CN105272940A - Propylene oxide production equipment - Google Patents
Propylene oxide production equipment Download PDFInfo
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- CN105272940A CN105272940A CN201410353885.3A CN201410353885A CN105272940A CN 105272940 A CN105272940 A CN 105272940A CN 201410353885 A CN201410353885 A CN 201410353885A CN 105272940 A CN105272940 A CN 105272940A
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Abstract
The present invention relates to propylene oxide production equipment. A purpose of the present invention is mainly to solve the high energy consumption problem in the prior art. According to the present invention, the equipment containing the reactor, the flash evaporation tank, 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 equipment 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 production of propylene oxide equipment.
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) DMBA and H
2hydrogenolysis occurs in the presence of a catalyst and generates isopropyl benzene, 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 new production of propylene oxide equipment.It is low that this equipment 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 production of propylene oxide equipment, comprising:
Reactor, generates containing α for raw material hydrogen peroxide isopropyl benzene and propylene being reacted, the liquid phase stream of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane; Described reactor inlet is connected with Propylene pipes with hydrogen phosphide cumene pipeline, and described reactor outlet is connected with described liquid phase stream pipeline;
Flash tank, for containing α to described, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene are separated with the liquid phase stream of propane, thus obtain the first light component stream at tank deck, obtain the first heavy constituent logistics at the bottom of tank; The entrance of described flash tank is connected with described liquid phase stream pipeline, and roof door is connected with the first light component stream pipeline, and tank bottom outlet is connected with the first heavy constituent logistics pipeline;
High pressure propylene recovery tower, for accepting the first light component stream from described flash tank tank deck, thus obtains the second light component stream at tower top, obtains the second heavy constituent logistics containing propylene oxide and discharged in tower reactor; The entrance of described high pressure propylene recovery tower is connected with the first light component stream pipeline, and tower top outlet is connected with the second light component stream pipeline, and tower reactor outlet is connected with the second heavy constituent logistics pipeline; Described second light component stream pipeline communicates with the first pipeline, for shunting a part of second light component stream;
Low pressure propylene recovery tower, for accepting the first heavy constituent logistics at the bottom of from described flash tank tank, thus obtains the 3rd light component stream at tower top, obtains the triple component streams containing propylene oxide and discharged in tower reactor; The entrance of described low pressure propylene recovery tower is connected with the first heavy constituent logistics pipeline, and tower top outlet is connected with the 3rd light component stream pipeline, and tower reactor outlet is connected with triple component streams pipeline;
Depropanizing tower, for accepting the by-passing portions from described second light component stream, and is separated it, thus obtains the 4th light component stream at tower top, obtains the quadruple component streams containing propane and discharged in tower reactor; The entrance of described depropanizing tower is connected with the first pipeline, and tower top outlet is connected with the 4th light component stream pipeline, and tower reactor outlet is connected with quadruple component streams pipeline;
Second light component stream pipeline, the 3rd light component stream pipeline and the 4th light component stream pipeline, all communicate with described Propylene pipes.
In technique scheme, preferably, the working pressure of described high pressure propylene recovery tower counts 0.1 ~ 1.0MPa with gauge pressure, and the working pressure of described low pressure propylene recovery tower counts 0.1 ~ 0.3MPa with gauge pressure.More preferably, the working pressure of described high pressure propylene recovery tower counts 0.5 ~ 0.9MPa 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 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.More 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%, 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%.
In technique scheme, preferably, described high pressure propylene recovery column overhead service temperature is-30 ~ 20 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 ~-16 DEG C, and tower reactor service temperature is 85 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
In technique scheme, preferably, the service temperature of flash tank is 10 ~ 120 DEG C, and working pressure counts 0.1 ~ 5.0MPa with gauge pressure.
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 by-passing portions that described second light component stream enters depropanizing tower is 0.1 ~ 0.5 of described second light component stream weight.
In the present invention, the epoxidation reaction of hydrogen phosphide cumene and propylene is for known in the art.Usually, temperature of reaction is 40 ~ 120 DEG C, and reaction pressure is 3.5 ~ 6.8MPa, and propylene/CHP mol ratio is 5 ~ 20, CHP air speed is 0.2 ~ 1.2 hour
-1.Catalyzer used can be the SiO 2 molecular sieve catalyzer of titaniferous.
Adopt the propylene recovery purification apparatus containing flash tank, high pressure propylene recovery tower, low pressure propylene recovery tower and depropanizing tower in the present invention, first liquid phase epoxidation propane reaction product carries out preliminary separation by flash tank, and the propylene of the overwhelming majority flashes to gas phase.The propylene gas phase containing a small amount of propylene oxide that flash distillation obtains is sent into high pressure propylene recovery tower and is refined, and tower top obtains highly purified propylene (in raw material, the propylene of 50 ~ 98 % by weight is recycled at this), and tower reactor obtains propylene oxide heavy constituent.Because high pressure propylene recovery tower tower reactor is not containing isopropyl benzene and DMBA, under control bottom temperature is no more than 120 DEG C of situations, tower pressure can be improved, make tower top that the cryogen of comparatively high temps can be used to carry out condensation high-purity propylene.Meanwhile, from the propylene of recovered overhead, separate a part and send into depropanizing tower separation, to remove the propane impurity that fresh propylene brings recycle system of reaction into.Liquid-phase reaction product at the bottom of flash tank also surplus a small amount of propylene needs to recycle, and therefore sends into low pressure propylene recovery tower and proceeds to refine.Adopt present device, from reactor liquid phase stream out, the propylene of 50 ~ 98 % by weight obtains recovery by flash tank and high pressure propylene recovery tower, decreases the inlet amount of low pressure propylene recovery tower.Therefore, the condensation that high pressure propylene recovery column overhead can take the cryogen of comparatively high temps to carry out propylene is reclaimed, and only has low pressure propylene recovery column overhead need adopt the cryogen of lower temperature.Compared with prior art, energy consumption 55% can be reduced.In addition, adopt present device, 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 present device schematic diagram.
In Fig. 1, I is reactor, II is flash tank, III is high pressure propylene recovery tower, IV is low pressure propylene recovery tower, V is depropanizing tower, 1 is raw material hydrogen peroxide isopropyl benzene pipeline, 2 is Propylene pipes, 3 for containing propylene oxide, the liquid phase stream pipeline of propylene and propane, 4 is that the first light component stream pipeline is (wherein for flash tank tank deck gas-phase product, main containing propylene, propane and propylene oxide), 5 is the first heavy constituent logistics pipeline (wherein liquid product at the bottom of flash tank tank, main containing α, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide and propylene), 6 is that the second light component stream pipeline is (wherein for high pressure propylene recovery column overhead stream, main containing propylene and propane), 7 is that the second heavy constituent logistics pipeline is (wherein for the logistics of high pressure propylene recovery tower tower reactor, containing propylene oxide), 8 is the first pipeline (wherein for entering the by-passing portions of depropanizing tower in high pressure propylene recovery column overhead stream), 9 is quadruple component streams pipeline (being wherein depropanizing tower tower reactor propylene oxide stream), 10 is the 4th light component stream pipeline (being wherein depropanizing tower recovered overhead propylene), 11 is the 3rd light component stream pipeline (being wherein low pressure propylene recovery column overhead Propylene recovery), 12 is that triple component streams pipeline is (wherein for the logistics of low pressure propylene recovery tower tower reactor, main containing α, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, in raw material, the PO of 10 ~ 90 is separated at this.
In Fig. 1, raw material hydrogen peroxide isopropyl benzene 1 and propylene 2 react the liquid phase stream 3 generated containing propylene oxide, propylene and propane in reactor I.Logistics 3 is sent into flash tank II and is separated, and the gas-phase product 4 that flash distillation tank deck obtains is sent into high pressure propylene recovery tower III and refined, and the liquid product 5 obtained at the bottom of flash tank is sent into low pressure propylene recovery tower IV and refined.High pressure propylene recovery tower III overhead stream is divided into two portions, and small portion logistics 8 (accounting for 0.1 ~ 0.5 of the second light component stream 6 weight) enters depropanizing tower V and refines.Depropanizing tower V tower top obtains propylene, and tower reactor removes propane 9.The logistics 12 that the logistics 7 that high pressure propylene recovery tower III tower reactor obtains and low pressure propylene recovery tower IV tower reactor obtain is crude propene oxide, sends into follow-up separation system.High pressure propylene recovery tower III overhead stream removes the by-passing portions, low pressure propylene recovery column overhead stream and the depropanizing tower overhead stream that enter depropanizing tower, loops back reactor and participates 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, raw material hydrogen peroxide isopropyl benzene 1 and propylene 2 react the liquid phase stream 3 generated containing propylene oxide, propylene and propane in reactor I.Logistics 3 is sent into flash tank II and is separated, and the gas-phase product 4 that flash distillation tank deck obtains is sent into high pressure propylene recovery tower III and refined, and the liquid product 5 obtained at the bottom of flash tank is sent into low pressure propylene recovery tower IV and refined.High pressure propylene recovery tower III overhead stream is divided into two portions, and small portion logistics 8 enters depropanizing tower V and refines.Depropanizing tower V tower top obtains propylene, and tower reactor removes propane 9.The logistics 12 that the logistics 7 that high pressure propylene recovery tower III tower reactor obtains and low pressure propylene recovery tower IV tower reactor obtain is crude propene oxide, sends into follow-up separation system.High pressure propylene recovery tower III overhead stream removes the by-passing portions, low pressure propylene recovery column overhead stream and the depropanizing tower overhead stream that enter depropanizing tower, loops back reactor and participates in reaction.
Wherein, in liquid phase stream 3, 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 flash tank is: working pressure is 1.0MPa, and tower top service temperature is 58 DEG C.
The operational condition of high pressure propylene recovery tower is: working pressure is 0.9MPa, and tower top service temperature is 19 DEG C, and tower reactor service temperature is 116 DEG C, and theoretical plate number is 30 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 30 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 55 DEG C, and theoretical plate number is 50 pieces.
The logistics 8 entering depropanizing tower is 10% of high pressure propylene recovery column overhead stream 6 weight.
Result is: high pressure propylene recovery column overhead takes temperature to be that the condensation that the refrigerated water 774 tons/hour (by 10 DEG C of differential thermal calculations) of 9 DEG C carries out propylene as cryogen is reclaimed, and low pressure propylene recovery column overhead adopts temperature to be the cryogen 28.3 tons/hour (by 8 DEG C of differential thermal calculations) of-20 DEG C.
The yield of propylene is 99.9%, and the purity of Propylene recovery is the yield of 95%, PO product is 99.9%.Its mesohigh propylene recovery tower reclaims total propylene 82%.
[embodiment 2]
With [embodiment 1], just raw material and operational condition change.
In liquid phase stream 3, 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 flash tank is: working pressure is 2.0MPa, and tower top service temperature is 93 DEG C.
The operational condition of high pressure propylene recovery tower is: working pressure is 0.9MPa, and tower top service temperature is 19 DEG C, and tower reactor service temperature is 120 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 30 pieces.
The operational condition of depropanizing tower is: working pressure is 2.0MPa, and tower top service temperature is 50 DEG C, and tower reactor service temperature is 55 DEG C, and theoretical plate number is 50 pieces.
The logistics 8 entering depropanizing tower is 25% of high pressure propylene recovery column overhead stream 6 weight.
Result is: high pressure propylene recovery column overhead takes temperature to be that the condensation that the refrigerated water 404 tons/hour (by 10 DEG C of differential thermal calculations) of 9 DEG C carries out propylene as cryogen is reclaimed, and low pressure propylene recovery column overhead adopts temperature to be the cryogen 32.6 tons/hour (by 8 DEG C of differential thermal calculations) of-20 DEG C.
The yield of propylene is 99.9%, and the purity of Propylene recovery is the yield of 95%, PO product is 99.9%.Its mesohigh propylene recovery tower reclaims total propylene 55%.
[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 (10)
1. a production of propylene oxide equipment, comprising:
Reactor, generates containing α for raw material hydrogen peroxide isopropyl benzene and propylene being reacted, the liquid phase stream of alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene and propane; Described reactor inlet is connected with Propylene pipes with hydrogen phosphide cumene pipeline, and described reactor outlet is connected with described liquid phase stream pipeline;
Flash tank, for containing α to described, alpha-alpha-dimethyl benzylalcohol, isopropyl benzene, propylene oxide, propylene are separated with the liquid phase stream of propane, thus obtain the first light component stream at tank deck, obtain the first heavy constituent logistics at the bottom of tank; The entrance of described flash tank is connected with described liquid phase stream pipeline, and roof door is connected with the first light component stream pipeline, and tank bottom outlet is connected with the first heavy constituent logistics pipeline;
High pressure propylene recovery tower, for accepting the first light component stream from described flash tank tank deck, thus obtains the second light component stream at tower top, obtains the second heavy constituent logistics containing propylene oxide and discharged in tower reactor; The entrance of described high pressure propylene recovery tower is connected with the first light component stream pipeline, and tower top outlet is connected with the second light component stream pipeline, and tower reactor outlet is connected with the second heavy constituent logistics pipeline; Described second light component stream pipeline communicates with the first pipeline, for shunting a part of second light component stream;
Low pressure propylene recovery tower, for accepting the first heavy constituent logistics at the bottom of from described flash tank tank, thus obtains the 3rd light component stream at tower top, obtains the triple component streams containing propylene oxide and discharged in tower reactor; The entrance of described low pressure propylene recovery tower is connected with the first heavy constituent logistics pipeline, and tower top outlet is connected with the 3rd light component stream pipeline, and tower reactor outlet is connected with triple component streams pipeline;
Depropanizing tower, for accepting the by-passing portions from described second light component stream, and is separated it, thus obtains the 4th light component stream at tower top, obtains the quadruple component streams containing propane and discharged in tower reactor; The entrance of described depropanizing tower is connected with the first pipeline, and tower top outlet is connected with the 4th light component stream pipeline, and tower reactor outlet is connected with quadruple component streams pipeline;
Second light component stream pipeline, the 3rd light component stream pipeline and the 4th light component stream pipeline, all communicate with described Propylene pipes.
2. production of propylene oxide equipment according to claim 1, it is characterized in that the working pressure of described high pressure propylene recovery tower counts 0.1 ~ 1.0MPa with gauge pressure, the working pressure of described low pressure propylene recovery tower counts 0.1 ~ 0.3MPa with gauge pressure.
3. production of propylene oxide equipment according to claim 2, it is characterized in that the working pressure of described high pressure propylene recovery tower counts 0.5 ~ 0.9MPa with gauge pressure, the working pressure of described low pressure propylene recovery tower counts 0.15 ~ 0.25MPa with gauge pressure.
4. production of propylene oxide equipment 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.
5. production of propylene oxide equipment according to claim 4, 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%.
6. production of propylene oxide equipment according to claim 1, it is characterized in that described high pressure propylene recovery column overhead service temperature is-30 ~ 20 DEG C, tower reactor service temperature is 45 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
7. production of propylene oxide equipment according to claim 1, it is characterized in that described low pressure propylene recovery column overhead service temperature is-30 ~-16 DEG C, tower reactor service temperature is 85 ~ 120 DEG C, and theoretical plate number is 10 ~ 50.
8. production of propylene oxide equipment according to claim 1, it is characterized in that the service temperature of flash tank is 10 ~ 120 DEG C, working pressure counts 0.1 ~ 5.0MPa with gauge pressure.
9. production of propylene oxide equipment 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.
10. production of propylene oxide equipment according to claim 1, is characterized in that the by-passing portions that described second light component stream enters depropanizing tower is 0.1 ~ 0.5 of described second light component stream weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410353885.3A CN105272940A (en) | 2014-07-24 | 2014-07-24 | Propylene oxide production equipment |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410353885.3A CN105272940A (en) | 2014-07-24 | 2014-07-24 | Propylene oxide production equipment |
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| CN105272940A true CN105272940A (en) | 2016-01-27 |
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| CN201410353885.3A Pending CN105272940A (en) | 2014-07-24 | 2014-07-24 | Propylene oxide production equipment |
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- 2014-07-24 CN CN201410353885.3A patent/CN105272940A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李文忠: "CHP法生产CA 和PO的分离模拟与研究", 《中国优秀硕士学位论文工程科技1辑》 * |
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Application publication date: 20160127 |