CN104109138A - Epoxypropane purifying method - Google Patents
Epoxypropane purifying method Download PDFInfo
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- CN104109138A CN104109138A CN201310129862.XA CN201310129862A CN104109138A CN 104109138 A CN104109138 A CN 104109138A CN 201310129862 A CN201310129862 A CN 201310129862A CN 104109138 A CN104109138 A CN 104109138A
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- tower
- logistics
- propylene oxide
- extraction agent
- isopropyl benzene
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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Abstract
The invention relates to an epoxypropane purifying method. The problems of high extractant cost and bad product quality due to the introduction of a system outside medium in the prior art are mainly solved. The epoxypropane purifying method is characterized in that a crude epoxypropane solution containing epoxypropane, water, acetaldehyde, propionaldehyde, methanol, acetone and C5C7 hydrocarbon impurities and obtained after a reaction of cumene hydroperoxide and propylene is extracted and distilled by an extractant, wherein the extractant is isopropyl benzene. The epoxypropane purifying method well solves the problems, and can be used in the industrial production of epoxypropane purification.
Description
Technical field
The present invention relates to a kind of purification process of propylene oxide.
Background technology
Propylene oxide is important organic compound raw material, is the third-largest propylene analog derivative that is only second to polypropylene and vinyl cyanide.Propylene oxide is mainly for the production of polyether glycol, propylene glycol and all kinds of nonionogenic tensides etc., wherein polyether glycol is the important source material of production polyurethane foam, lagging material, elastomerics, tackiness agent and coating etc., and all kinds of nonionic surface active agent are used widely in industries such as oil, chemical industry, agricultural chemicals, weaving, daily use chemicals.But the propylene oxide only with higher degree can be for the manufacture of polyvalent alcohol, therefore will be to synthetic propylene oxide thick product carry out can being applied to and preparing polyvalent alcohol after purification processes.And the desired condition of propylene oxide generation polymerization not only requires propene oxide purity to reach 99.9wt%, water impurity, aldehyde, the content of non-volatile point are had to strict demand.
In hydrogen phosphide cumene method (CHP method) propylene oxide process processed, hydrogen phosphide cumene reacts the crude propene oxide that the product that obtains obtains after Propylene recovery, separating by-products with propylene, still contains water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the impurity such as hydro carbons.Therefore,, in order to obtain meeting the high purity propylene oxide of polymerization requirement, the impurity containing must be separated and removes in propylene oxide.Due to acetaldehyde and propylene oxide boiling temperature approach and relative volatility close to 1, propylene oxide and 2-methylpentane, methyl alcohol all form the features such as azeotrope, the method for conventional distillation has been difficult to the purifying of propylene oxide.
As the purification process of propylene oxide, in the patents of invention such as US5133839, US5262017, US5354430/1, US7285187, US8093412 and US20120077996, all have disclosed.With regard to the purifying of propylene oxide, the main C that uses at present
7~ C
20straight chain and side chain hydro carbons and glycols carry out the method for extractive distillation as extraction agent.For example, US Patent No. 3578568 discloses one, and to make spent glycol, propylene glycol, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether be extraction solvent, and propylene oxide is carried out to extractive distillation, makes it the method separating with water, methyl alcohol, acetone and acetaldehyde.The alkane that discloses octane and so in US3843488 has C to removing
6hydrocarbon impurity as effective in 2-methylpentane.The alkane that discloses octane and so in US3607669 is to except anhydrating effectively.It is effective to removing in propylene oxide the impurity such as contained methyl alcohol, propionic aldehyde, acetone that the hydrocarbon such as octane are disclosed in US5133839.It is effective to removing the oxygenatedchemicalss such as water impurity, propionic aldehyde, acetone that glycol is disclosed in US5354430/1.The mode that US20120077996 adopts glycol and the two extraction agent multi-stage counter current extractions of octane and octane extracting rectifying to combine is carried out propylene oxide purification, utilizes extraction process to reduce sepn process energy consumption.
But the material of above-mentioned technique outside all will introducing system, as hydro carbons such as octanes, increased extraction agent cost, and quality product is had a certain impact, and extraction agent closed cycle in system, is beneficial to impurity and accumulates in system, and be unfavorable for improving the quality of products.
Summary of the invention
Technical problem to be solved by this invention is prior art due to the outer medium of introducing system, exists extraction agent cost high, and the problem of poor product quality provides a kind of purification process of new propylene oxide.The method is not introduced new impurity, has quality product high, the advantage that extraction agent cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of purification process of propylene oxide, for extraction agent, hydrogen phosphide cumene is reacted with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the crude propene oxide solution of hydrocarbon impurities carries out the purification process of the propylene oxide of extractive distillation, and wherein, described extraction agent is isopropyl benzene.
In one embodiment of the present invention, the present invention relates to a kind of purification process of propylene oxide, comprise the following steps:
A) optionally, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the crude propene oxide solution of hydrocarbon impurities enters weight-removing column, and after conventional distillation separates, tower reactor obtains containing water, propionic aldehyde, acetone and C
7the logistics of hydro carbons, tower top obtains logistics I;
B) logistics I enters extraction tower bottom, and extraction agent isopropyl benzene enters extraction tower top, and after separation, tower top obtains the logistics that contains water, methyl alcohol and acetaldehyde, and tower reactor obtains logistics II;
C) logistics II enters de-lighter hydrocarbons tower bottom, and extraction agent isopropyl benzene enters de-lighter hydrocarbons tower top, and after separation, tower top obtains product propylene, and tower reactor obtains logistics III;
D) optionally, logistics III enters extraction agent recovery tower, and after separation, tower top obtains containing C
5~ C
6hydrocarbon material flow, tower reactor is extracted agent isopropyl benzene.
In technique scheme, preferably, the theoretical plate number of described weight-removing column is 30 ~ 65, and service temperature is 42 ~ 55 DEG C, and working pressure is 120 ~ 200kPa, and reflux ratio is 1 ~ 5.
Preferably, the theoretical plate number of described extraction tower is 55 ~ 80, and working pressure is 120 ~ 200kPa, and reflux ratio is 50 ~ 200, and tower reactor temperature is no more than 130 DEG C, and the ratio of extraction agent isopropyl benzene flow and logistics I flow is 3 ~ 7.More preferably, in described extraction tower, the ratio of extraction agent isopropyl benzene flow and logistics I flow is 4 ~ 6.
Preferably, the theoretical plate number of described de-lighter hydrocarbons tower is 28 ~ 55, and service temperature is 42 ~ 52 DEG C, and working pressure is 120 ~ 180kPa, and reflux ratio is 1 ~ 4, and the ratio of extraction agent isopropyl benzene flow and logistics II flow is 0.2 ~ 0.6.More preferably, in described de-lighter hydrocarbons tower, the ratio of extraction agent isopropyl benzene flow and logistics II flow is 0.3 ~ 0.6.
Preferably, the theoretical plate number of described extraction agent recovery tower is 25 ~ 40, and service temperature is 42 ~ 51 DEG C, and working pressure is 120 ~ 160kPa, and reflux ratio is 500 ~ 2000.
Preferably, the isopropyl benzene that step d) extraction agent recovery tower tower reactor obtains is circulated to extraction tower top or de-lighter hydrocarbons tower top, as extractant feed.
Preferably, logistics III is divided into two strands, and first strand enters extraction agent recovery tower and carry out extraction agent recovery, and second strand is circulated to extraction tower top as extractant feed, and first strand is 1:(2 ~ 3 with the weight ratio of second strand); Or logistics III enters isopropyl benzene peroxidation unit as reaction raw materials.
In the inventive method, described pressure all refers to absolute pressure.
[0016]purification process of the present invention material solution used be hydrogen phosphide cumene react with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the reaction soln of the impurity such as hydro carbons.CHP legal system propylene oxide technology mainly comprises three reactions: isopropyl benzene peroxidation, propylene ring oxidation reaction and α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis.First, isopropyl benzene is oxidised with air to hydrogen phosphide cumene (CHP), hydrogen phosphide cumene is selective oxidation propylene propylene oxide processed and α under super-hydrophobicity titaniferous SiO 2 catalyst exists, alpha-alpha-dimethyl benzylalcohol, under proprietary palladium/SiO 2 catalyst exists, α, alpha-alpha-dimethyl benzylalcohol and hydrogen generation hydrogenolysis generate isopropyl benzene, and then isopropyl benzene is got back to peroxidation and is recycled.Hydrogen phosphide cumene passes through Propylene recovery with the reaction product of propylene, separates the reaction soln obtaining after overwhelming majority by products, be the reaction soln that contains propylene oxide that purification process of the present invention uses, in the present invention, be called crude propene oxide solution.
Impurity in crude propene oxide solution described in the inventive method, mainly comprises water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7hydro carbons, its composition is in table 1.Wherein, C
5~ C
7hydro carbons mainly comprises 2-methylpentane, 2-methylpentene, 1,5-hexadiene, methylcyclopentane, 3-methyl hexane etc.
Table 1
| Composition | Weight content |
| Acetone | 0.001~0.010 |
| Propionic aldehyde | 50ppm~0.005 |
| Acetaldehyde | 50ppm~0.002 |
| Propylene oxide | 0.970~0.999 |
| Water | 200ppm~0.002 |
| C 5~C 7Hydro carbons | 20ppm~0.002 |
In impurity in crude propene oxide, water, acetaldehyde, C
5~ C
6deng the relative volatility of hydro carbons and propylene oxide, close to 1, propylene oxide and 2-methylpentane, methyl alcohol all form azeotrope, are difficult to separate with conventional distillation.For example, in the propylene oxide that contains methyl alcohol 0.1wt%, 1-hexene 0.1wt%, more various compositions are during to the relative volatility of propylene oxide, under atmospheric pressure, the relative volatility of methyl alcohol is 1.0, the relative volatility of 1-hexene is 1.1, and relative volatility is equal to or close to 1, common fractionation by distillation difficulty.Extractive distillation is commonly used to separate relative volatility and approaches or equal 1 system.
The relative volatility under equilibrium conditions such as the propylene oxide during to use extraction agent isopropyl benzene and impurity methyl alcohol, water, acetaldehyde, 2-methylpentane compares.Condition is under 1atm, in the propylene oxide that contains above-mentioned impurity, adds the extraction agent isopropyl benzene of 3 ~ 5 times of weight ratios to measure, and impurity methyl alcohol, water, acetaldehyde, 2-methylpentane and propylene oxide relative volatility change in table 2.
Table 2
The inventive method adopts raw material isopropyl benzene in system as extraction agent, crude propene oxide solution to be carried out to separation and purification.Extraction agent isopropyl benzene, has the ability of impurity to propylene oxide relative volatility that change.The method can not introduced new impurity, the isopropyl benzene of Separation and Recovery, at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, and obtains the polymerization-grade product propylene that purity exceedes 99.99wt%, the propylene oxide rate of recovery reaches 99.2 ~ 99.8%, has obtained good technique effect.
The inventive method preferably uses isopropyl benzene as extraction agent, and crude propene oxide solution is carried out to the purification process that conventional distillation and extracting rectifying combine, and impurity wherein is effectively separated successively, removed.First in weight-removing column, remove the water, propionic aldehyde, acetone, the C that in crude propene oxide, contain
7the impurity such as hydro carbons; Extraction tower adopts isopropyl benzene to do extraction agent extracting rectifying and removes water, methyl alcohol, acetaldehyde geometric ratio propylene oxide impurity heavily, and propylene oxide is dissolved in extraction agent, discharges from tower reactor, sends into de-lighter hydrocarbons tower; De-lighter hydrocarbons tower adopts isopropyl benzene to make extraction agent extracting rectifying and removes C
5~ C
6deng hydrocarbon impurities, tower top obtains the polymerization-grade product propylene that purity exceedes 99.99wt%.
Brief description of the drawings
Fig. 1 is the process flow diagram of the inventive method.
In Fig. 1, T101 is weight-removing column, T102 is extraction tower, T103 is de-lighter hydrocarbons tower, T104 is extraction agent recovery tower, 1 is crude propene oxide solution, 2 is weight-removing column overhead stream, 3 is the logistics of weight-removing column tower reactor, 4 is extraction tower top extractant feed, 5 is the logistics of extraction tower tower reactor, 6 is extraction tower overhead stream, 7 is de-lighter hydrocarbons tower top extractant feed, 8 is de-lighter hydrocarbons column overhead product propylene, 9 is de-lighter hydrocarbons tower tower reactor logistics, 10 for taking off the part that enters extraction agent recovery tower in the logistics of lighter hydrocarbons tower tower reactor, 11 for being circulated to extraction tower top in de-lighter hydrocarbons tower tower reactor logistics, as the logistics of extractant feed, 12 isopropyl benzenes for recovery, 13 is extraction agent recovery tower overhead stream.
In Fig. 1, contain propylene oxide and contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the crude propene oxide solution 1 of hydrocarbon impurities enters weight-removing column T101 from bottom, after conventional distillation separates, tower reactor obtains containing water, propionic aldehyde, acetone C
7the logistics 3 of hydro carbons and a small amount of propylene oxide, logistics 3 is to system; It is logistics I that tower top obtains logistics 2().Logistics 2 enters extraction tower T102 bottom after supercharging, and extraction agent isopropyl benzene 4 enters extraction tower T102 top, and after separation, tower top obtains the logistics 6 that contains water, methyl alcohol, acetaldehyde impurities and a small amount of propylene oxide, and it is logistics II that tower reactor obtains logistics 5().Logistics 5 enters de-lighter hydrocarbons tower T103 bottom, and extraction agent isopropyl benzene 7 enters de-lighter hydrocarbons tower T103 top, and after separation, tower top obtains product propylene 8, and it is logistics III that tower reactor obtains logistics 9().Logistics 9 is divided into two strands, and first strand enters extraction agent recovery tower T104 recovery extraction agent, and second strand is circulated to extraction tower T102 top as extractant feed 4.Logistics 10 enters extraction agent recovery tower T104, and after separation, tower top obtains containing C
5~ C
6hydrocarbon material flow 13, the extraction agent isopropyl benzene 12 that tower reactor is recycled, extraction agent isopropyl benzene 12 is circulated to de-lighter hydrocarbons tower T103 top, as extractant feed 7.Logistics 8(product propylene) in propylene oxide content exceed 99.99wt%, water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the foreign matter contents such as hydro carbons are as shown in table 3.
Table 3
| Composition | Weight content |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 2~20 ppm |
| Methyl alcohol | 2~20 ppm |
| Water | 2~20 ppm |
| Hydro carbons | 2~20 ppm |
In addition, logistics 9 also can all enter extraction agent recovery tower T104, the extraction agent isopropyl benzene 12 that extraction agent recovery tower T104 tower reactor obtains can be divided into two strands, one is circulated to extraction tower T102 top, as extractant feed 4, another thigh is circulated to de-lighter hydrocarbons tower T103 top, as extractant feed 7.This part content does not show in Fig. 1.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in table 4.
Table 4
| Composition | Content, wt |
| Acetone | 0.008 |
| Propionic aldehyde | 0.002 |
| Acetaldehyde | 0.001 |
| Propylene oxide | 0.987 |
| Water | 0.001 |
| C 5~C 7Hydro carbons | 0.001 |
Logistics 1 is from T101 tower underfeed, and flow is 10000kg/h, logistics 3(T101 tower bottoms) mainly contain water, propionic aldehyde, acetone, C
7hydro carbons, to system, logistics 2(T101 overhead distillate) be pressurized to 400 kPa from T102 tower underfeed through pump.T101 tower theoretical plate number 50, feed plate position is the 32nd block of plate, working pressure is controlled at 150kPa, reflux ratio 2.6.
Logistics 4(T103 still liquid) from the top charging of T102 tower, logistics 6(T102 overhead distillate) mainly contain impurity and a small amount of propylene oxide such as water, methyl alcohol, acetaldehyde, T102 tower solvent ratio (the mass flow rate ratio of logistics 4 and logistics 2) is 5.5, T102 tower theoretical plate number 75, logistics 4 feed entrance points are the 2nd block of plate, and logistics 2 feed entrance points are the 32nd block of plate, and working pressure is controlled at 160kPa, reflux ratio 120,112 DEG C of tower reactor temperature.
Logistics 5(T102 tower bottoms) enter from T103 tower bottom, logistics 7(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio (the mass flow rate ratio of logistics 7 and logistics 5) is 0.35, T103 overhead distillate 8 is product propylene, logistics 9(T103 tower bottoms) be pressurized to 600 kPa through pump, a part (logistics 10) enters T104 tower, a part (logistics 11) is circulated to T102 as extraction agent through being cooled to 50 DEG C, logistics 11 is 2.3 with the ratio of logistics 10 flows, T103 tower theoretical plate number 45, logistics 7 feed entrance points are the 9th block of plate, logistics 5 feed entrance points are the 26th block of plate, working pressure is controlled at 140kPa, reflux ratio 2.
Logistics 13(T104 overhead distillate), mainly contain the C such as 2-methylpentane, 2-methylpentene
5~ C
6hydro carbons and a small amount of propylene oxide, to system, logistics 12(T104 tower bottoms) be pressurized to 500kPa through pump, after being cooled to 50 DEG C, be circulated to again T103 tower as extraction agent, T104 tower theoretical plate number 32, logistics 10 feed entrance points are the 12nd block of plate, and working pressure is controlled at 140kPa, reflux ratio 1500.
Logistics 8(product propylene) in propylene oxide content exceed 99.99wt%, water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the foreign matter contents such as hydro carbons are as shown in table 5, the propylene oxide rate of recovery 99.70%, and product has reached product propylene standard.
Table 5
| Composition | Weight content |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 3 ppm |
| Methyl alcohol | 2 ppm |
| Water | 3 ppm |
| Hydro carbons | 3 ppm |
As can be seen from the above, in employing system, raw material isopropyl benzene, as extraction agent, can not introduced new impurity, and the isopropyl benzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can separate and obtain polymerization-grade propylene oxide qualified product with method easily with economical.
[embodiment 2]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in table 6.
Table 6
| Composition | Content, wt |
| Acetone | 0.008 |
| Propionic aldehyde | 0.002 |
| Acetaldehyde | 0.001 |
| Propylene oxide | 0.987 |
| Water | 0.001 |
| C 5~C 7Hydro carbons | 0.001 |
Logistics 1 is from T101 tower underfeed, and flow is 10000kg/h, logistics 3(T101 tower bottoms) mainly contain water, propionic aldehyde, acetone, C
7hydro carbons, to system, logistics 2(T101 overhead distillate) be pressurized to 400 kPa from T102 tower underfeed through pump.T101 tower theoretical plate number 55, feed plate position is the 34th block of plate, working pressure is controlled at 160kPa, reflux ratio 2.5.
Logistics 4(T103 still liquid) from the top charging of T102 tower, logistics 6(T102 overhead distillate) mainly contain impurity and a small amount of propylene oxide such as water, methyl alcohol, acetaldehyde, T102 tower solvent ratio (the mass flow rate ratio of logistics 4 and logistics 2) is 5.4, T102 tower theoretical plate number 72, logistics 4 feed entrance points are the 2nd block of plate, and logistics 2 feed entrance points are the 35th block of plate, and working pressure is controlled at 150kPa, reflux ratio 125,110 DEG C of tower reactor temperature.
Logistics 5(T102 tower bottoms) enter from T103 tower bottom, logistics 7(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio (the mass flow rate ratio of logistics 7 and logistics 5) is 0.38, T103 overhead distillate 8 is product propylene, logistics 9(T103 tower bottoms) be pressurized to 600 kPa through pump, a part (logistics 10) enters T104 tower, a part (logistics 11) is circulated to T102 as extraction agent through being cooled to 50 DEG C, logistics 11 is 2.4 with the ratio of logistics 10 flows, T103 tower theoretical plate number 43, logistics 7 feed entrance points are the 9th block of plate, logistics 5 feed entrance points are the 25th block of plate, working pressure is controlled at 150kPa, reflux ratio 2.1.
Logistics 13(T104 overhead distillate), mainly contain the C such as 2-methylpentane, 2-methylpentene
5~ C
6hydro carbons and a small amount of propylene oxide, to system, logistics 12(T104 tower bottoms) be pressurized to 550kPa through pump, after being cooled to 50 DEG C, be circulated to again T103 tower as extraction agent, T104 tower theoretical plate number 30, logistics 10 feed entrance points are the 12nd block of plate, and working pressure is controlled at 140kPa, reflux ratio 1600.
Logistics 8(product propylene) in propylene oxide content exceed 99.99wt%, water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the foreign matter contents such as hydro carbons are as shown in table 7, the propylene oxide rate of recovery 99.60%, and product reaches product propylene standard.
Table 7
| Composition | Weight content |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 2 ppm |
| Methyl alcohol | 4 ppm |
| Water | 3 ppm |
| Hydro carbons | 3 ppm |
As can be seen from the above, in employing system, raw material isopropyl benzene, as extraction agent, can not introduced new impurity, and the isopropyl benzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can separate and obtain polymerization-grade propylene oxide qualified product with method easily with economical.
[embodiment 3]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in table 8.
Table 8
| Composition | Content, wt |
| Acetone | 0.009 |
| Propionic aldehyde | 0.003 |
| Acetaldehyde | 0.002 |
| Propylene oxide | 0.982 |
| Water | 0.002 |
| C 5~C 7Hydro carbons | 0.002 |
Logistics 1 is from T101 tower underfeed, and flow is 10000kg/h, logistics 3(T101 tower bottoms) mainly contain water, propionic aldehyde, acetone, C
7hydro carbons, to system, logistics 2(T101 overhead distillate) be pressurized to 400 kPa from T102 tower underfeed through pump.T101 tower theoretical plate number 58, feed plate position is the 35th block of plate, working pressure is controlled at 160kPa, reflux ratio 2.4.
Logistics 4(T103 still liquid) from the top charging of T102 tower, logistics 6(T102 overhead distillate) mainly contain impurity and a small amount of propylene oxide such as water, methyl alcohol, acetaldehyde, T102 tower solvent ratio (the mass flow rate ratio of logistics 4 and logistics 2) is 5.5, T102 tower theoretical plate number 79, logistics 4 feed entrance points are the 2nd block of plate, and logistics 2 feed entrance points are the 36th block of plate, and working pressure is controlled at 160kPa, reflux ratio 116,112 DEG C of tower reactor temperature.
Logistics 5(T102 tower bottoms) enter from T103 tower bottom, logistics 7(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio (the mass flow rate ratio of logistics 7 and logistics 5) is 0.34, T103 overhead distillate 8 is product propylene, logistics 9(T103 tower bottoms) be pressurized to 600 kPa through pump, a part (logistics 10) enters T104 tower, a part (logistics 11) is circulated to T102 as extraction agent through being cooled to 50 DEG C, logistics 11 is 2.3 with the ratio of logistics 10 flows, T103 tower theoretical plate number 45, logistics 7 feed entrance points are the 9th block of plate, logistics 5 feed entrance points are the 26th block of plate, working pressure is controlled at 140kPa, reflux ratio 2.
Logistics 13(T104 overhead distillate), mainly contain the C such as 2-methylpentane, 2-methylpentene
5~ C
6hydro carbons and a small amount of propylene oxide, to system, logistics 12(T104 tower bottoms) be pressurized to 500kPa through pump, after being cooled to 50 DEG C, be circulated to T103 as extraction agent again, T104 tower theoretical plate number 35, logistics 10 feed entrance points are the 14th block of plate, and working pressure is controlled at 140kPa, reflux ratio 1416.
Logistics 8(product propylene) in propylene oxide content exceed 99.99wt%, water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the foreign matter contents such as hydro carbons are as shown in table 9, the propylene oxide rate of recovery 99.62%, and product has reached product propylene standard.
Table 9
| Composition | Weight content |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 4 ppm |
| Methyl alcohol | 3 ppm |
| Water | 5 ppm |
| Hydro carbons | 5 ppm |
As can be seen from the above, in employing system, raw material isopropyl benzene, as extraction agent, can not introduced new impurity, and the isopropyl benzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can separate and obtain polymerization-grade propylene oxide qualified product with method easily with economical.
[embodiment 4]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in table 10.
Table 10
| Composition | Content, wt |
| Acetone | 0.008 |
| Propionic aldehyde | 0.002 |
| Acetaldehyde | 0.001 |
| Propylene oxide | 0.987 |
| Water | 0.001 |
| C 5~C 7Hydro carbons | 0.001 |
Logistics 1 is from T101 tower underfeed, and flow is 10000kg/h, logistics 3(T101 tower bottoms) mainly contain water, propionic aldehyde, acetone, C
7hydro carbons, to system, logistics 2(T101 overhead distillate) be pressurized to 400 kPa from T102 tower underfeed through pump.T101 tower theoretical plate number 50, feed plate position is the 32nd block of plate, working pressure is controlled at 150kPa, reflux ratio 2.6.
Logistics 4(T103 still liquid) from the top charging of T102 tower, logistics 6(T102 overhead distillate) mainly contain impurity and a small amount of propylene oxide such as water, methyl alcohol, acetaldehyde, T102 tower solvent ratio (the mass flow rate ratio of logistics 4 and logistics 2) is 5.2, T102 tower theoretical plate number 75, logistics 4 feed entrance points are the 2nd block of plate, and logistics 2 feed entrance points are the 32nd block of plate, and working pressure is controlled at 160kPa, reflux ratio 120,112 DEG C of tower reactor temperature.
Logistics 5(T102 tower bottoms) enter from T103 tower bottom, logistics 7(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio (the mass flow rate ratio of logistics 7 and logistics 5) is 0.36, T103 overhead distillate 8 is product propylene, logistics 9(T103 tower bottoms) be pressurized to 600 kPa through pump, logistics 9 all enters extraction agent recovery tower T104, the isopropyl benzene 12 that extraction agent recovery tower T104 tower reactor obtains is divided into two strands, one is circulated to extraction tower T102 top, as extractant feed 4, another thigh is circulated to de-lighter hydrocarbons tower T103 top, as extractant feed 7.T103 tower theoretical plate number 45, logistics 7 feed entrance points are the 9th block of plate, and logistics 5 feed entrance points are the 26th block of plate, and working pressure is controlled at 140kPa, reflux ratio 2.
Logistics 13(T104 overhead distillate), mainly contain the C such as 2-methylpentane, 2-methylpentene
5~ C
6hydro carbons and a small amount of propylene oxide, to system, logistics 12(T104 tower bottoms) be pressurized to 500kPa through pump, after being cooled to 50 DEG C, be circulated to again T103 tower as extraction agent, T104 tower theoretical plate number 32, logistics 10 feed entrance points are the 12nd block of plate, and working pressure is controlled at 140kPa, reflux ratio 1500.
Logistics 8(product propylene) in propylene oxide content exceed 99.99wt%, water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the foreign matter contents such as hydro carbons are as shown in table 11, the propylene oxide rate of recovery 99.50%, and product has reached product propylene standard.
Table 11
| Composition | Weight content |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 5 ppm |
| Methyl alcohol | 4 ppm |
| Water | 5 ppm |
| Hydro carbons | 6 ppm |
As can be seen from the above, in employing system, raw material isopropyl benzene, as extraction agent, can not introduced new impurity, and the isopropyl benzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can separate and obtain polymerization-grade propylene oxide qualified product with method easily with economical.
Claims (10)
1. a purification process for propylene oxide, for extraction agent, hydrogen phosphide cumene is reacted with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the crude propene oxide solution of hydrocarbon impurities carries out the purification process of the propylene oxide of extractive distillation, it is characterized in that, described extraction agent is isopropyl benzene.
2. the purification process of propylene oxide according to claim 1, is characterized in that said method comprising the steps of:
A) optionally, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the crude propene oxide solution of hydrocarbon impurities enters weight-removing column, and after conventional distillation separates, tower reactor obtains containing water, propionic aldehyde, acetone and C
7the logistics of hydro carbons, tower top obtains logistics I;
B) logistics I enters extraction tower bottom, and extraction agent isopropyl benzene enters extraction tower top, and after separation, tower top obtains the logistics that contains water, methyl alcohol and acetaldehyde, and tower reactor obtains logistics II;
C) logistics II enters de-lighter hydrocarbons tower bottom, and extraction agent isopropyl benzene enters de-lighter hydrocarbons tower top, and after separation, tower top obtains product propylene, and tower reactor obtains logistics III;
D) optionally, logistics III enters extraction agent recovery tower, and after separation, tower top obtains containing C
5~ C
6hydrocarbon material flow, tower reactor is extracted agent isopropyl benzene.
3. the purification process of propylene oxide according to claim 2, the theoretical plate number that it is characterized in that described weight-removing column is 30 ~ 65, and service temperature is 42 ~ 55 DEG C, and working pressure is 120 ~ 200kPa, and reflux ratio is 1 ~ 5.
4. the purification process of propylene oxide according to claim 2, the theoretical plate number that it is characterized in that described extraction tower is 55 ~ 80, and working pressure is 120 ~ 200kPa, and reflux ratio is 50 ~ 200, tower reactor temperature is no more than 130 DEG C, and the ratio of extraction agent isopropyl benzene flow and logistics I flow is 3 ~ 7.
5. the purification process of propylene oxide according to claim 4, is characterized in that in described extraction tower, and the ratio of extraction agent isopropyl benzene flow and logistics I flow is 4 ~ 6.
6. the purification process of propylene oxide according to claim 2, the theoretical plate number that it is characterized in that described de-lighter hydrocarbons tower is 28 ~ 55, service temperature is 42 ~ 52 DEG C, working pressure is 120 ~ 180kPa, reflux ratio is 1 ~ 4, and the ratio of extraction agent isopropyl benzene flow and logistics II flow is 0.2 ~ 0.6.
7. the purification process of propylene oxide according to claim 6, is characterized in that, in described de-lighter hydrocarbons tower, the ratio of extraction agent isopropyl benzene flow and logistics II flow is 0.3 ~ 0.6.
8. the purification process of propylene oxide according to claim 2, the theoretical plate number that it is characterized in that described extraction agent recovery tower is 25 ~ 40, and service temperature is 42 ~ 51 DEG C, and working pressure is 120 ~ 160kPa, and reflux ratio is 500 ~ 2000.
9. the purification process of propylene oxide according to claim 2, is characterized in that the isopropyl benzene that step d) extraction agent recovery tower tower reactor obtains is circulated to extraction tower top or de-lighter hydrocarbons tower top, as extractant feed.
10. the purification process of propylene oxide according to claim 2, it is characterized in that logistics III is divided into two strands, first strand enters extraction agent recovery tower and carries out extraction agent recovery, and second strand is circulated to extraction tower top as extractant feed, and first strand is 1:(2 ~ 3 with the weight ratio of second strand); Or logistics III enters isopropyl benzene peroxidation unit as reaction raw materials.
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| CN105585543A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Propylene oxide refining method |
| CN107286118A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The refining plant of expoxy propane |
| WO2020075417A1 (en) | 2018-10-11 | 2020-04-16 | 住友化学株式会社 | Propylene oxide purification system and method for producing propylene oxide |
| CN113651777A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Reaction rectification dealdehyding process |
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| CN105585543A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Propylene oxide refining method |
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| CN113651777A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Reaction rectification dealdehyding process |
| CN113651777B (en) * | 2020-05-12 | 2023-08-29 | 中国石油化工股份有限公司 | Reaction rectification formaldehyde removal process |
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