources consumption is big, a large amount of waste water and waste residue, chloropharin are generated
Method produces waste water, the 2.1t calcium chloride waste residue that 1t epoxides generates 40-50t chloride, which has temperature height, pH value
" five is high " feature high, chloride content is high, COD content is high and suspension content is high, it is difficult to handle, seriously pollute environment.
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 epoxides 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.
Oil refinery dry gas refers to the noncondensable gas (also referred to as distillation gas) for generating and recycling in oil plant oil refining process, mainly at
It is divided into ethylene, propylene and methane, ethane, propane, butane etc., is mainly used as fuel and industrial chemicals.Wherein, in oil refinery dry gas most
Main component is that ingredient is methane, ethane, ethylene, and three about respectively accounts for one third.Oil refinery dry gas mainly from crude oil two
Secondary process, such as heavy oil catalytic cracking, thermal cracking, delayed coking, wherein catalytic cracking (FCC) generate dry gas amount compared with
Greatly, gas pipe network of usually all being made a gift to someone is used as fuel gas, some are even put into torch burning and fall, and cause the very big wave of resource
Take.A small number of oil plants domestic at present are by the utilization of dry gas, and mainly have: 1. preparing vinylbenzene: catalytic cracked dry gas is not required to through any
Special purified to be directly used as reaction gas, with benzene-alkylation ethylbenzene (or being vinylbenzene), second is stupid cheap, economical
It is of poor benefits, commonly use the seldom of this method.2. preparing styrene: it is stupid first to prepare second, then styrene is made by ethylene unit.But
It is that ethylene unit is at high price, few oil plant domestic at present has ethylene unit.3. preparing ethylene oxide.It is dry with catalytic cracking
Gas is the technology that raw material produces ethylene oxide, and what is generallyd use at present is chlorohydrination process route, the ring produced with the method
Oxidative ethane product can also further produce the products such as ethylene glycol, ethanol amine, glycol ether.But there are chlorohydrinations for such method
Intrinsic problem.
Summary of the invention
The inventor of the present application found through research that using dry gas, halogen simple substance and H2O2Halogen ethyl alcohol is prepared, is then saponified,
Ethylene oxide can be prepared using the ethylene ingredient in dry gas with high selectivity and yield；Bipolar membrane electrodialysis is used simultaneously
Device handles by-product, considerably reduces the discharge of waste water, waste residue.
The first embodiment provided according to the present invention provides a kind of method that dry gas prepares halogen ethyl alcohol:
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
(1) H halogen alcoholization: is added in reaction unit2O2, halogen simple substance, dry gas, carry out halogen alcoholization reaction and obtain halogen second
Alcohol.
In the present invention, catalyst is used in the step (1), which is selected from solid acids (such as wolframic acid, niobium
Acid), molecular sieve (such as Ti- molecular sieve), the compound species of vanadium phosphorus oxygen, molybdenum vanadium type metal composite oxide class, the compound gold of molybdenum bismuth type
Belong to oxide-based, molybdenum tungsten type metal composite oxide class, one of Salen transition metal-type catalyst or heteropllyacids, two
Kind is a variety of.
In the present invention, the dry gas is the dry gas that oil plant generates.In general, in dry gas ethylene volume content
For 25-40vol%, preferably 27-37vol%, more preferable 29-35vol%.
In the present invention, the halogen simple substance is one of chlorine, bromine, iodine or a variety of.
In the present invention, the volume ratio of dry gas and halogen simple substance (such as chlorine) is 1:0.1-100 in step (1), preferably 1:
0.15-50, more preferable 1:0.2-30, more preferable 1:0.25-10, more preferable 1:0.3-5, more preferable 1:0.35-2, more preferable 1:
0.4-1。
In the present invention, dry gas and H in step (1)2O2Volume 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, in general, H2O2Be or present aqueous solution form.The H2O2H in aqueous solution2O2Concentration
It (wt%) is 2-100%, preferably 5-90%, more preferably 8-80%, more preferably 10-70%, more preferably 15-60%, more
It is preferred that 20-50%.
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, the reaction unit in the step (1) is single reactor, concatenated multiple reactors, tubular type
Reactor or micro passage reaction.
In the present invention, the reaction wherein 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, do
The weight ratio of gas 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 ratio of dry gas and catalyst is 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.
Preferably, the chlorohydrin action in step (1) is the bubble tower type or turbulent flow pipe reaction in no internal component
It is carried out in device or micro passage reaction.Reaction pressure can be for higher than normal pressure, or normal pressure or close to normal pressure.Such as temperature
Degree is 0~60 DEG C, and the conversion ratio of ethylene reaches 97%, and hydrogen peroxide substantially completely converts.
Second of the embodiment provided according to the present invention provides a kind of method that dry gas prepares ethylene oxide:
A kind of method that dry gas prepares ethylene oxide, comprising the following steps:
(1) H halogen alcoholization: is added in reaction unit2O2, halogen simple substance, dry gas, carry out halogen alcoholization reaction and obtain halogen second
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 passes through Bipolar Membrane
Electrodialysis obtains the hydroxide and hydrogen halides of alkali metal.
Preferably, the method also includes: the purification of (4) ethylene oxide, the ethylene oxide refined；Preferably
It is that step (2) are obtained into ethylene oxide and pass through the ethylene oxide that rectifying is refined.
In the present invention, catalyst is used in the step (1), which is selected from solid acids (such as wolframic acid, niobium
Acid), molecular sieve (such as Ti- molecular sieve), the compound species of vanadium phosphorus oxygen, molybdenum vanadium type metal composite oxide class, the compound gold of molybdenum bismuth type
Belong to oxide-based, molybdenum tungsten type metal composite oxide class, one of Salen transition metal-type catalyst or heteropllyacids, two
Kind is a variety of.
In the present invention, the dry gas is the dry gas that oil plant generates.Preferably, in dry gas ethylene volume content
For 25-40vol%, preferably 27-37vol%, more preferable 29-35vol%.
In the present invention, the halogen simple substance is one of chlorine, bromine, iodine or a variety of.
In the present invention, the hydroxide of the alkali metal is one in sodium hydroxide or potassium hydroxide or lithium hydroxide
Kind is a variety of.
In the present invention, the halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, bromination
One of lithium, sodium iodide, potassium iodide, lithium iodide are a variety of.
In the present invention, the volume ratio of dry gas and halogen simple substance (such as chlorine) is 1:0.1-100 in step (1), preferably 1:
0.15-50, more preferable 1:0.2-30, more preferable 1:0.25-10, more preferable 1:0.3-5, more preferable 1:0.35-2, more preferable 1:
0.4-1。
In the present invention, dry gas and H in step (1)2O2Volume 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, in general, H2O2Be or present aqueous solution form.The H2O2H in aqueous solution2O2Concentration
It (wt%) is 2-100%, preferably 5-90%, more preferably 8-80%, more preferably 10-70%, more preferably 15-60%, more
It is preferred that 20-50%.
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 (1) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.
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℃。
In the present invention, the reaction unit in the step (1) is single reactor, concatenated multiple reactors, tubular type
Reactor or micro passage reaction.
In the present invention, the reaction wherein 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, do
The weight ratio (or molar ratio) of gas and catalyst is 1:0.001-0.1, preferably 1:0.005-0.08, more preferably 1:0.01-
0.06, more preferable 1:0.015-0.04.When carrying out in step (1) according to continuously or semi-continuously mode, catalyst can be with solid
The mode of fixed catalyst bed is arranged in the continuously or semi-continuously reactor of mode, such as concatenated multiple reactors, tubular type
In reactor or micro passage reaction.At this point, the dosage of catalyst is then more.In catalyst bed, the weight of dry gas and catalyst
Amount is than being 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.
The reaction temperature in step (1) or step (2) is not limited strictly in this application.For example, in step (1)
Reaction temperature be 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.For example, the reaction temperature in step (2) is 0-100
DEG C, preferably 5-90 DEG C, preferably 10-80 DEG C, more preferable 20-60 DEG C.
Preferably, the chlorohydrin action in step (1) is the bubble tower type or turbulent flow pipe reaction in no internal component
It is carried out in device or micro passage reaction.Reaction pressure can be for higher than normal pressure, or normal pressure or close to normal pressure.Such as temperature
Degree is 0~60 DEG C, and the conversion ratio of ethylene reaches 97%, and hydrogen peroxide substantially completely converts.
It is preferred that saponification carries out in the tower reactor of steel, upper design is sieve-plate tower.Steam enters from tower bottom
Blow out the thick ethylene oxide generated from tower top.At 0~100 DEG C, tower top pressure is normal pressure or negative pressure for saponification temperature control.Saponification
Reactor design and the key problem in technology of operation are to be sufficiently mixed and control with lye into the halogenohydrin aqueous solution before saponification column
PH flows out the ethylene oxide generated from tower top as early as possible.
Preferably, catalyst of the invention can be hetero-atom molecular-sieve containing Ti, HTS molecular sieve, the tool of hetero atom containing Zr
There is one of MFI structure molecular sieve etc. or a variety of.
Hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or a variety of.
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 ginseng
According to CN200910013070.X.Ti-MWW shows more excellent in the epoxidation reaction to linear alpha-olefin and cyclic olefin
Catalytic oxidation performance, and very high trans selective is shown in alkene asymmetric epoxidation reaction；Synthetic method ginseng
According to CN200710037012.1.Ti-Beta molecular sieve has the twelve-ring channel design and stronger acidity of three-dimensional staggered,
There is good catalytic performance in heterogeneous catalytic reaction；Specific synthesis is referring to " synthesis of Beta molecular sieve and its grinding for catalytic performance
Study carefully ", author: Liu Shuping, 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.
HTS molecular sieve includes HTS-1 molecular sieve, HTS-2 molecular sieve, HTS-3 molecular sieve.In HTS-1 molecular sieve surface acid
Heart catalytic activity with higher, influence of its diffusion and solvent polarity to reactivity are very big；Specific synthesized reference
" the probe reaction research of HTS-1 molecular sieve surface acidification catalysis ", author: Liu Xuanyan, 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 reason
Change performance；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, being uniformly distributed for molecular sieve surface titanium shorten crystallization time, improve synthesis
Stability and repeatability.HTS-3 molecular sieve catalyst has more activated centres, and better catalytic performance is more advantageous to anti-
Object molecule is answered to spread；Specific synthesized reference " development of monocrystalline Multihollow HTS-3 molecular sieve catalyst ", " petroleum refining and change
Work ".
Hetero atom containing Zr is the typical solid Lewis acid catalyst of one kind with MFI structure molecular sieve, is reacted in MPV
Good catalytic activity is shown in (Meerwein-Ponndorf-Verley reactions).Hetero atom containing Zr, tool
MFI structure molecular sieve is common are in metalloid element zirconium incorporation MFI structure (orthogonal system, mesh straight hole) molecule
ZSM-5, Silicalite-1 etc..ZSM-5 molecular sieve is prepared referring to the method for patent 200510029462.7.Silicalite-1
Molecular sieve is prepared referring to the method for patent 201010220796.3.
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.
In this application:
(1) reaction system combined using tubular reactor (including micro passage reaction) with tower reactor is mitigated
The load of chlorohydrination tower.
(2) saponification column decompression operation, steam consumption are few.
(3) effect of separating ethylene oxide is good.Tower and rectifying column are evaporated before rectification working process setting, production second is made in 2 towers respectively
The ethylene oxide of glycol and the ethylene oxide of production polyethers.
(4) dichloroether in the waste water that saponification process generates is separated by the scattered tower with special tower tray, reduced
Biological oxygen content, chemical oxygen content in waste liquid.
In the prior art, halogenohydrin method prepares the process (by taking chlorine as an example) of ethylene oxide:
CH2=CH2+Cl2+H2O——CHCI-CHOH+HCl
The present invention provides the process (by taking hydrogen chloride as an example) that a kind of novel halogenohydrin method prepares ethylene oxide:
CH2=CH2+Cl2+H2O2--- (catalyst is added) in CHCI-CHOH
NaCl (KaCl or LiCl) becomes NaOH (KOH, LiOH) and HCl by bipolar membrane electrodialysis.
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.
In the present invention, the bipolar membrane electrodialysis device in step (3) is used to handle halogenated alkali metal salt, halogenation alkali metal
Salt passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.The hydroxide and hydrogen halides of alkali metal can be with
As other purposes, can also sell.Further, the hydroxide of alkali metal is the raw material of this method；Meanwhile hydrogen halides is logical
Crossing techniques, available halogen, the halogens such as electrolysis is also the raw material in this method, can be recycled.Method gram of the invention
It has taken and has led to the problem of a large amount of chloride containing calcium waste water in the prior art, realized green production, intermediate product or by-product can be with
It recycles.
In the prior art, after being passed through in water due to halogen, solution rate is very slow and solubility is low；Halogen is passed through in water
Halogen and water react, and generate hydrogen halides and hypohalogenous acids, this reaction is a reversible reaction, very slow due to reacting, and present
The phenomenon that be exactly halogen solution rate it is slow and solubility is low.Water is substituted with hydrogen peroxide in method of the invention, so that halogen
It is reacted with hydrogen peroxide, the hydrogen peroxide reaction of 1 molecule and halogen and 1 molecule generates the hypohalogenous acids of 2 molecules, the not production of hydrogen halides
It is raw；Ethylene reaction in hypohalogenous acids and dry gas generates halogen ethane；Halogen, which is constantly reacted with water, generates hypohalogenous acids, to accelerate
The reaction speed of halogen alcoholization.
In the prior art, ethylene oxide is produced using chlorohydrination, since the solubility of halogen in water is very low, so preparation
Ethylene oxide concentration it is also very low.The present invention uses hydrogen peroxide in halogen alcoholization reaction, increases the dissolution of halogen in water
Speed, with the progress of reaction, hypohalogenous acids is constantly utilized, to can prepare the epoxy of high concentration using method of the invention
Ethane.Halogen can also effectively be avoided and addition reaction occurs for ethylene.
Advantages of the present invention:
In the prior art, epoxides is produced using chlorohydrination, 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
Epoxides, 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 epoxides.Intrinsic prejudice, chlorohydrination prepare the useless of epoxides
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 that bipolar membrane electrodialysis technology is applied to 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.
Halogen simple substance and alkali are the raw materials of this programme, and the acid that bipolar membrane electrodialysis generates (further passes through the modes such as electrolysis
Prepare halogen simple substance) and alkali just and can be used as raw material be applicable in, so as to formed circulation, realize cleaning, circulation, without waste
Production.Original waste is become into present raw material, while saving material, the discharge of waste is reduced, protects environment.
Compared with electrolysis process, the energy of bipolar membrane electrodialysis consumption greatly reduces, and effect gets a promotion instead.Together
When, bipolar membrane electrodialysis generates 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, 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. being substituted using hydrogen peroxide
Water, after the reaction of first step halogen alcoholization, without other by-products, raw material can be fully converted to halogen ethyl alcohol；2. due to hydrogen peroxide
Reaction is participated in, intermediate addition side reaction is greatly reduced, reduces the generation of organic by-products；3. in saponification process, alkali is used
Amount greatly reduces, only 1/2 or so of original process.
2, in order to reduce the generation of side reaction, the concentration (mass fraction) for preparing halogenohydrin can only generally control the prior art
4.5% or less；And new halogenohydrin method technique of the invention, since side reaction is few, the concentration of halogenohydrin is unrestricted；Using the present invention
Method preparation ethylene oxide concentration can achieve 60% or more.1) saponification process energy consumption, saponification energy consumption of the invention are saved
Only 1/10 or so of original process；2) saving water resource, the 1/10 of water consumption deficiency original process of the invention；Meanwhile subtracting significantly
The discharge of wastewater flow rate is lacked, 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.
Olefin conversion:
Halogen ethanol selectivity:
Halogen ethanol yield: YHalogenohydrin=CAlkene×SAlkene
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
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.
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
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
(1) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed tungstic acid catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2, chlorine and dry gas (volume content of ethylene is 33.7vol%), 45 DEG C at a temperature of into
Row chlorohydrin action, the wherein oxydol H of 70wt% concentration2O2, chlorine and dry gas three flow should make H2O2With chlorine with
The volume ratio of dry gas is about 1.1:0.5:1.Obtain chlorethanol.
Comparative example 1
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
(1) water halogen alcoholization: is added in tubular reactor (wherein having loaded fixed tungstic acid catalyst bed in pipe)
H2O, chlorine and dry gas, 45 DEG C at a temperature of carry out chlorohydrin action, wherein water H2O, chlorine and the flow of dry gas three should make
Obtain H2The volume ratio of O and chlorine and dry gas is about 88:3.6:1.Obtain chlorethanol.
Embodiment 2
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
1) oxydol H of tungstic acid catalyst, 35wt% concentration halogen alcoholization: is added in tower reactor2O2, chlorine and dry gas,
35 DEG C at a temperature of carry out chlorohydrin action, wherein the mass ratio of tungstic acid catalyst and dry gas be 0.05:1,35wt% concentration
Oxydol H2O2, chlorine and dry gas three additional amount should make H2O2Volume ratio with chlorine and dry gas is about 2:1:1.
Obtain chlorethanol.
Comparative example 2
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
1) tungstic acid catalyst, water H halogen alcoholization: is added in tower reactor2O, chlorine and dry gas, 35 DEG C at a temperature of into
Row chlorohydrin action, wherein the mass ratio of tungstic acid catalyst and dry gas is 0.05:1, water H2O, chlorine and dry gas alkene three plus
H should be made by entering amount2The volume ratio of O and chlorine and dry gas is about 80:3.3:1.Obtain chlorethanol.
Comparative example 3
A kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
Halogen alcoholization: the oxydol H of 70wt% concentration is added in tubular reactor2O2, chlorine and dry gas, in 45 DEG C of temperature
Degree is lower to carry out chlorohydrin action, wherein the oxydol H of 705wt% concentration2O2, chlorine and dry gas three flow should make H2O2
Volume ratio with HCl and dry gas is about 1.1:0.5:1.Obtain chlorethanol.
Embodiment 3
A kind of method that dry gas prepares ethylene oxide, method includes the following steps:
(1) oxydol H of tungstic acid catalyst, 70wt% concentration halogen alcoholization: is added in tower reactor2O2, chlorine and dry
Gas, 35 DEG C at a temperature of carry out chlorohydrin action, the wherein oxydol H of 70wt% concentration2O2, chlorine and dry gas alkene three
Flow should make H2O2Volume ratio with chlorine and dry gas is about 1.1:0.5:1.Obtain chlorethanol.
(2) be saponified: the chlorethanol and sodium hydroxide that step (1) is obtained carry out saponification, and it is organic to obtain ethylene oxide
Phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam from tower bottom into
The thick ethylene oxide that entering makes to generate is blown out from tower top.Saponification temperature is controlled at 60~70 DEG C.
(3) electrodialysis: the sodium chloride solution that step (2) are obtained is by bipolar membrane electrodialysis (I type of TRPB8040-, north
Jing Tingrun 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
To sodium hydroxide and hydrogen chloride.
(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%).
Comparative example 4
A kind of method that dry gas prepares ethylene oxide, method includes the following steps:
(1) oxydol H of tungstic acid catalyst, 70wt% concentration halogen alcoholization: is added in tower reactor2O2, chlorine and dry
Gas, 35 DEG C at a temperature of carry out chlorohydrin action, the wherein oxydol H of 70wt% concentration2O2, chlorine and dry gas alkene three
Flow should make H2O2Volume ratio with chlorine and dry gas is about 1.1:0.5:1.Obtain chlorethanol；
(2) be saponified: the chlorethanol and sodium hydroxide that step (1) is obtained carry out saponification, and it is organic to obtain ethylene oxide
Phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam from tower bottom into
The thick ethylene oxide that entering makes to generate is blown out from tower top.Saponification temperature is controlled at 60~70 DEG C.
Embodiment 4
(1) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed tungstic acid catalyst bed in pipe)
The oxydol H of 35wt% concentration2O2, chlorine and dry gas, 45 DEG C at a temperature of carry out chlorohydrin action, wherein 35wt% concentration
Oxydol H2O2, chlorine and dry gas alkene three flow should make H2O2Volume ratio with chlorine and dry gas is about 2:1:1.
Obtain chlorethanol.
(2) be saponified: the chlorethanol and sodium hydroxide that step (1) is obtained carry out saponification, and it is organic to obtain ethylene oxide
Phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam from tower bottom into
The thick ethylene oxide that entering makes to generate is blown out from tower top.Saponification temperature is controlled at 30~40 DEG C.
(3) electrodialysis: the sodium chloride solution that step (2) are obtained is by bipolar membrane electrodialysis (I type of TRPB8040-, north
Jing Tingrun 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
To sodium hydroxide and hydrogen chloride.
(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 chlorine with bromo.
Embodiment 6
Embodiment 3 is repeated, fixed Catalyst of niobic acid bed has only been loaded in the pipe of tubular reactor, that is, has used niobic acid
Instead of wolframic acid.
Embodiment 7
Embodiment 3 is repeated, molybdenum bismuth type metal composite oxide Mo is only used12Bi1.6Fe2.2Co5.5Ni2.5Sb0.5Zn0.3K0. 1O32.8
Embodiment 8
Embodiment 3 is repeated, the catalyst bed of fixed TS-1 has only been loaded in the pipe of tubular reactor, that is, has been used
TS-1 replaces wolframic acid.Embodiment 1 of the synthetic method of TS-1 referring to CN201410812216.8.
Embodiment 9
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 10
Embodiment 3 is repeated, the catalyst bed of HTS-1 is only used.
Embodiment 11
Embodiment 3 is repeated, the catalyst bed of ZSM-5 molecular sieve is only used.ZSM-5 molecular sieve is referring to patent
200510029462.7 prepared by the method for middle embodiment 1-3.
Embodiment 12
Embodiment 3 is repeated, the catalyst bed of Silicalite-1 molecular sieve is only used.Silicalite-1 molecular sieve ginseng
According to the method preparation of embodiment 1 in patent 201010220796.3.
Embodiment 13
Embodiment 3 is repeated, only the sodium hydroxide in step (2) is substituted with potassium hydroxide.
Embodiment 14
Embodiment 3 is repeated, only in step (1) are as follows: the oxydol H of 65wt% concentration2O2, chlorine and dry gas three stream
Amount should make H2O2Volume ratio with chlorine and dry gas is about 2:2.5:1.
Embodiment 15
Embodiment 3 is repeated, only in step (1) are as follows: the oxydol H of 20wt% concentration2O2, 35wt% concentration HCl solution
It should make H with the flow of dry gas three2O2Volume ratio with HCl and dry gas alkene is about 3:0.6:1.
Embodiment 16
Embodiment 3 is repeated, only the reaction temperature in step (1) is 20 DEG C.
Embodiment 17
Embodiment 3 is repeated, only the temperature in step (2) is controlled at 50 DEG C.
Embodiment 18
Embodiment 3 is repeated, micro passage reaction is only used.
1 embodiment 1-26 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.
Embodiment 3 compares with comparative example 4, and using bipolar membrane electrodialysis treatment waste water of the invention, base amount subtracts significantly
Lack, only 1/2 or so of original process；Moreover, obtaining bronsted lowry acids and bases bronsted lowry in the present embodiment after electrodialysis, acid can pass through the modes such as electrolysis
Halogen is prepared, with raw material in this present embodiment, alkali can be used for being saponified, and achieve the effect that recycling.
Using the water in hydrogen peroxide substitution original process in embodiment 3, saponification process energy consumption, the saponification in embodiment 3 are saved
Energy consumption is only 1/10 of original process or so；In addition, water resource is saved, the 1/10 of the water consumption deficiency original process of the present embodiment；Together
When, the discharge of wastewater flow rate is greatly reduced, and the waste water is easily handled.
Claims (47)
1. a kind of method that dry gas prepares halogen ethyl alcohol, method includes the following steps:
(1) H halogen alcoholization: is added in reaction unit2O2, halogen simple substance, dry gas, carry out halogen alcoholization reaction and obtain halogen ethyl alcohol；
Wherein: catalyst being added in step (1), which is selected from wolframic acid, niobic acid, Mo12Bi1.6Fe2.2Co5.5Ni2.5
Sb0.5Zn0.3K0.1O32.8、TS-1、TS-2、Ti-MWW、Ti-Beta、Ti-SBA-15、HTS-1、HTS-2、HTS-3、ZSM-5、
One of Silicalite-1, two or more；Reaction temperature in step (1) is 10-50 DEG C.
2. according to the method described in claim 1, it is characterized by: the dry gas is the dry gas that oil plant generates；And/or
The halogen simple substance is one of chlorine, bromine, iodine or a variety of.
3. according to the method described in claim 2, it is characterized by: the volume content of ethylene is 25- in the dry gas
40vol%.
4. according to the method described in claim 3, it is characterized by: the volume content of ethylene is 27- in the dry gas
37vol%.
5. according to the method described in claim 4, it is characterized by: the volume content of ethylene is 29- in the dry gas
35vol%.
6. method according to any one of claims 1-5, it is characterised in that: dry gas and halogen simple substance in step (1)
Volume ratio is 1:0.1-100.
7. according to the method described in claim 6, it is characterized by: the volume ratio of dry gas and halogen simple substance is 1 in step (1):
0.15-50。
8. according to the method described in claim 7, it is characterized by: the volume ratio of dry gas and halogen simple substance is 1 in step (1):
0.2-30。
9. according to claim 1-5, method described in any one of 7-8, it is characterised in that: dry gas and H in step (1)2O2Body
Product is than being 1:0.1-100；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 5-90%2O2Aqueous solution form.
10. according to the method described in claim 6, it is characterized by: dry gas and H in step (1)2O2Volume ratio be 1:0.1-
100；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 5-90%2O2Aqueous solution form.
11. according to the method described in claim 9, it is characterized by: dry gas and H in step (1)2O2Volume ratio be 1:0.5-
50；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 8-80%2O2Aqueous solution form.
12. according to the method described in claim 10, it is characterized by: dry gas and H in step (1)2O2Volume ratio be 1:0.5-
50；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 8-80%2O2Aqueous solution form.
13. method according to claim 11 or 12, it is characterised in that: dry gas and H in step (1)2O2Volume ratio be 1:
0.8-30；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 10-70%2O2Aqueous solution form.
14. according to claim 1-5, method described in any one of 7-8,10-12, it is characterised in that: the reaction in step (1)
Temperature is 20-45 DEG C.
15. according to the method described in claim 6, it is characterized by: the reaction temperature in step (1) is 20-45 DEG C.
16. a kind of method that dry gas prepares ethylene oxide, comprising the following steps:
(1) H halogen alcoholization: is added in reaction unit2O2, halogen simple substance, dry gas, 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 epoxy second
Alkane and halogenated alkali metal salt；
Wherein: catalyst being added in step (1), which is selected from wolframic acid, niobic acid, Mo12Bi1.6Fe2.2Co5.5Ni2.5
Sb0.5Zn0.3K0.1O32.8、TS-1、TS-2、Ti-MWW、Ti-Beta、Ti-SBA-15、HTS-1、HTS-2、HTS-3、ZSM-5、
One of Silicalite-1, two or more；Reaction temperature in step (1) is 10-50 DEG C.
17. according to the method for claim 16, it is characterised in that: the method also includes: (3) electrodialysis: by step (2)
The halogenated alkali metal salt of acquisition passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.
18. according to the method for claim 17, it is characterised in that: the method also includes: the purification of (4) ethylene oxide,
The ethylene oxide refined.
19. according to the method for claim 18, it is characterised in that: step (2) are obtained ethylene oxide and are obtained by rectifying
The ethylene oxide of purification.
20. method described in any one of 6-19 according to claim 1, it is characterised in that: the dry gas is what oil plant generated
Dry gas；And/or
The halogen simple substance is one of chlorine, bromine, iodine or a variety of.
21. according to the method for claim 20, it is characterised in that: the volume content of ethylene is 25- in the dry gas
40vol%.
22. according to the method for claim 21, it is characterised in that: the volume content of ethylene is 27- in the dry gas
37vol%.
23. according to the method for claim 22, it is characterised in that: the volume content of ethylene is 29- in the dry gas
35vol%.
24. method described in any one of 6-19,21-23 according to claim 1, it is characterised in that: the hydrogen-oxygen of the alkali metal
Compound 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.
25. according to the method for claim 20, 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.
26. method described in any one of 6-19,21-23,25 according to claim 1, it is characterised in that: dry gas in step (1)
Volume ratio with halogen simple substance is 1:0.1-100.
27. according to the method for claim 20, it is characterised in that: the volume ratio of dry gas and halogen simple substance is in step (1)
1:0.1-100.
28. according to the method for claim 26, it is characterised in that: the volume ratio of dry gas and halogen simple substance is in step (1)
1:0.15-50.
29. according to the method for claim 27, it is characterised in that: the volume ratio of dry gas and halogen simple substance is in step (1)
1:0.15-50.
30. the method according to claim 28 or 29, it is characterised in that: the volume of dry gas and halogen simple substance in step (1)
Than for 1:0.2-30.
31. method described in any one of 6-19,21-23,25,27-29 according to claim 1, it is characterised in that: step (1)
Middle dry gas and H2O2Volume ratio be 1:0.1-100；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 5-90%2O2Aqueous solution form.
32. according to the method for claim 20, it is characterised in that: dry gas and H in step (1)2O2Volume ratio be 1:0.1-
100；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 5-90%2O2Aqueous solution form.
33. according to the method for claim 31, it is characterised in that: dry gas and H in step (1)2O2Volume ratio be 1:0.5-
50；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 8-80%2O2Aqueous solution form.
34. according to the method for claim 32, it is characterised in that: dry gas and H in step (1)2O2Volume ratio be 1:0.5-
50；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 8-80%2O2Aqueous solution form.
35. the method according to claim 33 or 34, it is characterised in that: dry gas and H in step (1)2O2Volume ratio be 1:
0.8-30；And/or
The H2O2It is H2O2Concentration (wt%) is the H of 10-70%2O2Aqueous solution form.
36. method described in any one of 6-19,21-23,25,27-29,32-34 according to claim 1, it is characterised in that: step
Suddenly the molar ratio of halogen ethyl alcohol and alkali metal hydroxide is 1:0.1-50 in (2).
37. according to the method for claim 20, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
Molar ratio is 1:0.1-50.
38. according to the method for claim 36, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
Molar ratio is 1:0.5-30.
39. according to the method for claim 37, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
Molar ratio is 1:0.5-30.
40. the method according to claim 38 or 39, it is characterised in that: halogen ethyl alcohol and alkali metal hydroxide in step (2)
The molar ratio of object is 1:0.8-20.
41. method described in any one of 6-19,21-23,25,27-29,32-34,37-39 according to claim 1, feature
Be: the reaction temperature in step (1) is 20-45 DEG C；And/or
Reaction temperature in step (2) is 0-100 DEG C.
42. according to the method for claim 20, it is characterised in that: the reaction temperature in step (1) is 20-45 DEG C；And/or
Reaction temperature in step (2) is 0-100 DEG C.
43. according to the method for claim 41, it is characterised in that: the reaction temperature in step (2) is 5-90 DEG C.
44. according to the method for claim 42, it is characterised in that: the reaction temperature in step (2) is 5-90 DEG C.
45. the method according to claim 43 or 44, it is characterised in that: the reaction temperature in step (2) is 10-80 DEG C.
46. method described in any one of 6-19,21-23,25,27-29,32-34,37-39,42-44 according to claim 1,
It is characterized by: reaction unit in the step (1) be single reactor, concatenated multiple reactors, tubular reactor or
Micro passage reaction；And/or
Wherein the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
47. according to the method for claim 20, it is characterised in that: the reaction unit in the step (1) is single reaction
Device, concatenated multiple reactors, tubular reactor or micro passage reaction；And/or
Wherein the reaction in step (1) is carried out according to intermittent, semi continuous or continuous mode.
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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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2016
- 2016-08-30 CN CN201610784079.0A patent/CN106518615B/en active Active
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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