CN103664831A - System and method for producing derivatives of olefin - Google Patents
System and method for producing derivatives of olefin Download PDFInfo
- Publication number
- CN103664831A CN103664831A CN201210339611.XA CN201210339611A CN103664831A CN 103664831 A CN103664831 A CN 103664831A CN 201210339611 A CN201210339611 A CN 201210339611A CN 103664831 A CN103664831 A CN 103664831A
- Authority
- CN
- China
- Prior art keywords
- propylene
- hydrogen peroxide
- propylene oxide
- methanol
- epoxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a system for producing derivatives of olefin. The system comprises a methanol-to-olefin system and a system for producing epoxypropane through hydrogen peroxide epoxydized propylene, wherein the methanol to olefin system comprises a methanol-to-propylene device. The invention also discloses a method for producing the derivatives of olefin by the system. The method comprises steps of (1) converting raw material methyl alcohol into propylene, and (2) preparing the epoxypropane through hydrogen peroxide epoxydized propylene. According to the method, oversupply methyl alcohol is taken as the raw material, related technological processes are integrated so as to produce epoxypropane and high value-added derivatives of olefin, so that the downstream industrial chain of methyl alcohol is improved, integrated production of chemical products is realized, the investment cost of equipment and production cost are reduced, furthermore, the technical problem about tail gas treatment of reaction product is solved, and the purposes of energy conservation and emission reduction and promotion of economical efficiency are reached.
Description
Technical field
The present invention relates to organic chemical industry field, particularly relate to a kind of system of producing alkene derivatives, and based on this system, produce the method for alkene derivatives.
Background technology
Methyl alcohol is one of main product of Modern Coal-based Chemical, is to be tightly the tie of petrochemical complex and Coal Chemical Industry.The various production technology GRAMERCY of relevant methyl alcohol are in maturation, and its production capacity speedup is swift and violent.At present, the actual production capacity of methyl alcohol is seriously superfluous, market saturation, and seriously drug on the market for product, and have the sign growing in intensity.Developing and improve the downstream industry chain of methyl alcohol, realize the integrated, integrated of Chemicals production, is solution.
MTO technology (Methanol to Olefins, claim again MTO technique) be to take the production technology that have feasibility and economy of coal as low-carbon alkenes such as raw materials for ethylene production, propylene, butylene, it both can solve the raw material gap problem of alkene, can also alleviate methyl alcohol problem of excess production capacity, be expected to replace and take the route of oil as raw material production low-carbon alkene.
MTO technology generally comprises product synthesis system and product purification system, and wherein product purification system comprises alkali cleaning, hydrogenation, demethanizing, deethanizing, ethene fractionation, depropanizing, propylene fractionation and de-C
4+in device, process is complicated, it is huge to invest; In addition, for obtaining ethene (boiling point is-103.9 ℃) and the propylene (boiling point is for-47.7 ℃) of polymerization-grade, need to carry out chilling separation to product, separating energy consumption is very high, facility investment is large, thereby affects the economy of MTO technology, and has limited the process of this technique industrialization.
The oxygenatedchemicals with high added value is one of most important derived product of alkene, is also important basic organic chemical industry raw material.Propylene oxide (propylene oxide, Propylene Oxide are called for short PO) is the third-largest Organic chemical products that in acryloyl derivative, output is only second to polypropylene and vinyl cyanide.Propylene oxide is widely used in the industries such as chemical industry, light industry, medicine, food and weaving, mainly for the production of propylene glycol, polyether glycol, propylene glycol, α-amino isopropyl alcohol etc., it is also the main raw material of preparing nonionogenic tenside, oil field demulsifier, farm chemical emulgent, softening agent, lubricant, fire retardant etc.
At present, the industrial process of propylene oxide mainly contains two kinds: chlorohydrination and conjugated oxidation., but there is the shortcomings such as equipment is perishable, environmental pollution is serious in chlorohydrination technical maturity, does not meet the requirement of Green Chemistry and cleaner production, and less economical, gradually superseded; Conjugated oxidation complex process, a large amount of byproducts of coproduction and be subject to the serious restriction in market, cost of investment is high.
Hydrogen peroxide (H
2o
2, be called for short HP) and be generally acknowledged Green Oxidant, its oxidized byproduct only has water.Under titanium-silicon molecular sieve catalyst, utilize hydrogen peroxide epoxidation propylene to prepare the technique of propylene oxide, i.e. HPPO technique, have reaction conditions gentleness, transformation efficiency and selectivity high, without co-product, the advantage such as pollution-free, at present existing industrial installation.
Hydrogen peroxide epoxidation propylene is prepared in the technique of propylene oxide, in reaction system, because hydrogen peroxide decomposes, causes accumulating of oxygen, if reach finite concentration, will form explosive mixed gas with some organism.While isolating unreacting propylene from product mixtures, if the concentration of propylene and oxygen reaches flammable mixtures concentration, also there is potential safety hazard.For this reason, generally can in reaction system, supply with the rare gas elementes such as nitrogen, carbonic acid gas, and methane, ethane, propane etc., certainly will increase like this separation sequence of later separation operation.Publication number is the Chinese invention patent of CN1678387A, has proposed the recovery method of propylene in a kind of propylene oxide process.The method absorbs propylene with propane, and propane major part is evaporated in exhaust by resorber, thereby propane is separated from system.Publication number is the Chinese invention patent of CN101432271A, has proposed a kind of preparation method of propylene oxide.Use hydrogen peroxide, under the existence of epoxidation catalyst, in containing nitrile solvent (acetonitrile and water), with propylene ring oxidation reaction, prepare propylene oxide; Use the acetonitrile solvent reclaiming to absorb the recycling composition in discharge gas.Publication number is the Chinese invention patent of CN101693703A, has proposed a kind of energy-saving and emission-reducing technique of producing propane epoxide by using hydrogen peroxide epoxidation propylene.This technique is divided into reactive moieties, separate part and vent gas treatment part.Tail gas is qualified discharge after partial condensation, absorption Propylene recovery.Above-mentioned patent all solution in various degree the problem of epoxidation product vent gas treatment (unreacting propylene recovery), reduced the danger that forms explosive mixed gas, but all existed separating technology route long, facility investment is large, economic benefit is the shortcoming such as not good totally.
The industrialized restraining factors of HPPO technique are mainly the economy problems of hydrogen peroxide manufacture and accumulating.Hydrogen peroxide manufacture process and propylene oxide production process are carried out to the system integration, and with simplification device flow process, save energy and reduce the cost, reduce production costs, this is to take the development trend of HP as oxygenant epoxidation propylene PO technique processed.
That hydrogen peroxide manufacture technique mainly contains is anthraquinone, isopropanol oxidation method and hydrogen-oxygen direct method.Anthraquinone technique is tediously long, device complicated, process cost high (Pd catalyst costs is large, anthraquinone is repeatedly used can degraded); Hydrogen-oxygen direct synthesis technique technique is simple, cost is low, pollution is few, is important field of research always, and is limited to the bottleneck of selectivity and yield, not yet realizes so far suitability for industrialized production.
Because Virahol is the raw material of synthesize hydrogen peroxide, can be used as again the solvent of epoxidation reaction, and isopropanol oxidation does not need catalyzer, the partner of whole process is reduced, the consistency of synthesis process of hydrogen peroxide and epoxidation process increases greatly, so isopropanol oxidation method and propylene ring oxidation reaction integrated has good industrial prospect.
Propylene oxide chemical property is active, be unsuitable for long distance transportation, yet its derived product added value is higher, therefore domestic and international most production of propylene oxide enterprise all adopts integration operation pattern, auxiliary construction propylene oxide derived product production equipment, be mainly the devices such as coproduction polyether glycol, propylene glycol and propylene glycol, comprise in addition the derived product devices such as tensio-active agent, nonionogenic tenside, propylene carbonate, treated starch, methylcarbonate, Vltra tears.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of system of producing alkene derivatives, and this system energy consumption is low, and integrated level is high, not only environmental protection, and also economical.
For solving the problems of the technologies described above, the system of production alkene derivatives of the present invention, comprises methanol-to-olefins system and hydrogen peroxide epoxidation propylene propylene oxide system processed; Described methanol-to-olefins system comprises preparing propylene from methanol device.
Two of the technical problem to be solved in the present invention is to provide a kind of method of the production alkene derivatives based on said system.
For solving the problems of the technologies described above, the method for production alkene derivatives of the present invention, comprises the following steps:
1) material benzenemethanol is sent into methanol-to-olefins system, obtained including the gas-phase product of propylene;
2) this gas-phase product is sent into hydrogen peroxide epoxidation propylene propylene oxide system processed, utilized hydrogen peroxide epoxidation propylene, prepare propylene oxide.
It is raw material that serious easy methyl alcohol in New Coal Chemical product is take in the present invention, integrated allied processes, introduce membrane separation technique, produce the alkene derivatives of propylene oxide and high added value thereof, the not only perfect downstream industry chain of methyl alcohol, also realize the integrated and integrated of Chemicals productions, reduced cost of investment and the production cost of equipment.In addition, the present invention has also solved in methanol-to-olefins process, and the technical barrier of epoxidation reaction product vent gas treatment has reached energy-saving and emission-reduction, promoted the object of economy, meets the requirement of green, low-carbon (LC), environmental protection industry standard instantly.
Accompanying drawing explanation
Fig. 1 is the system architecture schematic diagram of the production alkene derivatives of the embodiment of the present invention 1.
Fig. 2 is the system architecture schematic diagram of the production alkene derivatives of the embodiment of the present invention 2.
In figure, description of reference numerals is as follows:
101: methanol-to-olefins system
102: hydrogen peroxide epoxidation propylene propylene oxide system processed
1011:MTP device
1021: propylene ring oxidation reaction device
1022:PO tripping device
1023: membrane separation unit
201: methanol-to-olefins system
202: isopropanol oxidation hydrogen peroxide system processed
203: hydrogen peroxide epoxidation propylene propylene oxide system processed
204: propylene oxide derivative production system
2011:MTP device
2021: isopropanol oxidation reaction unit
2022: acetone separation device
2023: acetone hydrogenation apparatus
2031: propylene ring oxidation reaction device
2032:PO tripping device
2033: membrane separation unit
2041: polyether glycol production equipment
2042: propylene glycol production equipment
2043: propylene glycol production equipment
2044: other PO derivative production equipment
Embodiment
For technology contents of the present invention, feature and effect being had more specifically, understand, existing in conjunction with illustrated embodiment, details are as follows.In embodiment, unspecified production equipment and processing method all adopt existing known production equipment and processing method.
Embodiment 1
As shown in Figure 1, the system integration of the production alkene derivatives of the present embodiment methanol-to-olefins system 101 and hydrogen peroxide epoxidation propylene propylene oxide system 102 processed.Wherein,
Methanol-to-olefins system 101 comprises preparing propylene from methanol device 1011(Methanol to Propylene, claims again MTP device).MTP device 1011 further comprises pre-reactor, MTP reactor, separator and water treatment device.
Hydrogen peroxide epoxidation propylene propylene oxide system 102 processed comprises propylene ring oxidation reaction device 1021, PO tripping device 1022 and membrane separation unit 1023.In propylene ring oxidation reaction device 1021, load titanium-silicon molecular sieve catalyst.
Utilize the system of the present embodiment to produce the method for alkene derivatives as follows:
First, material benzenemethanol is sent into MTP device 1011.In MTP device 1011, material benzenemethanol is preheated to 250～350 ° of C by MTP reactor effluent, then enters pre-reactor.In pre-reactor, part methyl alcohol is converted to dme and water, enters subsequently MTP reactor.After MTP reaction product is cooled, deliver to separator, wherein, liquid hydrocarbon returns to MTP reactor, and water section is delivered to water treatment device, part is circulated to MTP reactor.Liquid hydrocarbon returns after MTP reactor, obtains MTP gas-phase product (comprising ethene, propylene and light paraffins etc.), after compressor compression, separated without chilling, directly enters propylene ring oxidation reaction device 1021.
In propylene ring oxidation reaction device 1021, MTP gas-phase product, hydrogen peroxide and the propylene, hydrogen peroxide, the methyl alcohol that through subsequent handling, reclaim, under the effect of titanium-silicon molecular sieve catalyst, carry out epoxidation reaction, reaction product enters PO tripping device 1022, by property qualitative differences such as boiling points, product is carried out to separation.
Wherein, the portion of product of separating through PO tripping device 1022 enters membrane separation unit 1023.In membrane separation unit 1023, separately (alkane of separating can be through Oxidative Dehydrogenation alkene by alkene and alkane first to utilize Ag-ZSM-5 molecular screen membrane, in Fig. 1, do not indicate), and then utilizing SAPO-34 molecular screen membrane (aperture is 0.38 nanometer) separating ethene and propylene, the propylene of recovery returns to propylene ring oxidation reaction device 1021.Mixture after all the other separation returns to PO tripping device 1022.
In another part product of separating through PO tripping device 1022, unreacted hydrogen peroxide returns to propylene ring oxidation reaction device 1021; Solvent methanol returns to propylene ring oxidation reaction device 1021 and MTP device 1011; After all the other purification of products, obtain product P O, or enter propylene oxide derivative production system (not indicating in Fig. 1).
Embodiment 2
As shown in Figure 2, the system integration of the production alkene derivatives of the present embodiment methanol-to-olefins system 201, isopropanol oxidation hydrogen peroxide system 202 processed, hydrogen peroxide epoxidation propylene propylene oxide system 203 processed and propylene oxide derivative production system 204.Wherein,
Methanol-to-olefins system 201 comprises preparing propylene from methanol device 2011(Methanol to Propylene, claims again MTP device); MTP device 2011 further comprises pre-reactor, MTP reactor, separator and water treatment device.
Isopropanol oxidation hydrogen peroxide system 202 processed comprises isopropanol oxidation reaction unit 2021, acetone separation device 2022, acetone hydrogenation apparatus 2023;
Hydrogen peroxide epoxidation propylene propylene oxide system 203 processed comprises propylene ring oxidation reaction device 2031, PO tripping device 2032, membrane separation unit 2033; Wherein, in propylene ring oxidation reaction device 2031, load titanium-silicon molecular sieve catalyst.
Propylene oxide derivative production system 204 comprises polyether glycol production equipment 2041, propylene glycol production equipment 2042, propylene glycol production equipment 2043, other PO derivative production equipment 2044.
Utilize the system of the present embodiment to produce the method for alkene derivatives as follows:
Material benzenemethanol is sent into MTP device 2011.In MTP device 2011, material benzenemethanol is preheated to 250～350 ° of C by MTP reactor effluent, then enters pre-reactor.In pre-reactor, part methyl alcohol is converted to dme and water, enters subsequently MTP reactor.After MTP reaction product is cooled, deliver to separator, wherein, liquid hydrocarbon returns to MTP reactor, and water section is delivered to water treatment device, part is circulated to MTP reactor.Liquid hydrocarbon returns after MTP reactor, obtains MTP gas-phase product (comprising ethene, propylene and light paraffins etc.), after compressor compression, separated without chilling, directly enters propylene ring oxidation reaction device 2031.
The Virahol that raw material Virahol, oxygen and subsequent handling are reclaimed and the azeotrope of water are sent into isopropanol oxidation reaction unit 2021 and are carried out isopropanol oxidation and react.Reaction product enters acetone separation device 2022, by distillating method with acetone.The acetone that separation obtains enters acetone hydrogenation apparatus 2023, at catalyzer, (can adopt any catalyzer that is applicable to oxy-compound hydrogenation, such as copper-based catalysts, nickel-base catalyst or platinum class catalyzer etc., the nickel-base catalyst that the tripoli of preferably take is carrier) the lower hydrogenation of effect obtains Virahol, then delivers to PO tripping device 2032.The isopropanol oxidation reaction product (hydrogen peroxide) containing acetone does not enter propylene ring oxidation reaction device 2031.
In propylene ring oxidation reaction device 2031, the azeotrope of propylene, hydrogen peroxide, Virahol and the water that does not contain isopropanol oxidation reaction product, the MTP gas-phase product of acetone and reclaim through subsequent handling, under the effect of titanium-silicon molecular sieve catalyst, carry out epoxidation reaction.Reaction product enters PO tripping device 2032, by property qualitative differences such as boiling points, product is carried out to separation.
The portion of product of separating through PO tripping device 2032 enters membrane separation unit 2033.In membrane separation unit 2033, first utilize Ag-ZSM-5 molecular screen membrane that alkene and alkane are separated to (alkane of separating is through Oxidative Dehydrogenation alkene), and then utilizing SAPO-34 molecular screen membrane (aperture is 0.38 nanometer) separating ethene and propylene, the propylene of recovery returns to propylene ring oxidation reaction device 2031.Mixture after all the other separation returns to PO tripping device 2032.
In another part product of separating through PO tripping device 2032, unreacted hydrogen peroxide returns to propylene ring oxidation reaction device 2031; The azeotrope of Virahol and water returns to propylene ring oxidation reaction device 2031 and isopropanol oxidation reaction unit 2021.
Through the product propylene of purifying, enter respectively polyether glycol production equipment 2041, propylene glycol production equipment 2042, propylene glycol production equipment 2043 and other PO derivative production equipment 2044 to produce propylene oxide derivative.Aforementioned each PO derivative production equipment, can accept or reject according to actual production planning.
Claims (14)
1. a system of producing alkene derivatives, is characterized in that, comprises methanol-to-olefins system and hydrogen peroxide epoxidation propylene propylene oxide system processed; Described methanol-to-olefins system comprises preparing propylene from methanol device.
2. system according to claim 1, is characterized in that, described hydrogen peroxide epoxidation propylene propylene oxide system processed comprises propylene ring oxidation reaction device, propylene oxide tripping device and membrane separation unit.
3. system according to claim 2, is characterized in that, in described propylene ring oxidation reaction device, loads titanium-silicon molecular sieve catalyst.
4. system according to claim 2, is characterized in that, sets gradually Ag-ZSM-5 molecular screen membrane and SAPO-34 molecular screen membrane in described membrane separation unit.
5. the system described in any one according to claim 1-4, is characterized in that, also comprises isopropanol oxidation hydrogen peroxide system processed.
6. system according to claim 5, is characterized in that, described isopropanol oxidation hydrogen peroxide system processed comprises isopropanol oxidation reaction unit, acetone separation device and acetone hydrogenation apparatus.
7. the system described in any one according to claim 1 to 4, is characterized in that, also comprises propylene oxide derivative production system.
8. system according to claim 7, is characterized in that, described propylene oxide derivative production system comprises one or more in polyether glycol production equipment, propylene glycol production equipment, propylene glycol production equipment.
9. a method of producing alkene derivatives, is characterized in that, comprises the following steps:
1) material benzenemethanol is sent into methanol-to-olefins system, obtained including the gas-phase product of propylene;
2) this gas-phase product is sent into hydrogen peroxide epoxidation propylene propylene oxide system processed, utilized hydrogen peroxide epoxidation propylene, prepare propylene oxide.
10. method according to claim 9, is characterized in that step 2), the catalyzer of epoxidation reaction is titanium-silicon molecular sieve catalyst.
11. methods according to claim 9, is characterized in that step 2), also comprise separated from epoxidation reaction product and Propylene recovery.
12. methods according to claim 11, is characterized in that step 2), the method for separation of propylene is: first use Ag-ZSM-5 molecular screen membrane the separation of olefins and alkane, then use SAPO-34 molecular screen membrane separating ethene and propylene.
13. methods according to claim 9, is characterized in that step 2) before, also comprise step: by Virahol and oxygen generation oxidizing reaction, prepare hydrogen peroxide.
14. methods according to claim 9, is characterized in that step 2) afterwards, also comprise step: take propylene oxide as raw material, produce propylene oxide derivative; Described propylene oxide derivative comprises polyether glycol, propylene glycol or propylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210339611.XA CN103664831A (en) | 2012-09-14 | 2012-09-14 | System and method for producing derivatives of olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210339611.XA CN103664831A (en) | 2012-09-14 | 2012-09-14 | System and method for producing derivatives of olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103664831A true CN103664831A (en) | 2014-03-26 |
Family
ID=50303707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210339611.XA Pending CN103664831A (en) | 2012-09-14 | 2012-09-14 | System and method for producing derivatives of olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103664831A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI629269B (en) * | 2015-11-26 | 2018-07-11 | 贏創德固賽有限責任公司 | Process for the epoxidation of an olefin |
| CN108997263A (en) * | 2018-06-29 | 2018-12-14 | 华电煤业集团有限公司 | A kind of system and method for propylene oxide co-production aromatic hydrocarbons |
| CN112592251A (en) * | 2020-12-23 | 2021-04-02 | 上海睿碳能源科技有限公司 | Process and apparatus for separating a light hydrocarbon-containing stream |
| CN113512013A (en) * | 2021-06-30 | 2021-10-19 | 中国石油化工股份有限公司 | System and method for preparing propylene oxide from large-scale industrial methanol |
-
2012
- 2012-09-14 CN CN201210339611.XA patent/CN103664831A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI629269B (en) * | 2015-11-26 | 2018-07-11 | 贏創德固賽有限責任公司 | Process for the epoxidation of an olefin |
| CN108997263A (en) * | 2018-06-29 | 2018-12-14 | 华电煤业集团有限公司 | A kind of system and method for propylene oxide co-production aromatic hydrocarbons |
| CN108997263B (en) * | 2018-06-29 | 2020-07-03 | 华电煤业集团有限公司 | System and method for co-producing aromatic hydrocarbon from propylene oxide |
| CN112592251A (en) * | 2020-12-23 | 2021-04-02 | 上海睿碳能源科技有限公司 | Process and apparatus for separating a light hydrocarbon-containing stream |
| CN113512013A (en) * | 2021-06-30 | 2021-10-19 | 中国石油化工股份有限公司 | System and method for preparing propylene oxide from large-scale industrial methanol |
| CN113512013B (en) * | 2021-06-30 | 2023-09-05 | 中国石油化工股份有限公司 | System and method for preparing propylene oxide from large-scale industrial methanol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105272941B (en) | The production method of propylene oxide | |
| CN103772125B (en) | Take oil refinery dry gas as the method for waste ethylbenzene | |
| CN104230856B (en) | The production method of butylene oxide ring | |
| CN101475429A (en) | Method for comprehensive utilization of cracking C4 | |
| CN103664831A (en) | System and method for producing derivatives of olefin | |
| CN102516006B (en) | Method and device for recovering ethylene in vinyl acetate production process | |
| CN104277013A (en) | Method for preparing epoxybutane | |
| CN105294604B (en) | Produce the device of expoxy propane | |
| CN103506158B (en) | A kind of tert-butyl alcohol dehydration preparing isobutene catalysts and preparation method thereof | |
| CN102219680A (en) | Method for preparing oxalic ester by CO gas-phase process | |
| CN102618316A (en) | Technique method for producing oil product and co-producing propylene by utilizing methyl alcohol and mixing fixed bed | |
| CN104829406A (en) | Method for preparing ethylene by heterogeneous reaction | |
| CN103193581A (en) | Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 | |
| CN105315234B (en) | The method for producing expoxy propane | |
| CN102584518B (en) | Industrial production method and production device of isobutene | |
| CN102070390B (en) | The method of refinery's mixed c 4 propylene | |
| CN105315238B (en) | The production equipment of expoxy propane | |
| CN105439792B (en) | The method of the refined propylene of recovery | |
| CN104672046B (en) | Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation | |
| CN103420768A (en) | Method for preparing isobutene from isobutane | |
| CN103121904A (en) | Utilization method for hydrocarbon fuel gas rich in alkyne | |
| US8859791B2 (en) | Process for producing an alkylene oxide by olefin epoxidation | |
| CN103664520A (en) | Method for preparing isopropyl alcohol through hydration reaction of propylene | |
| CN105272808A (en) | Propylene recovery device | |
| CN105272810A (en) | Method for separating ethylene/propylene mixed gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |