CN104327016A - Method for preparing epoxypropane - Google Patents
Method for preparing epoxypropane Download PDFInfo
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- CN104327016A CN104327016A CN201410615468.1A CN201410615468A CN104327016A CN 104327016 A CN104327016 A CN 104327016A CN 201410615468 A CN201410615468 A CN 201410615468A CN 104327016 A CN104327016 A CN 104327016A
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- propylene
- propylene oxide
- hydrogen peroxide
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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
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for preparing epoxypropane. The method comprises the following steps: adding raw materials propylene and oxydol, a solvent methanol and a titanium silicon molecular sieve catalyst into a reaction kettle according to the mole ratio, and regulating the temperature and pressure in the reaction kettle to establish circulation; continuously adding the raw materials and solvent into the pipeline reactor from the outside of the reaction kettle to react, mixing with a static mixer, and sending into the reaction kettle; discharging the reaction mixture from the bottom of the reaction kettle, delivering to a primary heat exchanger through a circulating pump to perform cooling, separating the product epoxypropane and catalyst in a cross-flow filter membrane separator to obtain the product epoxypropane, and returning the trapped catalyst into the reaction kettle via the pipeline reactor, heat exchanger, static mixer and other apparatuses to form the circulation and continue entering into the reaction; and carrying out backflush every other 3-5 hours. The raw materials sufficiently contact the catalyst, the conversion rate of oxydol is at least 96%, and the epoxypropane selectivity is at least 95%. The epoxypropane has stable membrane flux, thereby lowering the membrane pollution, enhancing the product purity and lowering the production cost.
Description
Technical field
The present invention relates to a kind of organism preparation method, is exactly specifically a kind of method preparing propylene oxide.
Background technology
Propylene oxide (PO) is the third-largest acryloyl derivative except polypropylene and vinyl cyanide, it is important basic organic chemical industry raw material, 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. simultaneously.In prior art, the preparation method of propylene oxide mainly contains chlorohydrination, conjugated oxidation and hydrogen peroxide method.The a large amount of chlorine of chlorohydrination consumption, equipment corrosion and environmental pollution serious.The alkyl peroxide that conjugated oxidation generates with ethylbenzene or Trimethylmethane autoxidation is for oxygen source, and make propylene catalysis epoxidation generate propylene oxide, its production process is complicated and facility investment is larger.At present, production of propylene oxide mainly adopts hydrogen peroxide to prepare propylene oxide process (HPPO method), only propylene oxide and water is generated in this art production process, technical process is simple, product yield is high, there is no other joint product, substantially pollution-free, belong to eco-friendly clean-production system.HPPO method refers to that H2O2 catalysis epoxidation propylene on TS-1 catalyzer generates propylene oxide, and solvent is methyl alcohol, operates under middle temperature, low pressure and liquid-phase reaction condition.At present, produce in propylene oxide in HPPO method, epoxidation reactor adopts shell-tubular fixed-bed reactor, three open one standby, n (propylene): n (H2O2)=2:1, m (methyl alcohol): m (H2O2)=1:0.25, temperature of reaction 40 ~ 50 DEG C, reaction pressure 2.0 MPa.H2O2 transformation efficiency and propylene oxide selectivity are respectively 96% and 95%; Also have fixed-bed reactor to adopt one group of parallel heat exchanger plates, in the passage of catalyst loading between heat exchanger plates, reaction mass flows through catalyst layer from top to bottom and reacts, and removes reaction heat by the heat-eliminating medium flowed through in plate.Adopt fixed bed reaction still, effective contact area of reaction raw materials and catalyzer is little, the low conversion rate of raw material; Catalyzed reaction is concentrated on a fixed bed, and local easily produces temperature runaway, causes damage to reactor, and reaction hazard level is high; In operating process, catalyzer can not be changed, and it is poor that the time has grown catalytic efficiency.For this reason, prepare propylene oxide process improve propylene ring oxidation reaction, for the transformation efficiency improving raw material, the danger coefficient reducing reaction has positive effect.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of method preparing propylene oxide be provided,
With the selectivity of transformation efficiency and propylene oxide improving hydrogen peroxide and the efficiency of catalyzer, reduce energy consumption.
It is such that the present invention solves the technical scheme that its technical problem takes.Prepare a method for propylene oxide, comprise the following steps:
(1) be (1.2 ~ 2) according to mol ratio in reactor: 1:(2 ~ 4) add raw material propylene, hydrogen peroxide and solvent methanol and titanium-silicon molecular sieve catalyst, regulate reactor temperature 40 ~ 60 DEG C, pressure 0.3 ~ 2.0Mpa, sets up circulation;
(2) according to catalyst consumption, in reactor, add titanium-silicon molecular sieve catalyst in good time, material is reacted, ON cycle pump and agitator;
Outside reactor, raw material propylene, hydrogen peroxide and solvent methanol are added in pipeline reactor continuously, in pipeline reactor, the reaction under the existence of solvent methanol and catalyzer of raw material propylene and hydrogen peroxide generates propylene oxide, enter secondary heat exchanger again, lower the temperature laggard enter static mixer, enter reactor after mixing;
In reactor, fully react on reactor top through the unreacted a small amount of hydrogen peroxide of pipeline reactor and propylene, obtain the mixing solutions of propylene oxide and catalyzer, now transformation efficiency >=96% of hydrogen peroxide, selectivity >=95% of propylene oxide;
Wherein, the mol ratio of propylene, hydrogen peroxide and methyl alcohol is (1.2 ~ 2): 1:(2 ~ 4);
(3) flow out bottom reactor through step (2) reacted propylene oxide and catalyst mixed liquid, first-class heat exchanger cooling is delivered to through recycle pump, product propene oxide is separated through cross flow filter membrane separation apparatus with catalyzer, isolate product propene oxide, proceed epoxidation of propylene catalyzed reaction synthesizing epoxypropane after catalyzer and leftover materials mix again with the raw material newly added from pipeline reactor, be back in reactor continue reaction through secondary heat exchanger, static mixer;
Once recoil from the propylene oxide clear liquid of cross flow filter membrane separation apparatus clear liquid side infiltration every 3 ~ 5 h, continuously flow out along with propylene oxide clear liquid and be separated, raw material, solvent and catalyzer are constantly added, and realize carrying out continuously of propylene oxide production process.
Wherein in cross flow filter membrane separation apparatus, membrane element is ceramic membrane or metallic membrane, and the filtering accuracy of film is 0.05 ~ 5 μm.
Method of the present invention, reactor is slurry reactor still.Slurry reactor still is also known as slurry reaction still, and in reactor, catalyzer minute solid particles is suspended in liquid medium.
Membrane separation apparatus used is ceramic membrane or metal film filter, is distributed on the pipeline outside reactor, and filter type is cross flow filter, thus can ensure the stability that product propene oxide is separated, and improves separation efficiency.
In order to ensure the stationarity of reaction system, the quality sum of the raw material propylene added by pipeline reactor, hydrogen peroxide and solvent methanol equals the quality of oozing out propylene oxide clear liquid.
The beneficial effect that the present invention obtains is as follows:
1, adopt slurry reactor still to replace current fixed-bed reactor, between reaction raw materials, effective contact area increases, and improves the transformation efficiency of raw material, reduces energy consumption and production costs simultaneously.
2, raw material propylene, hydrogen peroxide and solvent methanol first pre-mixing carry out catalyzed reaction in pipeline reactor before entering reactor, reduces the back-mixing degree of reaction mass in reactor, makes reaction more complete; Simultaneous reactions still internal structure is simplified, and reduces equipment cost.
3, distribute condensing heat exchanger on reactor external pipe, reaction heat can be recycled, and guarantees that temperature of reaction is steady, reaction process safety.
4, ceramic membrane or metal film separator are distributed on the pipeline outside reactor, adopt cross flow filter mode, ensure that the stability of separation, reduce the pollution of film, improve separation efficiency.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Following examples are for illustration of the present invention.
Embodiment 1
See the present invention process schematic flow sheet that Fig. 1 provides, present invention process process comprises the steps:
(1) in reactor in molar ratio (1.2 ~ 2): 1:(2 ~ 4) add raw material propylene, hydrogen peroxide and solvent methanol and proper catalyst HTS, the temperature in reactor is regulated to be 40 ~ 60 DEG C, pressure is 0.3 ~ 2.0Mpa, sets up circulation;
(2) temperature and pressure controlled in reactor is above condition, and according to catalyst consumption, every order of classes or grades at school adds catalyst Ti-si molecular sieves in reactor, and material reacts.ON cycle pump and agitator, on reactor external pipe, raw material propylene, hydrogen peroxide and solvent methanol continuously add in pipeline reactor respectively, propylene and hydrogen peroxide enter in reactor after reacting under the existence of solvent methanol and catalyzer and generating propylene oxide after interchanger, static mixer mix, and wherein the add-on mol ratio of propylene, hydrogen peroxide and solvent methanol is (1.2 ~ 2): 1:(2 ~ 4);
At the reactor first half, fully react through the unreacted a small amount of hydrogen peroxide of pipeline reactor and propylene, make transformation efficiency >=96% of hydrogen peroxide, selectivity >=95% of propylene oxide;
(3) flow out bottom reactor through step (2) reacted propylene oxide and catalyst mixed liquid, first-class heat exchanger is delivered to through recycle pump, cooling after product propylene oxide is separated through cross flow filter membrane separation apparatus with catalyzer, isolate product propene oxide clear liquid, proceed epoxidation of propylene catalyzed reaction synthesizing epoxypropane after catalyzer and leftover materials mix again with the raw material newly added from pipeline reactor, be back in reactor continue reaction through secondary heat exchanger, static mixer;
Once recoil from the propylene oxide clear liquid of cross flow filter membrane separation apparatus clear liquid side infiltration every 3 ~ 5 h, continuously ooze out along with propylene oxide clear liquid and be separated, raw material, solvent and catalyzer are constantly added, and realize carrying out continuously of propylene oxide production process.
In the present embodiment, reactor is slurry reactor still, and product propene oxide and being separated in the ceramic membrane separation device of reactor outside of catalyzer are carried out, and filter type is cross flow filter.Wherein the filtering accuracy of ceramic membrane is 0.05 ~ 5 μm.
The quality sum of the reaction raw materials propylene added through pipeline reactor, hydrogen peroxide, solvent methanol equals to ooze out the quality of propylene oxide clear liquid.
Embodiment 2
The present embodiment product propene oxide and being separated in the metal film separator of reactor outside of catalyzer are carried out, and filter type is similarly cross flow filter, and other processing condition are identical with embodiment 1.
Claims (4)
1. prepare a method for propylene oxide, it is characterized in that comprising the following steps:
(1) be (1.2 ~ 2) according to mol ratio in reactor: 1:(2 ~ 4) add raw material propylene, hydrogen peroxide and solvent methanol and titanium-silicon molecular sieve catalyst, regulate reactor temperature 40 ~ 60 DEG C, pressure 0.3 ~ 2.0Mpa, sets up circulation;
(2) according to catalyst consumption, in reactor, add titanium-silicon molecular sieve catalyst in good time, material is reacted, ON cycle pump and agitator;
Outside reactor, raw material propylene, hydrogen peroxide and solvent methanol are added in pipeline reactor continuously, in pipeline reactor, the reaction under the existence of solvent methanol and catalyzer of raw material propylene and hydrogen peroxide generates propylene oxide, enter secondary heat exchanger again, lower the temperature laggard enter static mixer, enter reactor after mixing;
In reactor, fully react on reactor top through the unreacted a small amount of hydrogen peroxide of pipeline reactor and propylene, obtain the mixing solutions of product propene oxide and catalyzer;
Wherein, the mol ratio of propylene, hydrogen peroxide and methyl alcohol is (1.2 ~ 2): 1:(2 ~ 4);
(3) flow out bottom reactor through step (2) reacted propylene oxide and catalyst mixed liquid, first-class heat exchanger cooling is delivered to through recycle pump, product propene oxide is separated through cross flow filter membrane separation apparatus with catalyzer, isolate product propene oxide, proceed epoxidation of propylene catalyzed reaction synthesizing epoxypropane after catalyzer and leftover materials mix again with the raw material newly added from pipeline reactor, be back in reactor continue reaction through secondary heat exchanger, static mixer;
Once recoil from the propylene oxide clear liquid of cross flow filter membrane separation apparatus clear liquid side infiltration every 3 ~ 5 h, continuously ooze out along with propylene oxide clear liquid and be separated, constantly adding of raw material, solvent and catalyzer, realizes carrying out continuously of propylene oxide production process.
2. preparation method according to claim 1, is characterized in that described reactor is slurry reactor still.
3. preparation method according to claim 1, is characterized in that the quality sum of raw material propylene, hydrogen peroxide and the solvent methanol added by pipeline reactor equals to ooze out the quality of propylene oxide clear liquid.
4. preparation method according to claim 1, it is characterized in that in cross flow filter membrane separation apparatus, membrane element is ceramic membrane or metallic membrane, the filtering accuracy of film is 0.05 ~ 5 μm.
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| CN201410615468.1A CN104327016B (en) | 2014-11-05 | 2014-11-05 | A kind of method preparing propylene oxide |
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| CN201410615468.1A CN104327016B (en) | 2014-11-05 | 2014-11-05 | A kind of method preparing propylene oxide |
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| CN104327016B CN104327016B (en) | 2016-01-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033107A (en) * | 2017-04-20 | 2017-08-11 | 河北美邦工程科技股份有限公司 | A kind of method for preparing epoxychloropropane |
| CN108997264A (en) * | 2018-08-22 | 2018-12-14 | 湖南长科诚享石化科技开发有限公司 | A kind of consersion unit and technique of hydrogen peroxide legal system propylene oxide |
| CN109180611A (en) * | 2018-10-12 | 2019-01-11 | 胜帮科技股份有限公司 | A kind of HPPO method of raw material segmentation injection prepares the device and method of propylene oxide |
| CN109928943A (en) * | 2019-04-08 | 2019-06-25 | 江苏扬农化工集团有限公司 | A kind of method of micro passage reaction synthesizing epoxypropane |
| CN115197171A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Method and system for producing propylene oxide |
| CN116283833A (en) * | 2023-04-11 | 2023-06-23 | 南京舒宜汇科学仪器有限公司 | Process for preparing epoxypropane by directly oxidizing propylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1525965A (en) * | 2001-04-27 | 2004-09-01 | 住友化学工业株式会社 | Process for producing propylene oxide |
| CN101314596A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for continuous preparation of epoxypropane |
| CN102453002A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing epoxypropane |
-
2014
- 2014-11-05 CN CN201410615468.1A patent/CN104327016B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1525965A (en) * | 2001-04-27 | 2004-09-01 | 住友化学工业株式会社 | Process for producing propylene oxide |
| CN101314596A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for continuous preparation of epoxypropane |
| CN102453002A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing epoxypropane |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033107A (en) * | 2017-04-20 | 2017-08-11 | 河北美邦工程科技股份有限公司 | A kind of method for preparing epoxychloropropane |
| CN108997264A (en) * | 2018-08-22 | 2018-12-14 | 湖南长科诚享石化科技开发有限公司 | A kind of consersion unit and technique of hydrogen peroxide legal system propylene oxide |
| CN109180611A (en) * | 2018-10-12 | 2019-01-11 | 胜帮科技股份有限公司 | A kind of HPPO method of raw material segmentation injection prepares the device and method of propylene oxide |
| CN109180611B (en) * | 2018-10-12 | 2023-03-21 | 胜帮科技股份有限公司 | Device and method for preparing propylene oxide by HPPO method through raw material segmented injection |
| CN109928943A (en) * | 2019-04-08 | 2019-06-25 | 江苏扬农化工集团有限公司 | A kind of method of micro passage reaction synthesizing epoxypropane |
| CN109928943B (en) * | 2019-04-08 | 2020-12-18 | 江苏扬农化工集团有限公司 | Method for synthesizing propylene oxide by using microchannel reactor |
| CN115197171A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Method and system for producing propylene oxide |
| CN116283833A (en) * | 2023-04-11 | 2023-06-23 | 南京舒宜汇科学仪器有限公司 | Process for preparing epoxypropane by directly oxidizing propylene |
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| CN104327016B (en) | 2016-01-20 |
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Address after: 12, building 050035, Yee Yee building, 98 the Yellow River Avenue, Hebei, Shijiazhuang Patentee after: Hebei Mei Bang engineering science and technology limited-liability company Address before: 050035 Shijiazhuang Changjiang Road, Hebei, No. 9 building high-tech international A-17L Patentee before: Hebei Meibang Engineering Technology Co., Ltd. |