CN104151270A - Method for refining epoxypropane - Google Patents
Method for refining epoxypropane Download PDFInfo
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- CN104151270A CN104151270A CN201310179942.6A CN201310179942A CN104151270A CN 104151270 A CN104151270 A CN 104151270A CN 201310179942 A CN201310179942 A CN 201310179942A CN 104151270 A CN104151270 A CN 104151270A
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- ethylbenzene
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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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- 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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Abstract
The invention relates to a method for refining epoxypropane and is mainly used for solving the problems of high cost of an extraction agent and poor quality of a product caused by introduction of an outside-of-system medium existing in the prior art. The method for refining epoxypropane disclosed by the invention comprises the following steps of: by virtue of an extraction agent, extracting the crude epoxypropane solution obtained by reacting hydrogen peroxide ethylbenzene with propylene and containing epoxypropane, water, acetaldehyde, propionaldehyde, methanol, acetone and C3-C7 hydrocarbon impurities and distilling. The problem is well solved by the technical scheme that ethylbenzene is adopted as the extraction agent; the method can be used in the industrial production of refining epoxypropane.
Description
Technical field
The present invention relates to a kind of process for purification 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.Yet the propylene oxide only with higher degree can, for the manufacture of polyvalent alcohol, therefore will carry out can being applied to prepare polyvalent alcohol after purification processes by thick product to synthetic propylene oxide.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 minute are had to strict demand.
In hydrogen peroxide ethylbenzene (EBHP) legal system propylene oxide process, hydrogen peroxide ethylbenzene reacts the crude propene oxide that the product that obtains obtains after Propylene recovery, separating by-products with propylene, still contains a small amount of water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
5~ C
7the impurity such as hydro carbons.Due to acetaldehyde and propylene oxide boiling temperature approach and relative volatility close to 1, propylene oxide forms the features such as azeotrope with 2-methylpentane, the method for conventional distillation has been difficult to refining of propylene oxide.
As the process for purification of propylene oxide, in the patents of invention such as US5133839, US5262017, US5354430/1, US7285187, US8093412, US20120077996, all have disclosed.With regard to propylene oxide refining, 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, it is extraction solvent that US Patent No. 3578568 discloses a kind of spent glycol, propylene glycol, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether of making, and propylene oxide is carried out to extractive distillation, makes it the method separated with water, methyl alcohol, acetone and acetaldehyde.The alkane of octane and so on is disclosed in US3843488 to removing C
6hydrocarbon impurity is 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 the closed cycle in system of extraction agent hydro carbons, 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 process for purification 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 process for purification of propylene oxide, for extraction agent, hydrogen peroxide ethylbenzene is reacted with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the crude propene oxide solution of hydrocarbon impurities carries out the process for purification of the propylene oxide of extractive distillation, and wherein said extraction agent is ethylbenzene.
In one embodiment of the present invention, the present invention relates to a kind of process for purification of propylene oxide, comprise the following steps:
(1) optionally, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the crude propene oxide solution of hydrocarbon impurities enters lightness-removing column, and after conventional distillation separation, tower top obtains containing acetaldehyde and C
3~ C
4the logistics of hydro carbons, tower reactor obtains logistics I;
(2) optionally, logistics I enters weight-removing column, and after conventional distillation separation, tower reactor obtains containing propionic aldehyde, acetone, methyl alcohol, water and C
7the logistics of hydro carbons, tower top obtains logistics II;
(3) logistics II enters extraction tower bottom, and extraction agent ethylbenzene enters extraction tower top, and after separation, that tower top obtains is moisture, the logistics of methyl alcohol and acetaldehyde, and tower reactor obtains logistics III;
(4) logistics III enters product propylene tower bottom, and extraction agent ethylbenzene enters product propylene tower top, and after separation, tower top obtains product propylene, and tower reactor obtains logistics IV;
(5) optionally, logistics IV enters solvent recovery tower, and after separation, tower top obtains containing C
5~ C
6hydrocarbon material flow, tower reactor is extracted agent ethylbenzene.
In technique scheme, preferably, described lightness-removing column theoretical plate number is 40 ~ 60, and working pressure is 240 ~ 300kPa, and reflux ratio is 50 ~ 300.
Preferably, described weight-removing column theoretical plate number is 25 ~ 40, and working pressure is 120 ~ 220kPa, and reflux ratio is 1 ~ 3.
Preferably, described extraction tower theoretical plate number is 50 ~ 80; Working pressure is 150 ~ 220kPa; Reflux ratio is 20 ~ 200; Tower reactor temperature is no more than 130 ℃; The ratio of extraction agent ethylbenzene flow and logistics II flow is 3 ~ 8, and more preferably, the ratio of extraction agent ethylbenzene flow and logistics III flow is 4 ~ 6.
Preferably, described product propylene tower theoretical plate number is 30 ~ 50; Working pressure is 120 ~ 200kPa; Reflux ratio is 0.5 ~ 3; The ratio of extraction agent ethylbenzene flow and logistics III flow is 0.2 ~ 0.6, and more preferably, the ratio of extraction agent ethylbenzene flow and logistics III flow is 0.3 ~ 0.5.
Preferably, described solvent recovery tower theoretical plate number is 20 ~ 40, and working pressure is 120 ~ 160kPa, and reflux ratio is 500 ~ 1500.
Preferably, the ethylbenzene that solvent recovery tower tower reactor obtains is circulated to extraction tower top or product propylene tower top, as extractant feed.
Preferably, logistics IV is divided into two strands, and first strand is circulated to extraction tower top as extractant feed, and second strand enters solvent recovery tower recovery extraction agent, and first strand is 2 ~ 3 with the weight ratio of second strand.
Preferably, the logistics of product propylene tower tower reactor enters ethylbenzene peroxidation unit as reaction raw materials.
In the inventive method, described pressure all refers to absolute pressure.
Process for purification of the present invention material solution used for by hydrogen peroxide ethylbenzene, react with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the reaction soln of the impurity such as hydro carbons.EBHP legal system propylene oxide technology mainly comprises three reactions: ethylbenzene peroxidation, propylene ring oxidation reaction and benzylalcohol hydrogenolysis.First, ethylbenzene is oxidised with air to hydrogen peroxide ethylbenzene (EBHP), and hydrogen peroxide ethylbenzene is selective oxidation propylene propylene oxide processed and benzylalcohol under super-hydrophobicity titaniferous SiO 2 catalyst exists, at proprietary Pd/SiO
2under catalyzer exists, benzylalcohol and hydrogen generation hydrogenolysis generation ethylbenzene, then ethylbenzene is got back to peroxidation and is recycled.Hydrogen peroxide ethylbenzene and the reaction soln that the reaction product of propylene obtains through Propylene recovery, separated most by products afterwards, be the reaction soln that contains propylene oxide that process for purification of the present invention is used, and is called crude propene oxide solution in the present invention.
Impurity in crude propene oxide solution described in the inventive method, mainly comprises water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7hydro carbons, it forms in Table 1.Wherein, C
3mainly comprise propylene, propane, C
4mainly comprise 1-butylene etc., C
5~ C
7hydro carbons mainly comprises 2-methylpentane, 2-methylpentene, 1,5-hexadiene, methylcyclopentane, 3-methyl hexane etc.
Table 1
In impurity in propylene oxide, water, acetaldehyde, C
5~ C
6deng the relative volatility of hydro carbons and propylene oxide, close to 1, propylene oxide and 2-methylpentane, the formation of methanol azeotrope, be difficult to separated with conventional distillation.Extractive distillation is commonly used to separated relative volatility and approaches or equal 1 system.
Propylene oxide and methyl alcohol, water, acetaldehyde, 2-methylpentane impurity during to use extraction agent ethylbenzene compare in the relative volatility under equilibrium conditions.Under 1atm, in the propylene oxide that contains above-mentioned impurity, add the extraction agent ethylbenzene of 3 ~ 6 times of weight ratios to measure, impurity methyl alcohol, water, acetaldehyde, 2-methylpentane and propylene oxide relative volatility change as follows.Its result is as shown in table 2.
Table 2
The inventive method adopts material ethylbenzene in system as extraction agent, crude propene oxide solution to be carried out to separation and purification.Extraction agent ethylbenzene, has the ability of impurity to propylene oxide relative volatility that change.The method can not introduced new impurity, the ethylbenzene 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 surpasses 99.99wt%, the propylene oxide rate of recovery reaches 99.2 ~ 99.8%, has obtained good technique effect.
The inventive method preferably uses ethylbenzene as extraction agent, and crude propene oxide solution is carried out to the purification process that conventional distillation and extracting rectifying combine, by impurity wherein successively effectively separated, remove.Those can be distillated from tower top as water and methyl alcohol etc. than the heavy components of propylene oxide under normal circumstances, and propylene oxide is dissolved in extraction agent, from tower reactor, discharges, and sends into PO product tower.Make the adding of ethylbenzene those under normal circumstances than the light component of propylene oxide as C
5and C
6alkane etc. can shift out from tower reactor together with extraction solvent, and product propylene distillates from tower top.Therefore, first in lightness-removing column, remove acetaldehyde, the C containing in crude propene oxide
3~ C
4hydro carbons, lightness-removing column still liquid enters weight-removing column and removes oxygenatedchemicals, the C such as propionic aldehyde, acetone, methyl alcohol, water
7hydro carbons, weight-removing column overhead distillate enters extraction tower, the impurity such as the water that extraction tower adopts ethylbenzene to make extraction agent to remove micro residue, acetaldehyde, methyl alcohol, tower bottoms enters PO product tower, and PO product tower adopts ethylbenzene to make extraction agent and removes C
5~ C
6hydrocarbon impurities, tower top obtains the polymerization-grade product propylene that purity surpasses 99.9wt%.
Accompanying drawing explanation
Fig. 1 is Refining Technology of Propylene Epoxide schematic flow sheet of the present invention.
In Fig. 1, T101 is lightness-removing column, T102 is weight-removing column, T103 is extraction tower, T104 is propylene oxide (PO) product tower, T105 is solvent recovery tower, 1 is crude propene oxide solution, 2 is lightness-removing column tower top non-condensable gas, 3 is lightness-removing column overhead stream, 4 is lightness-removing column still liquid (being logistics I), 5 is weight-removing column overhead stream (being logistics II), 6 is weight-removing column still liquid, 7 is extraction tower charging, 8 is extraction tower extractant feed, 9 is extraction tower overhead stream, 10 is extraction tower tower reactor logistics (being logistics III), 11 is PO product tower extractant feed, 12 is product propylene, 13 is PO product tower tower bottoms (being logistics IV), 14 is solvent recovery tower charging, 15 is solvent recovery tower overhead stream, 16 is solvent recuperation tower reactor liquid.
In Fig. 1, contain propylene oxide and contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the crude propene oxide solution 1 of hydrocarbon impurities enters lightness-removing column from bottom, and after conventional distillation separation, tower top obtains mainly containing the logistics 3 of acetaldehyde and a small amount of propylene oxide, and logistics 3 is to system; Tower top non-condensable gas 2 mainly contains C
3~ C
4hydro carbons, acetaldehyde, non-condensable gas is to torch; It is logistics I that tower reactor obtains logistics 4().Logistics 4 is from the charging of weight-removing column middle and upper part, and weight-removing column still liquid 6 mainly contains propionic aldehyde, acetone, water, C
7the impurity such as hydro carbons and a small amount of propylene oxide, logistics 6 is to system; It is logistics II that tower top obtains logistics 5().The logistics 7 after pump supercharging of weight-removing column tower bottoms enters from extraction tower tower bottom, and extraction agent ethylbenzene stream 8 is from the top charging of extraction tower tower, and extraction tower overhead distillate 9 mainly contains the impurity such as water, acetaldehyde, methyl alcohol, and logistics 9 is to system; It is logistics III that tower reactor obtains logistics 10().Extraction tower tower bottoms 10 is from PO product Ta Ta middle and lower part charging, and extraction agent ethylbenzene stream 11 is from PO product Ta Ta top charging, and after separation, tower top obtains PO product stream 12; It is logistics IV that tower reactor obtains logistics 13().Logistics 13, after pump supercharging, is divided into two strands, and first burst of logistics 14 enters solvent recovery tower, and second strand is circulated to extraction tower top as extractant feed 8.Logistics 14 enters solvent recovery tower, and after separation, tower top obtains logistics 15, and logistics 15 mainly contains C
5~ C
6hydro carbons and a small amount of propylene oxide, logistics 15 is to system; Tower reactor obtains logistics 16, and logistics 16 is cooled to 40 ~ 50 ℃ through supercooler again after pump supercharging, is circulated to PO product tower as extractant stream 11.Logistics 12(product propylene) in, propylene oxide content surpasses 99.99wt%, the propylene oxide rate of recovery 99.0 ~ 99.9%, and product forms as shown in table 3.
Table 3
In addition, product propylene tower tower reactor logistics 13 also can all enter solvent recovery tower.The ethylbenzene that solvent recovery tower tower reactor obtains also can be divided into two strands, and one is circulated to extraction tower top as extractant feed, and one is circulated to product propylene tower top as extractant feed.This part content does not show in Fig. 1.
Below by embodiment, the invention will be further elaborated.In embodiment, T103 tower solvent ratio is logistics 8 and the ratio of logistics 7 flows, and T104 tower solvent ratio is logistics 11 and the ratio of logistics 10 flows.
Embodiment
[embodiment 1]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in Table 4.
Table 4
| Form | Content, wt |
| Acetone | 0.005 |
| Propionic aldehyde | 0.002 |
| Acetaldehyde | 0.001 |
| Propylene oxide | 0.988 |
| Water | 0.002 |
| C 3~C 7Hydro carbons | 0.001 |
Logistics 1 is from T101 tower underfeed, logistics 3(T101 overhead distillate) mainly contain acetaldehyde and a small amount of propylene oxide, to system, logistics 2(T101 tower top non-condensable gas) mainly contain C
3~ C
4hydro carbons, acetaldehyde, to torch.T101 tower theoretical plate number 55, working pressure 250kPa, reflux ratio 200.
Logistics 4(T101 tower bottoms), from the middle and upper part charging of T102 tower, T102 tower bottoms (logistics 6) mainly contains propionic aldehyde, acetone, water, C
7the impurity such as hydro carbons and a small amount of propylene oxide, logistics 5(T102 column overhead distillate) through pump, be pressurized to 350kPa, send into T103.T102 tower theoretical plate number 30, working pressure 140kPa, reflux ratio 2.2.
Logistics 7(T102 tower bottoms) from T103 tower bottom, enter logistics 8(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio is 4.2, logistics 9(T103 overhead distillate) mainly contain the impurity such as water, acetaldehyde, methyl alcohol.T103 tower theoretical plate number 75, working pressure is controlled at 160kPa, reflux ratio 100,112 ℃ of tower reactor temperature.
Logistics 10(T103 tower bottoms) from the middle and lower part charging of T104 tower, logistics 11(lean solvent) from the top charging of T104 tower, T104 tower solvent ratio is 0.3, logistics 13(T104 still liquid, rich solvent) through pump, be pressurized to 400kPa, logistics 14 enters T105 tower, logistics 8 is circulated to T103 as extraction agent, and logistics 8 is 2.5 with the ratio of logistics 14 flows.T104 tower theoretical plate number 39, working pressure is controlled at 140kPa, reflux ratio 1.
Logistics 14 enters T105 tower, logistics 15(T104 overhead distillate) mainly contain C
5~ C
6hydro carbons and a small amount of propylene oxide, to system; Logistics 16(T105 tower bottoms, lean solvent) through pump, be pressurized to 450 kPa, through being cooled to 40 ℃, logistics 11 is circulated to T104 as extraction agent.T105 tower theoretical plate number 29, working pressure is controlled at 140kPa, reflux ratio 1200.
Logistics 12(product propylene) in, propylene oxide content surpasses 99.99wt%, the propylene oxide rate of recovery 99.7%, and foreign matter content is as shown in table 5.
Table 5
| Form | Content, wt |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 6 ppm |
| Methyl alcohol | 6 ppm |
| Water | 3 ppm |
| Hydro carbons | 10 ppm |
As can be seen from the above, in employing system, material ethylbenzene, as extraction agent, can not introduced new impurity, and the ethylbenzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can be with economical and separated polymerization-grade propylene oxide qualified product that obtain of method easily.
[embodiment 2]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in Table 6.
Table 6
| Form | Content, wt |
| Acetone | 0.006 |
| Propionic aldehyde | 0.003 |
| Acetaldehyde | 0.001 |
| Propylene oxide | 0.985 |
| Water | 0.003 |
| C 3~C 7Hydro carbons | 0.002 |
Logistics 1 is from T101 tower underfeed, logistics 3(T101 overhead distillate) mainly contain acetaldehyde and a small amount of propylene oxide, to system, logistics 2(T101 tower top non-condensable gas) mainly contain C
3~ C
4hydro carbons, acetaldehyde, to torch.T101 tower theoretical plate number 65, working pressure 230kPa, reflux ratio 180.
Logistics 4(T101 tower bottoms), from the middle and upper part charging of T102 tower, T102 tower bottoms (logistics 6) mainly contains propionic aldehyde, acetone, water, C
7the impurity such as hydro carbons and a small amount of propylene oxide, logistics 5(T102 column overhead distillate) through pump, be pressurized to 400kPa, send into T103.T102 tower theoretical plate number 35, working pressure 140kPa, reflux ratio 2.4.
Logistics 7(T102 tower bottoms) from T103 tower bottom, enter logistics 8(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio is 4.8, logistics 9(T103 overhead distillate) mainly contain the impurity such as water, acetaldehyde, methyl alcohol.T103 tower theoretical plate number 75, working pressure is controlled at 160kPa, reflux ratio 100,116 ℃ of tower reactor temperature.
Logistics 10(T103 tower bottoms) from the middle and lower part charging of T104 tower, logistics 11(lean solvent) from the top charging of T104 tower, T104 tower solvent ratio is 0.35, logistics 13(T104 still liquid, rich solvent) through pump, be pressurized to 400kPa, logistics 14 enters T105 tower, logistics 8 is circulated to T103 as extraction agent, and logistics 8 is 3 with the ratio of logistics 14 flows.T104 tower theoretical plate number 42, working pressure is controlled at 140kPa, reflux ratio 1.1.
Logistics 14 enters T105 tower, logistics 15(T104 overhead distillate) mainly contain C
5~ C
6hydro carbons and a small amount of propylene oxide, to system; Logistics 16(T105 tower bottoms, lean solvent) through pump, be pressurized to 420 kPa, through being cooled to 50 ℃, logistics 11 is circulated to T104 as extraction agent.T105 tower theoretical plate number 32, working pressure is controlled at 150kPa, reflux ratio 1150.
Logistics 12(product propylene) in, propylene oxide content surpasses 99.99wt%, the propylene oxide rate of recovery 99.8%, and foreign matter content is as shown in table 7.
Table 7
| Form | Content, wt |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 5 ppm |
| Methyl alcohol | 5 ppm |
| Water | 4 ppm |
| Hydro carbons | 8 ppm |
As can be seen from the above, in employing system, material ethylbenzene, as extraction agent, can not introduced new impurity, and the ethylbenzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can be with economical and separated polymerization-grade propylene oxide qualified product that obtain of method easily.
[embodiment 3]
Adopt flow process shown in Fig. 1, contain water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the logistics 1(crude propene oxide solution of the impurity such as hydro carbons) form in Table 8.
Table 8
| Form | Content, wt |
| Acetone | 0.005 |
| Propionic aldehyde | 0.004 |
| Acetaldehyde | 0.002 |
| Propylene oxide | 0.984 |
| Water | 0.003 |
| C 3~C 7Hydro carbons | 0.002 |
Logistics 1 is from T101 tower underfeed, logistics 3(T101 overhead distillate) mainly contain acetaldehyde and a small amount of propylene oxide, to system, logistics 2(T101 tower top non-condensable gas) mainly contain C
3~ C
4hydro carbons, acetaldehyde, to torch.T101 tower theoretical plate number 60, working pressure 250kPa, reflux ratio 200.
Logistics 4(T101 tower bottoms), from the middle and upper part charging of T102 tower, T102 tower bottoms (logistics 6) mainly contains propionic aldehyde, acetone, water, C
7the impurity such as hydro carbons and a small amount of propylene oxide, logistics 5(T102 column overhead distillate) through pump, be pressurized to 350kPa, send into T103.T102 tower theoretical plate number 30, working pressure 140kPa, reflux ratio 2.2.
Logistics 7(T102 tower bottoms) from T103 tower bottom, enter logistics 8(T104 still liquid) from the top charging of T103 tower, T103 tower solvent ratio is 5.2, logistics 9(T103 overhead distillate) mainly contain the impurity such as water, acetaldehyde, methyl alcohol.T103 tower theoretical plate number 70, working pressure is controlled at 160kPa, reflux ratio 100,120 ℃ of tower reactor temperature.
Logistics 10(T103 tower bottoms) from the middle and lower part charging of T104 tower, logistics 11(lean solvent) from the top charging of T104 tower, T104 tower solvent ratio is 0.40, logistics 13(T104 still liquid, rich solvent) through pump, be pressurized to 400kPa, logistics 14 enters T105 tower, logistics 8 is circulated to T103 as extraction agent, and logistics 8 is 2.8 with the ratio of logistics 14 flows.T104 tower theoretical plate number 42, working pressure is controlled at 140kPa, reflux ratio 1.
Logistics 14 enters T105 tower, logistics 15(T104 overhead distillate) mainly contain C
5~ C
6hydro carbons and a small amount of propylene oxide, to system; Logistics 16(T105 tower bottoms, lean solvent) through pump, be pressurized to 450 kPa, through being cooled to 40 ℃, logistics 11 is circulated to T104 as extraction agent.T105 tower theoretical plate number 26, working pressure is controlled at 150kPa, reflux ratio 1250.
Logistics 12(product propylene) in, propylene oxide content surpasses 99.99wt%, the propylene oxide rate of recovery 99.8%, and foreign matter content is as shown in table 9.
Table 9
| Form | Content, wt |
| Propylene oxide | ＞0.9999 |
| Aldehyde (in propionic aldehyde) | 4 ppm |
| Methyl alcohol | 5 ppm |
| Water | 2 ppm |
| Hydro carbons | 8 ppm |
As can be seen from the above, in employing system, material ethylbenzene, as extraction agent, can not introduced new impurity, and the ethylbenzene of Separation and Recovery is at whole system internal recycle, can reduce the disadvantageous effect that circulation accumulation causes, can be with economical and separated polymerization-grade propylene oxide qualified product that obtain of method easily.
Claims (10)
1. a process for purification for propylene oxide, for extraction agent, hydrogen peroxide ethylbenzene is reacted with propylene obtain, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the crude propene oxide solution of hydrocarbon impurities carries out the process for purification of the propylene oxide of extractive distillation, it is characterized in that, described extraction agent is ethylbenzene.
2. the process for purification of propylene oxide according to claim 1, is characterized in that said method comprising the steps of:
(1) optionally, contain propylene oxide and water, acetaldehyde, propionic aldehyde, methyl alcohol, acetone, C
3~ C
7the crude propene oxide solution of hydrocarbon impurities enters lightness-removing column, and after conventional distillation separation, tower top obtains containing acetaldehyde and C
3~ C
4the logistics of hydro carbons, tower reactor obtains logistics I;
(2) optionally, logistics I enters weight-removing column, and after conventional distillation separation, tower reactor obtains containing propionic aldehyde, acetone, methyl alcohol, water and C
7the logistics of hydro carbons, tower top obtains logistics II;
(3) logistics II enters extraction tower bottom, and extraction agent ethylbenzene enters extraction tower top, and after separation, that tower top obtains is moisture, the logistics of methyl alcohol and acetaldehyde, and tower reactor obtains logistics III;
(4) logistics III enters product propylene tower bottom, and extraction agent ethylbenzene enters product propylene tower top, and after separation, tower top obtains product propylene, and tower reactor obtains logistics IV;
(5) optionally, logistics IV enters solvent recovery tower, and after separation, tower top obtains containing C
5~ C
6hydrocarbon material flow, tower reactor is extracted agent ethylbenzene.
3. the process for purification of propylene oxide according to claim 2, is characterized in that described lightness-removing column theoretical plate number is 40 ~ 60, and working pressure is 240 ~ 300kPa, and reflux ratio is 50 ~ 300.
4. the process for purification of propylene oxide according to claim 2, is characterized in that described weight-removing column theoretical plate number is 25 ~ 40, and working pressure is 120 ~ 220kPa, and reflux ratio is 1 ~ 3.
5. the process for purification of propylene oxide according to claim 2, is characterized in that described extraction tower theoretical plate number is 50 ~ 80; Working pressure is 150 ~ 220kPa; Reflux ratio is 20 ~ 200; Tower reactor temperature is no more than 130 ℃; The ratio of extraction agent ethylbenzene flow and logistics II flow is 3 ~ 8, is preferably 4 ~ 6.
6. the process for purification of propylene oxide according to claim 2, is characterized in that described product propylene tower theoretical plate number is 30 ~ 50; Working pressure is 120 ~ 200kPa; Reflux ratio is 0.5 ~ 3; The ratio of extraction agent ethylbenzene flow and logistics III flow is 0.2 ~ 0.6, is preferably 0.3 ~ 0.5.
7. the process for purification of propylene oxide according to claim 2, is characterized in that described solvent recovery tower theoretical plate number is 20 ~ 40, and working pressure is 120 ~ 160kPa, and reflux ratio is 500 ~ 1500.
8. the process for purification of propylene oxide according to claim 2, is characterized in that the ethylbenzene that solvent recovery tower tower reactor obtains is circulated to extraction tower top or product propylene tower top, as extractant feed.
9. the process for purification of propylene oxide according to claim 2, it is characterized in that logistics IV is divided into two strands, first strand is circulated to extraction tower top as extractant feed, and second strand enters solvent recovery tower recovery extraction agent, and first strand is 2 ~ 3 with the weight ratio of second strand.
10. the process for purification of propylene oxide according to claim 2, is characterized in that the logistics of product propylene tower tower reactor enters ethylbenzene peroxidation unit as reaction raw materials.
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|---|---|---|---|
| CN201310179942.6A CN104151270A (en) | 2013-05-16 | 2013-05-16 | Method for refining epoxypropane |
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| CN201310179942.6A Pending CN104151270A (en) | 2013-05-16 | 2013-05-16 | Method for refining epoxypropane |
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Cited By (13)
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| CN105524027A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Epoxypropane composition |
| CN109020926A (en) * | 2017-12-19 | 2018-12-18 | 华东理工大学 | A method of it separated from propylene gas-phase epoxidation product, purify propylene oxide |
| CN109851590A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process of propylene oxide |
| CN109851582A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process of propylene oxide |
| CN111655673A (en) * | 2018-02-05 | 2020-09-11 | 利安德化学技术有限公司 | Alkylene oxide separation system |
| CN112694455A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | System and method for removing aldehyde and ketone by hydrogenation |
| CN112694456A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for pretreating and supplementing extracting agent in propylene oxide purification process |
| CN112694454A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method and system for processing crude propylene oxide material |
| CN113651778A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Extraction agent pretreatment and supplement method |
| CN113651775A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Method for removing aldehyde |
| CN113651777A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Reaction rectification dealdehyding process |
| CN113979828A (en) * | 2021-11-18 | 2022-01-28 | 万华化学集团股份有限公司 | Method for recovering byproduct ethylbenzene in production of epoxypropane by using co-oxidation method |
| CN114634467A (en) * | 2020-12-15 | 2022-06-17 | 中国石油化工股份有限公司 | Method for removing impurities in epoxypropane |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524027A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Epoxypropane composition |
| CN109851590A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process of propylene oxide |
| CN109851582A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process of propylene oxide |
| CN109020926A (en) * | 2017-12-19 | 2018-12-18 | 华东理工大学 | A method of it separated from propylene gas-phase epoxidation product, purify propylene oxide |
| CN111655673A (en) * | 2018-02-05 | 2020-09-11 | 利安德化学技术有限公司 | Alkylene oxide separation system |
| CN111655673B (en) * | 2018-02-05 | 2021-09-10 | 利安德化学技术有限公司 | Alkylene oxide separation system |
| CN112694454B (en) * | 2019-10-23 | 2023-04-07 | 中国石油化工股份有限公司 | Method and system for processing crude propylene oxide material |
| CN112694455A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | System and method for removing aldehyde and ketone by hydrogenation |
| CN112694456A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for pretreating and supplementing extracting agent in propylene oxide purification process |
| CN112694454A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method and system for processing crude propylene oxide material |
| CN112694456B (en) * | 2019-10-23 | 2023-09-29 | 中国石油化工股份有限公司 | Method for pretreating and supplementing extractant in epoxypropane purification process |
| CN112694455B (en) * | 2019-10-23 | 2023-08-08 | 中国石油化工股份有限公司 | System and method for hydrogenation removal of aldehydes and ketones |
| CN113651775A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Method for removing aldehyde |
| CN113651778B (en) * | 2020-05-12 | 2023-06-06 | 中国石油化工股份有限公司 | Extraction agent pretreatment and replenishment method |
| 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 |
| CN113651778A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Extraction agent pretreatment and supplement method |
| CN113651775B (en) * | 2020-05-12 | 2024-05-03 | 中国石油化工股份有限公司 | Process for removing aldehydes |
| CN114634467A (en) * | 2020-12-15 | 2022-06-17 | 中国石油化工股份有限公司 | Method for removing impurities in epoxypropane |
| CN114634467B (en) * | 2020-12-15 | 2024-05-03 | 中国石油化工股份有限公司 | Method for removing impurities in epoxypropane |
| CN113979828A (en) * | 2021-11-18 | 2022-01-28 | 万华化学集团股份有限公司 | Method for recovering byproduct ethylbenzene in production of epoxypropane by using co-oxidation method |
| CN113979828B (en) * | 2021-11-18 | 2023-09-19 | 万华化学集团股份有限公司 | Recovery method for byproduct ethylbenzene in propylene oxide production by co-oxidation method |
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