CN108395418A - A kind of technique that chloropropene Direct Epoxidation prepares epoxychloropropane - Google Patents
A kind of technique that chloropropene Direct Epoxidation prepares epoxychloropropane Download PDFInfo
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- CN108395418A CN108395418A CN201810316178.5A CN201810316178A CN108395418A CN 108395418 A CN108395418 A CN 108395418A CN 201810316178 A CN201810316178 A CN 201810316178A CN 108395418 A CN108395418 A CN 108395418A
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- chloropropene
- epoxychloropropane
- water
- hydrogen peroxide
- direct epoxidation
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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
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Abstract
The present invention relates to the techniques that a kind of chloropropene Direct Epoxidation prepares epoxychloropropane, and more particularly to a kind of chloropropene in the presence of modified heteropoly acid solid-supported catalyst, using hydrogen peroxide as oxygen source, Direct Epoxidation prepares the process route of epoxychloropropane.The technique main advantage is that:1. the ratio of chloropropene and hydrogen peroxide is low, chloropropene dosage is few;2. reaction and separation process coupling, save equipment, process is simple;3. avoid epoxychloropropane in acid condition, the side reaction hydrolyzed with water, epoxychloropropane yield and high selectivity.
Description
Technical field
The present invention relates to the techniques that a kind of chloropropene Direct Epoxidation prepares epoxychloropropane, more particularly to one kind
For chloropropene in the presence of modified heteropoly acid solid-supported catalyst, using hydrogen peroxide as oxygen source, Direct Epoxidation prepares epoxy chloropropionate
The process route of alkane.
Background technology
Epoxychloropropane is a kind of important petrochemicals, mainly for the production of epoxy resin and synthetic glycerine.Mesh
The industrial preparative method of preceding epoxychloropropane mainly has acetate propylene ester process, propylene method and a glycerine method, wherein propylene method be divided into for
Chlorohydrination and Direct Epoxidation method.Acetate propylene ester process, glycerine method and chlorohydrination are all first to generate dichlorohydrin, then pass through soap
Change cyclization and generate epoxychloropropane, both techniques can all bring the waste water of a large amount of chloride containing calcium, more and more inadaptable green
The thinking of development of chemistry.In order to solve the problems, such as that a large amount of brine wastes, scientists study are prepared with chloropropene Direct Epoxidation
Epoxychloropropane, common catalyst mainly have Titanium Sieve Molecular Sieve and heteropoly acid salt compounds.
CN1769277A discloses a kind of epichlorohydrin production process, using Titanium Sieve Molecular Sieve as catalyst, to a kind of spy
In different rotating bed with helix channel or rotary packed bed supergravity reactor simultaneously be continuously added to liquid phase or gas phase chloropropene and
Hydrogen peroxide directly carries out epoxidation reaction and prepares epoxychloropropane.
Carlo Venturello in 1985 et al. propose one kind [PW4O24]3-Type quaternary ammonium salt phosphorus heteropoly tungstic acid catalyzer
Preparation method, and reported for the first time using hydrogen peroxide as oxygen source in 1988, Catalyzed by Phosphotungstic Acid chloropropene Direct Epoxidation
Reaction prepares epoxychloropropane, [the R of heteropoly acid in reaction process4N+]3{PO4[WO(O2)2]4}3-For catalytic active species, benzene is
Solvent reacts 2.5h, and the yield of epoxychloropropane is 85%.1988, Japanese Yasutaka Ishii were in J.Org.Chem.
On have studied in detail application of the phosphorus heteropoly tungstic acid catalyzer of different quaternary ammonium salts modification in terms of catalyst double bond epoxidation, simultaneously
Reaction mechanism is proposed, i.e., be catalyst is undissolved solid before reaction, is dissolved in instead due to the effect of hydrogen peroxide in reaction
System is answered to carry out homogeneous catalytic reaction;When hydrogen peroxide exhausts, catalyst can be precipitated from reaction system again, can be with by separation
It recycles.Later Chinese patent CN101205219, CN10104571 and CN100532371 are each provided with phosphorus within 2000
Heteropoly tungstic acid quaternary ammonium salt is catalyst, and hydrogen peroxide is oxygen source, the process of preparing epichlorohydrin by chloropropene epoxidation, difference
Having studied hydrogen peroxide concentration, solvent type and auxiliary agent type etc. overcomes water phase to there is the adverse effect brought to epoxidation reaction.
So far nearly 30 years in 1988, document and the patent for studying transition metal heteropoly acid are relatively more, but disclosed report
Substantially without the industrialized example of realization in road.It is following insufficient existing for existing preparing epichlorohydrin by chloropropene epoxidation technique:
1. using Titanium Sieve Molecular Sieve as the technique of catalyst preparation epoxychloropropane, the overwhelming majority need to use methanol, methanol one side conduct
Solvent, another aspect activated catalyst;And catalyst need to often regenerate use;2. using phosphorus heteropoly tungstic acid as catalyst preparation epoxy
The molar ratio of the technique of chloropropane, chloropropene and hydrogen peroxide is 4:1 or more, dosage is larger;3. reacting the epoxychloropropane of generation
In acid condition, it is easily hydrolyzed in water phase, epoxychloropropane yield and selectivity be not high.
Invention describes in a kind of modified heteropoly acid solid-supported catalyst, chloropropene and hydrogen peroxide Direct Epoxidation system
The technique of standby epoxychloropropane.The technique main advantage is that:1. the ratio of chloropropene and hydrogen peroxide is low, chloropropene dosage
It is few;2. reaction and separation process coupling, save equipment, process is simple;3. avoiding epoxychloropropane in acid condition, sent out with water
The side reaction of unboiled water solution, epoxychloropropane yield and high selectivity.
Invention content
The first technical problem to be solved by the present invention is to provide a kind of chloropropene in the presence of a catalyst, is with hydrogen peroxide
Oxygen source, the method that Direct Epoxidation prepares epoxychloropropane, this method have the ratio of chloropropene and hydrogen peroxide low, and chloropropene is used
It measures low;Reaction and separation process coupling, avoid epoxychloropropane in acid condition, the side reaction hydrolyzed with water, epoxy
The advantages that chloropropane yield and high selectivity.
To achieve the object of the present invention, the present invention uses following experimental method:In decompression system, with metering pump by certain
Air speed chloropropene is pumped into from bottom in the fixed bed reactors equipped with modified heteropoly acid solid-supported catalyst, hydrogen peroxide with
Chloropropene is pumped into fixed bed reactors by certain molar ratio from top, is reacted under certain temperature and pressure;While reaction,
System, glycerine monochlorohydrin and another part water is stripped off from reactor in chloropropene, epoxychloropropane and water at the top of reactor
Bottom go out system;Top reaction solution grease layering, measures composition, after water layer is incorporated to bottom reaction solution postcooling after oil reservoir cooling
Composition is measured, hydrogen peroxide conversion ratio, epoxychloropropane and glycerine monochlorohydrin yield, epoxychloropropane selectivity and hydrogen peroxide are calculated
Utilization rate.
Chloropropene and hydrogen peroxide of the present invention are 0.85~2.00 by certain molar ratio:1, preferably 0.95~
1.50:1;
Chloropropene feedstock quality air speed of the present invention is 1.5~10.0h-1, preferably 3.0~6.0h-1;
Reaction temperature of the present invention is 30~90 DEG C, preferably 40~80 DEG C;Decompression system vacuum degree is 5~65kPa,
It is preferred that 20~60kPa.
Description of the drawings
Fig. 1 is reacting flow chart of the present invention.
Specific implementation mode
Illustrate technical scheme of the present invention with specific example below, but the scope of the present invention is not limited thereto.
Embodiment 1
By air speed it is 8.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.10 are pumped into fixed bed reactors from top, at 30 DEG C
It is to be reacted under 5KPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped off at the top of reactor
System, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, after oil reservoir cooling
Group becomes chloropropene 26.1%, epoxychloropropane 73.5% and water 0.4%, and group becomes after water layer is incorporated to bottom reaction solution postcooling
Hydrogen peroxide 0.5%, epoxychloropropane 1.5%, glycerine monochlorohydrin 3.4% and water 94.6%, hydrogen peroxide conversion ratio are 99.0%, ring
Oxygen chloropropane and glycerine monochlorohydrin yield are respectively 69.0% and 2.1%, epoxychloropropane is selectively 97.1% and hydrogen peroxide
Utilization rate is 71.7%.
Embodiment 2
By air speed it is 4.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.20 are pumped into fixed bed reactors from top, at 60 DEG C
It is to be reacted under 20kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir cooling
Group becomes chloropropene 11.4%, epoxychloropropane 88.1% and water 0.5% afterwards, and water layer forms after being incorporated to bottom reaction solution postcooling
For hydrogen peroxide 0.4%, epoxychloropropane 1.3%, glycerine monochlorohydrin 4.5% and water 93.8%, hydrogen peroxide conversion ratio is 99.2%,
Epoxychloropropane and glycerine monochlorohydrin yield are respectively 89.7% and 2.7%, epoxychloropropane is selectively 97.0% and dioxygen
Water use efficiency is 93.2%.
Embodiment 3
By air speed it is 10.0h with metering pump-1Chloropropene is pumped into from bottom and is urged equipped with the modified heteropoly acid of self-control is immobilized
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:0.90 is pumped into fixed bed reactors from top, 60
DEG C and system vacuum degree be 15kPa under react;While reaction, the top vapour of chloropropene, epoxychloropropane and water from reactor
It is proposed system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir are cold
But group becomes chloropropene 21.9%, epoxychloropropane 77.5% and water 0.6% afterwards, and water layer is incorporated to group after the reaction solution postcooling of bottom
As hydrogen peroxide 0.3%, epoxychloropropane 1.6%, glycerine monochlorohydrin 5.4% and water 92.7%, hydrogen peroxide conversion ratio is
99.4%, epoxychloropropane and glycerine monochlorohydrin yield are respectively 59.7% and 3.3%, epoxychloropropane is selectively 94.8%
It is 63.4% with dioxygen water use efficiency.
Embodiment 4
By air speed it is 6.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.50 are pumped into fixed bed reactors from top, at 50 DEG C
It is to be reacted under 15kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir cooling
Group becomes chloropropene 21.9%, epoxychloropropane 77.5% and water 0.6% afterwards, and water layer forms after being incorporated to bottom reaction solution postcooling
For hydrogen peroxide 0.5%, epoxychloropropane 1.8%, glycerine monochlorohydrin 4.1% and water 93.6%, hydrogen peroxide conversion ratio is 99.0%,
Epoxychloropropane and glycerine monochlorohydrin yield are respectively 84.9% and 2.5%, epoxychloropropane is selectively 97.2% and dioxygen
Water use efficiency is 88.3%.
Embodiment 5
By air speed it is 3.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:2.00 are pumped into fixed bed reactors from top, at 90 DEG C
It is to be reacted under 60kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir cooling
Group becomes chloropropene 46.4%, epoxychloropropane 52.9% and water 0.7% afterwards, and water layer forms after being incorporated to bottom reaction solution postcooling
For hydrogen peroxide 0.1%, epoxychloropropane 1.1%, glycerine monochlorohydrin 7.3% and water 91.5%, hydrogen peroxide conversion ratio is 99.8%,
Epoxychloropropane and glycerine monochlorohydrin yield are respectively 89.6% and 4.4%, epoxychloropropane is selectively 95.3% and dioxygen
Water use efficiency is 94.2%.
Embodiment 6
By air speed it is 2.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.30 are pumped into fixed bed reactors from top, at 80 DEG C
With reacted under normal pressure;While reaction, system, a chlorine third is stripped off in chloropropene, epoxychloropropane and water at the top of reactor
Glycol and another part water go out system from the bottom of reactor;Top reactant grease layering, group becomes chlorine third after oil reservoir cooling
Alkene 15.9%, epoxychloropropane 83.3% and water 0.8%, group becomes hydrogen peroxide after water layer is incorporated to bottom reaction solution postcooling
0.1%, epoxychloropropane 1.2%, glycerine monochlorohydrin 6.4% and water 92.3%, hydrogen peroxide conversion ratio are 99.8%, epoxy chloropropionate
Alkane and glycerine monochlorohydrin yield are respectively 91.8% and 3.9%, epoxychloropropane is selectively 95.9% and dioxygen water use efficiency
It is 95.8%.
Embodiment 7
By air speed it is 3.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.10 are pumped into fixed bed reactors from top, at 60 DEG C
It is to be reacted under 20kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir cooling
Group becomes chloropropene 3.1%, epoxychloropropane 96.5% and water 0.4% afterwards, and water layer forms after being incorporated to bottom reaction solution postcooling
For hydrogen peroxide 0.2%, epoxychloropropane 1.7%, glycerine monochlorohydrin 4.8% and water 93.3%, hydrogen peroxide conversion ratio is 99.6%,
Epoxychloropropane and glycerine monochlorohydrin yield are respectively 90.3% and 2.9%, epoxychloropropane is selectively 96.9% and dioxygen
Water use efficiency is 93.6%.
Embodiment 8
By air speed it is 4.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:1.20 are pumped into fixed bed reactors from top, at 70 DEG C
It is to be reacted under 40kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;500h is run altogether, and catalyst activity is stablized.
Top reactant grease layering, group becomes chloropropene 9.6%, epoxychloropropane 89.9% and water 0.5%, water layer after oil reservoir cooling
Group becomes hydrogen peroxide 0.3%, epoxychloropropane 1.3%, glycerine monochlorohydrin 5.4% and water after being incorporated to bottom reaction solution postcooling
93.0%, hydrogen peroxide conversion ratio is 99.4%, epoxychloropropane and glycerine monochlorohydrin yield is respectively 91.5% and 3.3%, ring
Oxygen chloropropane selectivity is 96.5% and dioxygen water use efficiency is 95.3%.
Embodiment 9
With metering pump, by air speed, to be 3.0h-1 be pumped into chloropropene from bottom urges equipped with the modified heteropoly acid of self-control is immobilized
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:0.85 is pumped into fixed bed reactors from top, 50
DEG C and system vacuum degree be 50kPa under react;While reaction, the top vapour of chloropropene, epoxychloropropane and water from reactor
It is proposed system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir are cold
But group becomes epoxychloropropane 99.6% and water 0.4% afterwards, and group becomes hydrogen peroxide after water layer is incorporated to bottom reaction solution postcooling
0.3%, epoxychloropropane 1.8%, glycerine monochlorohydrin 0.5% and water 97.4%, hydrogen peroxide conversion ratio are 99.4%, epoxy chloropropionate
Alkane and glycerine monochlorohydrin yield are respectively 77.2% and 0.3%, epoxychloropropane is selectively 99.6% and dioxygen water use efficiency
It is 77.9%.
Embodiment 10
By air speed it is 3.0h with metering pump-1Chloropropene is pumped into from bottom equipped with the modified heteropoly acid solid-based catalysis of self-control
In the fixed bed reactors of agent, hydrogen peroxide and chloropropene in molar ratio 1:0.99 is pumped into fixed bed reactors from top, at 60 DEG C
It is to be reacted under 20kPa with system vacuum degree;While reaction, chloropropene, epoxychloropropane and water are stripped from the top of reactor
Go out system, glycerine monochlorohydrin and another part water go out system from the bottom of reactor;Top reactant grease layering, oil reservoir cooling
Group becomes chloropropene 0.1%, epoxychloropropane 99.5% and water 0.4% afterwards, and water layer forms after being incorporated to bottom reaction solution postcooling
For hydrogen peroxide 0.5%, epoxychloropropane 1.9%, glycerine monochlorohydrin 5.7% and water 91.9%, hydrogen peroxide conversion ratio is 99.1%,
Epoxychloropropane and glycerine monochlorohydrin yield are respectively 87.3% and 3.3%, epoxychloropropane is selectively 96.3% and dioxygen
Water use efficiency is 91.5%.
Claims (7)
1. a kind of method that chloropropene Direct Epoxidation prepares epoxychloropropane, which is characterized in that in decompression system, with metering
Chloropropene is pumped into from bottom in the fixed bed reactors equipped with modified heteropoly acid solid-supported catalyst by pump by certain air speed, double
Oxygen water is pumped into fixed bed reactors by certain molar ratio with chloropropene from top, is reacted under certain temperature and pressure;Reaction
While, chloropropene, epoxychloropropane and water be stripped off at the top of reactor system, glycerine monochlorohydrin and another part water from
The bottom of reactor goes out system;Top reaction solution grease layering, measures composition, after water layer is incorporated to bottom reaction solution after oil reservoir cooling
Composition is measured after cooling.
2. the method that chloropropene Direct Epoxidation according to claim 1 prepares epoxychloropropane, which is characterized in that described
Chloropropene and hydrogen peroxide molar ratio be 0.85~2.00:1.
3. the method that chloropropene Direct Epoxidation according to claim 2 prepares epoxychloropropane, which is characterized in that described
Chloropropene and hydrogen peroxide molar ratio be 0.95~1.50:1.
4. the method that chloropropene Direct Epoxidation according to claim 1 prepares epoxychloropropane, which is characterized in that described
Chloropropene feedstock quality air speed be 1.5~10.0h-1。
5. the method that chloropropene Direct Epoxidation according to claim 4 prepares epoxychloropropane, which is characterized in that described
Chloropropene feedstock quality air speed be 3.0~6.0h-1。
6. the method that chloropropene Direct Epoxidation according to claim 1 prepares epoxychloropropane, which is characterized in that described
Reaction temperature be 30-90 DEG C;Decompression system vacuum degree is 5~65kPa.
7. the method that chloropropene Direct Epoxidation according to claim 6 prepares epoxychloropropane, which is characterized in that described
Reaction temperature be 40-80 DEG C;Decompression system vacuum degree is 20~60kPa.
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CN201810316178.5A CN108395418A (en) | 2018-04-10 | 2018-04-10 | A kind of technique that chloropropene Direct Epoxidation prepares epoxychloropropane |
PCT/CN2019/080417 WO2019196681A1 (en) | 2018-04-10 | 2019-03-29 | Process for preparing epichlorohydrin by means of direct epoxidation of chloropropene, modified heteropolyacid immobilized catalyst and preparation method therefor |
JP2021504564A JP7061227B2 (en) | 2018-04-10 | 2019-03-29 | Epichlorohydrin production process by direct epoxidation of chloropropene, modified heteropolyacid-supported catalyst and production method |
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WO2019196681A1 (en) * | 2018-04-10 | 2019-10-17 | 江苏扬农化工集团有限公司 | Process for preparing epichlorohydrin by means of direct epoxidation of chloropropene, modified heteropolyacid immobilized catalyst and preparation method therefor |
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JP7061227B2 (en) | 2022-04-27 |
JP2021521272A (en) | 2021-08-26 |
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