CN105367366B - Utilize the method for mixing the production of carbon four ethene, propylene - Google Patents
Utilize the method for mixing the production of carbon four ethene, propylene Download PDFInfo
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- CN105367366B CN105367366B CN201410428789.0A CN201410428789A CN105367366B CN 105367366 B CN105367366 B CN 105367366B CN 201410428789 A CN201410428789 A CN 201410428789A CN 105367366 B CN105367366 B CN 105367366B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002156 mixing Methods 0.000 title claims abstract description 52
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- -1 C 4 olefin Chemical class 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 56
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 26
- 238000000895 extractive distillation Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 16
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 238000007037 hydroformylation reaction Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 27
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 12
- 239000001273 butane Substances 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of using the method for mixing the production of carbon four ethene, propylene, the problem of mainly solving to mix the not high utilization rate of carbon four and low added value in the prior art.The present invention is by using following steps：(a) selective hydrogenation technology is used, it is monoolefine to make the butadiene hydrogenation in mixing carbon four；(b) olefins by catalytic cracking technology is used, it is ethene, propylene to make the olefins by catalytic cracking in mixing carbon four；(c) by distillation technology, unreacted mixing carbon four is isolated；(d) extraction and distillation technology is used, the alkane in unreacted mixing carbon four is removed, remaining C 4 olefin circulation preferably solves the problem as the technical scheme of catalytic pyrolysis raw material, available for increasing output of ethylene, propylene, in the commercial Application for improving the mixing chemical comprehensive utilization rate of carbon four.
Description
Technical field
The method for mixing the production of carbon four ethene, propylene is utilized the present invention relates to a kind of.
Background technology
Ethene, propylene are the most basic raw materials of petrochemical industry, are the bases for producing various Organic chemical products, mainly pass through
Steam cracking and catalytic cracking are produced.And it is used as the mixing of one of steam cracking device and catalytic cracking unit Main By product
Carbon four, wherein iso-butane, normal butane, isobutene, butadiene, butene-1, butene-2 for not waited containing quantity etc., these components are
Widely used industrial chemicals, particularly C 4 olefin.Mixing carbon four is typically etherified by Butadiene Extraction, isobutene at present
Afterwards, remaining carbon four is used mostly as liquefied gas as fuel, and added value is relatively low.With the continuous growth of the yield of carbon four, how
It is enterprise's cost efficiency, the strong approach for lifting economic benefit to improve the comprehensive resource utilization rate of carbon four.
CA2297301 describes a kind of method for improving carbon four and the price value mixed above of carbon four.The method is using zeolite point
The raw material of carbon four is directly converted into low-carbon alkene, and isolated ethene, propylene by sub- sieve catalyst.The method is split comprising two catalysis
Reactor, selective hydrogenation reactor, methyltertiarvbutyl ether reactor etc. are solved, flow is complicated, and ethene, propene yield are low, warp
Ji property is poor.CN101279879B describes a kind of method for comprehensively utilizing the mixing production propylene of carbon four.The method first passes through catalysis and split
Solution technology makes olefins by catalytic cracking in mixing carbon four be ethene, propylene, then using isomerization technique by butene-1 isomerization
For butene-2, make butene-2 react with ethene to produce propylene finally by disproportionation technology.The method is without reference to containing fourth two
The processing of alkene raw material, a part of unreacted carbon four is directly discharged, and causes C 4 olefin loss larger, and mixed without handling
Alkane in carbon four so that a large amount of alkane cause equipment huge in system interior circulation.US6075173 describes one kind and utilizes carbon
The method that four hydrocarbon produce isobutene and propylene.The method by selective hydrogenation make butadiene hydrogenation be monoolefine, while by butylene-
1 is isomerized to butene-2, is then separated using rectifying, and overhead extraction isobutene and a small amount of butene-1, tower reactor contain butene-2 and fourth
After the cut of alkane is mixed with ethene, propylene is produced by disproportionated reaction.US6686510B2 is US6075173 modified technique.
The method has coupled an isomerization reaction when carrying out rectifying separation to selective hydrogenation product in rectifying column or outside tower
Process, makes butene-1 further be isomerized to butene-2, so as to obtain the isobutene of higher degree in rectifying tower top.This two kinds of sides
Method does not make full use of isobutene and for the higher raw material of isobutene content, and the yield of propylene is low, and consumes substantial amounts of ethene
Resource.
The content of the invention
The method for mixing the production of carbon four ethene, propylene is utilized the present invention relates to a kind of.Technology to be solved by this invention is asked
Topic is the problem of mixing utilization rate of carbon four is not high in the prior art, added value is low.There is provided a kind of new life of utilization mixing carbon four
Produce ethene, the method for propylene.This method has high mixing carbon four comprehensive utilization ratio, ethene and propene yield high, good economy performance
Feature.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind produces second using carbon four is mixed
The method of alkene, propylene, comprises the following steps：(a) the mixing raw material of carbon four and hydrogen enter in selective hydrogenation reactor, raw material
Butadiene is hydrogenated to monoolefine, and hydrogenation reaction product enters catalytic cracking reaction device after heat exchange and preheating；(b) catalysis is split
Solve reactor in, C _ 4 alkene catalytic pyrolysis be ethene, propylene, catalytic cracking reaction products by heat exchange, cooling, compression after,
Separated into rectifying column；(c) rectifying tower top extraction ethene, propylene light component, tower reactor extraction light dydrocarbon and above heavy constituent, side
Line produces unreacted carbon four；(d) unreacted carbon four enters in the middle part of extractive distillation column, and extractant is added from extractive distillation column top,
Overhead extraction butane, tower reactor must contain the distillate of C 4 olefin and extractant；(e) extractive distillation column reactor distillate enters molten
In the middle part of agent recovery tower, tower top C 4 olefin returns to catalytic cracking reaction device as catalytic pyrolysis raw material, and tower reactor extractant returns to extraction
Rectifier is taken, is recycled.
In the above-mentioned technical solutions, mixing carbon four and hydrogen enter selective hydrogenation reactor, and wherein butadiene is chosen
Property be hydrogenated to butene-1 and/or butene-2, the catalyst used be preferably load on the alumina support include selected from nickel,
At least one of zinc or palladium.Selective hydrogenation reactor inlet temperature preferred scope is 20~150 DEG C, the preferred model of reaction pressure
Enclose for 0.6~4.0MPaG, reaction velocity preferred scope is 1~20hr-1, hydrogen and butadiene mol ratio preferred scope be 0.9~
1.2。
Selective hydrogenation product enters catalytic cracking reaction device, reaction life after temperature needed for exchanging heat and being preheated to
Into ethene, propylene, the catalyst of use is preferably silicoaluminophosphate molecular sieve catalyst, and reaction temperature preferred scope is 500~600 DEG C,
Reaction pressure preferred scope is 0~0.2MPaG, and reaction velocity preferred scope is 15~30hr-1。
Catalytic cracking reaction products enter compressor after temperature needed for exchanging heat and being cooled to, by compressor compresses to institute
Need after pressure to be separated into rectifying column, overhead extraction carbon three and following components, tower reactor extraction light dydrocarbon and above component, not instead
The mixing carbon four answered is from tower side take-off, into extractive distillation column middle part, and extractant is added from tower top, and extractant is preferably two
At least one of NMF, 1-METHYLPYRROLIDONE, acetonitrile.Extracting rectifying tower top obtains butane, tower reactor carbon containing four
The distillate of alkene and extractant enters in the middle part of solvent recovery tower, and tower top C 4 olefin is all back to as catalytic pyrolysis raw material
Catalytic cracking reaction device, tower reactor extractant returns to extractive distillation column top, recycles, and supplement fresh extraction in right amount as needed
Take agent.The total number of theoretical plate preferred scope of extractive distillation column is 40~60, and operating pressure preferred scope is 0.3MPaG~0.9MPaG,
Solvent is 4~15 than preferred scope, and reflux ratio preferred scope is 3~10.The total number of theoretical plate preferred scope of solvent recovery tower be 5~
20, operating pressure preferred scope is 0.3MPaG~0.9MPaG, and reflux ratio preferred scope is 1~6.
In above-mentioned technical proposal, mixing carbon four by weight percentage, preferably comprises 10~60% butadiene；It is more excellent
Elect as 15~40% butadiene；
In above-mentioned technical proposal, mixing carbon four by weight percentage, preferably comprises 5~60% isobutene；It is more excellent
Elect 10~50% isobutenes as；
In above-mentioned technical proposal, mixing carbon four by weight percentage, preferably comprises 5~50% butene-1 and fourth
Alkene -2；More preferably 10~40% butene-1 and butene-2；
In above-mentioned technical proposal, mixing carbon four by weight percentage, preferably comprises 5~35% butane；More preferably
For 10~25% butane.
The present invention takes full advantage of mixed by using selective hydrogenation technology, deep catalytic cracking technology and extraction and distillation technology
Alkene production ethene, the propylene in the raw material of carbon four are closed, the utilization rate and added value of mixing carbon four, ethene and propene yield is improved
Height, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 mixes the production of carbon four ethene, the method process flow diagram of propylene for a kind of utilize of the present invention.
Fig. 2 is CA2297301 process flow diagrams.
1 is raw material mixing carbon four in Fig. 1, Fig. 2, and 2 be hydrogen, and 3 be selective hydrogenation reactor, and 4 be that selective hydrogenation is anti-
Product is answered, 5 be heat exchanger, and 6 be preheater, and 7 be catalytic cracking reaction device, and 8 be catalytic cracking reaction products, and 9 be cooler, 10
It is rectifying column for compressor, 11,12 be carbon three and following components, and 13 be light dydrocarbon and above component, and 14 be unreacted mixing carbon four,
15 be extractive distillation column, and 16 be fresh extractant, and 17 be butane, and 18 be distillating for unreacted carbon alkatetraenes and extractant
Thing, 19 be solvent recovery tower, and 20 be unreacted carbon alkatetraenes, and 21 be cycling extraction agent, and 22 be the first catalytic cracking reaction device, 23
It is light component for first rectifying column, 24,25 be ethene, and 26 be propylene, and 27 be carbon four, and 28 be heavy constituent, and 29 be selective hydrogenation
Reactor, 30 be methanol, and 31 be methyltertiarvbutyl ether reactor, and 32 be Second distillation column, and 33 be MTBE, and 34 be the second catalytic cracking reaction
Device.
Flow as shown in Figure 1, mixing carbon 41 and hydrogen 2 enter selective hydrogenation reactor 3, by selective hydrogenation
Reaction, butadiene is hydrogenated to monoolefine.Selective hydrogenation product 4 is preheated to reaction institute by heat exchanger 5 and preheater 6
Temperature is needed, subsequently into catalytic cracking reaction device 7.In catalytic cracking reaction device mix carbon four in olefin cracking for ethene,
Propylene, catalytic cracking reaction products 8 are cooled to required temperature through heat exchanger 5 and cooler 9, are then compressed to by compressor 10
Separated after required pressure into rectifying column 11.Rectifying tower top produces carbon three and following components 12, tower reactor extraction light dydrocarbon and with
Enter the middle part of extractive distillation column 15 after upper component 13, the side take-off of unreacted mixing carbon 4 14, fresh extractant 16 is smart from extraction
Evaporate tower top to add, overhead extraction butane 17, the distillate 18 of tower reactor unreacted carbon alkatetraenes and extractant enters solvent
Recovery tower 19, tower top unreacted carbon alkatetraenes 20 is recycled back into before catalytic cracking reaction device, and tower reactor cycling extraction agent 21 returns to extraction
Rectifier is taken, and supplements fresh extractant in right amount on extractive distillation column top as needed.
Below by specific embodiment, the present invention is further illustrated, still, and the scope of the present invention is not only limited in
The scope that embodiment is covered.
Embodiment
【Comparative example 1】
As shown in Figure 2, mixing carbon four constitutes (weight %) and is：Butadiene：40.0%, isobutene：12.0%, butene-1：
18.0%, butene-2：18.2%, butane：11.8%.Using CA2297301 technological processes, the first catalytic cracking reaction device and
Two catalytic cracking reaction devices use silica alumina ratio for 280 silicoaluminophosphate molecular sieve catalyst, 550 DEG C of reaction temperature, reaction pressure
0.1MPaG；First rectifying column is valve tower, the number of plates 110, tower top pressure 1.2MPaG；Selective hydrocatalyst is Metal Palladium
Series catalysts, 60 DEG C of reaction temperature, reaction pressure 3.0MPaG；Catalyst for etherification is ion exchange resin, 40 DEG C of reaction temperature,
Reaction pressure 1.2MPaG；Second distillation column is sieve-plate tower, the number of plates 60, tower top pressure 0.4MPaG.Experiment proof obtains ethene
It is respectively 5.7% and 17.0% (weight, for the alkene in raw material mixing carbon 4 1) with propylene.
【Embodiment 1】
As shown in Figure 1, mixing carbon four constitutes (weight %) and is：Butadiene：40.0%, isobutene：12.0%, butene-1：
18.0%, butene-2：18.2%, butane：11.8%.Using present invention process flow, selective hydrogenation catalyst is oxygen
Change aluminium carried metal palladium, 40 DEG C of reactor inlet temperature, reaction pressure 1.5MPaG, reaction velocity 6hr-1, hydrogen rubs with butadiene
You compare 1.08；Catalytic cracking reaction catalyst is the ZSM-5 molecular sieve of silica alumina ratio 200,530 DEG C of reaction temperature, reaction pressure
0.10MPaG, reaction velocity 20hr-1；The total number of theoretical plate 60 of rectifying column (counting from top to bottom, as follows), reflux ratio 5, the 38th piece of reason
By plate side take-off unreacted mixing carbon four, tower top pressure 1.5MPaG；The total number of theoretical plate 50 of extractive distillation column, tower top operation pressure
Power 0.5MPaG, reflux ratio 5, extractant dimethylformamide enters from the 2nd block of plate, and solvent compares 8；The total theoretical plate of solvent recovery tower
Number 15, operating pressure 0.5MPaG, reflux ratio 3.Experiment proves that it is respectively 10.6% and 37.6% to obtain ethene and the yield of propylene
(weight, for the alkene in raw material mixing carbon 4 1).
【Embodiment 2】
As shown in Figure 1, mixing carbon four constitutes (weight %) and is：Butadiene：25.0%, isobutene：20.0%, butene-1：
13.0%, butene-2：25.4%, butane：16.6%.Using present invention process flow, selective hydrogenation catalyst is oxygen
Change aluminium carried metal nickel, 30 DEG C of reactor inlet temperature, reaction pressure 2.0MPaG, reaction velocity 5hr-1, hydrogen rubs with butadiene
You compare 1.05；Catalytic cracking reaction catalyst is the ZSM-5 molecular sieve of silica alumina ratio 200,550 DEG C of reaction temperature, reaction pressure
0.06MPaG, reaction velocity 18hr-1；The total number of theoretical plate 65 of rectifying column (counting from top to bottom, as follows), reflux ratio 6, the 40th piece of reason
By plate side take-off unreacted mixing carbon four, tower top pressure 1.5MPaG；The total number of theoretical plate 50 of extractive distillation column, tower top operation pressure
Power 0.5MPaG, reflux ratio 5, extractant dimethylformamide enters from the 2nd block of plate, and solvent compares 6；The total theoretical plate of solvent recovery tower
Number 15, operating pressure 0.5MPaG, reflux ratio 3.Experiment proves that it is respectively 10.8% and 38.1% to obtain ethene and the yield of propylene
(weight, for the alkene in raw material mixing carbon 4 1).
【Embodiment 3】
As shown in Figure 1, mixing carbon four constitutes (weight %) and is：Butadiene：22.0%, isobutene：36.0%, butene-1：
8.0%, butene-2：13.4%, butane：20.6%.Using present invention process flow, selective hydrogenation catalyst is oxidation
Aluminium carried metal nickel, 40 DEG C of reactor inlet temperature, reaction pressure 2.5MPaG, reaction velocity 6hr-1, hydrogen and butadiene mole
Than 1.05；Catalytic cracking reaction catalyst is the ZSM-5 molecular sieve of silica alumina ratio 300,550 DEG C of reaction temperature, reaction pressure
0.08MPaG, reaction velocity 20hr-1；The total number of theoretical plate 65 of rectifying column (counting from top to bottom, as follows), reflux ratio 7, the 40th piece of reason
By plate side take-off unreacted mixing carbon four, tower top pressure 1.7MPaG；The total number of theoretical plate 55 of extractive distillation column, tower top operation pressure
Power 0.4MPaG, reflux ratio 5, extractant 1-METHYLPYRROLIDONE enters from the 2nd block of plate, and solvent compares 6；Solvent recovery tower premier discusses
Plate number 18, operating pressure 0.4MPaG, reflux ratio 4.Experiment proves that it is respectively 11.1% He to obtain ethene and the yield of propylene
38.3% (weight, for the alkene in raw material mixing carbon 4 1).
【Embodiment 4】
As shown in Figure 1, mixing carbon four constitutes (weight %) and is：Butadiene：15.0%, isobutene：50.0%, butene-1：
6.0%, butene-2：5.4%, butane：23.6%.Using present invention process flow, selective hydrogenation catalyst is oxidation
Aluminium carried metal palladium, 30 DEG C of reactor inlet temperature, reaction pressure 1.8MPaG, reaction velocity 8hr-1, hydrogen and butadiene mole
Than 1.03；Catalytic cracking reaction catalyst is the ZSM-5 molecular sieve of silica alumina ratio 300,560 DEG C of reaction temperature, reaction pressure
0.08MPaG, reaction velocity 18hr-1；The total number of theoretical plate 68 of rectifying column (counting from top to bottom, as follows), reflux ratio 7, the 42nd piece of reason
By plate side take-off unreacted mixing carbon four, tower top pressure 1.7MPaG；The total number of theoretical plate 55 of extractive distillation column, tower top operation pressure
Power 0.4MPaG, reflux ratio 6, extractant 1-METHYLPYRROLIDONE enters from the 2nd block of plate, and solvent compares 5；Solvent recovery tower premier discusses
Plate number 18, operating pressure 0.4MPaG, reflux ratio 4.Experiment proves that it is respectively 11.3% He to obtain ethene and the yield of propylene
38.6% (weight, for the alkene in raw material mixing carbon 4 1).
Claims (8)
1. it is a kind of using the production of carbon four ethene, the method for propylene is mixed, comprise the following steps：
(a) butadiene that the mixing raw material of carbon four and hydrogen enter in selective hydrogenation reactor, raw material is hydrogenated to monoolefine, plus
Hydroformylation reaction product enters catalytic cracking reaction device after heat exchange and preheating；
(b) in catalytic cracking reaction device, reaction velocity is 15~30hr-1, C _ 4 alkene catalytic pyrolysis is ethene, propylene, catalysis
Cleavage reaction product is separated after heat exchange, cooling, compression into rectifying column；
(c) rectifying tower top extraction ethene, propylene light component, tower reactor extraction light dydrocarbon and above heavy constituent, side take-off unreacted carbon
Four；
(d) unreacted carbon four enters in the middle part of extractive distillation column, and extractant is added from extractive distillation column top, the alkane of overhead extraction carbon four
Hydrocarbon, tower reactor must contain the distillate of C 4 olefin and extractant, the total number of theoretical plate 40~60 of extractive distillation column, operating pressure
0.3MPaG~0.9MPaG, solvent is than 4~15, reflux ratio 3~10；
(e) extractive distillation column reactor distillate enters in the middle part of solvent recovery tower, and tower top C 4 olefin is returned as catalytic pyrolysis raw material
Catalytic cracking reaction device, tower reactor extractant returns to extractive distillation column top, recycles.
2. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that butadiene is chosen
Property be hydrogenated to butene-1 and/or butene-2, the catalyst used for load on the alumina support include be selected from nickel, zinc or palladium
At least one of.
3. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that selective hydrogenation is anti-
Answer 20~150 DEG C of device inlet temperature, 0.6~4.0MPaG of reaction pressure, 1~20hr of reaction velocity-1, hydrogen and butadiene mole
Than 0.9~1.2.
4. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that mixing carbon four is catalyzed
Ethene, propylene are cracked into, the catalyst used is silicoaluminophosphate molecular sieve catalyst.
5. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that catalytic cracking reaction
500~600 DEG C of device reaction temperature, 0~0.2MPaG of reaction pressure.
6. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that extractant is selected from two
At least one of NMF, 1-METHYLPYRROLIDONE, acetonitrile.
7. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that solvent recovery tower is total
Number of theoretical plate 5~20, operating pressure 0.3MPaG~0.9MPaG, reflux ratio 1~6.
8. the method for mixing the production of carbon four ethene, propylene is utilized according to claim 1, it is characterised in that solvent recovery tower top
C 4 olefin all returns to catalytic cracking reaction device.
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| CN109369318B (en) * | 2018-12-07 | 2021-05-21 | 宁波旭合瑞石化工程有限公司 | Method for maximizing production of propylene by using C5 olefin as main raw material |
| CN112679300B (en) * | 2019-10-18 | 2023-03-03 | 中国石油化工股份有限公司 | Method for preparing propylene from carbon four raw material |
| CN112759500B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Method for producing propylene by using carbon tetrahydrocarbon |
| CN112694383A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene by catalytic cracking of olefin |
| CN112707780A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from raw materials with four or more carbon atoms |
| CN111233613A (en) * | 2020-04-01 | 2020-06-05 | 联泓新材料科技股份有限公司 | Hydrogenation device and hydrogenation method for producing ethylene and propylene |
| CN114426448B (en) * | 2020-09-09 | 2024-05-07 | 中国石油化工股份有限公司 | Method and device for increasing propylene yield |
| CN114426449B (en) * | 2020-09-09 | 2024-05-07 | 中国石油化工股份有限公司 | Method and device for improving utilization rate of mixed carbon four |
| CN114456025B (en) * | 2020-10-21 | 2024-05-28 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
| CN114456026B (en) * | 2020-10-21 | 2024-06-28 | 中国石油化工股份有限公司 | Method and device for increasing yield of ethylene and 1-butene |
| CN114516776A (en) * | 2020-11-19 | 2022-05-20 | 中国石油化工股份有限公司 | Method and apparatus for producing ethylene and propylene |
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