CN106560466B - A method of preparing halogen propyl alcohol and propylene oxide - Google Patents
A method of preparing halogen propyl alcohol and propylene oxide Download PDFInfo
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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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- 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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- 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
There is provided a kind of method for preparing halogen propyl alcohol, comprising the following steps: (1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；(2) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, propylene and through step (1) processed catalyst, carry out halogen alcoholization reaction and obtain halogen propyl alcohol；Optionally, (3) are saponified: the hydroxide of the halogen propyl alcohol of step (2) and alkali metal being carried out saponification, separates and obtains propylene oxide and halogenated alkali metal salt；Optionally, (4) electrodialysis: the halogenated alkali metal salt that step (2) are obtained passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.Method of the invention prepares halogen propyl alcohol with high selectivity and yield, and considerably reduces the discharge of waste water, waste residue.
Description
Technical field
The present invention relates to a kind of preparation methods of halogen propyl alcohol, and the method for preparing propylene oxide by halogen propyl alcohol；More specifically
A kind of method for using new halogenohydrin method to prepare halogen propyl alcohol as raw material using propylene is provided, and propylene oxide is prepared using new halogenohydrin method
Method.
Background technique
Propylene oxide (hereinafter referred to as PO) is a kind of important Organic Chemicals.Its third-largest derivative as propylene
Object, maximum purposes is to prepare polyether polyol, can also produce propylene glycol and nonionic surface active agent.PO is also wide in recent years
It is general to be used for the green products such as Synthesis of dimethyl carbonate, carbon dioxide polymer.
The production technology of propylene oxide mainly has chlorohydrination method, conjugated oxidation (also referred to as indirect oxidation method) and direct oxidation
Method.Major part enterprise, China also has number set conjugated oxidation and hydrogen peroxide direct oxidation method technique to throw using chlorohydrination technique
Enter to use.
Chlorohydrination production history is long, and the main processes of chlorohydrination are alcoholizing propenyl chloride, milk of lime saponification and product
Purification, its main feature is that mature production technology, operational load elasticity are big, selectivity is good, it is not high to the purity requirement of raw material propylene, from
And the safety of production can be improved, construction investment is few.Since fixed assets investment is few, product cost is lower, product have compared with
Strong cost competitiveness.Nowadays the production capacity of world's propylene oxide about 40% is chlorohydrination.
The chlorohydrination of the prior art prepares propylene oxide and is primarily present following problems: 1. addition occurs for raw material chlorine and propylene
Side reaction generates dichloropropane.Dichloropropane is difficult to be utilized, and wastes a large amount of raw material.In addition, chlorine is reacted with propylene,
A large amount of heat is released, heat is concentrated in the reaction vessel, causes to produce dangerous row very big.2. raw material chlorine is in process of production not
The evitable a small amount of oxygen of entrainment, with the progress of reaction, chlorine constantly participates in reaction, it is therefore desirable to chlorine is constantly supplemented,
And oxygen cannot participate in reacting, in reaction unit, with the progress of reaction, oxygen concentration is constantly increased, and anti-for constantly accumulation
Heat should be released, oxygen, chlorine, propylene exist simultaneously, and are easy to cause explosion under high temperature.3. reaction generates hydrochloric acid, need to consume
A large amount of alkali (such as calcium hydroxide) carrys out the product hydrochloric acid of neutralization reaction, can just be conducive to react.4. reaction generates a large amount of chlorine
Change calcium, calcium chloride causes the waste water COD generated higher, pollutes environment.5. the shortcomings that chlorohydrination is that water resources consumption is big, generate big
Waste water and waste residue are measured, chlorohydrination produces waste water, the 2.1t calcium chloride waste residue that 1t propylene oxide generates 40-50t chloride, this is useless
Water has the characteristics that " five is high " that temperature is high, pH value is high, chloride content is high, COD content is high and suspension content is high, it is difficult to it handles,
Serious pollution environment.6. the hypochlorous acid generated in production process is to the corrosion of equipment also than more serious.
Propylene oxide is produced with chlorohydrination technique, if waste water, waste residue problem, enterprise's process units cannot be efficiently solved
Ability is bigger, and the burden of environmental protection is bigger；Output is higher, deeper to the injury of environment.Thus, environmental protection has become system
The about primary factor of propylene oxide industrial development.It is earliest that U.S.'s development and application chlorohydrination prepares propylene oxide, using initial stage, chlorine
Alcohol method technique is widely developed and produces.2000, since the waste water of chlorohydrination technique generation, the U.S. cannot be effectively treated
It is forbidden to use chlorohydrination technique production epoxides.
Summary of the invention
The inventor of the present application found through research that using propylene, hydrogen halides and H2O2Halogen propyl alcohol is prepared, is then saponified, energy
It is enough that propylene oxide is prepared with high selectivity and yield, and considerably reduce the discharge of waste water, waste residue.
According to the first embodiment of the present invention, a kind of method for preparing halogen propyl alcohol is provided, this method includes following step
It is rapid:
(1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；
(2) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, propylene and through step (1) processed catalyst, into
The reaction of row halogen alcoholization obtains halogen propyl alcohol.
In the present invention, in step (1) acid be organic and or inorganic acids, preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid,
One of carbonic acid, chloric acid, acetic acid are a variety of.The concentration of acid is not required, concentrated acid is can be, is also possible to olefin(e) acid.It can be with
It is mixed acid.
Preferably, catalyst described in step (1) is hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecule
One of sieve is a variety of.
In the present invention, it is washed in step (1) with distilled water or deionized water.
In the present invention, hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
In the present invention, propylene and H in step (2)2O2Molar ratio be 1:0.1-100, preferably 1:0.5-50, more preferably
1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.
In the present invention, the H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more
Preferably 10-70%, more preferably 15-60%, more preferable 20-50%.
In the present invention, in step (2) molar ratio of propylene and hydrogen halides be 1:0.1-100, preferably 1:0.5-50, it is more excellent
Select 1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.
In the present invention, the reaction temperature in step (2) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.
In the present invention, there is no limit the purpose of immersion is the leaching for allowing catalyst first to pass in and out acid to soaking time in step (1)
Bubble, improves catalytic performance and the shelf life of catalyst.General soaking time be 0.1-72h, preferably 0.2-48h, more preferably
For 0.3-24h, such as 0.5h, 1h, 2h, 6h.
In the present invention, the purpose of washing catalyst is the acid on washing immersion rear catalyst.Generally with distilled water or go
Ionized water, or can also be washed with weak base.
In the present invention, the purpose dried in step (1) is the moisture on removal washing rear catalyst.Do not damaging catalysis
Agent structure and in the case where not influencing catalyst performance, the temperature of drying can be controlled arbitrarily.If high temperature is dried, when drying
Between it is shorter.If low temperature drying, drying time is appropriately extended.Achieve the purpose that moisture removal.Generally, drying temperature 5-
90 DEG C, drying time 0.1-48h；It is preferred that 10-60 DEG C of drying temperature, drying time 0.2-24h；More preferably drying temperature
20-50 DEG C, drying time is such as 30 DEG C of drying temperature of 0.5-12h., drying time 10h；40 DEG C of drying temperature, when drying
Between be 6h；45 DEG C of drying temperature, drying time 2h.
In the present invention, the concentration range of the acid of step (1) is unrestricted, can be weak acid, can be strong acid, can also be with
It is mixed acid.It can be low concentration acid, be also possible to high concentrated acid.In general, the concentration range of hydrochloric acid is 2-38%, preferably
10-35%.The concentration range 2-98% of sulfuric acid, preferably 5-80%.The concentration range 10-98% of nitric acid, preferably 20-80%.
According to the second embodiment of the present invention, a kind of method that halogenohydrin method prepares propylene oxide, this method packet are provided
Include following steps:
(1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；
(2) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, propylene and through step (1) processed catalyst, into
The reaction of row halogen alcoholization obtains halogen propyl alcohol.
(3) it is saponified: the hydroxide of the halogen propyl alcohol of step (2) and alkali metal being subjected to saponification, separates and obtains ring
Ethylene Oxide and halogenated alkali metal salt.
Preferably, the method also includes: (4) electrodialysis: the halogenated alkali metal salt that step (3) are obtained is by bipolar
Membrane electrodialysis obtains the hydroxide and hydrogen halides of alkali metal.
Preferably, the method also includes: the purification (such as distillation or rectifying) of (5) epoxides: by step (3) acquisition
Propylene oxide by distillation and/or rectifying, the propylene oxide refined.
In the present invention, in step (1) acid be organic and or inorganic acids, preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid,
One of carbonic acid, chloric acid, acetic acid are a variety of.The concentration of acid is not required, concentrated acid is can be, is also possible to olefin(e) acid.It can be with
It is mixed acid.
Preferably, catalyst described in step (1) is hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecule
One of sieve is a variety of.
In the present invention, it is washed in step (1) with distilled water or deionized water.
In the present invention, hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
In the present invention, propylene and H in step (2)2O2Molar ratio be 1:0.1-100, preferably 1:0.5-50, more preferably
1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.
In the present invention, the H2O2Concentration (wt%) be 2-100%, preferably 5-90%, more preferably 8-80%, more
Preferably 10-70%, more preferably 15-60%, more preferable 20-50%.
In the present invention, in step (2) molar ratio of propylene and hydrogen halides be 1:0.1-100, preferably 1:0.5-50, it is more excellent
Select 1:0.8-30, more preferable 1:0.9-20, more preferable 1:1.0-10, more preferable 1:1.1-5, more preferable 1:1.1-2.
In the present invention, the reaction temperature in step (2) is 0-60 DEG C, preferably 10-50 DEG C, more preferable 20-45 DEG C.
In the present invention, in step (3) molar ratio of halogen propyl alcohol and alkali metal hydroxide be 1:0.1-50, preferably 1:
0.5-30, more preferably 1:0.8-20, more preferable 1:1.0-10, more preferable 1:1.1-5.
In the present invention, the reaction temperature in step (3) is 0-100 DEG C, preferably 5-90 DEG C, preferably 10-80 DEG C, more preferably
20-60℃。
Preferably, the hydroxide of the alkali metal is sodium hydroxide or one of potassium hydroxide or lithium hydroxide
Or it is a variety of.
Preferably, the halogenated alkali metal salt be sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide,
One of sodium iodide, potassium iodide, lithium iodide are a variety of.
In the present invention, there is no limit the purpose of immersion is the leaching for allowing catalyst first to pass in and out acid to soaking time in step (1)
Bubble, improves catalytic performance and the shelf life of catalyst.General soaking time be 0.1-72h, preferably 0.2-48h, more preferably
For 0.3-24h, such as 0.5h, 1h, 2h, 6h.
In the present invention, the purpose of washing catalyst is the acid on washing immersion rear catalyst.Generally with distilled water or go
Ionized water, or can also be washed with weak base.
In the present invention, the purpose dried in step (1) is the moisture on removal washing rear catalyst.Do not damaging catalysis
Agent structure and in the case where not influencing catalyst performance, the temperature of drying can be controlled arbitrarily.If high temperature is dried, when drying
Between it is shorter.If low temperature drying, drying time is appropriately extended.Achieve the purpose that moisture removal.Generally, drying temperature 5-
90 DEG C, drying time 0.1-48h；It is preferred that 10-60 DEG C of drying temperature, drying time 0.2-24h；More preferably drying temperature
20-50 DEG C, drying time is such as 30 DEG C of drying temperature of 0.5-12h., drying time 10h；40 DEG C of drying temperature, when drying
Between be 6h；45 DEG C of drying temperature, drying time 2h.
In the present invention, the concentration of hydrogen halides can be any concentration in step (1), when using low concentration hydrogen halides,
It can be very good the carry out speed of control reaction；When using high concentration hydrogen halides, it can promote to react to production halogen propyl alcohol
Direction quickly carries out.As long as there is the presence of hydrogen halides in reaction system, regardless of the concentration of hydrogen halides is how many, reacting can be into
Row, can obtain halogen propyl alcohol.Preferably, the concentration of hydrogen halides is 1-40%, further preferred 2-30%, in preferred 3-
20%, more preferable 5-10%.
It is preferred that according in any method of first embodiment or second embodiment, the step (2)
In reaction unit be single reactor, concatenated multiple reactors, tubular reactor or micro passage reaction.
Preferably, the reaction in step (2) is carried out according to intermittent, semi continuous or continuous mode.
When step (2) carries out in single reactor according to intermittent mode, in step (1) when addition catalyst, third
The weight ratio of alkene and catalyst be 1:0.001-0.4, preferably 1:0.005-0.3, more preferably 1:0.01-0.2, more preferable 1:
0.015-0.1.When carrying out in step (1) according to continuously or semi-continuously mode, catalyst can be with fixed catalyst bed
Mode be arranged in the continuously or semi-continuously reactor of mode, such as concatenated multiple reactors, tubular reactor or microchannel
In reactor.At this point, the dosage of catalyst is then more.In catalyst bed, the weight of olefinic unsaturated compound and catalyst
Than for 1:0.001-0.99, preferably 1:0.005-0.8, more preferably 1:0.01-0.6, more preferable 1:0.015-0.4.
In the present invention, hetero-atom molecular-sieve containing Ti is including TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 etc..
TS-1 is a kind of Titanium Sieve Molecular Sieve, belongs to Pentasil type hetero-atom molecular-sieve, rhombic system, synthetic method reference
CN201410812216.8。
TS-2 molecular sieve has MEL topological structure, has good catalytic oxidation performance.Synthetic method reference
CN200910013070.X。
Ti-MWW shows more excellent catalysis oxidation in the epoxidation reaction to linear alpha-olefin and cyclic olefin
Performance, and very high trans selective is shown in alkene asymmetric epoxidation reaction.Synthetic method reference
CN200710037012.1。
Ti-Beta molecular sieve has the twelve-ring channel design and stronger acidity of three-dimensional staggered, anti-in heterogeneous catalysis
The good catalytic performance of Ying Zhongyou.Specific synthesis is referring to " synthesis of Beta molecular sieve and its research of catalytic performance ", author: Liu
Set duckweed, East China Normal University.
Ti-SBA-15 belongs to one kind of mesopore molecular sieve, and Ti-SBA-15 has two-dimentional six side's through-hole structures.Synthetic method
Referring to CN201110211854.0.
In the present invention, HTS molecular sieve refers to containing Ti, has multi-stage porous, MFI structure molecular sieve, including HTS-1, HTS-
2, HTS-3 molecular sieve.HTS molecular sieve has unique hollow tunnel structure, and the Ti content of framework of molecular sieve is high, makes it have
Good thermal stability, antianaphylaxis and higher catalytic activity and selectivity.
HTS molecular sieve includes HTS-1 molecular sieve, HTS-2 molecular sieve, HTS-3 molecular sieve.
HTS-1 molecular sieve surface acid site catalytic activity with higher, her diffusion and solvent polarity is to reaction
Active influence is very big.Specific synthesized reference " the probe reaction research of HTS-1 molecular sieve surface acidification catalysis ", author: Liu Xuan
Gorgeous, Yin Dulin, Zhu Huayuan, Shen Gang, " catalysis journal ".
Titanium Sieve Molecular Sieve HTS-2, with the identical catalytic oxidation activity of Titanium Sieve Molecular Sieve HTS, selectivity and general
Physicochemical property.Specific synthesized reference " synthesis of Titanium Sieve Molecular Sieve HTS-2 ", author: Zhu Bin, Lin Min, Shu Xingtian, Wang Xieqing.
Monocrystalline Multihollow titanium-silicon molecular sieve catalyst HTS-3, molecular sieve surface titanium is uniformly distributed, when shortening crystallization
Between, improve synthesising stability and repeatability.HTS-3 molecular sieve catalyst has more activated centres, better catalytic
Can, it is more advantageous to reactant molecule diffusion.Specific synthesized reference " development of monocrystalline Multihollow HTS-3 molecular sieve catalyst ", " stone
Oil refining and chemical industry ".
In the present invention, Zr-MFI molecular sieve refers to hetero atom containing Zr, has MFI structure molecular sieve.Zr-MFI molecular sieve
It is a kind of typical solid Lewis acid catalyst, reacts (Meerwein-Ponndorf-Verley reactions) in MPV
In show good catalytic activity.There is hetero atom containing Zr MFI structure molecular sieve to be metalloid element zirconium incorporation
In MFI structure (orthogonal system, mesh straight hole) molecule, ZSM-5, Silicalite-1 etc. common are.
ZSM-5 molecular sieve is prepared referring to the method for patent CN200510029462.7.
Silicalite-1 molecular sieve is prepared referring to the method for patent CN201010220796.3.
It is preferred that halogen alcoholization reaction carries out in the bubble tower type or turbulent flow tubular reactor of no internal component, reaction pressure
It can be for higher than normal pressure, or normal pressure or close to normal pressure.Such as temperature is 0~60 DEG C, the conversion ratio of propylene reaches 97%,
Hydrogen peroxide substantially completely converts.
Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam enters from tower bottom and makes to give birth to
At 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 designs and the key problem in technology of operation is to be sufficiently mixed and control pH with lye into the halogen aqueous propanol solution before saponification column,
Flow out the propylene oxide generated from tower top as early as possible.
Since traditional chlorohydrination technique is saponified using lime, all chlorine is finally with CaCl2Form consumption, generate a large amount of
Containing CaCl2With the sewage of organic chloride.Calculation shows that every production 1t propylene oxide, about generation 2.1t CaCl2Waste residue and extremely
Few 43t waste water.The present invention uses the hydroxide (such as sodium hydroxide, potassium hydroxide, lithium hydroxide) of alkali metal, saponification process
The salt applied afterwards can be reduced into the hydroxide and hydrogen halides of alkali metal, fully achieve circulation by bipolar membrane electrodialysis
It utilizes.
(1) reaction system combined using tubular reactor with tower reactor mitigates the load of chlorohydrination tower.
(2) saponification column decompression operation, steam consumption are few.
(3) tower and rectifying column are evaporated before rectification working process setting, propylene oxide and the production of production propylene glycol is made in 2 towers respectively
The propylene oxide of polyethers.
(4) nemamort in the waste water that saponification process generates, drop are separated by the scattered tower with special tower tray
Biological oxygen content, chemical oxygen content in low waste liquid.
In the prior art, halogenohydrin method prepares the process (by taking chlorine as an example) of propylene oxide:
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 (by taking hydrogen chloride as an example) that a kind of novel halogenohydrin method prepares propylene oxide:
CH3CH=CH2+HCl+H2O2——CH3CH(Cl)-CH2(OH)+CH3CH(OH)-CH2(Cl)
+H2(catalyst is added) in O
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) becomes NaOH (KOH, LiOH) and HCl by bipolar membrane electrodialysis.
The hydroxide and hydrogen halides of alkali metal after bipolar membrane electrodialysis can be recycled.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, it is usually hydrophilic by cation exchange layer (N-type film), interface
Layer (Catalytic Layer) and anion exchange layer (p-type film) are combined, and are reaction films truly.It is acted in DC electric field
Under, hydrolytic dissociation can be respectively obtained hydrogen ion and hydroxide ion in film two sides by Bipolar Membrane.Using this feature, by Bipolar Membrane
The bipolar membrane electrodialysis system being combined into other anion and cation exchange membranes, can will be water-soluble in the case where not introducing new component
Salt in liquid is converted into corresponding bronsted lowry acids and bases bronsted lowry, and this method is known as bipolar membrane electrodialysis method.
It is not particularly limited for the bipolar membrane electrodialysis equipment in the application.It is preferable, however, that using such a
Bipolar membrane electrodialysis equipment, it includes: the 1) film being made of Bipolar Membrane, cavity block, anode membrane, partition, pole plate as core component
Heap and 2) ancillary equipment, the ancillary equipment include water pot, flowmeter, pump, pipeline etc..Ancillary equipment includes rectifier cabinet.Core
The frame of stainless steel structure is used in component.The quantity of film and partition can according to specific treating capacity (volume of salting liquid) and
It is fixed.
Bipolar membrane, one kind of electric drive film, main function are that H+ ion and OH-ion are provided under electric field force, film
Side is the back, and the other side is sunny side, and the middle layer of the back and sunny side is water layer, under the action of applying direct current electric field power, water
H in layer2O splits into H+ ion and OH-ion, and is migrated respectively by sunny side and the back to two sides theme solution, so double
The effect of Polar Crystal Slab is to provide H+ ion and OH-ion source under electric field force effect.
When in the present invention, using bipolar membrane electrodialysis treatment brine waste, corresponding bronsted lowry acids and bases bronsted lowry is obtained.
Advantages of the present invention:
In the prior art, propylene oxide is produced using halogenohydrin method, generates a large amount of chloride containing calcium (or sodium chloride) waste water, given up
It is also thorough containing not separating also containing the raw material organic matter or intermediate product organic matter not reacted completely in reaction process in water
Propylene oxide, these debirs are difficult to degrade, and deal with extremely difficult, and never find effective processing side
Method.The main reason for disabling chlorohydrination technique of U.S. 2000 is exactly calcium chloride (or the chlorine containing the organic matter waste for being difficult to degrade
Change sodium) waste water is difficult to handle.The waste water that someone is generated using electrolysis method processing chlorohydrination technique, due to containing organic waste in waste water
Object, deals with extremely difficult, and the debirs in waste water are very sensitive to electrolysis with ion-exchange film system, damage electrolysis installation
It is larger；Meanwhile electrolysis wastewater needs to consume a large amount of energy, the benefit of acquisition is little；The biggest problems are that: electrolysis wastewater produces
Raw chlorine and hydrogen, organic matter there are the case where, it is abnormally dangerous, be easy explosion.
The present invention uses bipolar membrane electrodialysis technology, and bipolar membrane electrodialysis technology is the technology of a processing salt, and salt passes through
Bipolar membrane electrodialysis generates bronsted lowry acids and bases bronsted lowry.Someone is by bipolar membrane electrodialysis treatment sodium chloride-containing waste water before, but never
There is the production technology that bipolar membrane electrodialysis is applied to propylene oxide.Intrinsic prejudice, halogenohydrin method prepare the useless of propylene oxide
Containing the debirs for being difficult to degrade in water, common debirs are very sensitive to ionic membrane, and treatment effect is very poor.Inventor's warp
It crosses and explores and test many times, discovery bipolar membrane electrodialysis treatment halogenohydrin method prepares the waste water excellent of propylene oxide, halogenohydrin
The waste water containing debirs that method prepares propylene oxide generation does not influence the technique of bipolar membrane electrodialysis, can be very good to locate
Manage the salt in waste water.The present invention cleverly prepares the characteristics of propylene oxide generates useless Organic substance in water using halogenohydrin method, can be very
The good preparation applied bipolar membrane electrodialysis technology with propylene oxide, may be implemented clean manufacturing, solves halogenohydrin method and prepare ring
The reluctant problem of waste water that Ethylene Oxide generates.Waste water handling problem is captured, halogenohydrin method prepares the advantage of propylene oxide just
Quite obvious, less investment, high conversion rate is easy to control.Therefore, present invention introduces bipolar membrane electrodialysis technologies to have overturned traditional halogen
The method that alcohol method prepares propylene oxide the problem of completely solving 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 generates just can be used as raw material again and be applicable in,
So as to form circulation, realizes cleaning, circulation, produced without waste.Original waste is become into present raw material, saves material
While, the discharge of waste is reduced, environment is protected.
Compared with electrolysis process, the energy of bipolar membrane electrodialysis consumption greatly reduces, and effect gets a promotion instead.Together
When, bipolar membrane electrodialysis produces bronsted lowry acids and bases bronsted lowry, and dangerous property is not present, and overcomes electrolysis process danger, is easy the problem of explosion.Most
Importantly, electrolysis process handles waste water, the foreign organic matter in waste water can not be handled, can only be discharged, and this kind of organic
Waste is difficult to degrade, and greatly pollutes environment；And bipolar membrane electrodialysis treatment waste water, the foreign organic matter in waste water can restore
At raw material or product is directly obtained, so that the debirs in waste water have also been handled while handling salt in waste water, by organic waste
Object becomes raw material or product, takes full advantage of material, while waste zero-emission may be implemented, and protects environment well.
Compared with prior art, technical solution of the present invention has following advantageous effects:
1, overcome the problems, such as the by-product (chlorine, calcium chloride, side reaction product) of the prior art: 1. without using Cl2For raw material,
It avoids because of Cl2Lasting consumption the trace oxygen in chlorine can be made constantly to accumulate caused by explosion danger；2. without Cl2It participates in
Reaction greatly reduces intermediate addition side reaction, reduces the generation of organic by-products；3. in saponification process, base amount is big
Big reduction, only 1/2 or so of original process.
2, the prior art is to reduce the generation of side reaction, prepare halogen propyl alcohol concentration can only generally control 4.5% with
Under；And new halogenohydrin method technique of the invention, since side reaction is few, the concentration of halogen propyl alcohol is unrestricted.1) saponification process is saved
Energy consumption, only 1/10 or so of original process；2) saving water resource, the 1/10 of water consumption deficiency original process；Meanwhile it greatly reducing
The discharge of wastewater flow rate, and the waste water is easily handled.
3, using bipolar membrane electrodialysis technology, handle while containing organic wastewater, the NaOH (KOH, LiOH) of generation and
HCl is reusable.
4, catalyst of the invention first passes through sour processing, improves the catalytic performance of catalyst and improves the suitable of catalyst
Use the service life.
Detailed description of the invention
Fig. 1 is bipolar membrane electrodialysis artwork of the present invention；
Fig. 2 is bipolar membrane working principle diagram of the present invention.
Appended drawing reference: 1,2,3: mixing vessel.
Specific embodiment
Below by embodiment, the present invention will be further described, but content not thereby limiting the invention.
Qualitative analysis is carried out to product using Agilent 7890/5975C-GC/MSD type gas chromatography-mass spectrometry,
Quantitative analysis is carried out to product using Agilent 6890N type gas chromatograph and external standard method.
According to detection and analysis as a result, defining following objective function as inspection target.
Propylene conversion:
Halogen propyl alcohol selectivity:
Halogen propyl alcohol yield: YHalogen propyl alcohol=CPropylene×SHalogen propyl alcohol
Propylene oxide yield:
In formula, C is conversion ratio, and S is selectivity, and Y is yield, and n is the amount of substance after reaction, n0For the amount of parent material.
Bipolar membrane electrodialysis equipment is as depicted in figs. 1 and 2.
Bipolar membrane electrodialysis equipment, it includes: 1) as core component by Bipolar Membrane, cavity block, anode membrane, partition, pole plate
The membrane stack of composition and 2) ancillary equipment, the ancillary equipment include water pot, flowmeter, pump, pipeline etc..Ancillary equipment includes whole
Flow cabinet.The frame of stainless steel structure is used in core component.The quantity of film and partition can according to specific treating capacity (salting liquid
Volume) depending on.
Bipolar membrane, one kind of electric drive film, main function are that H+ ion and OH-ion are provided under electric field force, film
Side is the back, and the other side is sunny side, and the middle layer of the back and sunny side is water layer, under the action of applying direct current electric field power, water
H2O in layer splits into H+ ion and OH-ion, and is migrated respectively by sunny side and the back to two sides theme solution, so double
The effect of Polar Crystal Slab is to provide H+ ion and OH-ion source under electric field force effect.
The performance indicator of Bipolar Membrane is as follows:
* in 0.5Mol Na2SO4In solution, at 25 DEG C, 10-100mA/cm2It is measured under current density
Embodiment 1
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 1h, then use
Catalyst is dried 6h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and propylene, 45 DEG C at a temperature of carry out chloropharin
Change reaction, wherein the oxydol H of 70wt% concentration2O2, the HCl solution of 35wt% concentration and the flow of propylene three should make
H2O2Molar ratio with HCl and propylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propan-2-ol of 2- chloro propyl- 1-
Mixture.
Comparative example 1
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 1h, then use
Catalyst is dried 6h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) water halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
H2O, chlorine and propylene, 45 DEG C at a temperature of carry out chlorohydrin action, wherein water H2O, chlorine and the flow of propylene three are answered
So that H2The molar ratio of O and chlorine and propylene is about 87:3.6:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propyl- of 2- chloro propyl- 1-
The mixture of 2- alcohol.
Embodiment 2
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 25%, is impregnated 2h, then use
Catalyst is dried 2h in the environment of 50 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) oxydol H of TS-1 molecular sieve, 35wt% concentration halogen alcoholization: is added in tower reactor2O2, 20wt% it is dense
The HCl solution (hydrochloric acid) and propylene of degree, 35 DEG C at a temperature of carry out chlorohydrin action, the wherein matter of TS-1 molecular sieve and propylene
Amount is than being 0.05:1, the oxydol H of 35wt% concentration2O2, the HCl solution of 20wt% concentration and the additional amount of propylene three should make
Obtain H2O2Molar ratio with HCl and propylene is about 66:3.3:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propyl- 2- of 2- chloro propyl- 1-
The mixture of alcohol.
Comparative example 2
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 25%, is impregnated 2h, then use
Catalyst is dried 2h in the environment of 50 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) TS-1 molecular sieve, water H halogen alcoholization: are added in tower reactor2O, chlorine and propylene, 35 DEG C at a temperature of
Chlorohydrin action is carried out, wherein the molar ratio of TS-1 molecular sieve and propylene is 0.05:1, water H2O, the stream of chlorine and propylene three
Amount should make H2The molar ratio of O and chlorine and propylene is about 66:3.3:1.Obtain halogenohydrin, the i.e. pure and mild 1- chlorine of 2- chloro propyl- 1-
For the mixture of propan-2-ol.
Comparative example 3
1) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and propylene, 45 DEG C at a temperature of carry out chloropharin
Change reaction, wherein the oxydol H of 70wt% concentration2O2, the HCl solution of 35wt% concentration and the flow of propylene three should make
H2O2Molar ratio with HCl and propylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propan-2-ol of 2- chloro propyl- 1-
Mixture.Wherein, embodiment 1 of the synthetic method of TS-1 referring to CN201410812216.8.
Comparative example 4
1) oxydol H of 70wt% concentration halogen alcoholization: is added in tubular reactor2O2, 35wt% concentration HCl solution
(hydrochloric acid) and propylene, 45 DEG C at a temperature of carry out chlorohydrin action, the wherein oxydol H of 70wt% concentration2O2, 35wt% it is dense
The HCl solution of degree and the flow of propylene three should make H2O2Molar ratio with HCl and propylene is about 1.2:1.2:1.Obtain halogen
Alcohol, the i.e. mixture of the pure and mild 1- chloro propan-2-ol of 2- chloro propyl- 1-.
Comparative example 5
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 2h, then use
Catalyst is dried 2h in the environment of 50 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
The HCl solution (hydrochloric acid) and propylene of 35wt% concentration, 45 DEG C at a temperature of carry out chlorohydrin action, wherein 35wt% concentration
The flow of both HCl solution and propylene should make the molar ratio of HCl and propylene be about 1.2:1.
Embodiment 3
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 36%, is impregnated 1h, then use
Catalyst is dried 6h in the environment of 40 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) it halogen alcoholization: is added in tubular reactor (wherein having loaded fixed TS-1 catalyst bed in pipe)
The oxydol H of 70wt% concentration2O2, 35wt% concentration HCl solution (hydrochloric acid) and propylene, 45 DEG C at a temperature of carry out chloropharin
Change reaction, wherein the oxydol H of 70wt% concentration2O2, the HCl solution of 35wt% concentration and the flow of propylene three should make
H2O2Molar ratio with HCl and propylene is about 1.2:1.2:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propan-2-ol of 2- chloro propyl- 1-
Mixture.
3) be saponified: the halogenohydrin and sodium hydroxide that step 2) is obtained carry out saponification, separate and obtaining propylene oxide has
Machine phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from tower bottom
Into make generate crude propene oxide from tower top blow out.Saponification temperature is controlled at 60~70 DEG C.
4) electrodialysis: the sodium chloride solution that step 3) is obtained passes through bipolar membrane electrodialysis (I type of TRPB8040-, Beijing
Ting Run membrane technology development corporation, Ltd. produces and sells, and the transmembrane voltage of application is 1.3V, and operating temperature is 20-30 DEG C), it obtains
Sodium hydroxide and HCl.
5) purification of propylene oxide:
The propene oxide crude product obtained in step 3) is subjected to rectifying, obtains the epoxy third of high-purity (99.9wt%)
Alkane.
Embodiment 4
1) catalyst acid is handled: TS-1 molecular sieve being immersed in the hydrochloric acid that mass fraction is 15%, is impregnated 2h, then use
Catalyst is dried 2h in the environment of 50 DEG C by distilled water washing catalyst；Wherein, the synthetic method reference of TS-1
The embodiment 1 of CN201410812216.8.
2) oxydol H of TS-1 molecular sieve, 35wt% concentration halogen alcoholization: is added in tower reactor2O2, 20wt% it is dense
The HCl solution (hydrochloric acid) and propylene of degree, 35 DEG C at a temperature of carry out chlorohydrin action, the wherein matter of TS-1 molecular sieve and propylene
Amount is than being 0.05:1, the oxydol H of 35wt% concentration2O2, the HCl solution of 20wt% concentration and the additional amount of propylene three should make
Obtain H2O2Molar ratio with HCl and propylene is about 1.5:1.1:1.Obtain halogenohydrin, the i.e. pure and mild 1- chloro propyl- 2- of 2- chloro propyl- 1-
The mixture of alcohol.
3) be saponified: the halogenohydrin and sodium hydroxide that step 2) is obtained carry out saponification, separate and obtaining propylene oxide has
Machine phase and sodium chloride solution.Saponification carries out in the tower reactor of steel, and upper design is sieve-plate tower.Steam is from tower bottom
Into make generate crude propene oxide from tower top blow out.Saponification temperature is controlled at 40~50 DEG C.
4) electrodialysis: the sodium chloride solution that step 3) is obtained passes through bipolar membrane electrodialysis, obtains sodium hydroxide and HCl.
5) purification of propylene oxide:
The propene oxide crude product obtained in step 3) is subjected to rectifying, obtains the epoxy third of high-purity (99.9wt%)
Alkane.
Embodiment 5
Embodiment 3 is repeated, catalyst soak is only impregnated into 0.5h in the hydrochloric acid that mass fraction is 60%, uses deionization
Water washing dries 1h at 60 DEG C.
Embodiment 6
Embodiment 3 is repeated, only replaces HCl solution with HBr solution.
Embodiment 7
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of TS-2.TS-2 synthetic method reference
The specific embodiment (only one embodiment) of CN200910013070.X.
Embodiment 8
Embodiment 3 is repeated, fixed Ti-MWW catalyst bed substitution TS- has only been loaded in the pipe of tubular reactor
1 molecular sieve.Embodiment 1 of the Ti-MWW synthetic method referring to CN200710037012.1.
Embodiment 9
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Ti-Beta.
Embodiment 10
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Ti-SBA-15.The synthesis side Ti-SBA-15
Embodiment 1 of the method referring to CN201110211854.0.
Embodiment 11
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-1 molecular sieve.
Embodiment 12
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-2 molecular sieve.
Embodiment 13
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of HTS-3 molecular sieve.
Embodiment 14
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of ZSM-5 molecular sieve.ZSM-5 molecular sieve ginseng
According to the method preparation of embodiment 1-3 in patent 200510029462.7.
Embodiment 15
Embodiment 3 is repeated, only substitutes TS-1 molecular sieve with the catalyst bed of Silicalite-1 molecular sieve.
Method preparation of the Silicalite-1 molecular sieve referring to embodiment 1 in patent 201010220796.3.
Embodiment 16
Embodiment 3 is repeated, only the sodium hydroxide in step (2) is substituted with potassium hydroxide.
Embodiment 17
Repeat embodiment 3, only in step (1) 65wt% concentration oxydol H2O2, 35wt% concentration HCl solution and
The flow of propylene three should make H2O2Molar ratio with HCl and propylene is about 0.8:0.3:1.
Embodiment 18
Repeat embodiment 3, only in step (1) 20wt% concentration oxydol H2O2, 35wt% concentration HCl solution and
The flow of propylene three should make H2O2Molar ratio with HCl and propylene is about 0.9:1.1:1.
Embodiment 19
Embodiment 3 is repeated, only the reaction temperature in step (1) is 20 DEG C, and the residence time is 2 minutes.
Embodiment 20
Embodiment 3 is repeated, only the temperature in step (2) is controlled at 50 DEG C.
1 embodiment 1-20 of table and comparative example 1-4 reaction condition and reaction result
Catalyst amount is that " bed " refers to that catalyst is arranged in the reactor, such as in a manner of fixed catalyst bed
Concatenated multiple reactors, in tubular reactor or micro passage reaction.In catalyst bed, olefinic unsaturated compound with urge
The weight ratio of agent is 1:0.3.
Claims (30)
1. a kind of method for preparing halogen propyl alcohol, comprising the following steps:
(1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；
(2) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, propylene and through step (1) processed catalyst, carry out halogen
Alcoholization reaction and obtain halogen propyl alcohol；
Wherein: the catalyst is one of hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecular sieve or a variety of；
The hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or a variety of；It is described
HTS molecular sieve is one of HTS-1, HTS-2, HTS-3 or a variety of；The Zr-MFI molecular sieve be ZSM-5 and/or
Silicalite-1；Reaction temperature in step (2) is 10-50 DEG C.
2. a kind of method that halogenohydrin method prepares propylene oxide, comprising the following steps:
(1) catalyst acid is handled: by catalyst soak in acid, being washed out catalyst, catalyst is dried；
(2) hydrogen halides, H halogen alcoholization: are added in reaction unit2O2, propylene and through step (1) processed catalyst, carry out halogen
Alcoholization reaction and obtain halogen propyl alcohol；
(3) it is saponified: the hydroxide of the halogen propyl alcohol of step (2) and alkali metal being subjected to saponification, separates and obtains epoxy third
Alkane and halogenated alkali metal salt；
Wherein: the catalyst is one of hetero-atom molecular-sieve containing Ti, HTS molecular sieve, Zr-MFI molecular sieve or a variety of；
The hetero-atom molecular-sieve containing Ti is one of TS-1, TS-2, Ti-MWW, Ti-Beta, Ti-SBA-15 or a variety of；It is described
HTS molecular sieve is one of HTS-1, HTS-2, HTS-3 or a variety of；The Zr-MFI molecular sieve be ZSM-5 and/or
Silicalite-1；Reaction temperature in step (2) is 10-50 DEG C.
3. according to the method described in claim 2, it is characterized by: the method also includes: (4) electrodialysis: step (3) is obtained
The halogenated alkali metal salt obtained passes through bipolar membrane electrodialysis, obtains the hydroxide and hydrogen halides of alkali metal.
4. according to the method in claim 2 or 3, it is characterised in that: the method also includes: the purification of (5) epoxides:
The propylene oxide that step (3) are obtained is by distillation and/or rectifying, the propylene oxide refined.
5. method according to any one of claim 1-3, it is characterised in that: acid is organic acid and/or nothing in step (1)
Machine acid.
6. according to the method described in claim 4, it is characterized by: acid is organic and or inorganic acids in step (1).
7. according to the method described in claim 5, it is characterized by: acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carbon in step (1)
One of acid, chloric acid, acetic acid are a variety of.
8. according to the method described in claim 6, it is characterized by: acid is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carbon in step (1)
One of acid, chloric acid, acetic acid are a variety of.
9. according to claim 1-3, method described in any one of 6-8, it is characterised in that: with distilled water or gone in step (1)
Ion water washing, and/or
Hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
10. according to the method described in claim 4, it is characterized by: step (1) in washed with distilled water or deionized water, and/
Or
Hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
11. according to the method described in claim 5, it is characterized by: step (1) in washed with distilled water or deionized water, and/
Or
Hydrogen halides described in step (2) is one of hydrogen chloride, hydrogen bromide or hydrogen iodide or a variety of.
12. according to claim 1-3, method described in any one of 6-8,10-11, it is characterised in that: in step (2) propylene with
H2O2Molar ratio be 1:0.1-100；And/or
The H2O2Concentration (wt%) be 5-90%.
13. according to the method described in claim 4, it is characterized by: propylene and H in step (2)2O2Molar ratio be 1:0.1-
100；And/or
The H2O2Concentration (wt%) be 5-90%.
14. according to the method for claim 12, it is characterised in that: propylene and H in step (2)2O2Molar ratio be 1:0.5-
50；And/or
The H2O2Concentration (wt%) be 8-80%.
15. according to the method for claim 13, it is characterised in that: propylene and H in step (2)2O2Molar ratio be 1:0.5-
50；And/or
The H2O2Concentration (wt%) be 8-80%.
16. method according to claim 14 or 15, it is characterised in that: propylene and H in step (2)2O2Molar ratio be 1:
0.8-30；And/or
The H2O2Concentration (wt%) be 10-70%.
17. according to claim 1-3, method described in any one of 6-8,10-11,13-15, it is characterised in that: in step (2)
The molar ratio of propylene and hydrogen halides is 1:0.1-100.
18. according to the method described in claim 4, it is characterized by: the molar ratio of propylene and hydrogen halides is 1 in step (2):
0.1-100。
19. according to the method for claim 17, it is characterised in that: the molar ratio of propylene and hydrogen halides is 1 in step (2):
0.5-50；And/or
Reaction temperature in step (2) is 20-45 DEG C.
20. according to the method for claim 18, it is characterised in that: the molar ratio of propylene and hydrogen halides is 1 in step (2):
0.5-50；And/or
Reaction temperature in step (2) is 20-45 DEG C.
21. method described in 9 or 20 according to claim 1, it is characterised in that: the molar ratio of propylene and hydrogen halides in step (2)
For 1:0.8-30.
22. the method according to any one of claim 2,3,6,8,10,13,15,18,20, it is characterised in that: step
(3) molar ratio of halogen propyl alcohol and alkali metal hydroxide is 1:0.1-50 in；And/or
Reaction temperature in step (3) is 0-100 DEG C.
23. according to the method described in claim 4, it is characterized by: halogen propyl alcohol and alkali metal hydroxide rub in step (3)
You are than being 1:0.1-50；And/or
Reaction temperature in step (3) is 0-100 DEG C.
24. according to the method for claim 22, it is characterised in that: halogen propyl alcohol and alkali metal hydroxide in step (3)
Molar ratio is 1:0.5-30；And/or
Reaction temperature in step (3) is 5-90 DEG C.
25. according to the method for claim 23, it is characterised in that: halogen propyl alcohol and alkali metal hydroxide in step (3)
Molar ratio is 1:0.5-30；And/or
Reaction temperature in step (3) is 5-90 DEG C.
26. the method according to claim 24 or 25, it is characterised in that: halogen propyl alcohol and alkali metal hydroxide in step (3)
The molar ratio of object is 1:0.8-20；And/or
Reaction temperature in step (3) is 10-80 DEG C.
27. the method according to any one of claim 2,3,6,8,10,13,15,18,20,23-25, it is characterised in that:
The hydroxide of the alkali metal be sodium hydroxide or one of potassium hydroxide or lithium hydroxide or a variety of, and/or
The halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, sodium iodide, iodate
One of potassium, lithium iodide are a variety of.
28. according to the method described in claim 4, it is characterized by: the hydroxide of the alkali metal is sodium hydroxide or hydrogen
One of potassium oxide or lithium hydroxide are a variety of, and/or
The halogenated alkali metal salt is sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, sodium iodide, iodate
One of potassium, lithium iodide are a variety of.
29. according to claim 1-3, method described in any one of 6-8,10-11,13-15,18-20,23-25,28, special
Sign is: the reaction unit in the step (2) is single reactor, concatenated multiple reactors, tubular reactor or micro- logical
One of road reactor is a variety of；And/or
Wherein the reaction in step (2) is carried out according to intermittent, semi continuous or continuous mode.
30. according to the method described in claim 4, it is characterized by: the reaction unit in the step (2) is single reaction
One of device, concatenated multiple reactors, tubular reactor or micro passage reaction are a variety of；And/or
Wherein the reaction in step (2) is carried out according to intermittent, semi continuous or continuous mode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414976A (en) * | 1971-12-07 | 1975-11-26 | Degussa | Production of chloro-and bromo-hydrins |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1414976A (en) * | 1971-12-07 | 1975-11-26 | Degussa | Production of chloro-and bromo-hydrins |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
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