CN109928943A - A kind of method of micro passage reaction synthesizing epoxypropane - Google Patents
A kind of method of micro passage reaction synthesizing epoxypropane Download PDFInfo
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- CN109928943A CN109928943A CN201910275598.8A CN201910275598A CN109928943A CN 109928943 A CN109928943 A CN 109928943A CN 201910275598 A CN201910275598 A CN 201910275598A CN 109928943 A CN109928943 A CN 109928943A
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Abstract
The invention discloses a kind of methods of micro passage reaction synthesizing epoxypropane.The described method includes: being 1. pumped into propylene liguid, hydrogen peroxide solution, methanol solution in micro-channel mixer simultaneously, homogeneous mixed liquor is formed；It is preheated 2. the homogeneous mixed liquor is sent into the preheater of microchannel；It is reacted 3. the homogeneous mixed liquor after preheating is sent into micro passage reaction, TS-1 titanium-silicon molecular sieve catalyst is filled in the micro passage reaction；4. by step 3. obtained in reaction product product knockout drum is sent into after product cooler is cooling, gas-phase product is vented after separation, and liquid product, which is collected, enters collection of products tank.The present invention fires dangerous low, hydrogen peroxide high conversion rate, propylene oxide high income.
Description
Technical field
The invention belongs to technical field of petrochemical industry, are related to a kind of side by micro passage reaction synthesizing epoxypropane
Method.
Background technique
Propylene oxide existing for the oxidation base of high activity is to be only second to polyacrylic second major class acryloyl derivative, is being worked as
It is widely applied in modern chemical industry.Propylene oxide is production polyether polyol, isopropanolamine and hydroxypropylcelluloether ether etc.
Reactive intermediate, be also widely used in one of the raw material of plasticizer, fire retardant, demulsifier, emulsifier, lubricating oil etc..State at present
The process of interior production propylene oxide includes: chlorohydrination, conjugated oxidation and hydrogen peroxide direct oxidation method (HPPO method).
Waste water, waste sludge discharge amount are big in chlorohydrination production process, and waste water has the characteristics that " five is high ", and equipment is easily corroded, should
Technology is eliminated by many American-European countries.Realize that industrialized HPPO technique is titanium molecular sieve catalysis hydrogen peroxide oxidation
Propylene obtains propylene oxide.Main side reaction includes: decomposing hydrogen dioxide solution into oxygen and water, propylene oxide hydrolysis generate propylene glycol,
Propylene oxide is reacted with methanol generates propylene glycol monomethyl ether etc..The aerial explosion limit of propylene is 2%~11%, dioxygen
Firing for water propylene oxide propylene oxide reaction is dangerous very high.Danger is fired to reduce in production, it usually need to be to reactor
It is inside passed through carrier gas nitrogen, while also needing to increase deaeration plant, increases investment and operating cost.And in HPPO legal system
Exist mostly in the fixed bed reactors of propylene oxide poor heat-transfer effect, non-uniform temperature, device interior reaction temperature be difficult to control etc.
Problem.
Micro- Chemical Engineering Technology be rising in recent years be used to prepare the chemical intermediates such as pesticide, medicine by process intensification reality
One new technology of existing green syt, strengthens reaction process by changing fluid mass-transfer, heat transfer and flow behavior.Micro- reaction
The performance of device has great advantage in terms of temperature control, time control, security control.Microreactor has small in size, green peace
Entirely, the features such as side reaction is few, number increases amplification, i.e., realize volume production by increasing micro- reaction member, substantially without enlarge-effect.
Chinese patent CN107216296A settles sth. according to policy or law out a kind of method that propylene oxide is prepared in micro passage reaction.By third
Alkene is contacted in gas phase with the hydrogen peroxide that hydrogen, oxygen original position chemical combination generate, under the effect of the catalyst in micro passage reaction
Directly generate propylene oxide.At 100 DEG C, under the conditions of 0.5MPa, the velocity ratio into four kinds of gas of reaction zone is H2:O2:
C3H6:N2=5:5:5:10 (mL/min) measures propylene conversion 8.2%, propylene oxide selectivity 91.5%.This method raw material
All is gas-phase feed, but propylene conversion is low, and hydrogen, propylene, which directly contact to be also easy to produce with oxygen, fires risk, and is reacted
Temperature is higher, causes operating cost high, energy consumption is high.
Accordingly, it is desirable to provide a kind of method of new micro passage reaction synthesizing epoxypropane is to solve the above problems.
Summary of the invention
It can solve to fire dangerous, biography present in prior art synthesizing epoxypropane the object of the present invention is to provide one kind
Thermal effect is poor, heterogeneous charging, the problem that hydrogen peroxide conversion ratio is low, propylene oxide yield is low method.
The present invention relates to one kind by filled type micro-channel device, make propylene, hydrogen peroxide, methanol solution keep homogeneously into
Material, the method that propylene oxide is prepared by micro-channel mixer, preheater, reactor.
A kind of method of micro passage reaction synthesizing epoxypropane, it includes the following steps:
(1) propylene liguid, hydrogen peroxide solution, methanol solution are pumped into micro-channel mixer simultaneously；
(2) after mixing by step (1), homogeneous mixed liquor is sent into microchannel preheater；
(3) by the way that mixed liquor is sent into micro passage reaction reaction again after preheater preheating in microchannel in step (2)；
(4) reaction product is sent into product knockout drum after product cooler is cooling, and gas phase is vented after separation, and liquid phase enters production
Object collecting tank.
Hydrogen peroxide in above-mentioned steps (1): propylene: methanol molar ratio is 1:(1~3): (10~15)；
The concentration of the hydrogen peroxide solution is 50%, the concentration of the methanol solution is 99.5%~99.9%.
Microchannel preheater in above-mentioned steps (2) can control mixeding liquid temperature, and the temperature of the microchannel preheater is
25~80 DEG C；
The ratio of catalyst volume is in the flow velocity and micro passage reaction of mixed liquor in microchannel in above-mentioned steps (3)
0.25~6min-1；
The catalyst filled in micro passage reaction in above-mentioned steps (3) is TS-1 titanium-silicon molecular sieve catalyst；
The temperature of reaction described in above-mentioned steps (3) is 25~80 DEG C；
Reaction pressure is controlled by counterbalance valve on product knockout drum, the pressure is 1.0~4.0MPa.
The methanol solution can also be in ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutyl ketone, acetone, acetonitrile
At least one or several mixture replacings.
Compared with prior art, the present invention has the advantage that
(1) reaction raw materials are homogeneous charging, and contact sufficiently, is uniformly mixed, provides good environment, dioxygen for epoxidation of propylene
Water high conversion rate, propylene oxide high income；
(2) large specific surface area, mass transfer rate is high, and time of contact is short, and by-product is few, reduces the choosing of the by-products such as alcohol, ethers
Selecting property.It fires danger to substantially reduce, safety is high；
(3) quickly, it directly amplifies.It does not need to amplify the scale of microreactor, it is only necessary to increase plate quantity, account for
Ground is small, with low investment, high-efficient, can directly amplify for industrial production；
(4) good operability, it is highly-safe.Micro- reaction system good portability is, it can be achieved that use ground dispersion construction；Liquid holdup
Small, amount of heat can be removed in time, utmostly reduce a possibility that accident occurs.
Detailed description of the invention
Fig. 1 is flow diagram of the invention.
In figure, 1 is propylene, and 2 be hydrogen peroxide solution, and 3 be methanol solution, and 4 be micro-channel mixer, and 5 preheat for microchannel
Device, 6 be micro passage reaction, and 7 be product cooler, and 8 be product knockout drum, and 9 be counterbalance valve, and 10 be collection of products tank.
Specific embodiment
The concentration of present invention hydrogen peroxide solution as used in the following examples is 50%, the concentration of methanol solution is
99.5%, catalyst is TS-1 titanium-silicon molecular sieve catalyst.
Embodiment 1
Propylene liguid 1, hydrogen peroxide solution 2, methanol solution 3 are pumped into micro-channel mixer 4 simultaneously, control hydrogen peroxide:
Propylene: homogeneous mixed liquor is sent into microchannel preheater 5 by methanol molar ratio 1:2:12 after mixing, controls preheater temperature
It is 60 DEG C.It (is controlled by the counterbalance valve 9 being set on product knockout drum 10 under 60 DEG C of reaction temperature, reaction pressure 3.0MPa
Reaction pressure), the mixed liquor after preheating is sent into micro passage reaction 6 and is reacted.Wherein the flow velocity of mixed liquor is 30mL/
Min, catalyst reactor volume 5mL.Obtained reaction product is sent into product knockout drum 8 after product cooler 7 is cooling,
Gas-phase product is vented after separation, and liquid product, which is collected, enters collection of products tank 10.Analyze result are as follows: hydrogen peroxide conversion ratio
98.4%, propylene oxide yield 94.6%.
Embodiment 2
Propylene liguid 1, hydrogen peroxide solution 2, methanol solution 3 are pumped into micro-channel mixer 4 simultaneously, control hydrogen peroxide:
Propylene: homogeneous mixed liquor is sent into microchannel preheater 5 by methanol molar ratio 1:2:12 after mixing, controls preheater temperature
It is 80 DEG C.Under 80 DEG C of reaction temperature, reaction pressure 4.0MPa, the mixed liquor after preheating is sent into micro passage reaction 6 and is carried out
Reaction.Wherein the flow velocity of mixed liquor is 30mL/min, catalyst reactor volume 120mL.Reaction solution is collected after reaction, point
Analyse result are as follows: hydrogen peroxide conversion ratio 99.5%, propylene oxide yield 93.4%.
Embodiment 3~8
Reaction process referring to described in embodiment 1, change hydrogen peroxide-propylene-methanol molar ratio in reaction, preheater temperature,
Reaction temperature, reaction pressure, mixing flow velocity, catalyst volume, the yield of hydrogen peroxide conversion ratio and propylene oxide it is following (under
HP represents hydrogen peroxide in table, and P represents propylene, and MA represents methanol, and PO represents propylene oxide):
Comparative example 1
Propylene liguid 1, hydrogen peroxide solution 2, methanol solution 3 are pumped into micro-channel mixer 4 simultaneously, control hydrogen peroxide:
Propylene: heterogeneous mixed liquor is sent into microchannel preheater 5 by methanol molar ratio 2:3:10 after mixing, controls preheater temperature
Degree is 30 DEG C.Under 30 DEG C of reaction temperature, reaction pressure 3.0MPa, by after preheating mixed liquor be sent into micro passage reaction 6 into
Row reaction.Wherein the flow velocity of mixed liquor is 60mL/min, catalyst reactor volume 60mL.Reaction solution is collected after reaction, point
Analyse result are as follows: hydrogen peroxide conversion ratio 97.5%, propylene oxide yield 90.8%.
Comparative example 2
Propylene liguid 1, hydrogen peroxide solution 2, methanol solution 3 are pumped into micro-channel mixer 4 simultaneously, control hydrogen peroxide:
Propylene: heterogeneous mixed liquor is sent into microchannel preheater 5 by methanol molar ratio 2:4:15 after mixing, controls preheater temperature
Degree is 30 DEG C.Under 30 DEG C of reaction temperature, reaction pressure 3.0MPa, by after preheating mixed liquor be sent into micro passage reaction 6 into
Row reaction.Wherein the flow velocity of mixed liquor is 60mL/min, catalyst reactor volume 60mL.Reaction solution is collected after reaction, point
Analyse result are as follows: hydrogen peroxide conversion ratio 97.3%, propylene oxide yield 91.4%.
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It falls into the protection scope of the claims in the present invention.
Claims (7)
1. a kind of method of micro passage reaction synthesizing epoxypropane, which is characterized in that the described method includes:
1. propylene liguid (1), hydrogen peroxide solution (2), methanol solution (3) are pumped into micro-channel mixer (4) simultaneously, formed equal
Mix liquid；
It is preheated 2. the homogeneous mixed liquor is sent into microchannel preheater (5)；
It is reacted 3. the homogeneous mixed liquor after preheating is sent into micro passage reaction (6), the micro passage reaction
(6) TS-1 titanium-silicon molecular sieve catalyst is filled in；
4. by step 3. obtained in reaction product be sent into product knockout drum (8) after product cooler (7) are cooling, gas after separation
The emptying of phase product, liquid product, which is collected, enters collection of products tank (10).
2. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the step
1. middle hydrogen peroxide: propylene: methanol molar ratio is 1:(1~3): (10~15).
3. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the step
3. in, the ratio of the volume of the flow velocity of the homogeneous mixed liquor and the TS-1 titanium-silicon molecular sieve catalyst is 0.25~6min-1。
4. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the step
2. in, the temperature of the microchannel preheater (5) is 25~80 DEG C.
5. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the step
3. reaction temperature in is 25~80 DEG C.
6. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the product
Reaction pressure is controlled by setting counterbalance valve (9) on knockout drum (10), the reaction pressure is 1.0~4.0MPa.
7. a kind of method of micro passage reaction synthesizing epoxypropane as described in claim 1, which is characterized in that the dioxygen
The concentration of aqueous solution is 50%, and the concentration of the methanol solution is 99.5%~99.9%.
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| CN201910275598.8A CN109928943B (en) | 2019-04-08 | 2019-04-08 | Method for synthesizing propylene oxide by using microchannel reactor |
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| CN201910275598.8A CN109928943B (en) | 2019-04-08 | 2019-04-08 | Method for synthesizing propylene oxide by using microchannel reactor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979587A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for synthesizing propylene oxide by using microchannel reactor |
| CN113045515A (en) * | 2019-12-27 | 2021-06-29 | 上海化学试剂研究所有限公司 | Method for preparing 2, 3-epoxy-1, 4-butanediol by using microchannel reactor |
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| CN104327016A (en) * | 2014-11-05 | 2015-02-04 | 河北美邦工程科技有限公司 | Method for preparing epoxypropane |
| CN106883198A (en) * | 2017-03-01 | 2017-06-23 | 南京工业大学 | A kind of method that utilization micro-reaction device prepares expoxy propane |
| CN107216296A (en) * | 2016-03-22 | 2017-09-29 | 中国石油化工股份有限公司 | The method that expoxy propane is prepared in micro passage reaction |
| CN107602510A (en) * | 2017-10-12 | 2018-01-19 | 中石化炼化工程（集团）股份有限公司 | The preparation method and production equipment of expoxy propane |
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| CN104327016A (en) * | 2014-11-05 | 2015-02-04 | 河北美邦工程科技有限公司 | Method for preparing epoxypropane |
| CN107216296A (en) * | 2016-03-22 | 2017-09-29 | 中国石油化工股份有限公司 | The method that expoxy propane is prepared in micro passage reaction |
| CN106883198A (en) * | 2017-03-01 | 2017-06-23 | 南京工业大学 | A kind of method that utilization micro-reaction device prepares expoxy propane |
| CN107602510A (en) * | 2017-10-12 | 2018-01-19 | 中石化炼化工程（集团）股份有限公司 | The preparation method and production equipment of expoxy propane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979587A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for synthesizing propylene oxide by using microchannel reactor |
| CN112979587B (en) * | 2019-12-12 | 2022-12-02 | 中国科学院大连化学物理研究所 | Method for synthesizing propylene oxide by using microchannel reactor |
| CN113045515A (en) * | 2019-12-27 | 2021-06-29 | 上海化学试剂研究所有限公司 | Method for preparing 2, 3-epoxy-1, 4-butanediol by using microchannel reactor |
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