CN109535102A - A method of making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor - Google Patents
A method of making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor Download PDFInfo
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- CN109535102A CN109535102A CN201910023298.0A CN201910023298A CN109535102A CN 109535102 A CN109535102 A CN 109535102A CN 201910023298 A CN201910023298 A CN 201910023298A CN 109535102 A CN109535102 A CN 109535102A
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- tubular reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Abstract
The present invention relates to petrochemical industries, more particularly to a kind of method for making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor, it is mixed including catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid with hydrogen peroxide, organic solvent, the successively multi-level tubular reactor reaction through contacting after azeotropic dehydration, raw material liquid propylene point multiply is added separately to every grade of tubular reactor parallel, the reaction mixture flowed out in afterbody tubular reactor enters tower reactor, in tower reactor reaction to after into separation system.The present invention is ingenious in design, is combined using tubular reactor with tower reactor and the reasonable control of reaction temperature and reaction pressure, and eliminating needs N in reactor in laboratory process2The atmosphere of protection, and reactor is eliminated due to N2Protection and oxygen content control and tower apparatus is filtered in increased condensation.Equipment investment and vent gas treatment expense is greatly saved, reactor tail gas discharge is few, small to pollution environment.The present invention is worth with potential market.
Description
Technical field
The present invention relates to petrochemical industries, and in particular to a kind of to make hydrogen peroxide direct oxidation propylene using tubular reactor
The method of continuous preparation of epoxypropane.
Background technique
Propylene oxide (PO) is important Elementary Chemical Industry raw material, and industrial traditional production method mainly by chlorohydrination and is total to
Oxidizing process, for chlorohydrination due to that can generate a large amount of calcium chloride and chlorine-contained wastewater, environmental pollution is big；Although conjugated oxidation environmental pollution
It is few, but invest greatly, coproduction object amount is big, and co-product market can impact the production of propylene oxide.Currently, with peroxidating hydrogen-oxygen
Change production of propylene propylene oxide, since low in the pollution of the environment, coproduction object amount is few, catalysts and solvents are Ke Xunhuanliyong, gradually become
The Main way of propylene oxide production process, but the method is only completed the research of laboratory stage intermittence production, pilot scale now
It prepares with normal practical continuous producing method and device also in the development phase.
Summary of the invention
The technical problem to be solved by the present invention is to how to overcome the shortcomings of the prior art, provide during one kind can be applied to
Examination and normal practical quantity-produced make the side of hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor
Method.
The technical solution of the invention is as follows: a kind of to make hydrogen peroxide direct oxidation propylene continuous production using tubular reactor
The method of propylene oxide, which comprises the following steps: (1) catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid and hydrogen peroxide, organic
Solvent mixing, the azeotropic dehydration in dehydrating tower, dehydration column overhead product after condensation, return tank separation, return by water phase discharge, oily phase
Stream, dehydrating tower tower bottom flow out dewatered mixed liquor and enter multi-level tubular reactor；(2) dewatered mixed liquor is successively through contacting
Multi-level tubular reactor reaction, be equipped with force (forcing) pump and mixer before every grade of tubular reactor, raw material liquid propylene divides multiply
In mixer before being added separately to every grade of tubular reactor parallel, the reaction mixture that is flowed out in afterbody tubular reactor
Into tower reactor, reacted in tower reactor to terminating；Multi-level tubular reactor reaction temperature is 50~80 DEG C, reaction
Pressure is 3~6MPa, is equipped with cooling system on multi-level tubular reactor；(3) end reaction flowed out from tower reactor is mixed
Conjunction liquid enters separation system and is separated.
Further, dehydration column overhead temperature be 30~50 DEG C, column bottom temperature be 45~55 DEG C, tower top pressure be 3~
5KPa, tower bottom pressure are 7~9KPa；The dewatered mixed liquor moisture content for being dehydrated tower bottom outflow is less than 3300ppm.
Further, the reaction mixture flowed out in afterbody tubular reactor enters from the top of tower reactor,
Tower reactor reaction temperature is 40~50 DEG C, and reaction pressure is less than 3MPa, gas after tower reactor overhead product condenses and separates
Mutually enter separation system separation into the end reaction mixed liquor that deaerating plant processing, liquid phase and tower bottom flow out.
Further, multi-level tubular reactor is second level or three-level tubular reactor.
Further, multi-level tubular reactor is three-level tubular reactor.
Further, hydrogen peroxide mass concentration is 45~55%, and organic solvent is n-hexane, benzene, toluene, ethylo benzene, second
One or both of acetoacetic ester, trioctyl phosphate, tributyl phosphate, second cyanogen, dichloroethanes, chloroform；Hydrogen peroxide with it is organic molten
The molar ratio of agent is 1:2~4, and the molar ratio of hydrogen peroxide and catalyst is 1:0.0032~0.01, into three-level tubular reactor
H in the amount of the propylene liguid of front end mixer and each tubular reactor2O2Molar ratio be respectively 2~3:1,8.5~9.5:1,30
~40:1.
Further, organic solvent is benzene and tributyl phosphate.
The present invention is carried out for the intermittent hydrogen peroxide oxidation production of propylene propylene oxide process of laboratory stage research
It improves, develops suitable for pilot scale and normal practical quantity-produced production technology and device, achieve technology below and imitate
Fruit: (1) present invention reasonably selects type of reactor and two kinds of reactors match, and the reasonable control to reaction condition, makes
It does not need to be filled with N in reactor2Equal inert gases dilution hydrogen peroxide decomposes 0 generated2Safeguard protection is carried out to reaction environment,
Save equipment investment and operating cost；(2) reactor is without the additional N for increasing pressurization condensing tower and releasing to each reactor2
It waits the tail gas of inert gases, the oxygen and gaseous organic substance taken out of to be handled, saves equipment investment and operating cost；(3) it manages
It is reacted in formula reactor, reaction process is greatly improved reaction conversion ratio and propylene oxide closest to kinetics
Yield；(4) tubular reactor can make reaction mild, make hydrogen peroxide fully reacting as far as possible, reduce hydrogen peroxide and decompose, into
And it reduces 0 in system2Content, tubular reactor front force (forcing) pump pressure control and tubular reactor in temperature control
Under, 0 in system2It is dissolved in the liquid phase, gas phase wanders about as a refugee the 0 of state2It is less, increase reaction safety；(5) last tower reaction
Device is by dropping to 3MPa for pressure hereinafter, making to dissolve part 0 in the liquid phase2It is precipitated with gaseous state, is exported by tower top, into deoxygenation
Device, that is, propylene deaerating plant processing reduces vapor-phase reactant and the end reaction mixed liquor flowed out from tower bottom in tower reactor
In 02Content increases the safety of tower reactor and separation system；(6) since entire reactor assembly is without N2Equal indifferent gas
Body protection, is only precipitated in tower reactor tower top and contains 02Deaerating plant processing is carried out with the gas phase tail gas of the organic matters such as propylene, greatly
Reduce the treating capacity of tower reactor overhead condenser duty amount and tail gas greatly, drops bottom operation cost significantly.Present invention tool
There is market potential value.
Detailed description of the invention
Fig. 1 is a kind of side for making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor of the present invention
Method process flow diagram；
Label wherein in Fig. 1 is as follows: T-101 dehydrating tower；E-101 dehydrating tower condenser；V-101 dehydrating tower return tank；
E-102 dehydration column reboiler；R-101A level-one tubular reactor；R-101B second level tubular reactor；R-101C three-level tubular type is anti-
Answer device；P-101A level-one tubular reactor force (forcing) pump；P-101B second level tubular reactor force (forcing) pump；P-101C three-level pipe reaction
Device force (forcing) pump；MX-101A level-one tubular reactor mixer；MX-101B second level tubular reactor mixer；MX-101C three-level
Tubular reactor mixer；T-102 tower reactor；E-103 tower reactor condenser；V-102 gas-liquid diversion cans.
Specific embodiment
Below in conjunction with example, kind, which is described in detail, using tubular reactor makes hydrogen peroxide direct oxidation propylene continuous production epoxy
The method of propane.
As shown in Figure 1, a kind of side for making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor
Method, comprising the following steps: (1) catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid is mixed with hydrogen peroxide, organic solvent, in dehydrating tower T-101
Middle azeotropic dehydration, dehydrating tower T-101 overhead product is after dehydrating tower condenser E-101 condensation is separated with return tank V-101, water phase
Discharge, oil mutually flow back；(2) dehydrating tower T-101 tower bottom flows out the dewatered mixed liquor successively three-level tubular reactor through contacting
R-101A, R-101B, R-101C react, and force (forcing) pump P-101A, P-101B, P-101C are equipped with before every grade of tubular reactor and is mixed
Clutch MX-101A, MX-101B, MX-101C, before raw material liquid propylene point multiply is added separately to every grade of tubular reactor parallel
Mixer MX-101A, MX-101B, MX-101C in, the reaction mixture that is flowed out in afterbody tubular reactor R-101C
Into tower reactor T-102, reacted in tower reactor T-102 to terminating；Three-level tubular type reactor reaction temperature is 50
~80 DEG C, reaction pressure is 3~6MPa, is equipped with cooling system on three-level tubular reactor；(3) from tower reactor T-102
The end reaction mixed liquor of outflow enters separation system and is separated.
Further, dehydrating tower T-101 tower top temperature is 30~50 DEG C, and column bottom temperature is 45~55 DEG C, tower top pressure 3
~5KPa, tower bottom pressure are 7~9KPa；The dewatered mixed liquor moisture content of the bottom dehydrating tower T-101 outflow is less than
3300ppm.The reaction mixture flowed out in afterbody tubular reactor R-101C from the top of tower reactor T-102 into
Enter, tower reactor T-102 reaction temperature is 40~50 DEG C, and reaction pressure is less than 3MPa, tower reactor T-102 overhead product
Gas phase is handled into deaerating plant after tower reactor condenser E-103 condensation is separated with gas-liquid diversion cans V-102, liquid phase and tower
The end reaction mixed liquor of bottom outflow enters separation system separation.
Further, hydrogen peroxide mass concentration is 45~55%, and organic solvent is benzene and tributyl phosphate；Hydrogen peroxide with have
The molar ratio of solvent is 1:2~4, and the molar ratio of hydrogen peroxide and catalyst is 1:0.0032~0.01, anti-into three-level tubular type
Answer H in the amount and each tubular reactor of the propylene liguid of device front end mixer2O2Molar ratio be respectively 2~3:1,8.5~9.5:
1,30~40:1.
Pilot experiment result is as follows:
1 tubular reactor experimental conditions of table
Continued 1
| Reactor position number | PO selectivity (%) | PG selectivity (%) | PO yield (%) | 02Content (wt%) in the liquid phase |
| R-101A | >50 | <3 | >55 | <1.2 |
| R-101B | >40 | <2 | >40 | <0.7 |
| R-101C | >3 | <2 | >8 | <0.5 |
| It is total | >93 | <7 | >98 | <0.5 |
2 tower reactor experimental conditions of table
In order to make H in tubular reactor it can be seen from above experimental result2O2Fully reacting, propylene material is always
Be it is excessive, PO yield be greater than 98% or more, in this system, H2O2The oxygen of decomposition is dissolved in always the liquid phase of reaction system
In；In tower reactor, H2O2Further fully reacting, oxygen is released from reaction solution becomes gas phase, is filled by deoxygenation
Removing is set, while controlling the oxygen content in reactor cannot be exceeded, achievees the purpose that safety in production.
Simply to illustrate that technical concepts and features of the invention, its purpose is allows in the art above-described embodiment
Those of ordinary skill cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
It is the equivalent changes or modifications that the essence of content according to the present invention is made, should be covered by the scope of protection of the present invention.
Claims (7)
1. a kind of method for being made hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor, feature are existed
In, comprising the following steps:
(1) catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid is mixed with hydrogen peroxide, organic solvent, the azeotropic dehydration in dehydrating tower, dehydrating tower
After condensation, return tank separation, water phase discharge, oil mutually flows back overhead product, dehydrating tower tower bottom flow out dewatered mixed liquor into
Enter multi-level tubular reactor；
(2) successively the multi-level tubular reactor through contacting reacts dewatered mixed liquor, is equipped with and adds before every grade of tubular reactor
Press pump and mixer, raw material liquid propylene point multiply are added separately to parallel in the mixer before every grade of tubular reactor, finally
The reaction mixture flowed out in level-one tubular reactor enters tower reactor, is reacted in tower reactor to terminating；It is multistage
Tubular reactor reaction temperature is 50~80 DEG C, and reaction pressure is 3~6MPa, is equipped with cooling system on multi-level tubular reactor
System；
(3) enter separation system from the end reaction mixed liquor that tower reactor flows out to be separated.
2. a kind of utilization tubular reactor according to claim 1 makes hydrogen peroxide direct oxidation propylene continuous production epoxy third
The method of alkane, it is characterised in that: dehydration column overhead temperature be 30~50 DEG C, column bottom temperature be 45~55 DEG C, tower top pressure be 3~
5KPa, tower bottom pressure are 7~9KPa；The dewatered mixed liquor moisture content for being dehydrated tower bottom outflow is less than 3300ppm.
3. a kind of utilization tubular reactor according to claim 1 makes hydrogen peroxide direct oxidation propylene continuous production epoxy third
The method of alkane, it is characterised in that: the reaction mixture flowed out in afterbody tubular reactor from the top of tower reactor into
Enter, tower reactor reaction temperature is 40~50 DEG C, and reaction pressure is less than 3MPa, after tower reactor overhead product condenses and separates
Gas phase enters separation system separation into the end reaction mixed liquor that deaerating plant processing, liquid phase and tower bottom flow out.
4. a kind of described in any one of -3 claims according to claim 1 make hydrogen peroxide direct oxidation third using tubular reactor
The method of alkene continuous preparation of epoxypropane, it is characterised in that: multi-level tubular reactor is second level or three-level tubular reactor.
5. a kind of utilization tubular reactor according to claim 4 makes hydrogen peroxide direct oxidation propylene continuous production epoxy third
The method of alkane, it is characterised in that: multi-level tubular reactor is three-level tubular reactor.
6. a kind of utilization tubular reactor according to claim 5 makes hydrogen peroxide direct oxidation propylene continuous production epoxy third
The method of alkane, it is characterised in that: hydrogen peroxide mass concentration be 45~55%, organic solvent be n-hexane, benzene, toluene, ethylo benzene,
One or both of ethyl acetate, trioctyl phosphate, tributyl phosphate, second cyanogen, dichloroethanes, chloroform；Hydrogen peroxide with it is organic
The molar ratio of solvent is 1:2~4, and the molar ratio of hydrogen peroxide and catalyst is 1:0.0032~0.01, into three-level pipe reaction
H in the amount of the propylene liguid of device front end mixer and each tubular reactor2O2Molar ratio be respectively 2~3:1,8.5~9.5:1,
30~40:1.
7. a kind of utilization tubular reactor according to claim 6 makes hydrogen peroxide direct oxidation propylene continuous production epoxy third
The method of alkane, it is characterised in that: organic solvent is benzene and tributyl phosphate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910023298.0A CN109535102A (en) | 2019-01-10 | 2019-01-10 | A method of making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor |
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| CN201910023298.0A CN109535102A (en) | 2019-01-10 | 2019-01-10 | A method of making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tubular reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111408319A (en) * | 2020-03-26 | 2020-07-14 | 北京理工大学 | Method for preparing p-tert-butyl toluene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693703A (en) * | 2009-10-14 | 2010-04-14 | 大连理工大学 | Energy-saving and emission-reducing technique for producing propane epoxide by using hydrogen peroxide epoxidation propylene |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
| CN105712955A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Technical process for producing epichlorohydrin by chloropropene epoxidation |
| CN107250122A (en) * | 2015-02-17 | 2017-10-13 | 赢创德固赛有限公司 | With the method for hydrogen peroxide epoxidation propylene |
-
2019
- 2019-01-10 CN CN201910023298.0A patent/CN109535102A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693703A (en) * | 2009-10-14 | 2010-04-14 | 大连理工大学 | Energy-saving and emission-reducing technique for producing propane epoxide by using hydrogen peroxide epoxidation propylene |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
| CN105712955A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Technical process for producing epichlorohydrin by chloropropene epoxidation |
| CN107250122A (en) * | 2015-02-17 | 2017-10-13 | 赢创德固赛有限公司 | With the method for hydrogen peroxide epoxidation propylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111408319A (en) * | 2020-03-26 | 2020-07-14 | 北京理工大学 | Method for preparing p-tert-butyl toluene |
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Application publication date: 20190329 |