CN101817804A - Method for preparing propylene oxide by propylene epoxidation under pressure oscillations - Google Patents
Method for preparing propylene oxide by propylene epoxidation under pressure oscillations Download PDFInfo
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- CN101817804A CN101817804A CN 201010124763 CN201010124763A CN101817804A CN 101817804 A CN101817804 A CN 101817804A CN 201010124763 CN201010124763 CN 201010124763 CN 201010124763 A CN201010124763 A CN 201010124763A CN 101817804 A CN101817804 A CN 101817804A
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Abstract
The invention provides a method for preparing propylene oxide by propylene epoxidation under pressure oscillations, which comprises the following steps: propylene is fed in from the bottom of a reactor, catalyst and oxydol-methanol solution are fed in from the lower part of the reactor, the catalyst and the oxydol-methanol solution flows upwards, and the liquid-phase product is discharged from the upper part of the reactor; the gas-phase product is sent to a condenser to be condensed through a pipeline connected with the top of the reactor, the propylene obtained after condensation is discharged from a gas-phase outlet of the condenser, the condensate is discharged from a liquid-phase outlet of the condenser, and the gas-phase outlet of the condenser is provided with an electromagnetic valve connected with a timer; the amplitude of the oscillation pressure of the reaction is 0.02-0.20MPa; and the opening frequency of the electromagnetic valve 5-30 times/hour, and the valve is opened for 1-10 seconds each time. By using the invention, the percent conversion of oxydol can reach more than 98.0%, the selection rate of propylene oxide can reach 88.6%, and thus, the invention has wide prospects for industrial implement.
Description
Technical field
The present invention relates to the synthetic method of propylene oxide, particularly is the synthetic method of the propylene oxide of catalyzer with the HTS.
Background technology
Propylene oxide (being called for short PO) has another name called methyl oxirane or propylene oxide, is to be only second to polyacrylic second largest acryloyl derivative, is important Organic Chemicals.
The maximum purposes of propylene oxide is to produce polyethers, and polyethers is mainly used in the production urethane plastic; Secondly as tensio-active agent, as crude oil demulsifier, suds-stabilizing agent etc.; Also can be used as lubricant, heat exchange fluid etc.Propylene oxide also can be used to produce propylene glycol, and propylene glycol is the main raw material of unsaturated polyester resin, extensively utilization in industry such as medicine, food.The downstream derived product of propylene oxide is nearly hundred kinds at present, is widely used in numerous industries such as automobile, oil field, family's decorations articles for use, food, medicine and makeup.
The production technique of present industrial propylene oxide mainly is chlorohydrination and indirect oxidation method, and up to now, the throughput of these two kinds of methods accounts for more than 95% of whole world PO throughput.The chlorohydrination advantages such as maturation, flow process are simple, operational load elasticity is big, not high to the purity requirement of raw material propylene, selection rate is good, yield is high, initial cost is few that possess skills, but also exist equipment corrosion seriously, consume shortcomings such as a large amount of chlorine, chlorine-contained wastewater environmental pollution are serious; And the indirect oxidation method mainly comprises Trimethylmethane method and ethylbenzene method, and industrialization is succeeded in developing and realized to this method in the sixties in 20th century jointly by U.S. Halcon and ARCO company.Trimethylmethane or ethylbenzene generate Trimethylmethane superoxide or ethylbenzene superoxide through peroxidation, generate propylene oxide with the propylene reaction again, simultaneously the coproduction trimethyl carbinol or Alpha-Methyl phenylethyl alcohol (can further be processed into vinylbenzene).This technological process does not have corrosion substantially to equipment, and " three wastes " discharging is few, but long flow path, investment is big, should not build the device of middle and small scale, simultaneously because joint product are many, is subjected to market factor restriction serious.
As a kind of important basic Organic Chemicals, and continuous development along with global urethane industry, the propylene oxide annual requirement increases year by year, so indirect oxidation method and chlorohydrination will be the main technique routes of producing propylene oxide in one period from now on.But 21 century is Green Chemistry and recycling economy epoch, less economical, with serious pollution production technique will be replaced by economy, the process for cleanly preparing of a new generation, various new catalytic processs all develop towards the direction of low temperature, low pressure, high selectivity, low emission, the making full use of of organic raw material in the catalyzed oxidation technology, save energy and reduce the cost, the exploitation of environmentally friendly technology more and more is subjected to common concern, with serious pollution chlorohydrination will certainly be eliminated gradually by society.
Document: Monnier J R.The Direct Epoxidation of Higher Olefins using MolecularOxygen[J] .Appl.Catal.A:General, 2001,221 (1-2): 73-91 has reported a kind of, use the Ag heterogeneous catalyst to carry out the method that molecular oxygen and propylone direct opoxidation prepare propylene oxide, the propylene oxide selection rate is a little more than 60% under its optimal conditions, and this moment propylene conversion a little more than 10%, also far from practicality.
Document: Xi Z W, Wang H P, Sun Y, et al.Direct Epoxidation of Olefins Catalyzed byHeteropolyoxometalates with Molecular Oxygen and Recyclable Reductant[J] .J.Mol.Catal., 2001,168 (1-2): 299-301 has reported a kind of, and transition metal such as metalloporphyrin (IV-VIII) complex compound is as homogeneous catalyst, at superoxide such as H
2O
2Have the epoxidizing method that is used for carbon three above alkene down, this method need add a large amount of reductive agents such as zinc powder or aldehydes, will produce a large amount of co-product at a low price.
Reaction rectification method is a new and high technology that develops rapidly in recent years, it is a kind of reaction and special extract rectification technology that is separated into one of collecting, this technology organically combines the process characteristic of reaction process and the engineering characteristic of separating device, can utilize the centrifugation of rectifying to improve the equilibrium conversion of reaction, suppress the generation of series connection side reaction, can utilize the energy consumption of the heat effect reduction rectifying of thermopositive reaction again, reinforcing mass transfer.Therefore, in Chemical Manufacture, obtain more and more widely application.The initial imagination of this experiment adopts the method for reactive distillation to realize the operation of epoxidation of propylene production propylene oxide, but found through experiments reaction rectification method and under this system, exist implacable inner contradictions, mainly show as: at normal temperatures and pressures, propylene solubleness in methyl alcohol is less, and along with the solubleness of rising propylene in methyl alcohol of pressure increases obviously, confirm by experiment to have only reach 0.30MPa to the pressure of propylene after, it is constant that the solubleness of propylene in methyl alcohol just keeps substantially, therefore thereby the concentration of propylene improves the transformation efficiency of accelerating chemical reaction in the liquid phase in order to allow, and reaction must be carried out under the condition of pressurization.But the raising of pressure also is accompanied by the rising of reaction system boiling point, and reactive distillation needs reactant to keep boiling state in reaction process, methyl alcohol boiling point at normal temperatures and pressures is about 64 ℃, higher under the situation of pressurization, therefore, the ideal temperature of reaction should be able to be higher than 64 ℃ far away.By decomposing hydrogen dioxide solution experiment as can be known, under the condition that catalyzer exists, hydrogen peroxide is in decomposition that will be a large amount of more than 60 ℃, so that reactive distillation is applied to this system feasibility is little.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing propylene oxide by propylene epoxidation under pressure oscillations is to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps: the starting raw material propylene is sent into from the bottom of reactor, with the mixture of catalyzer and hydrogen peroxide-methanol solution, sends into from the bottom of reactor, upwards flows, and carries out organic epoxidation reaction;
Liquid product is discharged from reactor top, is sent to follow-up workshop section, wherein contains the mixture of the intact hydrogen peroxide of propylene oxide, methyl alcohol, catalyzer and unreacted;
The gas-phase product that contains unreacted propylene is sent to condenser by the pipeline that is connected with reactor head and carries out condensation, the propylene that obtains after the condensation is discharged from the gaseous phase outlet of described condenser, the phlegma that contains propylene oxide and methyl alcohol that obtains after the condensation, discharge from the liquid phase outlet of described condenser, the gaseous phase outlet place of described condenser is provided with the magnetic valve that is connected with timing register;
Hydrogen peroxide-methanol solution refers to the mixing solutions of hydrogen peroxide and methanol solution;
In hydrogen peroxide-methanol solution, the weight concentration of hydrogen peroxide is 10～15%; The weight concentration of described hydrogen peroxide is to be that 30% hydrogen peroxide is a benchmark with weight concentration.
Temperature of reaction is 45～55 ℃, and preferred 50 ℃ is 20～240 minutes when empty, and reaction pressure is 0.38～0.42Mpa, and reaction oscillation pressure amplitude is between 0.02～0.20Mpa;
The vibration of reaction pressure can realize that magnetic valve is opened frequency 5～30 times/hour by the switch of the magnetic valve that is connected with timing register, and each to open the back hold-time be 1～10 second, closes then;
Be 30% hydrogen peroxide in weight concentration:
Raw material propylene and weight concentration are that the weight ratio of 30% hydrogen peroxide is: propylene: weight concentration is 30% hydrogen peroxide=1: 0.215～2.58;
Catalyzer: weight concentration is 30% hydrogen peroxide=1: 14.5～29;
Describedly be defined as follows when empty:
Described catalyzer is a TS-1 type HTS, can adopt patent US 4410501 disclosed methods to be prepared, and perhaps adopting Beijing Research Institute of Petro-Chemical Engineering of China Petrochemical Industry trade mark is the commercially produced product of HTS200702;
Described timing register is general product, is the timing register of DH48S-S as model;
Described magnetic valve is general product, is the magnetic valve of MP-C-080 as model;
The form of described reactor can adopt conventional reactor, as bubble tower or CSTR;
Mechanism of the present invention is such:
According to the ultimate principle of chemical reaction engineering, the applicant analyzes the reason that by-products content significantly raises to be had:
At first, temperature rising along with reaction, the speed of chemical reaction will be accelerated, therefore the also corresponding increase of propylene oxide amount that in the unit time, produces, this will cause, and the concentration of propylene oxide raises rapidly in the reaction solution, therefore propylene oxide is further also accelerated with the speed of methyl alcohol and water reaction, finally causes by product to increase.Secondly, the increase of catalyst content makes and participates in the increase of reactive activity position, and the speed of reaction is accelerated, and therefore, propylene oxide concentrations raises rapidly in the unit time, and its result also can make by product increase.
Therefore, this reaction is typical cascade reaction, and back-mixing will be unfavorable for the raising of reaction preference, improve the selectivity of reaction, just must allow the product propylene oxide leave conversion zone as soon as possible.In case optimal response behaviour is to have propylene oxide just to generate to allow it leave conversion zone, so both can avoid production of by-products, can also effectively promote the transformation efficiency of epoxidation of propylene at once.
Method of the present invention, adopt " oscillating operation ", the periodical change of reaction pressure, promptly the amplitude of frequency by the pressure change in the forcibly changing reactor and pressure change is improved the kinetic characteristic of reactor, purpose is to allow propylene oxide leave conversion zone as early as possible, in time remove reaction heat, thereby improve the selection rate of epoxidation reaction.
In addition, this reaction is strong exothermal reaction, and removing of reaction heat also is a big key issue, and therefore, in the process of oscillating operation, the heat of a part can leave reactor together along with gaseous mixture such as propylene oxide, can save a large amount of colds like this.
This shows that method of the present invention has that flow process is simple, by product is few and characteristics such as environmental friendliness, the transformation efficiency of hydrogen peroxide can reach more than 98.0%, and this moment, the propylene oxide selection rate can reach 88.6%, had bigger industrializing implementation prospect.
The hydrogen peroxide transformation efficiency is defined as follows:
The propylene oxide selection rate is defined as follows:
In the formula, [H
2O
2]
0[H
2O
2]
iBe respectively the volumetric molar concentration of reaction front and back hydrogen peroxide, mol.L
-1n
PO, n
NME, n
PGBe respectively the propylene oxide of generation, propylene glycol monomethyl ether, the amount of substance of propylene glycol, mol.
Description of drawings
Fig. 1 is single bubble tower experiment process figure.
Fig. 2 is two bubble tower tandem test schemas.
Embodiment
Referring to Fig. 1, method of the present invention comprises the steps: the starting raw material propylene is sent into from the bottom of reactor 1, with the mixture of catalyzer and hydrogen peroxide-methanol solution, send into from the bottom of reactor 1, in reactor 1, upwards flow, carry out organic epoxidation reaction;
Liquid product is discharged from reactor 1 top, is sent to follow-up workshop section, wherein contains the mixture of the intact hydrogen peroxide of propylene oxide, methyl alcohol, catalyzer and unreacted;
The gas-phase product that contains unreacted propylene is sent to condenser 2 by the pipeline that is connected with reactor 1 top and carries out condensation, the propylene that obtains after the condensation is discharged from the gaseous phase outlet of described condenser 2, can be recycled, the phlegma that contains methyl alcohol and propylene oxide that obtains after the condensation, discharge from the liquid phase outlet of described condenser 2, the gaseous phase outlet place of described condenser 2 is provided with the magnetic valve 4. that is connected with timing register 3
Fig. 2 is a double-column process, this flow process is the further optimization at the flow process water of Fig. 1, referring to Fig. 2, liquid product is discharged from reactor 1 top, add second reactor 11, carry out organic epoxidation reaction once more with propylene, liquid product is discharged from second reactor, 11 tops, be sent to follow-up workshop section, the gas-phase product that contains unreacted propylene is sent to second condenser 22 by the pipeline that is connected with second reactor, 11 tops and carries out condensation, the propylene that obtains after the condensation is discharged from the gaseous phase outlet of described second condenser 22, can be recycled, the phlegma that contains methyl alcohol and propylene oxide that obtains after the condensation is discharged from the liquid phase outlet of described second condenser 22, the gaseous phase outlet place of described second condenser 22 is provided with the magnetic valve 4. that is connected with timing register 3
Adopt the flow process of Fig. 1, catalyzer is a TS-1 type HTS, adopts Beijing Research Institute of Petro-Chemical Engineering of China Petrochemical Industry commercially produced product:
Reactor is single bubble tower, and the model of timing register is DH48S-S, and the model of magnetic valve is MP-C-080; Magnetic valve is opened frequency 5 times/hour, and the hold-time is 10 seconds after each the unlatching, closes then;
Temperature of reaction is 45 ℃, is 240 minutes when empty;
In hydrogen peroxide-methanol solution, weight concentration is that the weight concentration of 30% hydrogen peroxide is 15%;
Reaction pressure is 0.4Mpa, and between 0.4～0.2Mpa change in oscillation, oscillation frequency is 5 times/hour;
The weight ratio of raw material propylene and hydrogen peroxide is: propylene: weight concentration is 30% a hydrogen peroxide=1: 2.58;
The weight ratio of catalyzer and hydrogen peroxide is: catalyzer: weight concentration is 30% a hydrogen peroxide=1: 29;
Under above-mentioned processing condition, the hydrogen peroxide transformation efficiency is 99.1%, and the propylene oxide selection rate is 51.2%.
Adopt the flow process of Fig. 1, catalyzer is a TS-1 type HTS, adopts Beijing Research Institute of Petro-Chemical Engineering of China Petrochemical Industry commercially produced product;
Reactor is single bubble tower, and the model of timing register is DH48S-S, and the model of magnetic valve is MP-C-080; Magnetic valve is opened frequency 30 times/hour, and the hold-time is 1 second after each the unlatching, closes then;
Temperature of reaction is 55 ℃, is 20 minutes when empty;
In hydrogen peroxide-methanol solution, weight concentration is that the weight concentration of 30% hydrogen peroxide is 10%;
Reaction pressure is 0.42Mpa, and between 0.42～0.40Mpa change in oscillation, oscillation frequency is 30 times/hour;
The weight ratio of raw material propylene and hydrogen peroxide is: propylene: weight concentration is 30% a hydrogen peroxide=1: 0.215;
The weight ratio of catalyzer and hydrogen peroxide is: catalyzer: weight concentration is 30% a hydrogen peroxide=1: 14.5;
Under above-mentioned processing condition, the hydrogen peroxide transformation efficiency is 88.1%, and the propylene oxide selection rate is 89.9%.
Adopt the flow process of Fig. 2, catalyzer is a TS-1 type HTS, adopts Beijing Research Institute of Petro-Chemical Engineering of China Petrochemical Industry commercially produced product
Reactor is two bubble tower tandem reactors, and the operational condition of two reactors is identical.
The model of timing register is DH48S-S, and the model of magnetic valve is MP-C-080; Magnetic valve is opened frequency 15 times/hour, and the hold-time is 2 seconds after each the unlatching, closes then;
Temperature of reaction is 50 ℃, is 60 minutes when empty;
In hydrogen peroxide-methanol solution, weight concentration is that the weight concentration of 30% hydrogen peroxide is 12.8%;
Reaction pressure is 0.38Mpa, and between 0.38～0.34Mpa change in oscillation, oscillation frequency is 15 times/hour;
The weight ratio of raw material propylene and hydrogen peroxide is: propylene: weight concentration is 30% a hydrogen peroxide=1: 0.645;
The weight ratio of catalyzer and hydrogen peroxide is: catalyzer: weight concentration is 30% a hydrogen peroxide=1: 17.5;
Under above-mentioned processing condition, the hydrogen peroxide transformation efficiency is 98.0%, and the propylene oxide selection rate is 88.6%.
Claims (5)
1. the method for preparing epoxypropane by epoxidation of propene under the pressure oscillation is characterized in that, comprises the steps: propylene is sent into from the bottom of reactor, mixture with catalyzer and hydrogen peroxide-methanol solution, send into from the bottom of reactor, upwards flow, carry out organic epoxidation reaction; Liquid product is discharged from reactor top;
The gas-phase product that contains unreacted propylene is sent to condenser by the pipeline that is connected with reactor head and carries out condensation, the propylene that obtains after the condensation is discharged from the gaseous phase outlet of described condenser, the phlegma that contains propylene oxide and methyl alcohol that obtains after the condensation, discharge from the liquid phase outlet of described condenser, the gaseous phase outlet place of described condenser is provided with the magnetic valve that is connected with timing register;
Reaction oscillation pressure amplitude is between 0.02～0.20Mpa;
Magnetic valve is opened frequency 5～30 times/hour, and the hold-time is 1～10 second after each the unlatching, closes then.
2. method according to claim 1 is characterized in that, temperature of reaction is 45～55 ℃, is 20～240 minutes when empty, and reaction pressure is 0.38～0.42Mpa.
3. method according to claim 1 is characterized in that, in hydrogen peroxide-methanol solution, the weight concentration of hydrogen peroxide is 10～15%; The weight concentration of described hydrogen peroxide is to be that 30% hydrogen peroxide is a benchmark with weight concentration.
4. method according to claim 1 is characterized in that, is 30% hydrogen peroxide in weight concentration: propylene and weight concentration are that the weight ratio of 30% hydrogen peroxide is: propylene: weight concentration is 30% hydrogen peroxide=1: 0.215～2.58.
5. method according to claim 1 is characterized in that, is 30% hydrogen peroxide in weight concentration: catalyzer: weight concentration is 30% hydrogen peroxide=1: 14.5～29.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017089079A1 (en) * | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of propene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219536A (en) * | 1997-11-07 | 1999-06-16 | 住友化学工业株式会社 | Method for producing opoxy propane |
| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| 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 |
-
2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219536A (en) * | 1997-11-07 | 1999-06-16 | 住友化学工业株式会社 | Method for producing opoxy propane |
| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017089079A1 (en) * | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of propene |
| CN108290851A (en) * | 2015-11-26 | 2018-07-17 | 赢创德固赛有限公司 | The method of epoxidation of propylene |
| KR20180087327A (en) * | 2015-11-26 | 2018-08-01 | 에보닉 데구사 게엠베하 | Epoxidation of propene |
| EA035589B1 (en) * | 2015-11-26 | 2020-07-13 | Эвоник Оперейшнс Гмбх | Process for the epoxidation of propene |
| TWI717418B (en) * | 2015-11-26 | 2021-02-01 | 德商贏創運營有限公司 | Process for the epoxidation of propene |
| CN108290851B (en) * | 2015-11-26 | 2021-02-09 | 赢创运营有限公司 | Process for the epoxidation of propene |
| KR102641591B1 (en) | 2015-11-26 | 2024-02-27 | 에보닉 오퍼레이션스 게엠베하 | Epoxidation method of propene |
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