CN106518621A - Method for preparing halogen propanol and epoxypropane - Google Patents
Method for preparing halogen propanol and epoxypropane Download PDFInfo
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- CN106518621A CN106518621A CN201610142802.5A CN201610142802A CN106518621A CN 106518621 A CN106518621 A CN 106518621A CN 201610142802 A CN201610142802 A CN 201610142802A CN 106518621 A CN106518621 A CN 106518621A
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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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Abstract
The invention provides a method for preparing halogen propanol. The method comprises the following steps (1) halogen alcoholization: adding halogen hydride, H2O2, propylene and an HTS molecular sieve into a reaction device, and carrying out halogen alcoholization reaction to obtain the halogen propanol. The invention also provides a method for preparing epoxypropane with a halogenohydrin method. The method comprises the following steps: (1) halogen alcoholization: adding halogen hydride, H2O2, propylene and an HTS molecular sieve into the reaction device, and carrying out the halogen alcoholization reaction to obtain halogen propanol; (2) saponification: carrying out saponification reaction on halogen propanol and a hydroxide of alkali metal in step (1), and separating to obtain the epoxypropane and alkali halide metal salt; optionally (3) electroosmosis: carrying out bipolar membrane electroosmosis on the alkali halide metal salt obtained in step (2) to obtain the hydroxide of alkali metal and the halogen hydride. According to the methods, the halogen propanol or the epoxypropane can be prepared at extremely high selectivity and yield, and the discharging of waste water and waste residues can be drastically lowered.
Description
Technical field
A kind of the present invention relates to preparation method of halogen propanol, and the method that expoxy propane is prepared by halogen propanol；More specifically
A kind of method for halogen propanol being prepared as raw material using new halogenohydrin method with propylene is provided, and expoxy propane is prepared using new halogenohydrin method
Method.
Background technology
Expoxy propane (hereinafter referred to as PO) is a kind of important Organic Chemicals.It is used as the third-largest derivative of propylene
Thing, its maximum purposes are to prepare polyether polyol, can also produce Propylene Glycol and nonionic surfactant.PO is also wide in recent years
It is general for green products such as Synthesis of dimethyl carbonate, carbon dioxide polymers.
The production technology of expoxy propane mainly has chlorohydrination method, conjugated oxidation (also referred to as indirect oxidation method) and direct oxidation
Method.Major part enterprise of China uses chlorohydrination technique, also has number set conjugated oxidation and hydrogen peroxide direct oxidation method technique to throw
Enter to use.
Chlorohydrination production history is long, and the main processes of chlorohydrination are alcoholizing propenyl chloride, lime cream saponification and product
It is refined, it is characterized in that the elastic big, selectivity of mature production technology, operational load is good, the purity requirement to raw material propylene is not high, from
And the safety of production can be improved, construction investment is few.As fixed assets investment is few, product cost is relatively low, its product with compared with
Strong cost competitiveness.Nowadays the production capacity of world's expoxy propane about 40% is chlorohydrination.
The chlorohydrination of prior art prepares expoxy propane and is primarily present problems with：1. there is addition with ethylene in raw material chlorine
Side reaction, generates dichloropropane.Dichloropropane is difficult to be utilized, and wastes substantial amounts of raw material.In addition, chlorine is reacted with propylene,
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, propylene 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. water resources consumption is big, produces a large amount of waste water and waste residue,
Chlorohydrination production 1t expoxy propane produces the waste water of 40-50t chlorides, 2.1t calcium chloride waste residues, the waste water have temperature it is high,
" five is high " feature that 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 expoxy propane, 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；Volume of production is higher, and the injury to environment is deeper.Thus, environmental protection has become system
The about primary factor of expoxy propane industrial development.U.S.'s development and application chlorohydrination prepares expoxy propane 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 epoxide.
The content of the invention
Present inventor is had found by studying, using propylene, hydrogen halides and H2O2Halogen propanol is prepared, then saponification, energy
It is enough that expoxy propane is prepared with high selectivity and yield, and considerably reduce the discharge of waste water, waste residue.
According to the first embodiment of the present invention, there is provided a kind of method for preparing halogen propanol, the method include following step
Suddenly：(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, propylene and containing Ti, with multi-stage porous, MFI structure molecular sieve
(referred to as " HTS molecular sieves "), carries out halogen alcoholization reaction and obtains halogen propanol.
Preferably, HTS molecular sieves described in step (1) be HTS-1, HTS-2, the one kind or many in HTS-3 molecular sieves
Kind.
In the present invention, hydrogen halides described in step (1) are one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide.
In the present invention, propylene and H in step (1)2O2Mol 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 H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more
Preferably 10-70%, more preferably 15-60%, more preferably 20-50%.
In the present invention, in step (1), propylene is 1 with the mol ratio of hydrogen halides：0.1-100, preferably 1：0.5-50, it is more excellent
Select 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 reaction temperature in step (1) is 0-60 DEG C, preferably 10-50 DEG C, more preferably 20-45 DEG C.
According to the second embodiment of the present invention, there is provided a kind of method that halogenohydrin method prepares expoxy propane, the method bag
Include following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, propylene and HTS molecular sieves, carry out halogen alcoholization reaction and
Obtain halogen propanol；
(2) saponification：The halogen propanol of step (1) and alkali-metal hydroxide are carried out into saponification, is separated and is obtained ring
Ethylene Oxide 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
EDBM, obtains alkali-metal hydroxide and hydrogen halides.
Preferably, methods described also includes：(4) refined (such as distillation or the rectification) of epoxide：Step (2) is obtained
Expoxy propane by distillation and/or rectification, obtain refined expoxy propane.
Preferably, HTS molecular sieves described in step (1) be HTS-1, HTS-2, the one kind or many in HTS-3 molecular sieves
Kind.
In the present invention, hydrogen halides described in step (1) are one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide.
In the present invention, propylene and H in step (1)2O2Mol 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 H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more
Preferably 10-70%, more preferably 15-60%, more preferably 20-50%.
In the present invention, in step (1), propylene is 1 with the mol ratio of hydrogen halides：0.1-100, preferably 1：0.5-50, it is more excellent
Select 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 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, in step (2), halogen propanol 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 (2) be 0-100 DEG C, preferably 5-90 DEG C, preferably 10-80 DEG C, more preferably
20-60℃。
Preferably, the alkali-metal hydroxide is sodium hydroxide or potassium hydroxide or the one kind in Lithium hydrate
Or it is various.
Preferably, the halogenated alkali metal salt be Sodium Chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide,
One or more in sodium iodide, potassium iodide, lithium iodide.
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 propanol
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, halogen propanol can be obtained.Preferably, the concentration of hydrogen halides is 1-40%, further preferred 2-30%, in preferred 3-
20%, more preferably 5-10%.
It is preferred that, in any method according to first embodiment or second embodiment, step (1)
In reaction unit be single reactor, multiple reactors of series connection, tubular reactor or micro passage reaction.
Preferably, the reaction in step (1) is carried out according to the mode of batch (-type), semi continuous or continuous way.
When step (1) is carried out in single reactor according to intermittent mode, in step (1) during addition catalyst, third
Alkene 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, the weight of alefinically unsaturated compounds and catalyst
Than for 1：0.001-0.99, preferably 1：0.005-0.8, more preferably 1：0.01-0.6, more preferably 1：0.015-0.4.
HTS molecular sieves have unique hollow tunnel structure, and the Ti content of framework of molecular sieve is high so as to good heat
Stability, antianaphylaxiss and higher catalysis activity and selectivity.HTS molecular sieves include HTS-1 molecular sieves, HTS-2 molecular sieves,
HTS-3 molecular sieves.
HTS-1 molecular sieve surfaces acid site has higher catalysis activity, her diffusion and solvent polarity to reaction
The impact of activity is very big.Concrete synthesized reference《The probe reaction research of HTS-1 molecular sieve surfaces acidifying catalysis》, author：Liu Xuan
Gorgeous, Yin Dulin, Zhu Huayuan, Shen Gang,《Catalysis journal》.
HTS HTS-2, which has HTS HTS identical catalytic oxidation activities, selectivity and general
Physicochemical property.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, molecular sieve surface titanium are uniformly distributed, when shortening crystallization
Between, improve synthesising stability and repeatability.HTS-3 molecular sieve catalysts have more active center, more preferable catalytic
Can, it is more beneficial for reactant molecule diffusion.Concrete synthesized reference《The development of monocrystalline Multihollow HTS-3 molecular sieve catalysts》,《Stone
Oil refining and chemical industry》.
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 propylene reaches 97%,
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 crude propene oxide from tower top blow out.At 0～100 DEG C, tower top pressure is normal pressure or negative pressure for saponification temperature control.Saponification
Device is designed and the key problem in technology of operation is must to be sufficiently mixed and control pH with alkali liquor into the halogen aqueous propanol solution before saponification column,
The expoxy propane of generation is made to flow out from tower top as early as possible.
As traditional chlorohydrination technique uses Calx 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 expoxy propane, about produce 2.1t CaCl2Waste residue and extremely
Few 43t waste water.The present invention adopts alkali-metal hydroxide (such as sodium hydroxide, potassium hydroxide, Lithium hydrate), saponification process
The salt applied afterwards, can be reduced into alkali-metal hydroxide and hydrogen halides, fully achieves circulation by bipolar membrane electrodialysis
Utilize.
(1) response 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 expoxy propane of production Propylene Glycol and production respectively
The expoxy propane of polyethers.
(4) nemamort in the waste water that saponification process is produced, drop are separated by the scattered tower with special tower tray
Biological oxygen content, chemical oxygen content in low waste liquid.
In prior art, halogenohydrin method prepares the process (by taking chlorine as an example) of expoxy propane：
CH3CH=CH2+Cl2+H2O——CH3CH(Cl)-CH2(OH)+CH3CH(OH)-CH2(Cl)+HCl
CH3CH(Cl)-CH2(OH)+Ca(OH)2——PO+CaCl2+H2O
CH3CH(OH)-CH2(Cl)+Ca(OH)2——PO+CaCl2+H2O
The present invention provides the process that a kind of new halogenohydrin method prepares expoxy propane (by taking hydrogen chloride as an example)：
CH3CH=CH2+HCl+H2O2——CH3CH(Cl)-CH2(OH)+CH3CH(OH)-CH2(Cl)
+H2O (addition catalyst)
CH3CH(Cl)-CH2(OH)+NaOH(KOH、LiOH)——PO+H2O+NaCl (KaCl or LiCl)
CH3CH(OH)-CH2(Cl)+NaOH(KOH、LiOH)——PO+H2O+NaCl (KaCl or LiCl)
NaCl (KaCl or LiCl) is changed into NaOH (KOH, LiOH) and HCl through bipolar membrane electrodialysis.
Alkali-metal hydroxide and hydrogen halides after bipolar membrane electrodialysis 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 hydrion 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, effusion meter, 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 saline solution)
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.
Advantages of the present invention：
In prior art, expoxy propane is produced using chlorohydrination, produce substantial amounts of chloride containing calcium (or Sodium Chloride) waste water, given up
Also containing the raw material Organic substance or intermediate product Organic substance not reacted completely in course of reaction in water, containing not separating thoroughly yet
Expoxy propane, these debirs are difficult to degrade, and deal with extremely difficult, and never find effective process side
Method.The main cause of the disabling chlorohydrination technique of U.S. 2000 is exactly (or the chlorine of the calcium chloride containing the Organic substance waste for being difficult to degrade
Change sodium) waste water is difficult to process.Someone processes the waste water that chlorohydrination technique is produced using electrolysis, due to containing organic waste in waste water
Thing, deals with extremely difficult, and the debirs in waste water are very sensitive to electrolysis with ion-exchange film system, and electrolysis installation is damaged
It is larger；Meanwhile, electrolysis wastewater needs to consume substantial amounts of energy, and the benefit of acquisition is little；Maximum problem is：Electrolysis wastewater is produced
Raw chlorine and hydrogen, in the situation that Organic substance is present, abnormally dangerous, easily blast.
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 expoxy propane.Intrinsic prejudice, halogenohydrin method prepare the useless of expoxy propane
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 expoxy propane, halogenohydrin
Method prepares the waste water containing debirs of expoxy propane 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 expoxy propane using halogenohydrin method and produces the characteristics of giving up Organic substance in water, can be very
Well by the application of bipolar membrane electrodialysis technology and the preparation of expoxy propane, it is possible to achieve clean manufacturing, solve halogenohydrin method and prepare ring
The reluctant problem of waste water that Ethylene Oxide is produced.Waste water handling problem is captured, halogenohydrin method just prepares the advantage of expoxy propane
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 expoxy propane, completely solves the problem containing organic runoff water, makes halogenohydrin method efficiently prepare epoxy
While propane, clean manufacturing is realized.
Bronsted lowry acids and bases bronsted lowry is the raw material of this programme, and the bronsted lowry acids and bases bronsted lowry that bipolar membrane electrodialysis are produced just again can be applicable as raw material,
Such that it is able to form circulation, realize cleaning, circulation, produce without waste.Original waste is changed into into present raw material, material is saved
While, reduce the discharge of waste, environmental protection.
Compared with electrolysis process, the energy of bipolar membrane electrodialysis consumption greatly reduces, and effect is got a promotion on the contrary.Together
When, bipolar membrane electrodialysis production bronsted lowry acids and bases bronsted lowry not there are danger, overcomes electrolysis process danger, holds explosive problem.Most
Importantly, electrolysis process processes waste water, the foreign organic matter in waste water can not be processed, can only be discharged, and this kind of organic
Waste is difficult degraded, greatly pollutes environment；And bipolar membrane electrodialysis process waste water, the foreign organic matter in waste water can be reduced
Into raw material or product is directly obtained, so as to process the debirs also processed while salt in waste water in waste water, by organic waste
Thing is changed into raw material or product, takes full advantage of material, while waste zero-emission can be realized, protects environment well.
Compared with prior art, technical scheme has following Advantageous Effects：
1st, overcome by-product (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, prior art is to reduce the generation of side reaction, prepare halogen propanol concentration can only typically control 4.5% with
Under；And the new halogenohydrin method technique of the present invention, as side reaction is few, the concentration of halogen propanol is unrestricted.1) save saponification process
Energy consumption, the 1/10 or so of only former technique；2) saving water resource, the 1/10 of water consumption deficiency original technique；Meanwhile, greatly reduce
The discharge of wastewater flow rate, 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 analyses are carried out to product using Agilent 7890/5975C-GC/MSD types gas chromatograph-mass spectrometer,
Quantitative analyses are carried out to product using Agilent 6890N types gas chromatograpies and external standard method.
According to detection and analysis result, following object function is defined as inspection target.
Propylene conversion：
Halogen propanol selectivity：
Halogen propanol yield：YHalogen propanol=CPropylene×SHalogen propanol
Expoxy propane yield：
In formula, C is conversion ratio, and S is selectivity, 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, effusion meter, 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 (saline solution
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
H2O in layer 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 NazSO4In solution, at 25 DEG C, 10-100mA/cm2Determine under electric current density
Embodiment 1
1) halogen alcoholization：Add in tubular reactor (wherein having loaded fixed HTS-1 mol sieve beds in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and propylene, 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 propylene three should cause
H2O2Mol ratio with HCl and propylene is of about 1.2:1.2:1.Obtain halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propan-2-ols
Mixture.
Comparative example 1
1) halogen alcoholization：The water H in tubular reactor (wherein having loaded fixed HTS-1 mol sieve beds in pipe)2O、
Chlorine and propylene, carry out chlorohydrin action, wherein water H at a temperature of 45 DEG C2The flow of O, chlorine and propylene three should be caused
H2O is of about 87 with the mol ratio of chlorine and propylene:3.6:1.Obtain halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propan-2-ols
Mixture.
Embodiment 2
1) halogen alcoholization：HTS-1 molecular sieves, the oxydol H of 35wt% concentration is added in tower reactor2O2, 20wt% it is dense
The HCl solution (hydrochloric acid) of degree and propylene, carry out chlorohydrin action, the time of staying in tubular reactor at a temperature of 35 DEG C
It it is 10 minutes, wherein HTS-1 molecular sieves are 0.05 with the mol ratio of propylene:The oxydol H of 1,35wt% concentration2O2, 20wt% it is dense
The flow of the HCl solution of degree and propylene three should cause H2O2Mol ratio with HCl and propylene is of about 1.5:1.1:1.Obtain halogen
The mixture of alcohol, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propan-2-ols.
Comparative example 2
1) halogen alcoholization：HTS-1 molecular sieves, water H is added in tower reactor2O, chlorine and propylene, in 35 DEG C of temperature
Under carry out chlorohydrin action, wherein HTS-1 molecular sieves are 0.05 with the mass ratio of propylene:1, water H2O, chlorine and propylene three's
Addition should cause H2O and HCl is of about 61 with the mol ratio of propylene:3.3:1.Obtain halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1-
The mixture of chloro propan-2-ol.
Comparative example 3
Halogen alcoholization：The oxydol H of 70wt% concentration is added in tubular reactor2O2, 35wt% concentration HCl solution (salt
Acid) and propylene, chlorohydrin action is carried out at a temperature of 45 DEG C, the time of staying in tubular reactor is 40 minutes, wherein
The oxydol H of 70wt% concentration2O2, the HCl solution of 35wt% concentration and the flow of propylene three should cause H2O2With HCl and third
The mol ratio of alkene is of about 1.2:1.2:1.Obtain the mixture of halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propan-2-ols.
Comparative example 4
Halogen alcoholization：Add in tubular reactor (wherein having loaded fixed HTS-1 beds in pipe)
The HCl solution (hydrochloric acid) of 35wt% concentration and propylene, carry out chlorohydrin action, at a temperature of 45 DEG C in tubular reactor
The time of staying is 40 minutes, and the flow of the wherein HCl solution and propylene of 35wt% concentration should cause the HCl with the mol ratio of propylene to be
About 1.2:1.
Embodiment 3
1) halogen alcoholization：Add in tubular reactor (wherein having loaded fixed HTS-1 mol sieve beds in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and propylene, 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 propylene three should cause
H2O2Mol ratio with HCl and propylene is of about 1.2:1.2:1.Obtain halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propan-2-ols
Mixture.
2) saponification：By step 1) halogenohydrin that obtains carries out saponification with sodium hydroxide, separates and obtaining expoxy propane has
Machine phase and sodium chloride solution.Saponification is carried out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from bottom of towe
Blow out into the crude propene oxide of generation is made from tower top.Saponification temperature is controlled at 60～70 DEG C.
3) electrodialysis：By step 2) sodium chloride solution that obtains is through bipolar membrane electrodialysis (I types of TRPB8040, Beijing
Ting Run 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
Sodium hydroxide and HCl.
4) expoxy propane is refined：
The propene oxide crude product obtained in step 2 is carried out into rectification, the expoxy propane of high-purity (99.9wt%) is obtained.
Embodiment 4
1) halogen alcoholization：HTS-1 molecular sieves, the oxydol H of 35wt% concentration is added in tower reactor2O2, 20wt% it is dense
The HCl solution (hydrochloric acid) of degree and propylene, carry out chlorohydrin action, wherein HTS-1 molecular sieves and propylene at a temperature of 35 DEG C
Mass ratio is 0.05:The oxydol H of 1,35wt% concentration2O2, the HCl solution of 20wt% concentration and the flow of propylene three should make
Obtain H2O2Mol ratio with HCl and propylene is of about 1.5:1.1:1.Obtain halogenohydrin, i.e. 2- chloros propyl- 1- alcohol and 1- chloro propyl-s 2-
The mixture of alcohol.
2) saponification：By step 1) halogenohydrin that obtains carries out saponification with sodium hydroxide, separates and obtaining expoxy propane has
Machine phase and sodium chloride solution.Saponification is carried out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from bottom of towe
Blow out into the crude propene oxide of generation is made from tower top.Saponification temperature is controlled at 40～50 DEG C.
3) electrodialysis：By step 2) sodium chloride solution that obtains, through bipolar membrane electrodialysis, obtains sodium hydroxide and HCl.
4) expoxy propane is refined：
The propene oxide crude product obtained in step 2 is carried out into rectification, the expoxy propane 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 with the beds of HTS-2.
Embodiment 7
Repeat embodiment 3, simply with the beds of HTS-3.
Embodiment 8
Repeat embodiment 3, simply the sodium hydroxide in step (2) is substituted with potassium hydroxide.
Embodiment 9
Repeat embodiment 3, simply the hydrogen chloride in step (1) is substituted with hydrogen bromide.
Embodiment 10
Repeat embodiment 3, simply in step (1) 65wt% concentration oxydol H2O2, 35wt% concentration HCl solution and
The flow of propylene three should cause H2O2Mol ratio with HCl and propylene is of about 0.8:0.3:1.
Embodiment 11
Repeat embodiment 3, simply in step (1) 65wt% concentration oxydol H2O2, 35wt% concentration HCl solution and
The flow of propylene three should cause H2O2Mol ratio with HCl and propylene is of about 0.9:1.1:1.
Embodiment 12
Repeat embodiment 3, simply the reaction temperature in step (1) is 20 DEG C, the time of staying is 2 minutes.
Embodiment 13
Repeat embodiment 3, simply the temperature control in step (2) is at 50 DEG C.
1 embodiment 1-13 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 (10)
1. a kind of method for preparing halogen propanol, comprises the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, propylene and HTS molecular sieves, carry out halogen alcoholization reaction and obtain
Halogen propanol.
2. a kind of method that halogenohydrin method prepares expoxy propane, comprises the following steps：
(1) halogen alcoholization：Hydrogen halides, H is added in reaction unit2O2, propylene and HTS molecular sieves, carry out halogen alcoholization reaction and obtain
Halogen propanol；
(2) saponification：The halogen propanol of step (1) and alkali-metal hydroxide are carried out into saponification, is separated and is obtained epoxy third
Alkane and halogenated alkali metal salt.
3. method according to claim 2, it is characterised in that：Methods described also includes：(3) electrodialysis：Step (2) is obtained
The halogenated alkali metal salt for obtaining obtains alkali-metal hydroxide and hydrogen halides through bipolar membrane electrodialysis.
4. according to the method in claim 2 or 3, it is characterised in that：Methods described also includes：(4) epoxide is refined：
The expoxy propane that step (2) is obtained obtains refined expoxy propane by distillation and/or rectification.
5. the method according to any one of claim 1-4, it is characterised in that：Described in step (1), HTS molecular sieves are
HTS-1, HTS-2, one or more in HTS-3 molecular sieves, and/or
Hydrogen halides described in step (1) are one or more in hydrogen chloride, hydrogen bromide or hydrogen iodide.
6. the method according to any one of claim 1-5, it is characterised in that：Propylene and H in step (1)2O2Mol 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 H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more preferably 10-70%, more
Preferably 15-60%, more preferably 20-50%.
7. the method according to any one of claim 1-6, it is characterised in that：In step (1), propylene and hydrogen halides rubs
You are than being 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
It is preferred that 1：1.1-5, more preferably 1：1.1-2；And/or
Reaction temperature in step (1) is 0-60 DEG C, preferably 10-50 DEG C, more preferably 20-45 DEG C.
8. the method according to any one of claim 2-7, it is characterised in that：Halogen propanol 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, and/or, 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
℃。
9. the method according to any one of claim 2-8, it is characterised in that：The alkali-metal hydroxide is hydrogen-oxygen
Change one or more in sodium or potassium hydroxide or Lithium hydrate,
And/or
The halogenated alkali metal salt is Sodium Chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, sodium iodide, iodate
One or more in potassium, lithium iodide.
10. the method according to any one of claim 1-9, it is characterised in that：Reaction unit in step (1) is
One or more in 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 continuous way.
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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
- 2016-03-14 CN CN201610142802.5A patent/CN106518621B/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 |
Non-Patent Citations (1)
| Title |
|---|
| HONGBO ZHANG ET AL: "Enhanced catalytic activity of sub-nanometer titania clusters confined inside double-wall carbon nanotubes", 《CHEMSUSCHEM》 * |
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