CN103588608A - Butadiene preparation method - Google Patents
Butadiene preparation method Download PDFInfo
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- CN103588608A CN103588608A CN201210289201.9A CN201210289201A CN103588608A CN 103588608 A CN103588608 A CN 103588608A CN 201210289201 A CN201210289201 A CN 201210289201A CN 103588608 A CN103588608 A CN 103588608A
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Abstract
The invention discloses a butadiene preparation method. The method comprises a step that a cracking raw material is subjected to a steam cracking reaction, the cracking raw material contains 5-100wt% of cyclohexene. The butadiene preparation method can substantially improve the butadiene yield.
Description
Technical field
The present invention relates to a kind of preparation method of divinyl.
Background technology
Divinyl is often referred to 1,3-butadiene, claims again ethylene vinyl, is the important petrochemical complex basic material that is only second to ethene and propylene.Divinyl is mainly used in synthetic rubber and resin, as polybutadiene rubber (BR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR), styrene-butadiene polymer latex, styrenic thermoplastic elastomer (SBC) and acrylonitrile-butadiene-styrene (ABS) (ABS) resin.In addition, divinyl also can be used for producing the Organic chemical products such as adiponitrile, hexanediamine, nylon-66, BDO, is widely used in numerous areas.
The industrial process of divinyl has successively experienced alcohol dehydrogenase method, butylene catalytic dehydrogenation method, catalytic dehydrogenation of butanes method, butylene oxidation-dehydrogenation method, ethylene by-product C 4 fraction partition method.At present, the source of divinyl raw material mainly contains two kinds, the hybrid C 4 cut of ethylene cracker by-product and refinery C 4 fraction.In the butadiene production in the whole world, 92% comes from ethylene by-product C 4 fraction partition method, and 8% comes from the dehydrogenating technology of normal butane and n-butene.
Ethylene by-product C 4 fraction partition method is cheap because of it, has larger economic advantages, becomes the production method of most of divinyl.Owing to using the difference of solvent, the C 4 fraction separation of produced divinyl of ethylene unit by-product has following methods: furfural method, acetonitrile method, dimethyl formamide method, N,N-DIMETHYLACETAMIDE method, N methylpyrrolidone process etc.The dimethyl formamide method (DMF) of ，Yi Nippon Zeon Co., Ltd., N methylpyrrolidone process (NMP) and the improved acetonitrile method of Japanese JSR company (ACN) of German BASF AG have competitive power most at present.The process of these techniques is basic identical, and the C 4 fraction from ethylene unit is contacted with extraction solvent, and the butenes/butanes blending ingredients of indissoluble removes from tower top, then the method with simple distillation removes extraction solvent from take out excess.Afterwards by further distillation by impurity removals such as methylacetylenes, obtain purity and be 99.5% ~ 99.9% product butadiene.In various extraction process, NMP method has the features such as flow process is relatively simple, cost of investment is lower, easy to operate, better economic benefit.In addition, C 4 fraction is selected the constantly development and application of novel process such as acetylene hydrogenation technique (being called for short KLP technique).
In recent years, American UOP and BASF AG's joint development go out extracting process integration, being about to the selective acetylene hydrocarbon hydrogenation technique (KLP technique) of UOP and the Butadiene Extraction distil process of BASF AG combines, first by the selective acetylene hydrocarbon hydrogenation in C 4 fraction, then adopt extractive distillation technology to reclaim 1,3-butadiene from butane and butylene.In hydrogenation process, raw material C 4 fraction mixes with the hydrogen of certain metering, enters in the fixed-bed reactor that KLP-60 catalyzer is housed, and adopts sufficiently high pressure to make reaction mixture keep liquid phase.KLP reactor effluent enters in distillation tower and vaporizes subsequently, and as the raw material of extracting operation, removes a small amount of heavy ends forming in technological process simultaneously.In Butadiene Extraction operation, from vaporizer top steam out, enter main washing tower, and carry out extractive distillation with NMP.The logistics that is rich in divinyl at the bottom of tower enters rectifying tower, and then enters last distillation tower, the 1,3-butadiene that can output purity be greater than 99.6%.The advantage of this technique is that product butadiene purity is high, yield is high, utility cost is low, maintenance cost is low and processing safety is high.
In addition, Mitsubishi chemical company announces in March, 2009, and it utilizes the proprietary catalyzer of independent research, develops the new technology that the little butylene of purposes is converted to 1,3-butadiene.Production base, this technological process Yi Mitsubishi Chemical Ind's Japanese water island completes pilot scale (ability is 200 tons/year).The said firm completed technological design in 2009, was intended to make this technology in 2010, to push commercial applications to.
In recent years, research about butadiene production technology focuses mostly in the improvement of C 4 fraction extraction process, the novel process (CN101665399A) that proposes a kind of butadiene production in 2009 as Beijing Chemical Research Institute, except selection hydrogenation is combined with extractive distillation technique, also at extraction overhead extraction place, degassing tower is set, isolate remaining hydrogen and the following light constituent of C4 after hydrogenation reaction, avoid losing divinyl.Aspect the raw material of production divinyl, the heals that is rich in alkynes that PetroChina Company Ltd. obtains after proposing to utilize Butadiene Extraction in 2009 selects hydrogenation to obtain divinyl (CN101434508A).
At present, on divinyl Downstream Market, the demand of rubber and ABS resin is continuing to increase, and divinyl consumption is with the speed increment of average annual 10% left and right, and production capacity expansion rate of increase is less than 8%, and the production of divinyl is still in the state that supply falls short of demand.In the preparation technology of traditional divinyl, the traditional raw material of steam cracking process mainly be take lighter hydrocarbons, petroleum naphtha, hydrogenation tail oil as main, the divinyl yield of lighter hydrocarbons steam cracking is below 3%, the divinyl yield of naphtha steam cracking is at 3-6%, and the divinyl yield of hydrogenation tail oil steam cracking is at 4-7%.Therefore the approach with traditional raw material volume increase divinyl is very limited.So, constantly expand butadiene production approach, exploitation new raw material and variation route, necessary for ethylene unit and divinyl industry.
Summary of the invention
The object of the invention is, in order to overcome the lower defect of divinyl yield in existing divinyl preparation process, provides a kind of preparation method of new divinyl.
The invention provides a kind of preparation method of divinyl, the method comprises carries out steam cracking reaction by cracking stock, and described cracking stock contains tetrahydrobenzene, and in described cracking stock, the content of tetrahydrobenzene is 5-100 % by weight.
In the preparation method of described divinyl of the present invention, by the cracking stock of the tetrahydrobenzene that contains 5-100 % by weight is carried out to steam cracking, can obtain the divinyl yield significantly improving.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The preparation method of divinyl according to the present invention comprises cracking stock carried out to steam cracking reaction, and described cracking stock contains tetrahydrobenzene, and in described cracking stock, the content of tetrahydrobenzene is 5-100 % by weight.
In order further to improve divinyl yield, in described cracking stock, tetrahydrobenzene content is preferably 10-100 % by weight, more preferably 20-100 % by weight, more preferably 50-100 % by weight.
In the present invention, described steam cracking reaction can carry out in pyrolyzer.In described cracking stock, except tetrahydrobenzene, described cracking stock can also contain the conventional cracking stock using in this area, as lighter hydrocarbons, petroleum naphtha, diesel oil, hydrogenation tail oil etc.Yet, because tetrahydrobenzene is combined with petroleum naphtha, relatively high divinyl yield can be obtained, and the convection zone coking of pyrolyzer can be prevented, therefore, described cracking stock preferably also contains petroleum naphtha.
In the situation that described cracking stock also contains petroleum naphtha, in described cracking stock, the content of tetrahydrobenzene can be 5-99 % by weight, and the content of petroleum naphtha can be 1-95 % by weight.Preferably, in described cracking stock, the content of tetrahydrobenzene is 10-99 % by weight, and the content of petroleum naphtha is 1-90 % by weight.
The preparation method of described divinyl of the present invention preferably implements in ethylene unit.Described ethylene unit comprises pyrolyzer and tripping device.Described pyrolyzer can be the pyrolyzer of the conventional preparing ethylene by steam cracking using in this area.Described pyrolyzer mainly comprises convection zone, radiation section, quenching boiler and gas burning system conventionally.In described pyrolyzer, by cracking stock be steam heated to generation steam cracking reaction, generate the splitting gas that is rich in ethene.In the preferred case, described pyrolyzer is preferably tube cracking furnace.Described tube cracking furnace comprises convection zone, radiation section, quenching boiler and gas burning system, and cracking stock enters radiation section in convection zone; In radiation section, cracking stock be steam heated to generation steam cracking reaction, generate the splitting gas that is rich in ethene; Splitting gas enters quenching boiler from radiation section out, and in quenching boiler, splitting gas is cooled to 300-600 ℃, so that scission reaction does not occur splitting gas, reclaims heat simultaneously; Fuel system is for providing heat to steam cracking reaction process.Described tripping device is for being separated into splitting gas the hydrocarbon of different carbon numbers.Conventionally, described tripping device mainly comprises: oil scrubber, water wash column, ice chest, compressor, demethanizing tower, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, carbon two and carbon three hydrogenation units, carbon two and carbon three rectifying tower, methanation device and butadiene extraction unit.The implementation method of described tripping device has been conventionally known to one of skill in the art, does not repeat them here.
In the present invention, in the situation that described steam cracking reaction carries out in pyrolyzer, in described steam cracking reaction process, the coil outlet temperature of described pyrolyzer is preferably 680-860 ℃, more preferably 760-850 ℃; Water weight of oil, than for 0.3-1, is preferably 0.45-0.65.In addition, in described steam cracking reaction process, other Parameter Conditions of described pyrolyzer can be implemented according to conventional processing condition, and there is no particular limitation in the present invention.
The invention will be further described by the following examples, but protection scope of the present invention is not limited in these embodiment.
In the following Examples and Comparative Examples, divinyl yield and methane yield calculate according to following formula:
Gross weight * 100% of weight/steam cracking reaction product of divinyl in divinyl yield=steam cracking reaction product.
For the petroleum naphtha using in following examples and comparative example, shown in the correlation parameter of this petroleum naphtha and the table 1 composed as follows that records according to ASTM D5443 method.
Table 1
Embodiment 1-4 and comparative example 1
Cracking stock is injected respectively to CBL-III type pyrolyzer (purchased from China PetroChemical Corporation) and carry out steam cracking reaction, and detect the yield of divinyl, wherein, cracking stock and reaction conditions are as shown in table 2 below, and the blending ratio in cracking stock is weight ratio.Collect splitting gas (being steam cracking reaction product), composition is wherein analyzed, and calculated divinyl yield, result is as shown in table 2 below.
Table 2
Data by table 2 can find out, the preparation method of divinyl according to the present invention can obtain the divinyl yield significantly improving.Concrete, by embodiment 1 is compared and can be found out with comparative example 1, the cracking stock using in comparative example 1 is petroleum naphtha, and the cracking stock using in embodiment 1 is tetrahydrobenzene, and acetonideexample 1 has obtained the divinyl yield of obvious raising.
Claims (8)
1. a preparation method for divinyl, the method comprises carries out steam cracking reaction by cracking stock, and described cracking stock contains tetrahydrobenzene, and in described cracking stock, the content of tetrahydrobenzene is 5-100 % by weight.
2. method according to claim 1, wherein, in described cracking stock, the content of tetrahydrobenzene is 10-100 % by weight.
3. method according to claim 1 and 2, wherein, described cracking stock also contains petroleum naphtha.
4. method according to claim 3, wherein, in described cracking stock, the content of tetrahydrobenzene is 5-99 % by weight, the content of petroleum naphtha is 1-95 % by weight.
5. method according to claim 4, wherein, in described cracking stock, the content of tetrahydrobenzene is 10-99 % by weight, the content of petroleum naphtha is 1-90 % by weight.
6. according to the method described in any one in claim 1-5, wherein, described steam cracking reaction carries out in pyrolyzer, and in described steam cracking reaction process, the coil outlet temperature of described pyrolyzer is 650-860 ℃, and water weight of oil is than being 0.3-1.
7. method according to claim 6, wherein, the coil outlet temperature of described pyrolyzer is 700-840 ℃, water weight of oil is than being 0.45-0.65.
8. method according to claim 6, wherein, described pyrolyzer is tube cracking furnace.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210289201.9A CN103588608A (en) | 2012-08-14 | 2012-08-14 | Butadiene preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210289201.9A CN103588608A (en) | 2012-08-14 | 2012-08-14 | Butadiene preparation method |
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| CN103588608A true CN103588608A (en) | 2014-02-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216329A (en) * | 2021-04-21 | 2022-10-21 | 中国石油大学(北京) | Steam cracking method using electricity for energy supply |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB596879A (en) * | 1942-06-29 | 1948-01-13 | Koppers Co Inc | A method of pyrolyzing a hydro-aromatic compound |
| US3317626A (en) * | 1964-02-19 | 1967-05-02 | Goodyear Tire & Rubber | Olefin pyrolysis initiators |
-
2012
- 2012-08-14 CN CN201210289201.9A patent/CN103588608A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB596879A (en) * | 1942-06-29 | 1948-01-13 | Koppers Co Inc | A method of pyrolyzing a hydro-aromatic compound |
| US3317626A (en) * | 1964-02-19 | 1967-05-02 | Goodyear Tire & Rubber | Olefin pyrolysis initiators |
Non-Patent Citations (1)
| Title |
|---|
| S.RUVENS MITH，ET AL.: "A STUDY OF THE PYROLYSIS OF CYCLOHEXENE", 《PYROLYSOIFS CYCLOHEXENE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216329A (en) * | 2021-04-21 | 2022-10-21 | 中国石油大学(北京) | Steam cracking method using electricity for energy supply |
| WO2022222708A1 (en) | 2021-04-21 | 2022-10-27 | 中国石油大学(北京) | Steam cracking method utilizing electricity for providing energy |
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Application publication date: 20140219 |