CN103880781B - Continuous production method for preparing cyclohexene oxide through cyclohexene oxidation with hydrogen peroxide under normal pressure - Google Patents
Continuous production method for preparing cyclohexene oxide through cyclohexene oxidation with hydrogen peroxide under normal pressure Download PDFInfo
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- CN103880781B CN103880781B CN201210555892.2A CN201210555892A CN103880781B CN 103880781 B CN103880781 B CN 103880781B CN 201210555892 A CN201210555892 A CN 201210555892A CN 103880781 B CN103880781 B CN 103880781B
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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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- 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
Abstract
The present invention discloses a continuous production method for preparing cyclohexene oxide through cyclohexene oxidation with hydrogen peroxide under a normal pressure. According to the continuous production method, a reaction part and a separation part are provided, wherein the reaction part reactor comprises two continuous reactors connected in series and two switchable batch reactors connected in parallel, a quaternary ammonium heteropolyphosphatotungstate is adopted as a catalyst, hydrogen peroxide is adopted as an oxidant, preparation of cyclohexene oxide through cyclohexene oxidation is performed under a normal pressure condition, and the separation part is separating an oil phase and a water catalyst mixture through a separator after completing the reaction, wherein the oil phase is subjected to rectification so as to respectively separate the solvent, cyclohexene and cyclohexene oxide, the water catalyst mixture is filtered through a filter to obtain the catalyst, and the water phase is subjected to rectification to separate cyclohexene and cyclohexene oxide contained in the water phase. With the process, the continuous production of cyclohexene oxide through cyclohexene oxidation with phase transfer catalyst catalysis is achieved, and the whole process has characteristics of simpleness, easy operation and mild reaction condition.
Description
Technical field
The invention belongs to petrochemical industry, under being specifically related to a kind of condition of normal pressure, take hydrogen peroxide as oxygen source, quaternary ammonium salt phosphor-tungstic heteropoly acid is the continuous production processes of catalyst rings hexene epoxy cyclohexane.
Technical background
Epoxy cyclohexane is a kind of important industrial chemicals and intermediate, and its purposes is very extensive, can be used for synthetic epoxy resin, surfactant, agricultural chemicals, sizing agent and macromolecular material etc.
The people such as Xi Zuwei develop reaction control phase transfer catalyst, [Reaction-Controlledphase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide.Science, 2001,292 (5519): 1139 ~ 1141.], the feature embodying homogeneous catalyst is dissolved in reaction system in reaction process, reaction terminates namely to return to initial structure and separates out from reaction system and change heterogeneous catalyst into, is the new catalyst of applicable large-scale industrial application.CN1355067A discloses reaction control phase transfer catalyst for oxidizing reaction and oxidation reaction process thereof.CN1401640A discloses the method that reaction control phase transfer catalyst catalysis epoxidation produces epoxy cyclohexane, and the transformation efficiency of tetrahydrobenzene to hydrogen peroxide reaches 96%, and epoxy cyclohexane is 97% to the selectivity of tetrahydrobenzene.
The CN1161346C reaction-controlled phase transfer catalysis cyclohexene oxide epoxy cyclohexane patent of this seminar invention is for Industrial processes, but production process is intermittent reaction, there is inefficiency, reaction and separation processes process tedious, simplification production technique can not be met, save production cost and realize continuous seepage.
Therefore the present invention is in order to simplify production technique, saving production cost and realize continuous seepage, provides a kind of continuous production processes of normal pressure hydrogen peroxide oxidation tetrahydrobenzene epoxy cyclohexane.
Summary of the invention
The invention provides a kind of continuous production processes of normal pressure hydrogen peroxide oxidation tetrahydrobenzene epoxy cyclohexane, reactive moieties is made up of with two changeable batch reactors in parallel two series connection flow reactors, this device can meet reaction control phase transfer catalyst catalyzed reaction feature, homogeneous catalysis epoxidation is carried out in flow reactor, in batch reactor, make epoxidation carry out completely, the catalyzer oxygen that loses activity is separated out from reaction system, phase-transfer catalysis epoxidation of cyclohexene epoxy cyclohexane continuous prodution process is controlled by the switching realization response of two batch reactors.
Reaction process is normal pressure condensing reflux process, and reaction process heat release can be displaced by normal pressure condensing reflux, and the oxygen produced in reaction process can be discharged by tail gas discharge system.Isolate oil phase and water catalyst mix phase through separator after reaction terminates, oil phase deviates from solvent, tetrahydrobenzene and epoxy cyclohexane respectively through three rectifying.Solvent is deviate from rectifying, the capable of circulation continuation to reactor of tetrahydrobenzene participates in reaction, and rectifying can obtain high-purity epoxy cyclohexane; Water catalyst mix is separated water outlet and catalyzer through catalyst separation system, the tetrahydrobenzene of aqueous phase in the recyclable aqueous phase of rectifying and epoxy cyclohexane, isolated catalyzer is capable of circulation is be made up of with two changeable batch reactors in parallel two series connection flow reactors to continuing to participate in reactive moieties reactor during reactor converges, take quaternary ammonium salt phosphor-tungstic heteropoly acid as catalyzer, take hydrogen peroxide as oxygenant, carry out cyclohexene oxide in atmospheric conditions and prepare epoxy cyclohexane.Oil phase and water catalyst mixture is isolated through separator after reaction terminates, oil phase isolates solvent, tetrahydrobenzene, epoxy cyclohexane respectively through rectifying, water catalyst mixture leaches catalyzer through strainer, and aqueous phase goes out the tetrahydrobenzene and epoxy cyclohexane that contain in aqueous phase through rectifying separation.
Technical scheme of the present invention is:
Successive reaction part is for be made up of two chain of stirred tanks formula flow reactors, and rhythmic reaction part is made up of two changeable stirred-tank reactors in parallel, and sequential portion reactor and rhythmic reaction partial reaction device are by being composed in series a whole set of reactive moieties.
The reactor head of reactive moieties is provided with atmospheric pressure reflux condensing works and normal pressure tail gas discharge system, and condensing reflux temperature is between 5 ~-5 DEG C, and exhaust emissions enters into surge tank after normal pressure condensing works, then by surge tank emptying after gas meter.
The reactor of reactive moieties is equipped with multistage temperature measuring and control device, pressure detecting system and explosion protection system.
In first step reactor R1, material overflow to the second stage is answered in device R2, and the second stage to answer in device R2 material overflow in third stage R3.
Reactor volume scope is 1 ~ 1000L, first step reactor R1 and second stage reactor R2 volume range are between 1:1 ~ 2, first step reactor R1 and third stage reactor R3 volume ratio scope all between 1:1.5 ~ 5, two third stage reactor R3 volume ratios are 1:1.The molar ratio of tetrahydrobenzene and hydrogen peroxide is 1:1 ~ 10, and the mol ratio of hydrogen peroxide and quaternary ammonium salt phosphor-tungstic heteropoly acid is 100 ~ 1000:1.
Catalyzer is the quaternary ammonium salt phosphor-tungstic heteropoly acid with reaction-controlled phase-transfer feature, and it consists of Q
mpW
po
4+3p, in formula, Q is cationic moiety, with [R
1r
2r
3r
4n
+] represent, wherein R
1, R
2, R
3, R
4c
5~ C
20alkyl, cycloalkyl, the benzyl of straight or branched, or R
1r
2r
3n is pyridine and homologue thereof; 2≤m≤7, p=2,3,4.
The oxygen source hydrogen peroxide concentration used is the aqueous hydrogen peroxide solution of 15 ~ 70%.Stopper is selected from one in 2,6 ditertiary butyl p cresol, 2,6-dinitro-p-cresols, p-ten.-butylcatechol or mixing.
React the solvent that uses and be selected from one in aromatic hydrocarbons, ester class, nitrile, halogenated hydrocarbon solvent or mixed solvent.
Technique provided by the invention achieves Catalyzed By Phase-transfer Catalyst cyclohexene oxide and prepares epoxy hexane continuous seepage, and whole set process is simple, processing ease, and reaction conditions is gentle.
Accompanying drawing explanation
Fig. 1 is the continuous production processes schematic flow sheet of normal pressure hydrogen peroxide oxidation tetrahydrobenzene epoxy cyclohexane.
Wherein in accompanying drawing 1, mark is as follows:
R1-first step reactor; R2-second stage reactor; R3-third stage reactor; E1-tail gas buffer tube 1; E2-tail gas buffer tube 2; E3-tail gas buffer tube 3; T1-tetrahydrobenzene rectifying tower; T2-solvent distillation tower; T3-epoxy cyclohexane rectifying tower; T4-aqueous phase rectifying tower; V1-separator; V2-water-and-oil separator; G1-catalyst separation system.
Embodiment
Below by specific embodiment, the present invention is described further.
Embodiment 1
As shown in Figure 1,35% hydrogen peroxide feed rate is 2kg/h.Tetrahydrobenzene, solvent and catalyst mix slurry feed are 20.5kg/h, in mixed slurry, tetrahydrobenzene feed rate is 5kg/h, and solvent toluene feed rate is 15kg/h, and catalyst charge amount is 0.5kg/h;
Stopper 2,6 ditertiary butyl p cresol add-on be tetrahydrobenzene add-on 100,000/;
First step reactor R1 and the second stage answer the volume ratio of device R2 to be 1:2, and second stage reactor R2 and the third stage answer the volume ratio of device R3 to be 1:1.5, and two third stage reactor volumes are than being 1:1;
Material enters reacting rear material overflow to the second stage in first step reactor R1 and answers continuation reaction in device R2, answers in device R2 form the overflow of homogeneous reaction material in third stage reactor R3 in the second stage.Third stage reactor R3 consists of the batch reactor of two changeable parallel connections, catalyzer is separated out from reaction system at third stage reactor R3, reactor R1, R2, R3 top is provided with atmospheric pressure reflux condensing works and normal pressure tail gas discharge system, condensing reflux temperature is at-5 DEG C, exhaust emissions enters and enters into tail gas buffer E1, tail gas buffer E2, tail gas buffer E3 respectively after normal pressure condensing works, then emptying after cuvette.
Reaction terminates rear material and isolates oil phase and water catalyst mixture through separator V1, oil phase obtains tetrahydrobenzene through tetrahydrobenzene rectifying tower TI rectifying, the capable of circulation continuation to reactor R1 of tetrahydrobenzene participates in reaction, solvent is obtained again through solvent distillation tower T2 rectifying, the capable of circulation continuation to reactor R1 of solvent participates in reaction, eventually passes epoxy cyclohexane rectifying tower T3 rectifying and obtains high purity epoxy cyclohexane.
Water catalyst mixture is separated water outlet and catalyzer through catalyst separation system G1, aqueous phase reclaims tetrahydrobenzene in aqueous phase and epoxy cyclohexane through aqueous phase rectifying tower T4, aqueous phase rectifying tower T4 tower top is by tetrahydrobenzene and water azeotropic extraction tetrahydrobenzene and water mixture, and tetrahydrobenzene and water mixture isolate tetrahydrobenzene and water through water-and-oil separator V2.
Concrete reaction result is in table 1.
Table 1
The present invention includes reactive moieties, separate part.Reactive moieties reactor is be made up of with two changeable batch reactors in parallel two series connection flow reactors, and being catalyzer with quaternary ammonium salt phosphor-tungstic heteropoly acid, take hydrogen peroxide as oxygenant, carries out cyclohexene oxide in atmospheric conditions and prepares epoxy cyclohexane.Separate part is isolate oil phase and water catalyst mixture through separator after reaction terminates, oil phase isolates solvent, tetrahydrobenzene, epoxy cyclohexane respectively through rectifying, water catalyst mixture leaches catalyzer through strainer, and aqueous phase goes out the tetrahydrobenzene and epoxy cyclohexane that contain in aqueous phase through rectifying separation.Technique provided by the invention achieves Catalyzed By Phase-transfer Catalyst cyclohexene oxide and prepares epoxy hexane continuous seepage, and whole set process is simple, processing ease, and reaction conditions is gentle.
Claims (9)
1. a continuous production method for normal pressure hydrogen peroxide oxidation tetrahydrobenzene epoxy cyclohexane, is characterized in that:
Reactive moieties reactor is be made up of with two changeable batch reactors in parallel two series connection flow reactors,
After being series at two series connection flow reactors after the batch reactor parallel connection of two changeable parallel connections;
Be catalyzer with quaternary ammonium salt phosphor-tungstic heteropoly acid, take hydrogen peroxide as oxygenant, carry out cyclohexene oxide in atmospheric conditions and prepare epoxy cyclohexane; Oil phase and water catalyst mixture is isolated through separator after reaction terminates, oil phase isolates solvent, tetrahydrobenzene, epoxy cyclohexane respectively through rectifying, water catalyst mixture leaches catalyzer through strainer, and aqueous phase goes out the tetrahydrobenzene and epoxy cyclohexane that contain in aqueous phase through rectifying separation.
2. in accordance with the method for claim 1, it is characterized in that:
Reaction unit comprises reactive moieties, separate part,
Reactive moieties reactor is be made up of with two changeable batch reactors in parallel, after being series at two series connection flow reactors after the batch reactor parallel connection of two changeable parallel connections two series connection flow reactors;
Separate part comprises separation of oil part and water catalyst mixture separate part, and separation of oil part comprises tetrahydrobenzene rectifying tower, solvent distillation tower, the epoxy cyclohexane rectifying tower of connecting successively; Water catalyst mixture separate part comprises catalyst separation system, the aqueous phase rectifying tower of connecting successively;
Tetrahydrobenzene, catalyzer, hydrogen peroxide, solvent add in first step reactor by the entrance that feeds in raw material, first step reactor lower part or bottom are provided with material inlet, the material outlet on first step reactor top is connected with the entrance of second stage reactor bottom, the material outlet on reactor top, the second stage is connected with the entrance of third stage reactor bottom, and the material outlet on third stage reactor top is connected with the material inlet of separator;
First step reactor and second stage reactor are two series connection flow reactors, third stage reactor is the batch reactor of two changeable parallel connections, atmospheric pressure reflux condensing works is equipped with on first step reactor, second stage reactor, third stage reactor top, atmospheric pressure reflux condensing works top is provided with pneumatic outlet, pneumatic outlet is connected with tail gas buffer material inlet, the outlet of tail gas buffer and a coated lycopene;
The oil phase outlet of separator is connected with material inlet in the middle part of tetrahydrobenzene rectifying tower, and the water catalyst mixture outlet of separator is connected with catalyst separation system entrance; The material outlet of tetrahydrobenzene rectifier bottoms is connected with the material inlet in the middle part of solvent distillation tower, and the material outlet of tetrahydrobenzene rectifier is connected with first step reactor content entrance; The material outlet of solvent distillation tower bottom is connected with the material inlet in the middle part of epoxy cyclohexane rectifying tower, and the material outlet on solvent distillation tower top is connected with first step reactor content entrance; The material outlet of epoxy cyclohexane rectifier bottoms is connected with a rectifying heavy constituent storage tank, and the material outlet on solvent distillation tower top is connected with an epoxy cyclohexane storage tank;
Catalyst outlet bottom catalyst separation system is connected with first step reactor content entrance, the outlet of catalyst separation system aqueous phase is connected with the material inlet in the middle part of aqueous phase rectifying tower, aqueous phase rectifier is connected with a water-and-oil separator material inlet, the oil phase of water-and-oil separator exports a road and is connected with the material inlet of in the middle part of aqueous phase rectifying tower or bottom, another road tetrahydrobenzene outlet is connected with first step reactor content entrance, aqueous phase outlet and a coated lycopene of water-and-oil separator, aqueous phase rectifier bottoms is connected with an epoxy cyclohexane storage tank;
Gas backstreaming condenser is equipped with in tetrahydrobenzene rectifying tower, solvent distillation tower, epoxy cyclohexane rectifying tower, aqueous phase rectifier.
3., according to the method described in claim 1 or 2, it is characterized in that:
The reaction process of reactor is normal pressure condensing reflux process, the reactor head of reactive moieties is provided with atmospheric pressure reflux condensing works and normal pressure tail gas discharge system, condensing reflux temperature is between 5 ~-5 DEG C, exhaust emissions enters into surge tank after normal pressure condensing works, then is entered in cuvette by surge tank.
4., according to the method described in claim 1 or 2, it is characterized in that:
Isolate oil phase and water catalyst mixture through separator after reaction terminates, oil phase deviates from solvent, tetrahydrobenzene and epoxy cyclohexane respectively through three rectifying; Solvent is deviate from rectifying, the capable of circulation continuation to first step reactor of tetrahydrobenzene participates in reaction, and rectifying can obtain pure epoxy cyclohexane; Water catalyst mixture is separated water outlet and catalyzer through separator, and the tetrahydrobenzene of aqueous phase in the recyclable aqueous phase of rectifying and epoxy cyclohexane, the capable of circulation continuation to first step reactor of isolated catalyzer participates in reaction.
5., according to the method described in claim 1 or 2, it is characterized in that:
The reactor of reactive moieties is equipped with multistage temperature measuring and control device, pressure detecting system and explosion protection system.
6., according to the method described in claim 1 or 2, it is characterized in that:
Two series connection flow reactors and the batch reactor of two changeable parallel connections of connecting thereafter, reactor volume scope is 1 ~ 1000L, first step reactor and second stage reactor volume than scope are between 1:1 ~ 2, first step reactor and third stage reactor volume proportional range all between 1:1.5 ~ 5, two third stage reactor volumes are than being 1:1.
7. in accordance with the method for claim 1, it is characterized in that:
In reactor, the molar ratio of tetrahydrobenzene and hydrogen peroxide is 1:1 ~ 10, and the mol ratio of hydrogen peroxide and quaternary ammonium salt phosphor-tungstic heteropoly acid is 100 ~ 1000:1.
8. in accordance with the method for claim 1, it is characterized in that:
Catalyzer is the quaternary ammonium salt phosphor-tungstic heteropoly acid with reaction-controlled phase-transfer feature, and it consists of Q
mpW
po
4+3p, in formula, Q is cationic moiety, with [R
1r
2r
3r
4n
+] represent, wherein R
1, R
2, R
3, R
4c
5~ C
20alkyl, cycloalkyl, the benzyl of straight or branched, or R
1r
2r
3n is pyridine and homologue thereof; 2≤m≤7, p=2,3 or 4;
The oxygen source hydrogen peroxide concentration used is the aqueous hydrogen peroxide solution of 15 ~ 70%.
9. in accordance with the method for claim 1, it is characterized in that:
In reaction system, be added with stopper, stopper is selected from one or two or more kinds mixing in 2,6 ditertiary butyl p cresol, 2,6-dinitro-p-cresols, p-ten.-butylcatechol; The mass ratio of stopper and tetrahydrobenzene is 1:1000 ~ 10000; The solvent that reaction uses is selected from one or two or more kinds mixed solvent in normal hexane, hexanaphthene, benzene, toluene, ethylbenzene, ethyl acetate, trioctyl phosphate, tributyl phosphate, acetonitrile, ethylene dichloride, chloroform solvent; The mass ratio of solvent and tetrahydrobenzene is 1 ~ 100:1.
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| CN112920143A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Reaction device for controlling dehydration in phase transfer catalytic reaction process |
| CN113444058B (en) * | 2020-03-26 | 2023-04-21 | 常州强力先端电子材料有限公司 | Continuous preparation method of alicyclic epoxy compound |
| CN111841644B (en) * | 2020-08-27 | 2022-10-28 | 郑州大学 | Metal-organic complex immobilized phosphotungstic acid catalyst for synthesizing epoxy cyclohexane |
| CN112142689B (en) * | 2020-11-26 | 2021-03-02 | 中化学科学技术研究有限公司 | Method and system for preparing cyclohexene oxide by using cyclohexene |
| CN113717130B (en) * | 2021-10-08 | 2024-04-05 | 中化学科学技术研究有限公司 | Continuous production method of epoxycyclohexane |
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