CN109553593A - The process of propylene glycol is removed in a kind of hydrogen peroxide direct oxidation legal system propylene oxide - Google Patents
The process of propylene glycol is removed in a kind of hydrogen peroxide direct oxidation legal system propylene oxide Download PDFInfo
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- CN109553593A CN109553593A CN201910029918.1A CN201910029918A CN109553593A CN 109553593 A CN109553593 A CN 109553593A CN 201910029918 A CN201910029918 A CN 201910029918A CN 109553593 A CN109553593 A CN 109553593A
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- Prior art keywords
- tower
- propylene glycol
- propylene
- propylene oxide
- enters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 138
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 239000012224 working solution Substances 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 239000007792 gaseous phase Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- QMGLMRPHOITLSN-UHFFFAOYSA-N 2,4-dimethyloxolane Chemical compound CC1COC(C)C1 QMGLMRPHOITLSN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 14
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004231 Riboflavin-5-Sodium Phosphate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- JHZRQBKLEHQTKF-UHFFFAOYSA-N 2-methyloxirane;prop-1-ene Chemical compound CC=C.CC1CO1 JHZRQBKLEHQTKF-UHFFFAOYSA-N 0.000 description 2
- 239000004229 Alkannin Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004235 Orange GGN Substances 0.000 description 2
- 239000004234 Yellow 2G Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004172 quinoline yellow Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002151 riboflavin Substances 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004230 Fast Yellow AB Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004173 sunset yellow FCF Substances 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to petrochemical industries, more particularly to the process for removing propylene glycol in a kind of hydrogen peroxide direct oxidation legal system propylene oxide, including catalyst and hydrogen peroxide, organic solvent mixed dehydration, it is reacted in reaction system after dehydration with propylene liguid, final reaction working solution enters crude tower and distillates the light components such as propylene and propylene oxide from tower top, the heavy constituents such as propylene glycol, catalyst are distillated from tower bottom, and tower top light component and tower bottom heavy constituent further separate.The final reaction working solution of the present invention separates weight component first with crude tower, heavy constituent major part direct reuse containing catalyst, small part recycles catalyst using the filter of water scrubber, reduce catalyst loss and filter investment, small part heavy constituent recycles propylene glycol using water scrubber and propylene glycol recovery tower, and the propylene glycol stayed in reaction system will not influence reaction, and the recombination component handled is few, reduce the investment and running cost of water scrubber and propylene glycol recovery tower.
Description
Technical field
The present invention relates to petrochemical industries, and in particular to removes third in a kind of hydrogen peroxide direct oxidation legal system propylene oxide
The process of glycol.
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 is prepared with practical normal continuous producing method and device and is especially the working solution of subsequent final reaction and separate, purify and benefit again
With technique 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 a kind of suitable for pilot scale
With the process for removing propylene glycol in practical normal quantity-produced hydrogen peroxide direct oxidation legal system propylene oxide.
The technical solution of the invention is as follows: the work of propylene glycol is removed in a kind of hydrogen peroxide direct oxidation legal system propylene oxide
Process, comprising the following steps: (1) catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid is mixed with hydrogen peroxide, organic solvent, in dehydrating tower
Azeotropic dehydration, after condensation, return tank separation, water phase discharge, oil mutually flows back dehydration column overhead product, and the outflow of dehydrating tower tower bottom is de-
Mixed liquor after water enters reaction system；
(2) raw material liquid propylene reacts in reaction system with dewatered mixed liquor generates final reaction working solution；
(3) final reaction working solution enters the preliminary rectifying separation of crude tower progress, and top gaseous phase is condensed through condenser and gas-liquid separation
After tank separation, discharge after gas phase treatment is up to standard, one is back in tower top liquid phase, enters after another stock-traders' know-how deaerating plant deoxygenation de-
Light tower carries out propylene and separates with propylene oxide rectifying；Lightness-removing column top gaseous phase enters reflux after condenser is condensed to 30~40 DEG C
Tank, one in return tank are back in lightness-removing column tower top, and another burst of Returning reacting system reuse, lightness-removing column tower bottom liquid phase enters
Propylene oxide rectifying column rectifying, propylene oxide rectifying tower top gaseous phase enter return tank after condenser is condensed to 30~40 DEG C,
One in return tank is back in propylene oxide the top of the distillation column, is left part and is used as product propylene, propylene oxide rectifying
Tower tower bottom liquid phase returns to crude tower and mixes with crude tower tower bottom liquid；(4) propylene oxide rectifying tower bottom liquid phase and crude tower tower
It is divided into two strands after condenser is cooling after the mixing of bottom liquid phase, one returns to dehydrating tower reuse, and another strand enters at the top of water scrubber, inhales
It receives agent water to enter from washing tower bottom, counter-current extraction enters the propylene glycol at the top of water scrubber in mixed liquor, washes column overhead and tower
Bottom is equipped with gun barrel, and the water phase that gun barrel is isolated is sent to propylene glycol recovery tower, and the oil isolated mutually returns de-
Water tower reuse, water scrubber is interior to be equipped with filter, filters out catalytic agent reuse；Propylene glycol recovery tower top gaseous phase is condensed through condenser
Enter surge tank after to 30~40 DEG C, one is back in propylene glycol recycling column overhead after surge tank outflow, another burst of return
Replenisher of the water scrubber as absorbent water, propylene glycol recovery tower tower bottom liquid phase is as propylene glycol product.
Further, through condensing after step (4) oxypropylene rectifying tower bottom liquid phase is mixed with crude tower tower bottom liquid
It is divided into two strands after device is cooling, one returns to dehydrating tower reuse, and another strand enters at the top of water scrubber, and two bursts of volume ratios are 2.0~
5.0:1.
Further, reaction working solution final in step (3) enters the preliminary rectifying separation of crude tower progress, top gaseous phase
After first-stage condenser is separated with level-one knockout drum, gas phase enters secondary condenser and second level again in level-one knockout drum
Knockout drum separation, the gas phase treatment rear discharge up to standard in second level knockout drum, in level-one knockout drum and second level
One is back in tower top after liquid phase in knockout drum is converged, and lightness-removing column is entered after another stock-traders' know-how deaerating plant deoxygenation and is carried out
Propylene is separated with propylene oxide rectifying.
Further, the filter in step (4) is ceramic element, ceramic membrane or metal agglomeration filter core.
The present invention is in the intermittent hydrogen peroxide oxidation production of propylene propylene oxide process of laboratory stage research
The separation system of end reaction working solution is improved, and is developed finally anti-suitable for pilot scale and practical normal quantity-produced
Answer working solution to post-process separating technology, achieve technical effect below: (1) final reaction working solution will first with crude tower
The separation of weight component, light component mainly includes propylene and propylene oxide, and heavy constituent mainly includes propylene glycol and catalyst, containing urging
The heavy constituent major part direct reuse of agent, small part recycle catalyst using the filter of water scrubber, reduce catalyst stream
Filter of becoming estranged investment；(2) small part heavy constituent recycles propylene glycol using water scrubber and propylene glycol recovery tower, makes to stay in reaction system
The amount of the propylene glycol of system is in certain level, will not influence reaction, and it is few to handle recombination component, reduces water scrubber and the third two
The investment and running cost of alcohol recovery tower；(3) heavy constituent of direct reuse and enter water scrubber heavy constituent volume ratio be 2.0~
5.0:1, appropriate will increase the propylene glycol stayed in reaction system not, and the amount of propylene glycol will not influence reaction process；(4) straight
The heavy constituent taken back is introduced into dehydrating tower and is dehydrated, and is rather than directly into reaction system, can to enter reaction system
In water controlled, reduce reaction system propylene oxide hydrolysis, improve the yield of propylene oxide；(5) weight of direct reuse
Component is introduced into dehydrating tower and is dehydrated, and is rather than directly into reaction system, and the effect of catalyst can be made more preferable.The present invention
It is worth with market potential.
Detailed description of the invention
Fig. 1 is that the process process of removing propylene glycol in a kind of hydrogen peroxide direct oxidation legal system propylene oxide of the present invention is shown
It is intended to；
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-101 reaction system；MX-101 mixer；T-102 crude tower；The condensation of E-103 crude tower level-one
Device；V-102 crude tower level-one knockout drum；E-104 crude tower secondary condenser；V-103 crude tower second level knockout drum；
E-105 rough segmentation tower reboiler；E-106 crude tower tower bottom condenser；T-103 lightness-removing column；E-107 condenser of light component removal column；V-104 is de-
Light tower return tank；E-108 lightness-removing column reboiler；T-104 propylene oxide rectifying column；E-109 propylene oxide rectifying column condenser；V-
105 propylene oxide rectifier column reflux tanks；E-110 propylene oxide rectifying tower reboiler；T-105 water scrubber；V-107 water scrubber tower bottom
Gun barrel；V-106 water scrubber tower top gun barrel；T-106 propylene glycol recovery tower；The condensation of E-111 propylene glycol recovery tower
Device；E-112 propylene glycol recycles tower reboiler；V-108 propylene glycol recovery tower surge tank.
Specific embodiment
With reference to embodiments, removing the third two in a kind of the present invention will be described in detail hydrogen peroxide direct oxidation legal system propylene oxide
The process of alcohol.
As shown in Figure 1, in a kind of hydrogen peroxide direct oxidation legal system propylene oxide remove propylene glycol process include with
Lower step: (1) catalyst quaternary ammonium salt phosphor-tungstic heteropoly acid is mixed with hydrogen peroxide, organic solvent, and azeotropic is de- in dehydrating tower T-101
Water, dehydrating tower T-101 overhead product are condensed through condenser E-101, after return tank V-101 separation, and water phase discharge, oil mutually flows back,
Dehydrating tower T-101 tower bottom flows out dewatered mixed liquor and enters reaction system R-101；(2) raw material liquid propylene with it is dewatered
Mixed liquor reacts in reaction system R-101 generates final reaction working solution；(3) final reaction working solution enters crude tower
T-102 carries out preliminary rectifying separation, and T-102 top gaseous phase is separated through first-stage condenser E-103 with level-one knockout drum V-102
Afterwards, gas phase enters secondary condenser E-104 again and separates with second level knockout drum V-103 in level-one knockout drum V-102,
It is discharged after gas phase treatment in second level knockout drum V-103, in level-one knockout drum V-102 and second level knockout drum V-
One is back in T-102 tower top after liquid phase in 103 is converged, and lightness-removing column T-103 is entered after another stock-traders' know-how deaerating plant deoxygenation
Propylene is carried out to separate with propylene oxide rectifying；Lightness-removing column T-103 top gaseous phase through condenser E-107 condense to 30~40 DEG C it is laggard
Enter return tank V-104, one in return tank V-104 is back in lightness-removing column T-103 tower top, another gang of Returning reacting system R-
101 reuses, lightness-removing column T-103 tower bottom liquid phase enter propylene oxide rectifying column T-104 rectifying, propylene oxide rectifying column T-104 tower
Top gas mutually enters return tank V-105 after condenser E-109 is condensed to 30~40 DEG C, one in return tank V-105 is back to ring
In Ethylene Oxide rectifying column T-104 tower top, it is left part and is used as product propylene, propylene oxide rectifying column T-104 tower bottom liquid phase
Crude tower T-102 is returned to mix with crude tower T-102 tower bottom liquid；(4) propylene oxide rectifying column T-104 tower bottom liquid phase and rough segmentation
Tower T-102 tower bottom liquid is divided into two strands after condenser E-106 is cooling after mixing, one returns to dehydrating tower T-101 reuse, another
Stock enters at the top of water scrubber T-105, and absorbent water enters from the bottom water scrubber T-105, and counter-current extraction enters the top water scrubber T-105
Propylene glycol in portion's mixed liquor, water scrubber T-105 tower top and tower bottom are equipped with gun barrel V-106, V-107, water-oil separating
The water phase that tank V-106, V-107 are isolated is sent to propylene glycol recovery tower T-106, and the oil isolated mutually returns to dehydrating tower T-101 and returns
With water scrubber T-105 is interior to be equipped with filter, filters out catalytic agent reuse；Propylene glycol recovery tower T-106 top gaseous phase is through condenser
E-111 is condensed to surge tank V-108 is entered after 30~40 DEG C, one is back to propylene glycol recycling after surge tank V-108 outflow
In tower T-106 tower top, replenisher of another gang of return water scrubber T-105 as absorbent water, propylene glycol recovery tower T-106 tower bottom
Liquid phase is as propylene glycol product.
Further, step (4) oxypropylene rectifying column T-104 tower bottom liquid phase and crude tower T-102 tower bottom liquid phase are mixed
It is divided into two strands after condenser E-106 is cooling after conjunction, one returns to dehydrating tower T-101 reuse, and another strand enters water scrubber T-105
Top, two bursts of volume ratios are 2.0~5.0:1.Filter in step (4) is ceramic element, ceramic membrane or metal agglomeration filter core.
Deaerating plant, return tank V-104, return tank V-105, surge tank V-108 gas phase tail gas qualified discharge after processing.
Pilot experiment result
(1) crude tower heavy constituent is all handled compared with the processing result of part: catalyst loss can reduce by 30~50%, mistake
Filter investment, which can save 70~80%, water scrubber scale, can reduce 75~85%.
(2) it due to being successive reaction in actual production, returns to dehydrating tower T-101 and enters two bursts of volumes of water scrubber T-105
Than for 2.0~5.0:1, under this proportion, the by-product propylene glycol that the accumulation in reaction process generates just can be from reactant
It is removed completely in system, reduces the reaction rate of side reaction, be conducive to reaction forward and be carried out continuously；It then will increase less than this proportion
The investment of water scrubber filter, uneconomical, the content greater than propylene glycol in this proportion then reaction system is higher, will affect catalyst
Activity.
(3) crude tower bottom heavy constituent enters back into reaction system ratio after carrying out dehydration qualification back to dehydrating tower and is returned directly to
The advantages of reaction system, is:
A. crude tower bottom heavy constituent can be by the outlet object of control dehydrating tower by entering back into reaction system after dehydrating tower
The water content of material controls the water in reaction system；
B. reaction system is entered back into after crude tower bottom heavy constituent dehydrating tower can be by the content of water in control reaction system
The hydrolysis of propylene oxide is reduced, to improve the yield of propylene oxide.
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 (4)
1. in a kind of hydrogen peroxide direct oxidation legal system propylene oxide remove propylene glycol process, which is characterized in that including with
Lower step:
(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 reaction system；
(2) raw material liquid propylene reacts in reaction system with dewatered mixed liquor generates final reaction working solution；
(3) final reaction working solution enters the preliminary rectifying separation of crude tower progress, and top gaseous phase is condensed through condenser and gas-liquid
After knockout drum separation, discharge after gas phase treatment is up to standard, one is back in tower top liquid phase, and another stock-traders' know-how deaerating plant deoxygenation is laggard
Enter lightness-removing column progress propylene to separate with propylene oxide rectifying；Lightness-removing column top gaseous phase enters after condenser is condensed to 30~40 DEG C
Return tank, one in return tank are back in lightness-removing column tower top, another burst of Returning reacting system reuse, lightness-removing column tower bottom liquid phase
Into propylene oxide rectifying column rectifying, propylene oxide rectifying tower top gaseous phase enters reflux after condenser is condensed to 30~40 DEG C
Tank, one in return tank are back in propylene oxide the top of the distillation column, are left part and are used as product propylene, propylene oxide essence
Tower tower bottom liquid phase return crude tower is evaporated to mix with crude tower tower bottom liquid；
(4) it is divided into two strands after propylene oxide rectifying tower bottom liquid phase and crude tower tower bottom liquid mix after condenser is cooling, one
Stock return dehydrating tower reuse, another strand enters at the top of water scrubber, and absorbent water enters from washing tower bottom, and counter-current extraction enters water
The propylene glycol in top of tower mixed liquor is washed, column overhead is washed and tower bottom is equipped with gun barrel, what gun barrel was isolated
Water phase is sent to propylene glycol recovery tower, and the oil isolated mutually returns to dehydrating tower reuse, is equipped with filter in water scrubber, is filtered out catalysis
Agent reuse；Propylene glycol recovery tower top gaseous phase enters surge tank after condenser is condensed to 30~40 DEG C, after surge tank outflow
One is back in propylene glycol recycling column overhead, replenisher of another strand of return water scrubber as absorbent water, propylene glycol recycling
Tower tower bottom liquid phase is as propylene glycol product.
2. removing the technique side of propylene glycol in a kind of hydrogen peroxide direct oxidation legal system propylene oxide according to claim 1
Method, it is characterised in that: step (4) oxypropylene rectifying tower bottom liquid phase is cold through condenser after mixing with crude tower tower bottom liquid
But it is divided into two strands afterwards, one returns to dehydrating tower reuse, and another strand enters at the top of water scrubber, and two bursts of volume ratios are 2.0~5.0:1.
3. removing the technique of propylene glycol in a kind of hydrogen peroxide direct oxidation legal system propylene oxide according to claim 1 or 2
Method, it is characterised in that: final reaction working solution enters the preliminary rectifying separation of crude tower progress, top gaseous phase in step (3)
After first-stage condenser is separated with level-one knockout drum, gas phase enters secondary condenser and second level again in level-one knockout drum
Knockout drum separation, the gas phase treatment rear discharge up to standard in second level knockout drum, in level-one knockout drum and second level
One is back in tower top after liquid phase in knockout drum is converged, and lightness-removing column is entered after another stock-traders' know-how deaerating plant deoxygenation and is carried out
Propylene is separated with propylene oxide rectifying.
4. removing the technique side of propylene glycol in a kind of hydrogen peroxide direct oxidation legal system propylene oxide according to claim 1
Method, it is characterised in that: the filter in step (4) is ceramic element, ceramic membrane or metal agglomeration filter core.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910029918.1A CN109553593B (en) | 2019-01-10 | 2019-01-10 | Process method for removing propylene glycol from epoxypropane prepared by direct oxidation of hydrogen peroxide |
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| CN201910029918.1A CN109553593B (en) | 2019-01-10 | 2019-01-10 | Process method for removing propylene glycol from epoxypropane prepared by direct oxidation of hydrogen peroxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204515A (en) * | 2019-05-28 | 2019-09-06 | 山东凯泰科技股份有限公司 | A kind of catalyst dewatering process of hydrogen peroxide direct oxidation method production epoxychloropropane |
| EP3988534A1 (en) * | 2020-10-21 | 2022-04-27 | Evonik Operations GmbH | A method for the preparation of 1,2-propanediol and dipropylene glycol |
| CN115697549A (en) * | 2020-06-26 | 2023-02-03 | 利安德化学技术有限公司 | Use of monopropylene glycol from a purge stream in the preparation of an epoxidation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204515A (en) * | 2019-05-28 | 2019-09-06 | 山东凯泰科技股份有限公司 | A kind of catalyst dewatering process of hydrogen peroxide direct oxidation method production epoxychloropropane |
| CN110204515B (en) * | 2019-05-28 | 2021-04-02 | 山东凯泰科技股份有限公司 | Catalyst dehydration process for producing epoxy chloropropane by hydrogen peroxide direct oxidation method |
| CN115697549A (en) * | 2020-06-26 | 2023-02-03 | 利安德化学技术有限公司 | Use of monopropylene glycol from a purge stream in the preparation of an epoxidation catalyst |
| EP3988534A1 (en) * | 2020-10-21 | 2022-04-27 | Evonik Operations GmbH | A method for the preparation of 1,2-propanediol and dipropylene glycol |
| WO2022084047A1 (en) * | 2020-10-21 | 2022-04-28 | Evonik Operations Gmbh | A method for the preparation of 1,2-propanediol and dipropylene glycol |
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