CN106518614A - Methods for preparing halogenated ethanol and ethylene oxide by dry gas - Google Patents
Methods for preparing halogenated ethanol and ethylene oxide by dry gas Download PDFInfo
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- CN106518614A CN106518614A CN201610778510.0A CN201610778510A CN106518614A CN 106518614 A CN106518614 A CN 106518614A CN 201610778510 A CN201610778510 A CN 201610778510A CN 106518614 A CN106518614 A CN 106518614A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A method for preparing halogenated ethanol by a dry gas is disclosed, and the method comprises the following steps: (1) halohydrination, to be more specific, adding hydrogen halide, H2O2 and the dry gas in a reactor for halohydrination to obtain the halogenated ethanol. A method of producing ethylene oxide by the dry gas is also disclosed, and the method comprises the following steps: (1) halohydrination, to be more specific, adding the hydrogen halide, the H2O2 and the dry gas in the reactor for halohydrination to obtain the halogenated ethanol; and (2) saponification, to be more specific, taking the halogenated ethanol obtained by the step (1) and an alkali metal hydroxide (preferably, sodium hydroxide, potassium hydroxide or lithium hydroxide) for saponification, and separating to obtain the ethylene oxide and a halogenated alkali metal salt. By preparation of the halogenated ethanol from the hydrogen halide, the H2O2 and the dry gas and then saponification, the ethylene oxide can be prepared by extremely-high-selectivity and high-yield use of an ethylene component in the dry gas, and waste water and waste residue discharge is greatly reduced.
Description
Technical field
A kind of the present invention relates to preparation method of halogen ethanol, and the method that oxirane is prepared by dry gas；More specifically carry
For a kind of method for preparing halogen ethanol as raw material using new halogenohydrin method with dry gas, and the side for preparing oxirane using new alcohol method
Method.
Background technology
Ethylene chlorhydrin (being also " chloroethanes ") is important organic solvent and organic synthesis raw material.For manufacturing epoxy second
Alkane, synthetic rubber, dyestuff, medicine and agricultural chemicals etc., also serve as organic solvent.For manufacturing ethylene glycol, oxirane, and medicine,
Dyestuff, synthesis of agricultural chemicals etc..
Epoxides contains epoxy radicals, and chemical property is active, and easy ring-opening polymerisation is a kind of important Organic Chemicals.
Oxirane is a kind of important Organic Chemicals.It is a kind of organic compound, and chemical formula is C2H4O, is a kind of poisonous
Carcinogen, is used to manufacture bactericide in the past.It is widely used in the industries such as washing, pharmacy, printing and dyeing.In the related product of chemical industry
Industry can be used as the initiator of cleaning agent.Oxirane (referred to as " EO ") is a kind of simplest cyclic ethers, belongs to heterocycle compound,
It is important petroleum chemicals.Oxirane is mainly for the manufacture of ethylene glycol (polyester fiber raw materials processed), synthetic detergent, nonionic
Surfactant, antifreeze, emulsifying agent and condensed ethandiol class product, are also used for producing plasticizer, lubricant, rubber and plastics
Deng.It is widely used in washing the various fields such as dye, electronics, medicine, agricultural chemicals, weaving, papermaking, automobile, oil exploitation and refining.
In prior art, the preparation method of oxirane：First, chlorohydrination：React in two steps, the first step is by ethene and chlorine
Gas is passed through in water, generates ethylene chlorhydrin.Second step is reacted with ethylene chlorhydrin with alkali (usually milk of lime), generates epoxy second
Alkane.2nd, oxidizing process：Two kinds of air method and oxygen method can be divided into；, with air as oxidant, the latter is more than 95% with concentration for the former
The oxygen of (volume) is used as oxidant；Oxidizing process adopts ethene directly and oxygen reaction, under the catalytic action of argent, prepares
Oxirane.
Epoxides is prepared, halogenohydrin method production history is long, the main processes of chlorohydrination are alkene halogen alcoholization, lime
Newborn saponification and product purification, are characterized in that mature production technology, operational load elasticity are big, selective good, to the pure of raw material olefin
Degree is less demanding, and so as to improve the security of production, construction investment is few.As fixed assets investment is few, product cost is relatively low,
Its product has stronger cost competitiveness.
The chlorohydrination of prior art prepares epoxides and is primarily present problems with：1. there is addition with alkene in raw material chlorine
Side reaction, generates dichloro alkanes.Dichloroethanes is difficult to be utilized, and wastes substantial amounts of raw material.In addition, chlorine and olefine reaction,
Substantial amounts of heat is released, heat is concentrated in reaction vessel, cause to produce dangerous row very big.2. raw material chlorine is not in process of production
Evitable to carry a small amount of oxygen secretly, with the carrying out of reaction, chlorine constantly participates in reaction, it is therefore desirable to constantly supplement chlorine,
And oxygen can not participate in reaction, constantly in reaction unit, with the carrying out of reaction, oxygen concentration is constantly raised, and anti-for accumulation
Heat should be released, oxygen, chlorine, alkene are present simultaneously, under high temperature, easily cause blast.3. reaction produces hydrochloric acid, needs to consume
Substantial amounts of alkali (such as calcium hydroxide) carrys out the product hydrochloric acid of neutralization reaction, can just be conducive to reaction.4. reaction produces a large amount of chlorine
Change calcium, calcium chloride causes the waste water COD for producing higher, pollutes environment.5. the shortcoming of chlorohydrination is that water resources consumption is big, is produced big
Amount waste water and waste residue, chlorohydrination production 1t epoxides produce the waste water of 40-50t chlorides, 2.1t calcium chloride waste residues, and this gives up
Water has " five is high " feature that temperature is high, pH value is high, chloride content is high, COD contents are high and suspension content is high, it is difficult to process,
Serious environment pollution.6. the hypochlorous acid for producing in production process is to the corrosion of equipment also than more serious.
With chlorohydrination technique productions oxirane, if waste water, waste residue problem, enterprise's process units can not be efficiently solved
Ability is bigger, and its environmentally friendly burden is bigger；Output is higher, and the injury to environment is deeper.Thus, environmental protection has become system
The about primary factor of epoxides industrial development.U.S.'s development and application chlorohydrination prepares epoxides earliest, using initial stage, chlorine
Alcohol method technique is widely developed and produces.2000, due to being unable to the waste water of effective process chlorohydrination technique generation, the U.S.
Prohibit the use of chlorohydrination technique productions epoxides.
Oxidizing process prepares oxirane, with high costs, and conversion rate is slow, and operation has high demands, and industrial production is generally not
Using the method.
The noncondensable gas (also referred to as distillation gas) that oil refinery dry gas are produced in referring to oil plant oil refining process and reclaimed, mainly into
It is divided into ethene, 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 methane, ethane, ethene, and three about respectively accounts for 1/3rd.Secondary operation of the oil refinery dry gas essentially from crude oil
The dry gas amount that process, such as RFCC, thermal cracking, delayed coking etc., wherein catalytic cracking (FCC) are produced is larger, and which leads to
Gas pipe network is all made a gift to someone often as fuel gas, some are even put into torch burning and fall, and cause the significant wastage of resource.At present
The utilization of dry gas is mainly had by domestic minority oil plant：1. prepare vinylbenzene：It is any special purified that catalytic cracked dry gas are not required to Jing
Reaction gas can be directly used as, with benzene-alkylation ethylbenzene (or referred to as vinylbenzene), second is stupid cheap, deficiency in economic performance,
Commonly use the little of this method.2. prepare styrene：Ethylbenzene is first prepared, then styrene is obtained by ethylene unit.But ethene
Device price is high, and few oil plant domestic at present possesses ethylene unit.3. prepare oxirane.With catalytic cracked dry gas as original
The technology of material production oxirane, generally uses chlorohydrination process route at present, with the oxirane of the method production
Product can also further produce the products such as ethylene glycol, monoethanolamine, glycol ether.But it is intrinsic to there is chlorohydrination in such method
Problem.
The content of the invention
Present inventor is had found by studying, using dry gas, hydrogen halides and H2O2Halogen ethanol is prepared, then saponification, energy
It is enough that oxirane is prepared using the ethene composition in dry gas with high selectivity and yield；Filled using bipolar membrane electrodialysis simultaneously
Process accessory substance is put, the discharge of waste water, waste residue is considerably reduced.
According to the first embodiment of the present invention, there is provided a kind of method that halogenohydrin method prepares halogenohydrin：
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, dry gas, carry out halogen alcoholization reaction and obtain halogen ethanol.
Preferably, add catalyst in the step (1), the catalyst be selected from solid acids (such as wolframic acid, niobic acid),
Molecular sieve (such as Ti- molecular sieves), vanadium phosphorus oxygen are combined species, molybdenum vanadium type metal composite oxide class, molybdenum bismuth type composition metal oxygen
One kind in compound class, molybdenum tungsten type metal composite oxide class, Salen transition metal-types catalyst or heteropllyacids, two kinds or
It is various.
In the present invention, the dry gas is the dry gas that oil plant is produced.In general, in dry gas ethene volume content
For 25-40vol%, more preferably preferably 27-37vol%, 29-35vol%.
In the present invention, the hydrogen halides is one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide.Hydrogen halides can
Use in form of an aqueous solutions or in gaseous form.
In the present invention, in step (1), dry gas is 1 with the volume ratio of hydrogen halides：0.1-100, preferably 1：0.2-50, it is more excellent
Select 1：0.5-30, more preferably 1：0.8-10, more preferably 1：1-8, more preferably 1：1.1-5, more preferably 1：1.2-2.
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 preferably 1：0.9-20, more preferably 1：1.0-10, more preferably 1：1.1-5, more preferably 1：1.1-2.
In the present invention, generally, H2O2Be or present the aqueous solution form.The H2O2H in the aqueous solution2O2Concentration
(wt%) it 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 preferably 20-45 DEG C.
In the present invention, the reaction unit in step (1) is single reactor, multiple reactors of series connection, tubular type
Reactor or micro passage reaction.
In the present invention, the reaction wherein in step (1) is carried out according to the mode of batch (-type), semi continuous or continous way.
In the present invention, in step (1), the concentration of hydrogen halides can be any concentration, when using low concentration hydrogen halides,
Can be very good control reaction carries out speed；When using high concentration hydrogen halides, can promote to react to production halogen ethanol
Direction is quickly carried out.As long as there is the presence of hydrogen halides in reaction system, no matter the concentration of hydrogen halides is how many, reaction can be entered
OK, halogenohydrin can be obtained.Preferably, the concentration of hydrogen halides is 1-40%, further preferred 2-30%, in preferred 3-20%,
More preferably 5-10%.
According to the second embodiment of the present invention, there is provided a kind of method that halogenohydrin method prepares oxirane：
A kind of method that dry gas prepares oxirane, the method are comprised the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, dry gas, carry out halogen alcoholization reaction and obtain halogen ethanol；
With
(2) saponification：The halogen ethanol of step (1) and alkali-metal hydroxide are carried out into saponification, is separated and is obtained ring
Oxidative ethane and halogenated alkali metal salt.
Preferably, methods described also includes：(3) electrodialysis：The halogenated alkali metal salt that step (2) is obtained is through Bipolar Membrane
Electrodialysis, obtains alkali-metal hydroxide and hydrogen halides.
Preferably, methods described also includes：(4) oxirane is refined, obtains refined oxirane；Preferably
It is that step (2) acquisition oxirane is obtained into refined oxirane through rectifying.
Preferably, add catalyst in the step (1), the catalyst be selected from solid acids (such as wolframic acid, niobic acid),
Molecular sieve (such as Ti- molecular sieves), vanadium phosphorus oxygen are combined species, molybdenum vanadium type metal composite oxide class, molybdenum bismuth type composition metal oxygen
One kind in compound class, molybdenum tungsten type metal composite oxide class, Salen transition metal-types catalyst or heteropllyacids, two kinds or
It is various.
It is preferred that, H2O2It is the form of the aqueous solution.
In the present invention, the dry gas is the dry gas that oil plant is produced.In general, in dry gas ethene volume content
For 25-40vol%, more preferably preferably 27-37vol%, 29-35vol%.
In the present invention, the hydrogen halides is one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide.It is preferred that, halogenation
Hydrogen is to use in form of an aqueous solutions.
In the present invention, the alkali-metal hydroxide is in NaOH or potassium hydroxide or lithium hydroxide
Plant or various.
In the present invention, the halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, KBr, bromination
One or more in lithium, sodium iodide, KI, lithium iodide.
In the present invention, in step (1), dry gas is 1 with the volume ratio of hydrogen halides：0.1-100, preferably 1：0.2-50, it is more excellent
Select 1：0.5-30, more preferably 1：0.8-10, more preferably 1：1-8, more preferably 1：1.1-5, more preferably 1：1.2-2.
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 preferably 1：0.9-20, more preferably 1：1.0-10, more preferably 1：1.1-5, more preferably 1：1.1-2.
In the present invention, the H2O2It is H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-
80%, the H of more preferably 10-70%, more preferably 15-60%, more preferably 20-50%2O2The aqueous solution.
In the present invention, in step (2), halogen ethanol is 1 with the mol ratio of alkali metal hydroxide：0.1-50, preferably 1：
0.5-30, more preferably 1：0.8-20, more preferably 1：1.0-10, more preferably 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 preferably 20-45 DEG C.
In the present invention, the reaction temperature in step (2) be 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 step (1) is single reactor, multiple reactors of series connection, tubular type
Reactor or micro passage reaction.
In the present invention, the reaction wherein in step (1) is carried out according to the mode of batch (-type), semi continuous or continous way.
In the present invention, in step (1), the concentration of hydrogen halides can be any concentration, when using low concentration hydrogen halides,
Can be very good control reaction carries out speed；When using high concentration hydrogen halides, can promote to react to production halogen ethanol
Direction is quickly carried out.As long as there is the presence of hydrogen halides in reaction system, no matter the concentration of hydrogen halides is how many, reaction can be entered
OK, halogenohydrin can be obtained.Preferably, the concentration of hydrogen halides is 1-40%, further preferred 2-30%, in preferred 3-20%,
More preferably 5-10%.
When step (1) is carried out in single reactor according to intermittent mode, in step (1) during addition catalyst, do
Gas is 1 with the weight ratio of catalyst：0.001-0.4, preferably 1：0.005-0.3, more preferably 1：0.01-0.2, more preferably 1：
0.015-0.1.When carrying out according to continuously or semi-continuously mode in step (1), catalyst can be with fixed beds
Mode be arranged in the continuously or semi-continuously reactor of mode, such as multiple reactors of series connection, tubular reactor or microchannel
In reactor.Now, the consumption of catalyst is then more.In beds, dry gas is 1 with the weight ratio of catalyst：0.001-
0.99, preferably 1：0.005-0.8, more preferably 1：0.01-0.6, more preferably 1：0.015-0.4.
Preferably, the catalyst of the present invention can be hetero-atom molecular-sieve containing Ti, HTS molecular sieves, the tool of hetero atom containing Zr
One or more had in MFI structure molecular sieve etc..
TS-1 is a kind of HTS, belongs to Pentasil type hetero-atom molecular-sieves, rhombic system, synthetic method reference
CN201410812216.8.TS-2 molecular sieves have MEL topological structures, with 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 show very high trans selective in alkene asymmetric epoxidation reaction, synthetic method ginseng
According to CN200710037012.1.Ti-Beta molecular sieves have the twelve-ring channel design and stronger acidity of three-dimensional staggered,
There is good catalytic performance in heterogeneous catalytic reaction, specifically synthesize reference《The synthesis of Beta molecular sieves and its catalytic performance grind
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 sides through-hole structure, synthetic method
With reference to CN201110211854.0.
HTS molecular sieves include HTS-1 molecular sieves, HTS-2 molecular sieves, HTS-3 molecular sieves.In the acid of HTS-1 molecular sieve surfaces
The heart has higher catalysis activity, and the impact of its diffusion and solvent polarity to reactivity is very big；Concrete synthesized reference
《The probe reaction research of HTS-1 molecular sieve surfaces acidifying catalysis》, author：Liu Xuanyan, Yin Dulin, Zhu Huayuan, Shen Gang,《Catalysis
Journal》.HTS HTS-2, which has HTS HTS identical catalytic oxidation activities, selective and general reason
Change performance；Concrete synthesized reference《The synthesis of HTS 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 catalysts have more activated centres, and more preferable catalytic performance is more beneficial for anti-
Thing molecule is answered to spread；Concrete synthesized reference《The development of monocrystalline Multihollow HTS-3 molecular sieve catalysts》,《Petroleum refining and change
Work》.
Hetero atom containing Zr, with MFI structure molecular sieve be a quasi-representative solid Lewis acid catalyst, in the reaction
Show good catalysis activity.Hetero atom containing Zr, it is that a metalloid element zirconium mixes MFI knots with MFI structure molecular sieve
In structure (orthogonal system, mesh straight hole) molecule, ZSM-5, Silicalite-1 etc. is common are.ZSM-5 molecular sieve is with reference to patent
200510029462.7 method prepare.Silicalite-1 molecular sieves are prepared with reference to the method for patent 201010220796.3.
It is preferred that, halogen alcoholization reaction is carried out in the bubble tower type without internals or turbulent flow tubular reactor, reaction pressure
Can be higher than normal pressure, or normal pressure is close to normal pressure.For example temperature is 0～60 DEG C, and the conversion ratio of ethene reaches 97%
More than, hydrogen peroxide is substantially completely converted.
Saponification is carried out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is entered from bottom of towe and makes life
Into thick oxirane 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 is designed and the key problem in technology of operation is must to be sufficiently mixed and control pH with alkali lye into the halogenohydrin aqueous solution before saponification column, is made
The oxirane of generation is flowed out from tower top as early as possible.
As traditional chlorohydrination technique uses lime saponification, all of chlorine is finally with CaCl2Form consumption, produce a large amount of
Containing CaCl2With the sewage of organic chloride.Calculating shows, often produces 1t oxirane, about produce 2.1t CaCl2Waste residue and extremely
Few 43t waste water.
(1) reaction system combined with tower reactor using tubular reactor, mitigates the load of chlorohydrination tower.
(2) saponification column decompression operation, steam consumption are few.
(3) rectification working process evaporates tower and rectifying column before arranging, and 2 towers are obtained the oxirane of production ethylene glycol and production respectively
The oxirane of polyethers.
(4) dichloroether in the waste water that saponification process is produced is separated by the scattered tower with special tower tray, is reduced
Biological oxygen content, chemical oxygen content in waste liquid.
In prior art, halogenohydrin method prepares the process (by taking chlorine as an example) of oxirane：
CH2=CH2+Cl2+H2O——CHCI-CHOH+HCl
The present invention provides the process that a kind of new halogenohydrin method prepares oxirane (by taking hydrogen chloride as an example)：
CH2=CH2+HCl+H2O2——CHCI-CHOH+H2O (addition catalyst)
NaCl (KaCl or LiCl) is changed into NaOH (KOH, LiOH) and HCl through bipolar membrane electrodialysis.Through Bipolar Membrane electricity
Alkali-metal hydroxide and hydrogen halides after dialysis can be circulated.
Bipolar Membrane is a kind of new ion-exchange composite membranes, and it is generally hydrophilic by cation exchange layer (N-type film), interface
Layer (Catalytic Layer) and anion exchange layer (p-type film) are composited, and are reaction films truly.Act in DC electric field
Under, hydrolytic dissociation can be respectively obtained hydrogen ion and hydroxide ion in film both 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 new component is not introduced
Salt in liquid is converted into corresponding bronsted lowry acids and bases bronsted lowry, and this method is referred to as bipolar membrane electrodialysis method.
It is not particularly limited for the bipolar membrane electrodialysis equipment in the application.It is preferable, however, that adopting such a
Bipolar membrane electrodialysis equipment, it includes：1) as the film being made up of Bipolar Membrane, cavity block, anode membrane, dividing plate, pole plate of core component
Heap, and 2) auxiliary equipment, the auxiliary equipment include water pot, flowmeter, pump, pipeline etc..Auxiliary equipment includes rectifier cabinet.Core
The framework of stainless steel structure is adopted in component.The quantity of film and dividing plate can be according to specific treating capacity (volume of salting liquid)
It is fixed.
Bipolar membrane, one kind of electric drive film, Main Function are to provide H+ ions and OH-ion under electric field force, film
Side is the back, and it is water layer that opposite side is the intermediate layer of sunny side, the back and sunny side, in the presence of applying direct current electric field power, water
H in layer2O splits into H+ ions and OH-ion, and passes through sunny side and the back respectively to both sides theme solution migration, so double
The effect of Polar Crystal Slab is under electric field force effect to provide H+ ions and OH-ion source.
In the present invention, when brine waste is processed using bipolar membrane electrodialysis, obtain corresponding bronsted lowry acids and bases bronsted lowry.
In the present invention, the bipolar membrane electrodialysis device in step (3) is used for processing halogenated alkali metal salt, halogenation alkali metal
Salt obtains alkali-metal hydroxide and hydrogen halides through bipolar membrane electrodialysis.Alkali-metal hydroxide and hydrogen halides can be with
As other purposes, it is also possible to sell.Further, alkali-metal hydroxide is the raw material of this method；Meanwhile, hydrogen halides
It is the raw material in this method, can recycles.The method of the present invention produces substantial amounts of chloride containing calcium in overcoming prior art
The problem of waste water, realizes that green production, intermediate product or accessory substance can be recycled.
Advantages of the present invention：
In prior art, epoxides is produced using chlorohydrination, produce substantial amounts of chloride containing calcium waste water, also contain in waste water
The raw material organic matter not reacted completely in course of reaction or intermediate product organic matter, containing not separating thoroughly oxirane yet,
These debirs are difficult to degrade, and deal with extremely difficult, and never find effective processing method.The U.S. 2000
It is exactly that the calcium chloride wastewater containing the organic matter waste for being difficult to degrade is difficult to process that year disables the main cause of chlorohydrination technique.Someone
The waste water that chlorohydrination technique is produced is processed using electrolysis, due to containing debirs in waste water, deal with it is extremely difficult, and
And the debirs in waste water are very sensitive to electrolysis with ion-exchange film system, larger is damaged to electrolysis installation；Meanwhile, electrolysis wastewater needs
Substantial amounts of energy is consumed, the benefit of acquisition is little；Maximum problem is：Electrolysis wastewater produces chlorine and hydrogen, in organic matter
The situation of presence, it is abnormally dangerous, easily explode.
The present invention adopt bipolar membrane electrodialysis technology, bipolar membrane electrodialysis technology be one process salt technology, salt pass through
Bipolar membrane electrodialysis produce bronsted lowry acids and bases bronsted lowry.Before someone by bipolar membrane electrodialysis process sodium chloride-containing waste water, but never
There is the production technology that bipolar membrane electrodialysis are 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 Jing
Cross, it is found that bipolar membrane electrodialysis process the waste water excellent that halogenohydrin method prepares oxirane, halogenohydrin
Method prepares the waste water containing debirs of oxirane generation not to be affected on the technique of bipolar membrane electrodialysis, can be very good place
Salt in reason waste water.The present invention cleverly prepares oxirane using halogenohydrin method and produces the characteristics of giving up Organic substance in water, can be very
The good preparation that bipolar membrane electrodialysis technology is applied to oxirane, it is possible to achieve clean manufacturing, solves halogenohydrin method and prepares ring
The reluctant problem of waste water that oxidative ethane is produced.Waste water handling problem is captured, halogenohydrin method just prepares the advantage of oxirane
Quite substantially, less investment, high conversion rate are easily controlled.Therefore, present invention introduces bipolar membrane electrodialysis technology has overturned traditional halogen
The method that alcohol method prepares oxirane, completely solves the problem containing organic runoff water, makes halogenohydrin method efficiently prepare epoxy
While ethane, clean manufacturing is realized.
In embodiments of the invention, 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 are produced is just
It is good to be suitable for as raw material again, such that it is able to form circulation, realize cleaning, circulation, produce without wasting.Original waste is become
For present raw material, the discharge of waste, environmental protection while saving material, is reduced.
Compared with electrolysis process, the energy of bipolar membrane electrodialysis consumption greatly reduces, and effect is got a promotion on the contrary.Together
When, the bronsted lowry acids and bases bronsted lowry that bipolar membrane electrodialysis are produced not there are danger, overcomes electrolysis process danger, holds explosive problem.
Most of all, electrolysis process processes waste water, the foreign organic matter in waste water can not be processed, can only be discharged, and this kind of have
Machine waste is difficult degraded, greatly pollutes environment；And bipolar membrane electrodialysis process waste water, the foreign organic matter in waste water can be also
Original is into raw material or directly obtains product, so as to process the debirs also processed while salt in waste water in waste water, will be organic
Waste is changed into raw material or product, takes full advantage of material, while waste zero-emission can be realized, protects environment well.
In embodiments of the invention, due to adopting hydrogen peroxide, prior art is substituted with hydrogen halides (such as hydrogen chloride)
In chlorine.As chlorine is gaseous state, ethene is also gaseous state, the easily generation addition side reaction under gaseous environment, and of the invention
Substituted with hydrogen halides, addition side reaction this problem for solving well；Meanwhile, substantial amounts of heat is released in addition side reaction, is made
Obtain reactivity hazard high, easily explode, and the present invention does not have this, safety, utilization rate are high.Meanwhile, using hydrogen halides
Chlorine is substituted, the transport of hydrogen halides and storage are more prone to and safety, are more beneficial for production.
Compared with prior art, technical scheme has following Advantageous Effects：
1st, overcome accessory substance (chlorine, the calcium chloride, side reaction product) problem of prior art：1. Cl is not used2For raw material,
Avoid because of Cl2Lasting consumption can make trace oxygen in chlorine constantly accumulation and caused explosion danger；2. no Cl2Participate in
Reaction, greatly reduces the addition side reaction of centre, reduces the generation of organic by-products；3., in saponification process, alkali consumption is big
It is big to reduce, the 1/2 or so of only former technique.
2nd, in order to reduce the generation of side reaction, the concentration (mass fraction) for preparing halogenohydrin can only typically be controlled prior art
Less than 4.5%；And the new halogenohydrin method technique of the present invention, as side reaction is few, the concentration of halogenohydrin is unrestricted.1) save saponification
Process energy consumption, the saponification energy consumption of the present invention are only the 1/10 or so of former technique；2) saving water resource, the water consumption of the present invention is not enough
The 1/10 of former technique；Meanwhile, the discharge of wastewater flow rate is greatly reduced, and the waste water is easily handled.
3rd, using bipolar membrane electrodialysis technology, process while containing organic wastewater, the NaOH (KOH, LiOH) of generation and
HCl is reusable.
Description of the drawings
Fig. 1 is bipolar membrane electrodialysis artwork of the present invention.
Fig. 2 is bipolar membrane fundamental diagram of the present invention.
Reference：1、2、3：Stainless steel.
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 types GC-MSs,
Quantitative analysis is carried out to product using Agilent 6890N types gas chromatographs and external standard method.
According to detection and analysis result, following object function is defined as inspection target.
Conversion of ethylene：
Halogen ethanol selectivity：
Halogen ethanol yield：YHalogenohydrin=CAlkene×SAlkene
Ethylene oxide output：
In formula, C is conversion ratio, and S is selective, and Y is yield, and n is the amount of material 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, dividing plate, pole plate
The membrane stack of composition, and 2) auxiliary equipment, the auxiliary equipment include water pot, flowmeter, pump, pipeline etc..Auxiliary equipment includes whole
Stream cabinet.The framework of stainless steel structure is adopted in core component.The quantity of film and dividing plate can according to specific treating capacity (salting liquid
Volume) depending on.
Bipolar membrane, one kind of electric drive film, Main Function are to provide H+ ions and OH-ion under electric field force, film
Side is the back, and it is water layer that opposite side is the intermediate layer of sunny side, the back and sunny side, in the presence of applying direct current electric field power, water
H in layer2O splits into H+ ions and OH-ion, and passes through sunny side and the back respectively to both sides theme solution migration, so double
The effect of Polar Crystal Slab is under electric field force effect to provide H+ ions and OH-ion source.
The performance indications of Bipolar Membrane are as follows：
* in 0,5Mol Na2SO4In solution, at 25 DEG C, 10-100mA/cm2Determine under current density
Embodiment 1
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
(1) halogen alcoholization：Add in tubular reactor (wherein having loaded fixed tungstic acid catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2(volume content of ethene is for the aqueous solution, the HCl solution (hydrochloric acid) of 35wt% concentration and dry gas
33.9vol%), chlorohydrin action, the wherein oxydol H of 70wt% concentration is carried out at a temperature of 45 DEG C2O2, 35wt% concentration
HCl solution and the flow of dry gas three should cause H2O2Volume ratio with HCl and dry gas is about 1.1:1.5:1.Obtain chloroethene
Alcohol.
Comparative example 1
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
(1) halogen alcoholization：Add water in tubular reactor (wherein fixed tungstic acid catalyst bed having been loaded in pipe)
H2O, chlorine and dry gas, carry out chlorohydrin action, wherein water H at a temperature of 45 DEG C2The flow of O, chlorine and dry gas three should make
Obtain H2O is of about 88 with the volume ratio of chlorine and dry gas:3.6:1.Obtain chlorethanol.
Embodiment 2
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
1) halogen alcoholization：The oxydol H of tungstic acid catalyst, 35wt% concentration is added in tower reactor2O2, 20wt% concentration
HCl solution (hydrochloric acid) and dry gas, carry out chlorohydrin action at a temperature of 35 DEG C, the wherein matter of tungstic acid catalyst and dry gas
Amount is than being 0.05:The oxydol H of 1,35wt% concentration2O2, the HCl solution of 20wt% concentration and the addition of dry gas three should make
Obtain H2O2Volume ratio with HCl and dry gas is about 2:3:1.Obtain chlorethanol.
Comparative example 2
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
1) halogen alcoholization：Tungstic acid catalyst, water H are added in tower reactor2O, chlorine and dry gas, enter at a temperature of 35 DEG C
Row chlorohydrin action, wherein tungstic acid catalyst are 0.05 with the mass ratio of dry gas:1, water H2O, chlorine and dry gas alkene three's adds
Enter amount and should cause H2O is about 80 with the volume ratio of chlorine and dry gas:3.3:1.Obtain chlorethanol.
Comparative example 3
A kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
Halogen alcoholization：The oxydol H of 70wt% concentration is added in tubular reactor2O2, 35wt% concentration HCl solution (salt
Acid) and dry gas, chlorohydrin action, the wherein oxydol H of 705wt% concentration is carried out at a temperature of 45 DEG C2O2, 35wt% concentration
HCl solution and the flow of dry gas three should cause H2O2Volume ratio with HCl and dry gas is about 1.1:1.5:1.Obtain chloroethene
Alcohol.
Embodiment 3
A kind of method that dry gas prepares oxirane, the method are comprised the following steps：
(1) halogen alcoholization：The oxydol H of tungstic acid catalyst, 35wt% concentration is added in tower reactor2O2, 20wt% concentration
HCl solution (hydrochloric acid) and dry gas, carry out chlorohydrin action, the wherein oxydol H of 35wt% concentration at a temperature of 35 DEG C2O2、
The flow of the HCl solution of 20wt% concentration and dry gas alkene three should cause H2O2Volume ratio with HCl and dry gas is about 1.1:
1.5:1.Obtain chlorethanol.
(2) saponification：The chlorethanol that step (1) is obtained carries out saponification with NaOH, obtains oxirane organic
Phase and sodium chloride solution.Saponification is carried out in the tower reactor of steel, and upper design is sieve-plate tower.Steam enters from bottom of towe
Enter to make the thick oxirane of generation to blow out from tower top.Saponification temperature is controlled at 60～70 DEG C.
(3) electrodialysis：The sodium chloride solution that step (2) is obtained is through bipolar membrane electrodialysis (I types of TRPB8040, north
Jing Tingrun membrane technologies development corporation, Ltd. production and selling, the transmembrane voltage of applying is 1.3V, and operating temperature is 20-30 DEG C), obtain
To NaOH and hydrogen chloride.
(4) oxirane is refined：
The oxirane crude product obtained in step 2 is carried out into rectifying, the oxirane of high-purity (99.9wt%) is obtained.
Embodiment 4
(1) halogen alcoholization：Add in tubular reactor (wherein having loaded fixed tungstic acid catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and dry gas, carry out chloropharin at a temperature of 45 DEG C
Change reaction, the wherein oxydol H of 70wt% concentration2O2, the HCl solution of 35wt% concentration and the flow of dry gas alkene three should cause
H2O2Volume ratio with HCl and dry gas is about 2:3:1.Obtain chlorethanol.
(2) saponification：The chlorethanol that step (1) is obtained carries out saponification with NaOH, obtains oxirane organic
Phase and sodium chloride solution.Saponification is carried out in the tower reactor of steel, and upper design is sieve-plate tower.Steam enters from bottom of towe
Enter to make the thick oxirane of generation to blow out from tower top.Saponification temperature is controlled at 30～40 DEG C.
(3) electrodialysis：The sodium chloride solution that step (2) is obtained is through bipolar membrane electrodialysis (I types of TRPB8040, north
Jing Tingrun membrane technologies development corporation, Ltd. production and selling, the transmembrane voltage of applying is 1.3V, and operating temperature is 20-30 DEG C), obtain
To NaOH and hydrogen chloride.
(4) oxirane is refined：
The oxirane crude product obtained in step 2 is carried out into rectifying, the oxirane of high-purity (99.9wt%) is obtained.
Embodiment 5
Repeat embodiment 3, simply replace HCl solution with HBr solution.
Embodiment 6
Repeat embodiment 3, simply fixed Catalyst of niobic acid bed has been loaded in the pipe of tubular reactor, that is, used niobic acid
Replace wolframic acid.
Embodiment 7
Repeat embodiment 3, simply with molybdenum bismuth type metal composite oxide
Mo12Bi1.6Fe2.2Co5.5Ni2.5Sb0.5Zn0.3K0.1O32.8。
Embodiment 8
Repeat embodiment 3, simply loaded the beds of fixed TS-1 in the pipe of tubular reactor, that is, used
TS-1 replaces wolframic acid.Embodiment 1 of the synthetic method of TS-1 with reference to CN201410812216.8.
Embodiment 9
Repeatedly embodiment 3, has simply loaded the Ti-MWW beds of fixation in the pipe of tubular reactor.Ti-MWW
Embodiment 1 of the synthetic method with reference to CN200710037012.1.
Embodiment 10
Repeat embodiment 3, simply with the beds of HTS-1.
Embodiment 11
Repeat embodiment 3, simply with the beds of ZSM-5 molecular sieve.ZSM-5 molecular sieve is with reference to patent
200510029462.7 it is prepared by the method for middle embodiment 1-3.
Embodiment 12
Repeat embodiment 3, simply with the beds of Silicalite-1 molecular sieves.Silicalite-1 molecular sieves are joined
Prepare according to the method for embodiment 1 in patent 201010220796.3.
Embodiment 13
Repeat embodiment 3, simply the NaOH in step (2) is substituted with potassium hydroxide.
Embodiment 14
Repeat embodiment 3, in step (1) be simply：The oxydol H of 65wt% concentration2O2, 35wt% concentration HCl solution
H should be caused with the flow of dry gas three2O2Volume ratio with HCl and dry gas is of about 1:2:1.
Embodiment 15
Repeat embodiment 3, in step (1) be simply：The oxydol H of 20wt% concentration2O2, 35wt% concentration HCl solution
H should be caused with the flow of dry gas three2O2Volume ratio with HCl and dry gas alkene is of about 3:1.2:1.
Embodiment 16
Repeat embodiment 3, simply the reaction temperature in step (1) is 20 DEG C.
Embodiment 17
Repeat embodiment 3, simply the temperature control in step (2) is at 50 DEG C.
1 embodiment 1-26 of table and comparative example 1-4 reaction condition and reaction result
For " bed ", catalyst amount refers to that catalyst is arranged in the way of fixed beds in the reactor, such as
Multiple reactors of series connection, in tubular reactor or micro passage reaction.In beds, alefinically unsaturated compounds with urge
The weight ratio of agent is 1：0.3.
Claims (11)
1. a kind of method that dry gas prepares halogen ethanol, the method are comprised the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, dry gas, carry out halogen alcoholization reaction and obtain halogen ethanol；It is excellent
Choosing, H2O2It is the form of the aqueous solution.
2. a kind of method that dry gas prepares oxirane, the method are comprised the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, dry gas, carry out halogen alcoholization reaction and obtain halogen ethanol；It is excellent
Choosing, H2O2It is the form of the aqueous solution；With
(2) saponification：The halogen ethanol of step (1) and alkali-metal hydroxide are carried out into saponification, is separated and is obtained epoxy second
Alkane and halogenated alkali metal salt；
Preferably, methods described also includes：(3) electrodialysis：The halogenated alkali metal salt that step (2) is obtained is through Bipolar Membrane electric osmose
Analysis, obtains alkali-metal hydroxide and hydrogen halides.
3. method according to claim 2, it is characterised in that：Methods described also includes：(4) oxirane is refined, obtains
To refined oxirane；Preferably, step (2) acquisition oxirane is obtained into refined oxirane through rectifying.
4. the method according to any one of claim 1-3, it is characterised in that：Catalyst is added in step (1), should
Catalyst is selected from solid acids (such as wolframic acid, niobic acid), molecular sieve (such as Ti- molecular sieves), vanadium phosphorus oxygen compound species, molybdenum vanadium
Type metal composite oxide class, molybdenum bismuth type metal composite oxide class, molybdenum tungsten type metal composite oxide class, Salen transition gold
Category class catalyst or heteropllyacids in one kind, two or more.
5. the method according to any one of claim 1-4, it is characterised in that：The dry gas is the dry of oil plant generation
Gas, it is preferred that in dry gas the volume content of ethene be 25-40vol%, preferably 27-37vol%, more preferably 29-
35vol%；And/or
The hydrogen halides is one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide, it is preferable that hydrogen halides is the shape with the aqueous solution
Formula is used.
6. the method according to any one of claim 1-5, it is characterised in that：The alkali-metal hydroxide is hydrogen-oxygen
Change one or more in sodium or potassium hydroxide or lithium hydroxide, and/or
The halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, KBr, lithium bromide, sodium iodide, iodate
One or more in potassium, lithium iodide.
7. the method according to any one of claim 1-6, it is characterised in that：The body of dry gas and hydrogen halides in step (1)
Product is than being 1：0.1-100, preferably 1：0.2-50, more preferably 1：0.5-30, more preferably 1：0.8-10, more preferably 1：1-8, more preferably
1：1.1-5, more preferably 1：1.2-2.
8. the method according to any one of claim 1-7, it is characterised in that：Dry gas and H in step (1)2O2Volume ratio
For 1：0.1-100, preferably 1：0.5-50, more preferably 1：0.8-30, more preferably 1：0.9-20, more preferably 1：1.0-10, more preferably
1：1.1-5, more preferably 1：1.1-2；
And/or
The H2O2It is H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more preferably 10-
70%, the H of more preferably 15-60%, more preferably 20-50%2O2The aqueous solution.
9. the method according to any one of claim 2-8, it is characterised in that：Halogen ethanol and alkali metal hydrogen in step (2)
The mol ratio of oxide is 1：0.1-50, preferably 1：0.5-30, more preferably 1：0.8-20, more preferably 1：1.0-10, more preferably
1：1.1-5.
10. the method according to any one of claim 1-9, it is characterised in that：Reaction temperature in step (1) is 0-60
DEG C, preferably 10-50 DEG C, more preferably 20-45 DEG C, and/or
Reaction temperature in step (2) is 0-100 DEG C, preferably 5-90 DEG C, preferably 10-80 DEG C, more preferably 20-60 DEG C.
11. methods according to any one of claim 1-10, it is characterised in that：Reaction unit in step (1)
For single reactor, multiple reactors of series connection, tubular reactor or micro passage reaction；And/or
Reaction wherein in step (1) is carried out according to the mode of batch (-type), semi continuous or continous way.
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