CN105272806A - Propylene recovery method - Google Patents
Propylene recovery method Download PDFInfo
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- CN105272806A CN105272806A CN201410355476.7A CN201410355476A CN105272806A CN 105272806 A CN105272806 A CN 105272806A CN 201410355476 A CN201410355476 A CN 201410355476A CN 105272806 A CN105272806 A CN 105272806A
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Abstract
The present invention relates to a propylene recovery method. A purpose of the present invention is mainly to solve the high energy consumption in the prior art. According to the present invention, the propylene recovery refining process containing the high pressure propylene recovery tower, the low pressure propylene recovery tower and the depropanization tower is used to well solve the problem in the prior art, and the method can be used for the propylene recovery through the propylene oxide device in the industrial production.
Description
Technical field
The present invention relates to a kind of method of propylene recovery, particularly relate to a kind of method of propylene ring oxidation reaction product being carried out to propylene recovery.
Background technology
Propylene oxide (PO) is very important Organic Chemicals, it is the third-largest Organic chemical products that in acryloyl derivative, output is only second to polypropylene and vinyl cyanide, mainly for the production of polyethers, propylene glycol, α-amino isopropyl alcohol, non-polyether polyvalent alcohol etc., and then produce unsaturated polyester resin, urethane, tensio-active agent, fire retardant etc., be widely used in the industries such as chemical industry, light industry, medicine, food, weaving, to chemical industry and the national economic development, there is far-reaching influence.Along with the expansion of propylene oxide purposes and the growth of downstream product consumption, make the demand in propylene oxide market increasing.
The method of current industrial production propylene oxide mainly contains chlorohydrination, has the conjugated oxidation of joint product (PO/SM method and PO/MTBE method or PO/TBA method) and without the hydrogen phosphide cumene method (CHP method) of joint product.Chlorohydrination owing to producing a large amount of chlorine-contained wastewaters in process of production, environmental pollution and equipment corrosion serious; Have the conjugated oxidation of joint product to overcome the shortcomings such as the pollution of chlorohydrination and corrosion, but long flow path, investment is large, co-product is many, joint product market have impact on the production of propylene oxide to a certain extent.CHP method is owing to polluting little and not having joint product to generate the developing direction having become Producing Process of Propylene Oxide.
The technology preparing propylene oxide compound by hydrogen phosphide cumene (CHP) and propylene under the existence of fixed-bed catalytic oxidant layer is known, mainly comprises three reaction process: (1) air-oxidation hydrogen phosphide cumene; (2) there is epoxidation reaction and produce propylene oxide (PO) and α, alpha-alpha-dimethyl benzylalcohol (DMBA) in CHP and propylene under heterogeneous catalyst exists; (3) there is hydrogenolysis generation isopropyl benzene in the presence of a catalyst in DMBA and H2, and isopropyl benzene is recycled to oxidation operation and produces CHP.For improving the transformation efficiency of CHP, usually make propylene excessive, mol ratio as n (propylene)/n (CHP) is 5 ~ 20, therefore propylene excessive is in a large number had in reaction product, for improving the refining load of epoxidation efficiency and minimizing PO, require the propylene in reaction product to carry out recycle, and circulation propylene needs higher purity, remove necessary impurity, avoid inert component to accumulate in the recycle system simultaneously.
Document CN1505616A discloses a kind of preparation method of propylene oxide, comprise the step making propylene and cumene hydroperoxide be obtained by reacting propylene oxide in the presence of a catalyst, carry out distilling with the reaction mixture making above-mentioned reactions steps obtain and from the step of distillation recovered overhead unreacted propylene, wherein the bottom temperature of distillation tower is set to 200 DEG C or lower.In the method, tower reactor goes out thick PO product, and tower top goes out propylene.Because PO has thermo-sensitivity, general industry production control bottom temperature is not higher than 130 DEG C, namely the working pressure of rectifying tower is defined, cause tower top service temperature lower than less than 40 DEG C, conventional water coolant cannot be adopted to do cryogen, the condensation that the cryogen of a large amount of lower temperature need be used to carry out propylene is reclaimed, and cause the difficulty of industrial operation, energy consumption is high.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the high problem of energy consumption, provides a kind of method of new propylene recovery.It is low that the method has energy consumption, and propylene recovery rate is high, and propane removes thoroughly, and product propylene yield is high, low equipment investment, and flow process is simple, the feature that industrializing implementation is strong.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of method of propylene recovery, comprises the following steps:
A) containing α, the raw material 11 of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane enters high pressure propylene recovery tower, after separation, tower top obtains high pressure propylene recovery column overhead stream 4, tower reactor obtains containing α, the logistics 5 of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, on a small quantity propylene and propane;
B) described containing α, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, the on a small quantity logistics 5 of propylene and propane enter low pressure propylene recovery tower, after separation, tower top obtains low pressure propylene recovery column overhead stream 6, and tower reactor obtains the crude propene oxide product stream 8 removing propylene;
C) described low pressure propylene recovery column overhead stream 6 is divided into two portions, and a part of logistics 7 wherein enters depropanizing tower, and after separation, tower top obtains depropanizing tower overhead stream 9, and tower reactor obtains propylene oxide stream 10;
D) in high pressure propylene recovery column overhead stream 4, low pressure propylene recovery column overhead stream 6, removing enters after the part of depropanizing tower and depropanizing tower overhead stream 9 converge, and is the propylene stream 12 of recovery;
Wherein, the working pressure of described high pressure propylene recovery tower counts 0.5 ~ 3.5MPa with gauge pressure, and the working pressure of described low pressure propylene recovery tower counts 0.1 ~ 0.4MPa with gauge pressure.
In technique scheme, preferably, described containing α, the raw material of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane is propylene and the reacted product of hydrogen phosphide cumene.
In technique scheme, preferably, described containing α, in the raw material of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane, by weight percentage, α, the content of alpha-alpha-dimethyl benzylalcohol is 19 ~ 50%, and the content of isopropyl benzene is 10 ~ 70%, and the content of propylene oxide is 5 ~ 20%, the content of propylene is 5 ~ 60%, and the content of propane is 0 ~ 10%.
In technique scheme, preferably, the working pressure of described high pressure propylene recovery tower counts 1.5 ~ 2.5MPa with gauge pressure, and the working pressure of described low pressure propylene recovery tower counts 0.15 ~ 0.25MPa with gauge pressure.
In technique scheme, preferably, described high pressure propylene recovery column overhead service temperature is 5 ~ 80 DEG C, and tower reactor service temperature is 45 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
In technique scheme, preferably, described low pressure propylene recovery column overhead service temperature is-30 ~-8 DEG C, and tower reactor service temperature is 85 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
In technique scheme, preferably, depropanizing tower working pressure counts 1.5 ~ 2.5MPa with gauge pressure, and tower top service temperature is 40 ~ 65 DEG C, and tower reactor service temperature is 40 ~ 65 DEG C, and theoretical plate number is 10 ~ 80.
In technique scheme, preferably, the logistics 7 entering depropanizing tower described in is 1:(1 ~ 10 with the weight ratio of described low pressure propylene recovery column overhead stream 6).
The inventive method adopts the propylene recovery process for refining containing high pressure propylene recovery tower, low pressure propylene recovery tower and depropanizing tower, first liquid phase epoxidation propane reaction product raw material enters high pressure propylene recovery tower and refines, in raw material, the propylene of 60 ~ 95 % by weight is from recovered overhead, and tower reactor obtains the crude propene oxide product containing a small amount of propylene.Crude propene oxide product containing a small amount of propylene is sent into low pressure propylene recovery tower and is proceeded to refine, recovered overhead propylene, and tower reactor obtains not containing the crude propene oxide product of propylene.Through high pressure propylene recovery tower and low pressure propylene recovery tower, in raw material, the propylene of 99 ~ 100 % by weight is recycled.Low pressure propylene recovery column overhead stream divides two portions, a part becomes Propylene recovery, another part sends into depropanizing tower, to remove the propane impurity that fresh propylene brings recycle system of reaction into, depropanizing tower tower reactor obtains the propane removed, after high pressure propylene recovery tower and low pressure propylene recovery tower still unsegregated propylene from depropanizing tower removed overhead.Adopt the inventive method, first the feed stream containing propylene is separated in high pressure propylene recovery tower, makes most of propylene from removed overhead, thus decreases the inlet amount of low pressure propylene recovery tower.Therefore, the condensation that high pressure propylene recovery column overhead takes conventional water coolant to carry out propylene as cryogen is reclaimed, and only has low pressure propylene recovery column overhead need adopt the cryogen of lower temperature.Compared with prior art, energy consumption 60% can be reduced.In addition, adopt the inventive method, ensure that propylene and unreacted in hydrogen phosphide cumene epoxidation reaction being separated of propylene and product propylene completely, and be stripped of in raw material propylene the inert component propane of system of bringing into, the propylene capable of circulation time propylene ring oxidation reaction system reclaimed does reaction raw materials, both ensure that the yield (can 99.9% be reached) of propylene, ensure that the purity requirement (can 95% be reached) of circulation propylene and the yield (can 99.9% be reached) of PO product simultaneously, flow process is simple, low equipment investment, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.
In Fig. 1,1 is high pressure propylene recovery tower, 2 is low pressure propylene recovery tower, 3 is depropanizing tower, 4 is high pressure propylene recovery column overhead stream, 5 is the logistics of high pressure propylene recovery tower tower reactor, 6 is low pressure propylene recovery column overhead stream, 7 for going the by-passing portions logistics of depropanizing tower in low pressure propylene recovery column overhead stream, 8 is that crude propene oxide product is (containing propylene oxide, α, alpha-alpha-dimethyl benzylalcohol and isopropyl benzene), 9 is depropanizing tower overhead stream, and 10 is propane, 11 is feed stream, and 12 is the propylene stream reclaimed.
In Fig. 1, from epoxidation reaction system containing α, first alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene are sent into high pressure propylene recovery tower 1 with the raw material 11 of propane and are separated, tower top obtains logistics 4, tower reactor obtains containing α, the logistics 5 of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, on a small quantity propylene and propane.Logistics 5 is sent into low pressure propylene recovery tower 2 and is separated, and tower top obtains logistics 6, and tower reactor obtains the crude propene oxide product stream 8 removing propylene.Low pressure propylene recovery tower 2 overhead stream 6 points of two portions, a part of logistics 7 wherein enters depropanizing tower, and after separation, tower top obtains logistics 9, and tower reactor obtains propylene oxide stream 10.In high pressure propylene recovery column overhead stream 4, low pressure propylene recovery column overhead stream 6, removing enters by-passing portions and the depropanizing tower overhead stream 9 of depropanizing tower, is the propylene stream 12 of recovery.Logistics 12 can be sent epoxidation reaction system back to and be participated in reaction.Wherein, the overhead condenser of each tower all omits and does not draw.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
As shown in Figure 1, for the PO device of 100,000 tons/year, from epoxidation reaction system containing α, first alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene are sent into high pressure propylene recovery tower 1 with the raw material 11 of propane and are separated, tower top obtains logistics 4, tower reactor obtains containing α, the logistics 5 of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, on a small quantity propylene and propane.Logistics 5 is sent into low pressure propylene recovery tower 2 and is separated, and tower top obtains logistics 6, and tower reactor obtains the crude propene oxide product stream 8 removing propylene.Low pressure propylene recovery tower 2 overhead stream 6 points of two portions, a part of logistics 7 wherein enters depropanizing tower, and after separation, tower top obtains logistics 9, and tower reactor obtains propylene oxide stream 10.In high pressure propylene recovery column overhead stream 4, low pressure propylene recovery column overhead stream 6, removing enters by-passing portions and the depropanizing tower overhead stream 9 of depropanizing tower, is the propylene stream 12 of recovery.
Wherein, in raw material, by weight percentage, α, the content of alpha-alpha-dimethyl benzylalcohol is 26%, and the content of isopropyl benzene is 6%, and the content of propylene oxide is 10%, and the content of propylene is 55%, and the content of propane is 3%.
The operational condition of high pressure propylene recovery tower is: working pressure is 1.6MPa, and tower top service temperature is 40 DEG C, and tower reactor service temperature is 72 DEG C, and theoretical plate number is 25 pieces.
The operational condition of low pressure propylene recovery tower is: working pressure is 0.3MPa, and tower top service temperature is-12 DEG C, and tower reactor service temperature is 120 DEG C, and theoretical plate number is 20 pieces.
The operational condition of depropanizing tower is: working pressure is 2.0MPa, and tower top service temperature is 51 DEG C, and tower reactor service temperature is 60 DEG C, and theoretical plate number is 50 pieces.
The logistics 7 entering depropanizing tower is 1:2.4 with the weight ratio of low pressure propylene recovery column overhead stream 6.
Result is: high pressure propylene recovery column overhead takes temperature to be that the condensation that the water coolant 575 tons/hour of 32 DEG C carries out propylene as cryogen is reclaimed, and low pressure propylene recovery column overhead adopts temperature to be the cryogen 29.3 tons/hour of-20 DEG C.
The yield of propylene is 99.9%, Propylene recovery purity be the yield of 95%, PO product be 99.9%.Its mesohigh propylene recovery column overhead propylene recovery rate is 70%.
[embodiment 2]
With [embodiment 1], just raw material and operational condition change.
In raw material, by weight percentage, α, the content of alpha-alpha-dimethyl benzylalcohol is 26%, and the content of isopropyl benzene is 21.5%, and the content of propylene oxide is 10.5%, and the content of propylene is 39%, and the content of propane is 2%.
The operational condition of high pressure propylene recovery tower is: working pressure is 1.6MPa, and tower top service temperature is 40 DEG C, and tower reactor service temperature is 87 DEG C, and theoretical plate number is 25 pieces.
The operational condition of low pressure propylene recovery tower is: working pressure is 0.2MPa, and tower top service temperature is-20 DEG C, and tower reactor service temperature is 120 DEG C, and theoretical plate number is 20 pieces.
The operational condition of depropanizing tower is: working pressure is 2.0MPa, and tower top service temperature is 51 DEG C, and tower reactor service temperature is 58 DEG C, and theoretical plate number is 50 pieces.
The logistics 7 entering depropanizing tower is 1:3 with the weight ratio of low pressure propylene recovery column overhead stream 6.
Result is: high pressure propylene recovery column overhead takes temperature to be that the condensation that the water coolant 340 tons/hour of 32 DEG C carries out propylene as cryogen is reclaimed, and low pressure propylene recovery column overhead adopts temperature to be the cryogen 32 tons/hour of-30 DEG C.
The yield of propylene is 99.9%, Propylene recovery purity be the yield of 95%, PO product be 99.9%.Its mesohigh propylene recovery column overhead propylene recovery rate is 60%.
[comparative example 1]
Raw material with [embodiment 1] enters a distillation tower, and from the unreacted propylene of distillation recovered overhead, tower reactor goes out thick PO product.
The operational condition of distillation tower is: working pressure is 0.3MPa, and tower top service temperature is-12 DEG C, and tower reactor service temperature is 120 DEG C, and theoretical plate number is 30 pieces.
Result is: tower top employing temperature is the cryogen 92.5 tons/hour of-20 DEG C.
Claims (8)
1. a method for propylene recovery, comprises the following steps:
A) containing α, the raw material (11) of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane enters high pressure propylene recovery tower, after separation, tower top obtains high pressure propylene recovery column overhead stream (4), tower reactor obtains containing α, the logistics (5) of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, on a small quantity propylene and propane;
B) described containing α, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, the on a small quantity logistics (5) of propylene and propane enter low pressure propylene recovery tower, after separation, tower top obtains low pressure propylene recovery column overhead stream (6), and tower reactor obtains the crude propene oxide product stream (8) removing propylene;
C) described low pressure propylene recovery column overhead stream (6) is divided into two portions, a part of logistics (7) wherein enters depropanizing tower, after separation, tower top obtains depropanizing tower overhead stream (9), and tower reactor obtains propylene oxide stream (10);
D) in high pressure propylene recovery column overhead stream (4), low pressure propylene recovery column overhead stream (6), removing enters by-passing portions and the depropanizing tower overhead stream (9) of depropanizing tower, is the propylene stream (12) of recovery;
Wherein, the working pressure of described high pressure propylene recovery tower counts 0.5 ~ 3.5MPa with gauge pressure, and the working pressure of described low pressure propylene recovery tower counts 0.1 ~ 0.4MPa with gauge pressure.
2. the method for propylene recovery according to claim 1, it is characterized in that described containing α, the raw material of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane is propylene and the reacted product of hydrogen phosphide cumene.
3. the method for propylene recovery according to claim 2, it is characterized in that described containing α, in the raw material of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane, by weight percentage, α, the content of alpha-alpha-dimethyl benzylalcohol is 19 ~ 50%, the content of isopropyl benzene is 10 ~ 70%, the content of propylene oxide is 5 ~ 20%, and the content of propylene is 5 ~ 60%, and the content of propane is 0 ~ 10%.
4. the method for propylene recovery according to claim 1, it is characterized in that the working pressure of described high pressure propylene recovery tower counts 1.5 ~ 2.5MPa with gauge pressure, the working pressure of described low pressure propylene recovery tower counts 0.15 ~ 0.25MPa with gauge pressure.
5. the method for propylene recovery according to claim 1, it is characterized in that described high pressure propylene recovery column overhead service temperature is 5 ~ 80 DEG C, tower reactor service temperature is 45 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
6. the method for propylene recovery according to claim 1, it is characterized in that described low pressure propylene recovery column overhead service temperature is-30 ~-8 DEG C, tower reactor service temperature is 85 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
7. the method for propylene recovery according to claim 1, it is characterized in that depropanizing tower working pressure counts 1.5 ~ 2.5MPa with gauge pressure, tower top service temperature is 40 ~ 65 DEG C, and tower reactor service temperature is 40 ~ 65 DEG C, and theoretical plate number is 10 ~ 80.
8. the method for propylene recovery according to claim 1, entering the logistics (7) of depropanizing tower described in it is characterized in that with the weight ratio of described low pressure propylene recovery column overhead stream (6) is 1:(1 ~ 10).
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| CN201410355476.7A CN105272806B (en) | 2014-07-24 | 2014-07-24 | The method of propylene recovery |
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| CN201410355476.7A CN105272806B (en) | 2014-07-24 | 2014-07-24 | The method of propylene recovery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107777706A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The method for reclaiming ammonia |
| CN107777704A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The recovery method of ammonia |
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| JP2003081955A (en) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | Method for producing propylene oxide |
| JP2003160519A (en) * | 2001-11-26 | 2003-06-03 | Sumitomo Chem Co Ltd | Method for producing propylene oxide and ethylbenzene |
| CN1505616A (en) * | 2001-04-27 | 2004-06-16 | ס�ѻ�ѧ��ҵ��ʽ���� | Process for producing propylene oxide |
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2014
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| CN1505616A (en) * | 2001-04-27 | 2004-06-16 | ס�ѻ�ѧ��ҵ��ʽ���� | Process for producing propylene oxide |
| JP2003081955A (en) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | Method for producing propylene oxide |
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Non-Patent Citations (1)
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| 于剑昆等: "用异丙苯过氧化氢作氧化剂合成环氧丙烷的新技术（待续）", 《化学推进剂与高分子材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107777706A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The method for reclaiming ammonia |
| CN107777704A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The recovery method of ammonia |
| CN107777704B (en) * | 2016-08-30 | 2021-06-18 | 中国石油化工股份有限公司 | Ammonia recovery method |
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