CN105272938A - Epoxidation cyclic method for preparing epoxy propane from ethylbenzene hydroperoxide and propylene - Google Patents
Epoxidation cyclic method for preparing epoxy propane from ethylbenzene hydroperoxide and propylene Download PDFInfo
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- CN105272938A CN105272938A CN201410353238.2A CN201410353238A CN105272938A CN 105272938 A CN105272938 A CN 105272938A CN 201410353238 A CN201410353238 A CN 201410353238A CN 105272938 A CN105272938 A CN 105272938A
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Abstract
The invention relates to an epoxidation cyclic process for preparing epoxy propane from ethylbenzene hydroperoxide and propylene, and is used for mainly solving the problems in the prior art that reaction temperature rising is higher and higher molar ratio of propylene to ethylbenzene hydroperoxide is needed for maintaining higher reaction efficiency. The problems are better solved through adopting the technical schemes that a raw material ethylbenzene hydroperoxide sectionally goes into at least two series-connection adiabatic reactors and a raw material liquid propylene goes into at least two series-connection adiabatic reactors, and under conditions of the reaction temperature of 15-160 DEG C, the pressure of 1.0-12.0 MPa and the total molar ratio of propylene to ethylbenzene hydroperoxide of 1-20, the raw materials make contact with a Ti-silica catalyst and subjected to an epoxidation reaction to generate epoxy propane, wherein a part of epoxidation reaction products containing epoxy propane circulate to catalyst bed layers of the reactors. The method can be used in industrial production of preparation of epoxy propane through epoxidation of ethylbenzene hydroperoxide and propylene.
Description
Technical field
The present invention relates to the epoxidation circulation means of a kind of hydrogen peroxide ethylbenzene and propylene propylene oxide.
Background technology
Propylene oxide is important basic chemical industry raw material, is the third-largest propylene analog derivative being only second to polypropylene and vinyl cyanide, mainly for the production of polyethers, propylene glycol etc.It is also the main raw material of forth generation washing composition nonionogenic tenside, oil field demulsifier, farm chemical emulgent etc.The derivative of propylene oxide is widely used in the industries such as automobile, building, food, tobacco, medicine and makeup.The derived product of having produced nearly hundred kinds is the important source material of fine chemical product.
The traditional processing technology of propylene oxide is chlorohydrination technique, and process comprises the chlorohydrination of propylene and hypochlorite solution, propylene chlorohydrin and milk of lime saponification and product purification three steps.The feature of this method is that flow process is shorter, and construction investment is few, technical maturity, not high to raw material propylene purity requirement.But owing to using chlorine in production process, produce the waste water of a large amount of chloride containing calcium, have corrosion to equipment, there is serious problem of environmental pollution.
For the problem of environmental pollution that chlorohydrination technique exists, the companies such as Lyondell develop co-oxidation propylene oxide green synthesis process.Conjugated oxidation is divided into Trimethylmethane conjugated oxidation and ethylbenzene conjugated oxidation two kinds of joint process, the former coproduction trimethyl carbinol, the latter's coproduction vinylbenzene, and its basic step is: (1) Trimethylmethane or ethylbenzene oxidation are corresponding superoxide; (2) propylene is produced propylene oxide and corresponding alcohol by superoxide epoxidation; (3) propylene oxide is refined; (4) be converted into can product sold for coproduction alcohol.Compared with chlorohydrination, conjugated oxidation overcomes environmental pollution, the equipment corrosion of chlorohydrination existence and consumes the shortcomings such as chlorine, but this method weak point is that technical process is long, investment cost is high (being about 2 times of chlorohydrination), and a large amount of joint product (joint product output is about 2 ~ 3 times of PO) need be balanced, the economic benefit certain degree of therefore conjugated oxidation depends on the sale of joint product.
To this, many companies are devoted to develop the propylene oxide Green Manufacturing Technology without coproduction.The company such as Degussa and KruppUnde and BASF and Dow is " HPPO " production technology of oxygenant with hydrogen peroxide in cooperative development.This method for raw material, take methyl alcohol as solvent with chemical grade propylene and hydrogen peroxide, adopts tubular reactor, reacts at the temperature and low pressure of gentleness in liquid phase.Hydrogen peroxide transforms completely, and propylene is Quantitative yield almost, only generates propylene oxide and water in production process, unreacting propylene can be used for other process or recycles, and technical process is simple, and product yield is high, there is no other joint product, substantially pollution-free, belong to eco-friendly process for cleanly preparing.The shortcoming of this technique is that hydrogen peroxide consumption is large, and propylene oxide per ton consumes hydrogen peroxidase 10 .7 ton.
SUMITOMO CHEMICAL chemical company develops the conjugated oxidation technique without by-product.This technique adopts isopropyl benzene to substitute Trimethylmethane or ethylbenzene, cumene oxidation is become hydrogen phosphide cumene (CHP), epoxidation of propylene is made to become propylene oxide with CHP again, the dimethyl benzyl alcohol simultaneously obtained can obtain alpha-methyl styrene after dewatering, and then hydrogenation becomes isopropyl benzene for recycling.
Compared with PO/SM co-production method, CHP method is without coproduction chemical, though the market risk because a large amount of by-product of coproduction brings can be reduced, but two kinds of explained hereafter devices, capital construction investments are more or less the same, have the market requirement to obtain countries and regions for propylene oxide and vinylbenzene, PO/SM co-production method generating apparatus economic benefit is better.
Some patents are had to relate to the conjugated oxidation technique of PO/SM co-production method.EP323663 discloses a kind of hydrogen peroxide ethylbenzene and epoxidation of propylene technique, and under the condition of temperature of reaction 100 DEG C, hydrogen peroxide ethylbenzene and propylene enter reactor, with Ti/SiO with the mol ratio of 16.7
2catalyst exposure reacts, and generates propylene oxide, reactor outlet pressure 26bar, and volatile components (as propylene) vaporization absorption epoxidation reaction heat, to maintain the temperature of reaction of reactor.US6153153 discloses a kind of epoxidation processes be made up of multiple adiabatic reaction district, raw material hydrogen peroxide ethylbenzene and propylene are with the mixed in molar ratio of 4.65:1, be divided into the reactant flow that multiple logistics cools each reaction zone respectively, reactor is entered to 80 ~ 107 DEG C with the hot reacting by heating raw material of epoxidation reaction, the outlet reactant decompression vaporization of last reaction zone, reduce temperature, the logistics of vaporization cools the inlet streams of last reaction zone, the temperature rise of each reaction zone keeps 6 ~ 28 DEG C, and reaction pressure is carried out in the liquid phase to keep reaction.US5883268 discloses the treatment process of ethylbenzene oxidation product.Hydrogen peroxide ethylbenzene disclosed in US5849937 and epoxidation of propylene technique and USUS6153153 different, epoxidation reaction is divided into 6 catalytic reaction zones, and wherein last reaction zone is for subsequent use.Raw material hydrogen peroxide ethylbenzene and propylene are divided into the outlet material that four strands of materials cool front four reaction areas respectively, the first reaction zone is entered to 38 ~ 101 DEG C with the hot reacting by heating raw material of epoxidation reaction, reaction zone temperature out 121 DEG C, reaction pressure keeps reaction zone entirety to be liquid phase.When the catalyst activity of the first reaction zone is reduced to a certain degree, close the valve of the turnover pipeline of the first reaction zone, switch out regeneration or replacing that reactive system carries out catalyzer, the 6th reaction zone of simultaneously coming into operation, steady with retaining ring oxidizing reaction.Epoxidation technique disclosed in US5760253, reaction is divided into multiple reaction zone, material between each reaction zone and charging heat exchange, remove the reaction heat of 25 ~ 75%, remaining reaction heat promotes the temperature of reaction mass, and the component that vaporization is easily vaporized, the temperature rise of each reaction zone is generally 20 ~ 100 DEG C.
In existing document or report, how the reaction process problem of shorter mention hydrogen peroxide ethylbenzene and propylene to prepare epoxy propane, particularly effectively reduce reaction temperature rising, the raising propylene of reaction bed and the problem of the mol ratio of hydrogen peroxide ethylbenzene.
Summary of the invention
Technical problem to be solved by this invention is in prior art, it is higher and for keep higher reaction efficiency to need the problems such as the mol ratio of higher propylene and hydrogen peroxide ethylbenzene to there is reaction temperature rising in the reaction process of hydrogen peroxide ethylbenzene and propylene to prepare epoxy propane, the epoxidation circulation technology of a kind of new hydrogen peroxide ethylbenzene and propylene propylene oxide is provided, the method, under the prerequisite of total mol ratio not increasing propylene and hydrogen peroxide ethylbenzene, effectively can reduce reaction temperature rising, improve the reaction propylene of beds and the mol ratio of hydrogen peroxide ethylbenzene.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the epoxidation circulation means of a kind of hydrogen peroxide ethylbenzene and propylene propylene oxide, hydrogen peroxide ethylbenzene and propylene carry out epoxidation reaction and generate product propene oxide under contacting with Ti-SiO 2 catalyst, the product generated is divided into extraction logistics and recycle stream, wherein, hydrogen peroxide ethylbenzene portions is circulated to each reactor inlet with different recycle streams, recycle stream is divided into n or (n-1) individual logistics, multiple series connection adiabatic reactor is divided into N number of, wherein, n be greater than 1 positive integer, N be greater than 1 positive integer, its step comprises:
1) raw material I 1 portions containing hydrogen peroxide ethylbenzene enters the adiabatic reactor being at least two series connection;
2) raw material I a2 of the first part of raw material I 1 namely containing hydrogen peroxide ethyl benzene mixtures is mixed into the first reactor with the raw material II 5 containing propylene and containing the recycle stream I 7 in the epoxidation reaction product of propylene oxide;
3) namely the second section of raw material I 1 contains raw material I b3 and the first reactor outlet product of hydrogen peroxide ethyl benzene mixtures and is mixed into the second reactor containing the recycle stream II 8 in the epoxidation reaction product of propylene oxide;
4) namely the n-th part of raw material I 1 contains raw material I n4 and (n-1) reactor outlet product of hydrogen peroxide ethyl benzene mixtures and is mixed into N reactor containing the recycle stream N9 in the epoxidation reaction product of propylene oxide;
Wherein, epoxidation reaction temperature is 15 ~ 160 DEG C, pressure is 1.0 ~ 12.0MPa, total mol ratio of propylene and hydrogen peroxide ethylbenzene is 1 ~ 20.
In technique scheme, preferably, the extraction logistics of epoxidation reaction product and the part by weight of recycle stream are 0.1 ~ 10.
In technique scheme, preferably, the part by weight of the logistics of epoxidation reaction product circulation and global cycle logistics that enter each catalyst reactor bed is 0.01 ~ 0.99.
In technique scheme, preferably, described multiple series connection adiabatic reactor is made up of 2 ~ 10 reactors in series.More preferably, described multiple series connection adiabatic reactor is made up of 2 ~ 4 reactors in series.
In technique scheme, in the adiabatic reactor of described multiple series connection, beds is single bed and/or multistage bed; Wherein, in each reactor above-mentioned, logistics flows to as upflowing or downflow system.
In technique scheme, the propylene in described raw material II is fresh propylene, the Propylene recovery of follow-up system or its mixture.
In technique scheme, the hydrogen peroxide ethylbenzene in described raw material I obtains with ethylbenzene oxidation, and be the mixture of ethylbenzene, hydrogen peroxide ethylbenzene, hydrogen peroxide ethylbenzene concentration is 5 ~ 65wt%.
In technique scheme, step 2) in, raw material I a2 mixes with the raw material II 5 containing propylene and containing the recycle stream I 7 in the epoxidation reaction product of propylene oxide outward at the first reactor or mixes in the first reactor; Step 3) in enter in the second reactor containing hydrogen peroxide ethyl benzene mixtures raw material I b3, mix with the recycle stream II 8 in the first reactor outlet thing and product outward at the second reactor or mix in the second reactor; Step 4) in enter in N reactor containing hydrogen peroxide ethyl benzene mixtures raw material I n4, mix outward at N reactor with the recycle stream N9 in (n-1) reactor outlet thing and product or mix in N reactor.In technique scheme, described epoxidation reaction is carried out in the liquid phase using solvent.Be liquid under the temperature and pressure of this solvent when reacting, and do not react with reactant and product.Time in raw material I 1 containing hydrogen peroxide ethylbenzene containing ethylbenzene, do not add in solvent technique scheme, preferably, epoxidation reaction temperature is 30 ~ 130 DEG C, and pressure is 1.5 ~ 6.0MPa, total mol ratio of propylene and hydrogen peroxide ethylbenzene is 2 ~ 15.
Epoxidation reaction temperature is generally 15 ~ 160 DEG C, considers economic utilization and the reaction preference of speed of reaction and catalyzer, preferably 30 ~ 130 DEG C.When the temperature is too low, speed of reaction is too low, and the amount therefore obtaining the catalyzer needed for required reacting weight increases.On the contrary, when temperature is too high, selectivity reduces, and catalyst regeneration cycle shortens.Particularly, when the amount of the compound with 4 carbon atoms increases, loss and the energy required when removing compound of valuable constituent increase.Pressure can be enough to keep reaction mixture to be in the pressure of liquid state, is generally 1.0 ~ 12.0MPa, preferential 1.5 ~ 6.0MPa.
The mol ratio propylene of propylene/hydrogen peroxide ethylbenzene and the total mol ratio of hydrogen peroxide ethylbenzene that are supplied to epoxidation step are generally 1 ~ 20, preferential 2 ~ 15, override 3 ~ 12.When this ratio is too low, speed of reaction reduces, and reaction preference is deteriorated, and the yield of object product will reduce.When this ratio is too high, the quantitative change of the propylene of recirculation obtains and excessively increases, and therefore in recycling step, needs many energy, and the energy consumption of device is increased.Method advantage provided by the invention is:
1, the insulation fix bed reaction process of multiple reactors in series is adopted, raw material is divided into multiply material and enters each beds, directly mix with reactant flow, can partly or entirely absorption reaction heat, the temperature of reaction effectively controlling each beds, in suitable scope, ensure that epoxidation reaction is carried out under the temperature of reaction condition of the best.
2, the mol ratio of low propylene and hydrogen peroxide ethylbenzene can more be adapted to.By the ratio of feed product flow and each reactor propylene and hydrogen peroxide ethylbenzene between adjustment tandem reactor quantity, reactor, reach the propylene circulation ratio reducing epoxidation reaction system, reduce energy consumption, reduce the object of investment.
3, adopt the intersegmental cooling of raw material hydrogen peroxide ethylbenzene and and the insulation fix bed reaction process of multiple series connection of epoxidation reaction product section circulation, effectively control reaction temperature rising, improve the propylene ratio of reactor catalyst bed, the selectivity of object product propene oxide can be improved.
4, because reaction temperature rising is lower, can suitably improve reactor inlet temperature of reaction, improve speed of response; Or the temperature of reaction of reactor outlet can be reduced, can reaction pressure be reduced under the condition keeping whole reaction zone in liquid phase.
Owing to adopting the insulation fix bed reaction process of multiple series connection of the intersegmental cooling of raw material hydrogen peroxide ethylbenzene and the circulation of epoxidation reaction product section in the present invention, can partly or entirely absorption reaction heat, effectively control reaction temperature rising, improve the propylene of beds and the ratio of hydrogen peroxide ethylbenzene, ensure that epoxidation reaction is carried out under the reaction conditions of the best, the selectivity of object product propene oxide can be improved.Prove to adopt technical scheme of the present invention through test, the insulation fix bed reaction process of two reactors in series, epoxidised reaction temperature rising is only 11.4 DEG C, lower than 32.1 in comparative example DEG C, under total propylene and hydrogen peroxide ethylbenzene mol ratio are the condition of 11.52, the mol ratio of beds is up to 33.6, and hydrogen peroxide ethylbenzene almost all transforms, the selectivity of object product propene oxide reaches 99.15%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the epoxidation circulation technology of hydrogen peroxide ethylbenzene of the present invention and propylene propylene oxide.
In Fig. 1, 1 is the mixture material I containing hydrogen peroxide ethylbenzene, 2 for entering raw material I a containing hydrogen peroxide ethyl benzene mixtures of the first reactor, 3 for entering raw material I b containing hydrogen peroxide ethyl benzene mixtures of the second reactor, 4 for entering raw material I n containing hydrogen peroxide ethyl benzene mixtures of the n-th reactor, 5 is the raw material II containing propylene, 6 for containing the extraction logistics of the peroxidation reaction product of propylene oxide, 7 for entering the recycle stream I of the peroxidation reaction product of the first reactor, 8 is the recycle stream II of the peroxidation reaction product of the second reactor, 9 is the recycle stream N of the peroxidation reaction product of the n-th reactor, 1a is adiabatic reactor, 2a is the beds of the first reactor, 3a is the beds of the second reactor, 4a is the beds of the n-th reactor, 5a is reactor inlet water cooler.
In Fig. 1, raw material I 1 containing hydrogen peroxide ethyl benzene mixtures is divided into raw material I a2, feedstream I b3, raw material I n4 at the temperature, pressure of regulation, enter the first reactor catalyst bed 2a of liquid-solid phase insulation fix bed reactor 1a, the second reactor catalyst bed 3a, the n-th reactor catalyst bed 4a respectively, propylene feedstocks II 5 enters the first reactor catalyst bed 2a.Propylene and hydrogen peroxide ethylbenzene to contact with Ti-SiO 2 catalyst with certain proportion and carry out epoxidation reaction, epoxidation reaction product is divided into containing the extraction logistics 6 in the reaction product of propylene oxide and recycle stream, wherein, recycle stream is divided into recycle stream I 7, recycle stream II 8, recycle stream N9, loop back first respectively to N reactor inlet, the reaction product stream 6 containing propylene oxide goes follow-up separation and purification unit to carry out separation and purification to obtain qualified product propylene.
Below by embodiment, the present invention is further elaborated.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, the present invention is described with following specific embodiment further, but the present invention is limited to absolutely not these examples.
[embodiment 1]
By the technical scheme shown in Fig. 1, raw material is containing the hydrogen peroxide ethyl benzene mixtures of 19.34% weight concentration, flow is 162367.5 kgs/hr, be divided into two strands in proportion, enter the insulation fix bed reactor of two many bed catalyst of series connection respectively, propylene flow in raw material II 10987.6 kgs/hr, circulation propylene 103863.5 kgs/hr, recycle stream I flow 69304.5 kgs/hr of peroxidation reaction product, mix with the hydrogen peroxide ethyl benzene mixtures entering the first reactor catalyst bed, temperature of reaction 76 DEG C, under the condition of reaction pressure 2.9MPaG, with Ti/SiO
2catalyst exposure, liquid phase epoxidation reaction generates propylene oxide and xylyl alcohol and other by product, the reactant flowing out the first reactor mixes with the hydrogen peroxide ethyl benzene mixtures entering the second reactor, the 115508 kgs/hr of logistics of Cyclic Rings oxidation reaction product, control temperature 76 DEG C, enter the second reactor, with Ti/SiO2 catalyst exposure, liquid phase epoxidation reaction generates propylene oxide and xylyl alcohol and other by product.Hydrogen peroxide ethylbenzene weight air speed 4.1hr
-1the mol ratio of total propylene and hydrogen peroxide ethylbenzene is 11.52, the propylene of the first reactor and the second reactor inlet and the mol ratio of hydrogen peroxide ethylbenzene then reach 33.6 and 31.0, the temperature out of the first reactor and the second reactor is respectively 87.4 DEG C, 86.6 DEG C, the total conversion rate of hydrogen peroxide ethylbenzene is 99.2%, and the molar selectivity of propylene oxide is 99.15%.
[embodiment 2]
With [embodiment 1], only change the flow of recycle stream: circulation propylene flow is 69242.5 kgs/hr, enter the Cyclic Rings oxidation reaction product 60649.4 kgs/hr of the first reactor, enter the Cyclic Rings oxidation reaction product 101082.4 kgs/hr of the second reactor, other [embodiment 1].Hydrogen peroxide ethylbenzene weight air speed 4.1hr
-1the mol ratio of total propylene and hydrogen peroxide ethylbenzene is 8.03, the propylene of the first reactor and the second reactor inlet and the mol ratio of hydrogen peroxide ethylbenzene then reach 23.3 and 21.1, the temperature out of the first reactor and the second reactor is respectively 89.0 DEG C, 88.3 DEG C, the total conversion rate of hydrogen peroxide ethylbenzene is 99.2%, and the molar selectivity of propylene oxide is 99.11%.
[embodiment 3]
With [embodiment 1], an altering reactor form: the insulation fix bed reactor series connection of two single bed catalyst, other is with [embodiment 1].Hydrogen peroxide ethylbenzene weight air speed 4.1hr
-1the mol ratio of total propylene and hydrogen peroxide ethylbenzene is 11.52, the propylene of the first reactor and the second reactor inlet and the mol ratio of hydrogen peroxide ethylbenzene then reach 33.6 and 31.0, the temperature out of the first reactor and the second reactor is respectively 87.4 DEG C, 86.6 DEG C, the total conversion rate of hydrogen peroxide ethylbenzene is 99.2%, and the molar selectivity of propylene oxide is 99.15%.
[embodiment 4]
With [embodiment 1], an altering reactor temperature in: reactor catalyst bed inlet temperatures is 79 DEG C, other is with [embodiment 1].Hydrogen peroxide ethylbenzene weight air speed 4.1hr
-1the mol ratio of total propylene and hydrogen peroxide ethylbenzene is 11.52, the propylene of the first reactor and the second reactor and the mol ratio of hydrogen peroxide ethylbenzene then reach 33.6 and 31.0, the temperature out of the first reactor and the second reactor is respectively 90.4 DEG C, 89.6 DEG C, the total conversion rate of hydrogen peroxide ethylbenzene is 99.22%, and the molar selectivity of propylene oxide is 99.12%.
[comparative example]
Epoxidation reactor is single insulation fix bed reactor, and epoxidation reaction product does not circulate.Raw material is containing the hydrogen peroxide ethyl benzene mixtures of 19.4% weight concentration, flow is 162367.5 kgs/hr, mixes with raw material propylene 10987.6 kgs/hr, circulation propylene 155795.5 kgs/hr, entrance temperature of reaction 76 DEG C, under the condition of reaction pressure 2.9MPaG, with Ti/SiO
2catalyst exposure, liquid phase epoxidation reaction generates propylene oxide and xylyl alcohol and other by product, hydrogen peroxide ethylbenzene weight air speed 4.1hr
-1, the mol ratio of total propylene and hydrogen peroxide ethylbenzene is 16.75, and the temperature out of reactor is 108.1 DEG C, and the total conversion rate of hydrogen peroxide ethylbenzene is 99.2%, and the molar selectivity of propylene oxide is 98.3%.
Claims (10)
1. the epoxidation circulation means of a hydrogen peroxide ethylbenzene and propylene propylene oxide, hydrogen peroxide ethylbenzene and propylene carry out epoxidation reaction and generate product propene oxide under contacting with Ti-SiO 2 catalyst, the product generated is divided into extraction logistics and recycle stream, wherein, hydrogen peroxide ethylbenzene and recycle stream recycle stream are divided into n or (n-1) individual logistics is circulated to each reactor inlet, multiple series connection adiabatic reactor is divided into N number of, wherein, n be greater than 1 positive integer; N be greater than 1 positive integer; Its step comprises:
1) raw material I (1) portions containing hydrogen peroxide ethylbenzene enters the adiabatic reactor being at least two series connection;
2) raw material I a (2) of the first part of raw material I (1) namely containing hydrogen peroxide ethyl benzene mixtures is mixed into the first reactor with the raw material II (5) containing propylene and containing the recycle stream I (7) in the epoxidation reaction product of propylene oxide;
3) raw material I b (3) of the second section of raw material I (1) namely containing hydrogen peroxide ethyl benzene mixtures is mixed into the second reactor with the first reactor outlet product with containing the recycle stream II (8) in the epoxidation reaction product of propylene oxide;
4) raw material I n (4) of the n-th part of raw material I (1) namely containing hydrogen peroxide ethyl benzene mixtures is mixed into N reactor with (N-1) reactor outlet product with containing the recycle stream N (9) in the epoxidation reaction product of propylene oxide;
Wherein, epoxidation reaction temperature is 15 ~ 160 DEG C, pressure is 1.0 ~ 12.0MPa, total mol ratio of propylene and hydrogen peroxide ethylbenzene is 1 ~ 20.
2. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that the extraction logistics of epoxidation reaction product and the part by weight of recycle stream are 0.1 ~ 10.
3. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that the recycle stream of the epoxidation reaction product entering each catalyst reactor bed and the part by weight of global cycle logistics are 0.01 ~ 0.99.
4. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that described multiple series connection adiabatic reactor is made up of 2 ~ 10 reactors in series.
5. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that the beds in the adiabatic reactor of multiple series connection is single bed and/or multistage bed; Wherein, in each reactor above-mentioned, logistics flows to as upflowing or downflow system.
6. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, the propylene that it is characterized in that in raw material II is fresh propylene, the Propylene recovery of follow-up system or its mixture; Hydrogen peroxide ethylbenzene in raw material I obtains with ethylbenzene oxidation, is the mixture of ethylbenzene, hydrogen peroxide ethylbenzene, and the concentration of hydrogen peroxide ethylbenzene is 5 ~ 65wt%.
7. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, it is characterized in that step 2) in, raw material I a (2) mixes outward at the first reactor with the raw material II (5) containing propylene and containing the recycle stream I (7) in the epoxidation reaction product of propylene oxide or mixes in reactor.
8. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 7, is characterized in that step 3) in enter raw material I b (3) containing hydrogen peroxide ethyl benzene mixtures in the second reactor, mix with the recycle stream II (8) in the first reactor outlet thing and product outward at the second reactor or mix in the second reactor; Step 4) in enter in N reactor containing hydrogen peroxide ethyl benzene mixtures raw material I n (4), mix outward at N reactor with the recycle stream N (9) in (N-1) reactor outlet thing and product or mix in N reactor.
9. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that described epoxidation reaction is carried out in the liquid phase using solvent, is liquid under the temperature and pressure of this solvent when reacting; Time in raw material I (1) containing hydrogen peroxide ethylbenzene containing ethylbenzene, do not add solvent.
10. the epoxidation circulation means of hydrogen peroxide ethylbenzene and propylene propylene oxide according to claim 1, is characterized in that epoxidation reaction temperature is 30 ~ 130 DEG C, pressure is 1.5 ~ 6.0MPa, total mol ratio of propylene and hydrogen peroxide ethylbenzene is 2 ~ 15.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112500371A (en) * | 2019-09-14 | 2021-03-16 | 南京延长反应技术研究院有限公司 | Etherification-free system and process for preparing propylene oxide by virtue of intensified propylene epoxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418200A (en) * | 2000-03-24 | 2003-05-14 | 住友化学工业株式会社 | Process for producing oxirane compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1418200A (en) * | 2000-03-24 | 2003-05-14 | 住友化学工业株式会社 | Process for producing oxirane compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112500371A (en) * | 2019-09-14 | 2021-03-16 | 南京延长反应技术研究院有限公司 | Etherification-free system and process for preparing propylene oxide by virtue of intensified propylene epoxidation |
| CN112500371B (en) * | 2019-09-14 | 2023-04-11 | 南京延长反应技术研究院有限公司 | Etherification-free system and process for preparing propylene oxide by virtue of intensified propylene epoxidation |
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Application publication date: 20160127 |