CN101798255A - Method for separating diolefin from petroleum cracking carbon five fraction by acetonitrile - Google Patents
Method for separating diolefin from petroleum cracking carbon five fraction by acetonitrile Download PDFInfo
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- CN101798255A CN101798255A CN 200910078045 CN200910078045A CN101798255A CN 101798255 A CN101798255 A CN 101798255A CN 200910078045 CN200910078045 CN 200910078045 CN 200910078045 A CN200910078045 A CN 200910078045A CN 101798255 A CN101798255 A CN 101798255A
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001993 dienes Chemical class 0.000 title claims abstract description 5
- 238000005120 petroleum cracking Methods 0.000 title abstract 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000002904 solvent Substances 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- KRNJJBUNWGLWNB-UHFFFAOYSA-N 2-methylbuta-1,3-diene hydrate Chemical compound O.CC(=C)C=C KRNJJBUNWGLWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- 238000000895 extractive distillation Methods 0.000 claims description 55
- 241000282326 Felis catus Species 0.000 claims description 53
- 238000010992 reflux Methods 0.000 claims description 32
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 20
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 16
- 150000001345 alkine derivatives Chemical class 0.000 claims description 13
- 230000011218 segmentation Effects 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- -1 p-ten.-butylcatechol Chemical compound 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 3
- 210000003918 fraction a Anatomy 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 abstract 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 abstract 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 238000004230 steam cracking 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for separating diolefin in petroleum cracking carbon five fractions by an acetonitrile method; feeding the carbon five fraction into a rough separation tower, passing through a de-alkyne tower, a first extraction rectification tower, a solvent analysis tower, a second extraction rectification tower side-cut tower, a second extraction rectification tower, an isoprene water washing tower, an isoprene light-removing tower, an isoprene heavy-removing tower, a raffinate carbon five water washing tower, a solvent recovery tower, a solvent refining tower and a piperylene rectification tower, wherein an extracting agent is a mixture of at least one of acetonitrile, dimethylformamide, N-methylpyrrolidone or water; the content of acetonitrile is 80-95%, and the content of at least one of dimethylformamide, N-methylpyrrolidone or water is 5-20%; the adopted polymerization inhibitor is sodium nitrite, p-tert-butyl catechol, diethyl hydroxylammonium or o-nitrophenol, and the concentration of the polymerization inhibitor in the material is 50-1000 ppm; obtaining isoprene with the purity of 99.3-99.8% and piperylene with the purity of more than 80%.
Description
Technical field
The present invention relates to a kind of separation method that adopts acetonitrile separating isoprene and m-pentadiene.
Background technology
Cracked C 5 fraction is close by nearly 30 kinds of boiling points, the easy component that forms azeotrope is formed each other, therefrom isolating purity, to meet the C 5 diene difficulty of application requiring bigger, complex process generally adopts extraction fractional distillation or azeotropic distillation to separate in the prior art.In the extracting rectifying, solvent commonly used has acetonitrile, dimethyl formamide (DMF) and N-Methyl pyrrolidone (NMP), as patent US2993841, disclosed processing methodes such as US4081332 and US3803258.US4081332 discloses the method for unsaturated hydrocarbons in a kind of acetonitrile extracting distillation separation C five, for improving the selectivity of acetonitrile, adds components such as a spot of dimethyl formamide, dimethyl sulfoxide (DMSO), morpholine and N-Methyl pyrrolidone in acetonitrile solution.U.S. Pat 3230157 discloses the processing method that a kind of isoprene reclaims, and the C5 fraction that will obtain by the hydro carbons steam cracking removes carbon four and light constituent by rectifying; Be that solvent carries out the extracting rectifying first time with the acetonitrile that has less water then, remove alkane and monoolefine, solvent uses by solvent recovery cycle; With the acetonitrile that has less water is that solvent carries out second extracting rectifying, removes alkene such as alkynes, cyclopentadiene and m-pentadiene, and solvent recycles by solvent recovery tower; Pass through operations such as water wash column again, cat head obtains highly purified isoprene product.Chinese patent CN100999434A discloses a kind of C5 fraction separation and comprehensive utilization method of acetonitrile solvent method, its technology comprises hot dipolymer reactor, decarburization five towers, decarburization six towers, dicyclopentadiene depolymerization weight-removing column, takes off gently, takes off heavy process after hot dimerization, obtain the purified dicyclopentadiene, the component that obtains in decarburization five column overhead enters the isoprene system, enter first extractive distillation column after the pre-separation of carrying out earlier expecting the carbon Wuyuan, obtain being rich in the solvent material of C 5 dienes such as isoprene, alkynes by the tower still; Then enter second extractive distillation column, operational condition and quantity of solvent by control tower, mainly carry out the extracting rectifying of alkynes, tower still material enters flashing tower, enters water wash system then, and components such as while cat head isoprene also enter water wash system, solvent is through can recycle and reuse behind the recovery tower, behind extraction process and water washing process, enter refining system, obtain highly purified isoprene at last.Carbon five separation process are long, are made up of a plurality of rectifying tower, extractive distillation column and solvent recovery tower, and energy consumption is big; Isoprene and m-pentadiene in the separating carbon 5 fraction adopt extracting rectifying more, its solvent ratio is big, the internal circulating load of solvent is big, energy expenditure is also big, liquid load height in the while tower, tray efficiency is low, and required stage number is many generally 20～40%, has offset to add the effect that solvent improves relative volatility minimizing stage number.
Summary of the invention
The objective of the invention is in advance most alkynes in the five fractions of petroleum cracked carbon to be removed, improve the security of device; Adopt hot integrated technology, the first extracting rectifying Tata still material is directly entered solvent Analytic Tower top, the solvolysis analysis system of first extractive distillation column and second extractive distillation column is merged into a cover.Between second extractive distillation column and solvent Analytic Tower, adopt hot integrated technology, cut down the consumption of energy saving equipment; Circulating solvent is refining, remove the polymkeric substance in the solvent, guarantee the long-period stable operation of carbon five tripping devices.
The technical solution used in the present invention comprises the steps:
(1) the cracked C 5 fraction a that will remove cyclopentadiene sends into rough segmentation tower 1 middle part, and cat head obtains being rich in the material b of isoprene, and the tower still obtains being rich in the material c of m-pentadiene;
(2) material b enters acetylene removal tower 2 middle and lower parts, and cat head obtains being rich in the material d of alkynes, and the tower still obtains the Materialien of enrichment isoprene;
(3) Materialien enters first extractive distillation column, 3 middle and lower parts, and the solvent that enters with tower top contacts, and carries out extracting rectifying, and cat head obtains containing the light constituent material I of alkane and monoolefine; The tower still obtains being rich in the solvent material f of isoprene;
(4) material f enters solvent Analytic Tower 11, solvent is resolved top of tower and is connected with second extractive distillation column, 5 bottoms, the material that is rich in isoprene that parses directly enters second extractive distillation column 5, contact with the solvent that enters from tower top and to carry out extracting rectifying, cat head obtains being rich in the material g of isoprene; Solvent is resolved the Tata still and is obtained solvent h, solvent Analytic Tower middle and lower part material, and approaching side is cut tower 12, and cat head obtains containing the material II of anti--2-amylene, isoprene, cyclopentadiene and alkynes, and the tower still obtains the material i of enrichment acetonitrile, returns solvent Analytic Tower 11;
(5) material g enters isoprene water wash column 6 middle parts, and the acetonitrile that contains among the material g is washed off, and the tower still obtains containing the washing water III of minor amounts of acetonitrile, and cat head obtains the material j of enrichment isoprene;
(6) material j enters isoprene lightness-removing column 7 middle parts, and cat head obtains containing the isoprene of a small amount of light constituent, and the tower still obtains further spissated isoprene material k;
(7) material k enters isoprene weight-removing column 8 middle parts, and the tower still obtains carbon five and raffinates oil, and cat head obtains purity at 99.3～99.8% isoprene product;
(8) material I, II enter raffinate carbon-5 water wash column 4 middle parts, and material III enters raffinate carbon-5 water wash column 4 tops, and the water-containing solvent n that the tower still obtains, cat head obtain carbon five and raffinate oil;
(9) water-containing solvent n enters solvent recovery tower 10 middle parts, and cat head obtains the azeotrope of acetonitrile and water, and retrieval system recycles, tower still discharge of wastewater;
(10) material h enters solvent treatment tower 13 middle parts, and cat head obtains that solvent acetonitrile is back to first extractive distillation column 3 and second extractive distillation column 5 recycles, and the tower still is the raffinate that contains polymkeric substance;
(11) material c enters m-pentadiene rectifying tower 9 middle parts, and the tower still obtains purity greater than 80% m-pentadiene product.
Rough segmentation tower, first extractive distillation column, second extractive distillation column, isoprene lightness-removing column and isoprene weight-removing column use stopper, and the stopper of employing is selected from least a in Sodium Nitrite, p-ten.-butylcatechol, diethyl hydroxylammonium and the o-NP; The solvent that uses in first extracting rectifying, the second extracting rectifying process is acetonitrile, and additive is at least wherein a kind of of dimethyl formamide, N-Methyl pyrrolidone and water.
In above-mentioned flow process, each operating unit operational condition is as follows:
(1) operational condition of rough segmentation tower 1: stage number is 60～90, and tower still temperature is 45～65 ℃, and tower top temperature is 27～40 ℃, and reflux ratio is 2～8, and working pressure is 100～300KPa;
(2) operational condition of acetylene removal tower 2: stage number is 40～80, and tower still temperature is 38～60 ℃, and tower top temperature is 24～38 ℃, and reflux ratio is 2～8, and working pressure is 100～300KPa;
The operational condition of (3) first extractive distillation columns 3: stage number is 90～120, and tower still temperature is 80～130 ℃, and tower top temperature is 30～50 ℃, and reflux ratio is 2～15, and working pressure is 100～300KPa, and the weight ratio of solvent and material c is 2～10;
(4) operational condition of raffinate carbon-5 water wash column 4: stage number is 20～40, and tower still temperature is 50～70 ℃, and tower top temperature is 30～65 ℃, and working pressure is 100～220KPa.
The operational condition of (5) second extractive distillation columns 5: stage number is 90～160, and tower top temperature is 34～50 ℃, and reflux ratio is 2～12, and working pressure is 100～400KPa, and the weight ratio of solvent and material f is 2～10;
(6) operational condition of isoprene water wash column 6: stage number is 20～40, and tower still temperature is 50～70 ℃, and tower top temperature is 30～50 ℃, and working pressure is 100～300KPa;
(7) operational condition of isoprene lightness-removing column 7: stage number is 70～120, and tower still temperature is 40～60 ℃, and tower top temperature is 30～40 ℃, and reflux ratio is 3～6, and working pressure is 100～300KPa;
(8) operational condition of isoprene weight-removing column 8: stage number is 60～120, and tower still temperature is 50～90 ℃, and tower top temperature is 35～50 ℃, and reflux ratio is 5～15, and working pressure is 100～400KPa;
(9) operational condition of m-pentadiene treating tower 9: stage number is 40～65, and tower still temperature is 60～110 ℃, and tower top temperature is 45～70 ℃, and reflux ratio is 5～20, and working pressure is 100～300KPa;
(10) operational condition of solvent recovery tower 10: stage number is 15～50, and tower still temperature is 85～120 ℃, and tower top temperature is 60～85 ℃, and reflux ratio is 2～6, and working pressure is 80～130KPa;
(11) operational condition of solvent Analytic Tower 11: stage number is 50～80, and tower still temperature is 80～140 ℃, and working pressure is 100～300KPa;
(12) side is cut the operational condition of tower 12: stage number is 15～30, and tower still temperature is 80～140 ℃, and tower top temperature is 30～70 ℃, and working pressure is 100～350KPa;
(13) operational condition of solvent treatment tower 13: stage number is 25～55, and tower still temperature is 90～150 ℃, and tower top temperature is 70～90 ℃, and reflux ratio is 2～5, and working pressure is 100～200KPa.
The stopper preferred version that first extracting rectifying and second extracting rectifying adopt is the composite polymerzation inhibitor of being made up of p-ten.-butylcatechol, diethyl hydroxylammonium and o-NP, wherein the mass ratio of p-ten.-butylcatechol, diethyl hydroxylammonium and o-NP is 1: 3～5: 0.6～4, and stopper is 50～1000ppm by mass concentration in above-mentioned solvent.
The inventive method is used stopper in whole sepn process, this stopper is developed at isoprene, has avoided isoprene in sepn process, and the loss that autohemagglutination or copolymerization cause takes place, and can improve 2～8% isoprene yield; By process optimization, reduce solvent ratio, can significantly reduce the solvent usage quantity, also can reduce solvent recovery tower and solvent Analytic Tower load; Adopt hot integrated technology that twice solvent resolved to synthesize in a tower and carry out, simultaneously second extractive distillation column and solvent Analytic Tower are advanced series connection, effectively cut down the consumption of energy; Adopt first acetylene removal hydrocarbon technology, can remove most of alkynes earlier, improved security; Adopt the circulating solvent process for refining, polymkeric substance in the solvent is separated, prolonged the device cycle of operation.
Description of drawings
Fig. 1 is the inventive method process flow diagram.
Wherein: 1 rough segmentation tower; 2 acetylene removal towers; 3 first extractive distillation columns; 4 raffinate carbon-5 water wash columns; 5 second extractive distillation columns; 6 isoprene water wash columns; 7 isoprene lightness-removing columns; 8 isoprene weight-removing columns; 9 m-pentadiene rectifying tower; 10 solvent recovery towers; 11 solvent Analytic Towers; 12 sides are cut tower; 13 solvent treatment towers.
Embodiment:
Embodiment implements according to the technical process shown in Fig. 1, comprises 1 rough segmentation tower; 2 acetylene removal towers; 3 first extractive distillation columns; 4 raffinate carbon-5 water wash columns; 5 second extractive distillation columns; 6 isoprene water wash columns; 7 isoprene lightness-removing columns; 8 isoprene weight-removing columns; 9 m-pentadiene rectifying tower; 10 solvent recovery towers; 11 solvent Analytic Towers; 12 sides are cut tower; 13 solvent treatment towers.
Rough segmentation tower 1 cat head is connected with acetylene removal tower 2 middle and lower parts; Be connected with m-pentadiene rectifying tower 9 middle parts at the bottom of the tower.
Be connected with first extractive distillation column, 3 middle and lower parts at the bottom of acetylene removal tower 2 towers.
First extractive distillation column, 3 cats head are connected with water wash column 4 middle parts; Be connected with solvent Analytic Tower 11 at the bottom of the tower, solvent is resolved top of tower and is connected with second extractive distillation column, 5 bottoms, and second extractive distillation column, 5 cats head are connected with isoprene water wash column 6 middle parts; Be connected with solvent treatment tower 13 middle parts at the bottom of solvent Analytic Tower 11 towers.
Solvent Analytic Tower 11 middle and lower parts are cut tower 12 with side and are connected, and side is cut tower 12 cats head and is connected with raffinate carbon-5 water wash column 4 middle parts; The tower still is connected with solvent Analytic Tower 11.
Isoprene water wash column 6 cats head are connected with isoprene lightness-removing column 7 middle parts; The tower still is connected with raffinate carbon-5 water wash column 4 tops.
Be connected with isoprene weight-removing column 8 middle parts at the bottom of isoprene lightness-removing column 7 towers.
Isoprene water wash column 6 tower stills are connected with carbon five water wash columns 4 tops, and carbon five water wash columns 4 tower stills are connected with solvent recovery tower 10 middle parts.
The cracked C 5 fraction a that removes cyclopentadiene is sent into rough segmentation tower 1 middle part, and cat head obtains being rich in the material b of isoprene, enters acetylene removal tower 2 middle and lower parts; The tower still obtains being rich in the material c of m-pentadiene, enters m-pentadiene rectifying tower 9 middle parts, obtains purity greater than 80% m-pentadiene product by m-pentadiene rectifying tower cat head.
Obtain being rich in the material d of alkynes by acetylene removal tower 2 cats head, mix with raffinate carbon-5; The tower still obtains the Materialien of enrichment isoprene, enters first extractive distillation column, 3 middle and lower parts, and the solvent that enters with tower top contacts, and carries out extracting rectifying.
The light constituent material I that is obtained containing alkane and monoolefine by first extractive distillation column, 3 cats head enters water wash column 4 middle parts; The solvent material f that the tower still obtains being rich in isoprene enters solvent Analytic Tower 11, solvent is resolved top of tower and is connected with second extractive distillation column, 5 bottoms, the material that is rich in isoprene that parses directly enters second extractive distillation column 5, contact with the solvent that enters from tower top and to carry out extracting rectifying, the material g that cat head obtains being rich in isoprene enters isoprene water wash column 6 middle parts; Solvent parsing Tata still obtains solvent h and enters solvent treatment tower 13 middle parts.
Solvent Analytic Tower 11 middle and lower part materials, approaching side is cut tower 12, and the material II that cat head obtains containing anti--2-amylene, isoprene, cyclopentadiene and alkynes enters raffinate carbon-5 water wash column 4 middle parts; The material i that the tower still obtains the enrichment acetonitrile returns solvent Analytic Tower 11.
The material j that isoprene water wash column 6 cats head obtain the enrichment isoprene enters isoprene lightness-removing column 7 middle parts; The washing water III that the tower still contains minor amounts of acetonitrile enters raffinate carbon-5 water wash column 4 tops.
Isoprene lightness-removing column 7 cats head obtain containing the isoprene of a small amount of light constituent, mix with raffinate carbon-5; The tower still obtains further spissated isoprene material k and enters isoprene weight-removing column 8 middle parts.
Isoprene weight-removing column 8 tower stills obtain carbon five and raffinate oil, and cat head obtains purity at 99.3～99.9% isoprene product.
Be mixed into raffinate carbon-5 water wash column 4 middle parts from the material I of first extractive distillation column, 3 cats head with from the material II that side is cut tower 12 cats head, material III from isoprene water wash column 6 tower stills enters raffinate carbon-5 water wash column 4 tops, and the water-containing solvent n that is obtained by the tower still enters solvent recovery tower 10 middle parts; Cat head obtains carbon five and raffinates oil.
Solvent recovery tower 10 cats head obtain the azeotrope of acetonitrile and water, and retrieval system recycles, tower still discharge of wastewater;
Enter solvent treatment tower 13 middle parts from the material h of solvent Analytic Tower 11 tower stills with from the material i that side is cut tower 12 tower stills, obtained by cat head that solvent acetonitrile is back to first extractive distillation column 3 and second extractive distillation column 5 recycles, the tower still is the raffinate that contains polymkeric substance.
The present invention is further elaborated below by embodiment.
Embodiment 1
Press the technical process of Fig. 1, the five fractions of petroleum cracked carbon that removes cyclopentadiene enters rough segmentation tower 1 by the 30th block of column plate, and cat head obtains the material b of enrichment isoprene, and the tower still obtains the material c of enrichment m-pentadiene.The feeding temperature of rough segmentation tower 1 is 50 ℃, and stage number is 60, and tower still temperature is 61 ℃, and tower top temperature is 37 ℃, and tower top pressure is 130KPa, and tower still pressure is 146KPa, reflux ratio 3; Stopper is the mixture of diethyl hydroxylammonium and o-NP 1: 3 (mass ratio), is refluxing and the feeding line adding respectively, and the concentration of stopper in carbon five is 300ppm.
Material b enters acetylene removal tower 2 by the 45th block of column plate, and cat head obtains the material d of enrichment alkynes, and the tower still obtains the Materialien of enrichment isoprene.35 ℃ of the feeding temperatures of acetylene removal tower 2, stage number are 70, and tower still temperature is 47 ℃, and tower top temperature is 32 ℃, and tower top pressure is 120KPa, and tower still pressure is 138KPa, and reflux ratio is 4.
Materialien enters first extractive distillation column 3 by the 84th block of column plate, and is contacted by the 7th solvent that column plate enters, and carries out extracting rectifying, and cat head obtains containing the light constituent material I of alkane and monoolefine; The tower still obtains being rich in the solvent material f of isoprene; The feeding temperature of first extractive distillation column is 50 ℃, and stage number is 120, and tower still temperature is 116 ℃, and tower top temperature is 39 ℃, and tower top pressure is 203KPa, and tower still pressure is 245KPa, and reflux ratio is 5, and solvent ratio is 3.5; The first extracting rectifying solvent for use is the mixed solvent of acetonitrile and water, and the content of acetonitrile is 90%; The used stopper of first extracting rectifying is the mixture of diethyl hydroxylammonium and p-ten.-butylcatechol 1: 4 (mass ratio), and the concentration of stopper in solvent is 200ppm, adds with solvent.
Material f enters solvent Analytic Tower 11 and carries out the solvent parsing, solvent is resolved top of tower and is connected with second extractive distillation column, 5 bottoms, the material that is rich in isoprene that parses directly enters second extractive distillation column 5, contact with the solvent that enters from tower top and to carry out extracting rectifying, cat head obtains being rich in the material g of isoprene; Solvent is resolved the Tata still and is obtained solvent h; Solvent Analytic Tower 11, tower still temperature is 118 ℃, tower still pressure is 212KPa.The stage number of second extractive distillation column 5 is 98, and tower top temperature is 49 ℃, and tower top pressure is 115KPa, and reflux ratio is 4; The second extracting rectifying solvent for use is the mixed solvent of acetonitrile and water, and ethane nitrile content is 92%; The used stopper of second extracting rectifying is the composite polymerzation inhibitor of diethyl hydroxylammonium and p-ten.-butylcatechol, the mixture of diethyl hydroxylammonium and p-ten.-butylcatechol 1: 4 (mass ratio), the concentration of stopper in solvent is 400ppm, adds with solvent.
Solvent Analytic Tower 11 is cut tower 12 by the 30th column plate discharging approaching side, and cat head obtains containing the material II of anti--2-amylene, isoprene, cyclopentadiene and alkynes, and the tower still obtains the material i of enrichment acetonitrile; The stage number that side is cut tower 12 is 30, and 103 ℃ of tower still temperature, tower top temperature are 69 ℃, and tower top pressure is 101KPa, and tower still pressure is 306KPa.
Material g enters isoprene water wash column 6 by the 22nd block of column plate, and the acetonitrile that contains among the material g is washed off, and cat head is not contained the isoprene material j of acetonitrile; The tower still obtains containing the wash water III of minor amounts of acetonitrile; The stage number of isoprene water wash column 6 is 40, and tower still temperature is 50 ℃, and tower top temperature is 35 ℃, and tower top pressure is 233KPa, and tower still pressure is 295KPa.
Material j enters isoprene lightness-removing column 7 by the 60th block of column plate, and cat head obtains carbon five and raffinates oil, and the tower still obtains the material k of enrichment isoprene; The stage number of isoprene lightness-removing column is 100,42 ℃ of tower still temperature, tower top temperature is 34 ℃, tower top pressure is 99KPa, tower still pressure is 123KPa, and reflux ratio is 3.5, and stopper is the mixture of diethyl hydroxylammonium and p-ten.-butylcatechol 1: 4 (mass ratio), the concentration of stopper in material is 400ppm, is added by the feed and return pipeline respectively.
Material k enters isoprene weight-removing column 8 by the 70th block of column plate, and the tower still obtains carbon five and raffinates oil, and cat head obtains purity at the isoprene more than 99.3%; The stage number of isoprene weight-removing column 8 is 100,61 ℃ of tower still temperature, tower top temperature is 39 ℃, tower top pressure is 115KPa, tower still pressure is 138KPa, and reflux ratio is 5.6, and stopper is a p-ten.-butylcatechol, the concentration of stopper in material is 200ppm, is added by the feed and return pipeline respectively.
Material I, II and III enter raffinate carbon-5 water wash column 4, and the solvent that the tower still obtains enters solvent recovery tower 10, the cat head carbon five that obtains raffinating oil; The stage number of raffinate carbon-5 water wash column 4 is 30, and tower still temperature is 55 ℃, and tower top temperature is 42 ℃, and tower top pressure is 178KPa, and tower still pressure is 202KPa.The stage number of solvent recovery tower is 50, and tower still temperature is 98 ℃, and tower top temperature is 76 ℃, and tower top pressure is 99KPa, and tower still pressure is 119KPa, and reflux ratio is 5.
Material h and i enter solvent treatment tower 13 by the 25th block of plate, and cat head obtains that solvent acetonitrile returns first extractive distillation column and second extractive distillation column recycles, and the tower still is a raffinate; The stage number of solvent treatment tower 13 is 50, and tower still temperature is 119 ℃, and tower top temperature is 82 ℃, and tower top pressure is 99KPa, and tower still pressure is 119KPa, and reflux ratio is 4.
Material c enters m-pentadiene rectifying tower 9 by the 35th block of column plate, and cat head obtains purity greater than 80% m-pentadiene product.The stage number of m-pentadiene rectifying tower is 60, and tower still temperature is 92 ℃, and tower top temperature is 50 ℃, and tower top pressure is 110KPa, and tower still pressure is 135KPa, and reflux ratio is 5.7, and stopper is an o-NP.
The weight percent composition of raw material and each unit component sees Table 1.
Table 1
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
By the technical process of [embodiment 1], the solvent of first extractive distillation column and second extractive distillation column is the mixture of acetonitrile and dimethyl formamide, and its ethane nitrile content is 94%; The stopper that all towers use is the diethyl hydroxylammonium, and stopper concentration in carbon five is 170ppm.
The purity that finally obtains isoprene is 99.79%, and the purity of m-pentadiene is 81.28%.Each unitary operational condition sees Table 2, and the weight percent composition of raw material and each unit component sees Table 3.
Table 2
| Operational condition | First rectifying tower 1 | |
First |
Water wash column 4 | Second |
Isoprene washing 6 |
| Feeding temperature (℃) | ??50 | ??35 | ??50 | |||
| Charging place stage number (piece) | ??30 | ??45 | ??80，8 | ??20 | ||
| Total stage number (piece) | ??64 | ??75 | ??118 | ??28 | ??100 | ??38 |
| Tower still temperature (℃) | ??63 | ??50 | ??120 | ??60 | ??51 | |
| Tower top temperature (℃) | ??36 | ??33 | ??33 | ??40 | ??48 | ??34 |
| Tower still pressure (KPa) | ??147 | ??140 | ??140 | ??212 | ??296 | |
| Tower top pressure (Kpa) | ??129 | ??122 | ??121 | ??176 | ??113 | ??232 |
| Solvent ratio | ??3.2 | |||||
| Reflux ratio | ??2.9 | ??3.8 | ??4.8 | ??3.9 |
Continuous table 2
| Operational condition | Isoprene lightness-removing column 7 | Isoprene weight-removing column 8 | M-pentadiene rectifying tower 9 | Solvent recovery tower 10 | |
Side is cut |
|
| Feeding temperature (℃) | |||||||
| Charging place stage number (piece) | ??65 | ??80 | ??36 | ??28 | |||
| Total stage number (piece) | ??110 | ??110 | ??62 | ??50 | ??28 | ??55 | |
| Tower still temperature (℃) | ??43 | ??60 | ??93 | ??101 | ??123 | ??107 | ??122 |
| Tower top temperature (℃) | ??35 | ??39 | ??49 | ??77 | ??68 | ??83 | |
| Tower still pressure (Kpa) | ??124 | ??137 | ??136 | ??121 | ??216 | ??308 | ??120 |
| Tower top pressure (Kpa) | ??100 | ??115 | ??109 | ??100 | ??100 | ??100 | |
| Solvent ratio | |||||||
| Reflux ratio | ??3.4 | ??5.4 | ??5.6 | ??4.1 |
Table 3
Continuous table 3
Continuous table 3
Continuous table 3
Continuous table 3
Press the technical process of embodiment 1, the solvent of first extractive distillation column and second extractive distillation column is the mixture of acetonitrile, N-Methyl pyrrolidone and water, and wherein ethane nitrile content 93%, and N-Methyl pyrrolidone content is 4%; The stopper that all towers use is the mixture of Sodium Nitrite and o-NP, and wherein the mass ratio of Sodium Nitrite and o-NP is 3: 1, and stopper concentration in carbon five is 240ppm.
The purity that finally obtains isoprene is 99.88%, and the purity of m-pentadiene is 82.17%.Each unitary operational condition sees Table 4, and the weight percent composition of raw material and each unit component sees Table 5.
Table 4
| Operational condition | First rectifying tower 1 | |
First |
Take out in carbon five water wash columns 4 | Second |
The isoprene dehydration washes 6 |
| Feeding temperature (℃) | ??50 | ??35 | ??50 | |||
| Charging place stage number (piece) | ??28 | ??40 | ??85，7 | ??25 | ||
| Total stage number (piece) | ??58 | ??68 | ??116 | ??25 | ??98 | ??40 |
| Tower still temperature (℃) | ??60 | ??48 | ??122 | ??60 | ??51 | |
| Tower top temperature (℃) | ??36 | ??34 | ??40 | ??42 | ??48 | ??35 |
| Tower still pressure (KPa) | ??140 | ??142 | ??249 | ??212 | ??295 | |
| Tower top pressure (Kpa) | ??129 | ??124 | ??205 | ??176 | ??115 | ??233 |
| Solvent ratio | ??3.3 | |||||
| Reflux ratio | ??3.1 | ??4.2 | ??5 | ??4 |
Continuous table 4
| Operational condition | Isoprene lightness-removing column 7 | Isoprene weight-removing column 8 | M-pentadiene rectifying tower 9 | Solvent recovery tower 10 | |
Side is cut |
|
| Feeding temperature (℃) | |||||||
| Charging place stage number (piece) | ??60 | ??70 | ??34 | ??25 | |||
| Total stage number (piece) | ??100 | ??100 | ??60 | ??48 | ??26 | ??50 | |
| Tower still temperature (℃) | ??44 | ??59 | ??92 | ??105 | ??125 | ??108 | ??122 |
| Tower top temperature (℃) | ??34 | ??38 | ??49 | ??76 | ??69 | ??82 | |
| Tower still pressure (Kpa) | ??125 | ??136 | ??136 | ??120 | ??220 | ??310 | ??121 |
| Tower top pressure (Kpa) | ??99 | ??114 | ??109 | ??100 | ??101 | ??100 | |
| Solvent ratio | |||||||
| Reflux ratio | ??3.4 | ??5.5 | ??5.7 | ??4.1 |
Table 5
| Component | Rough segmentation tower 1 | |
| Feed composition | Cat head is formed | The tower still is formed | Feed composition | Cat head is formed | The tower still is formed | |
| Normal butane | ??0.09 | ??0.12 | ??0.12 | ??0.51 | ||
| Anti-butylene | ??2.00 | ??2.51 | ??2.51 | ??13.02 | ||
| 1-butylene | ??0.70 | ??0.89 | ??0.89 | ??4.51 | ||
| Iso-butylene | ??0.37 | ??0.46 | ??0.46 | ??2.20 | ||
| Maleic | ??3.45 | ??4.35 | ??4.35 | ??20.84 | ??0.27 | |
| Pentamethylene | ??0.29 | ??0.29 | ??0.29 | ??0.32 | ||
| Iso-pentane | ??0.34 | ??0.42 | ??0.42 | ??0.52 | ??0.54 | |
| Skellysolve A | ??0.67 | ??0.82 | ??0.82 | ??0.69 | ??0.86 | |
| 1.2-divinyl | ??0.51 | ??0.65 | ??0.65 | ??3.57 | ||
| 1.3-divinyl | ??4.65 | ??5.86 | ??5.86 | ??30.26 | ||
| 3-methyl-1-butene | ??1.56 | ??1.96 | ??1.96 | ??9.09 | ||
| Cyclopentenes | ??5.53 | ??7.00 | ??0.32 | ??7.00 | ??8.42 | |
| Instead-the 2-amylene | ??4.02 | ??4.61 | ??2.52 | ??4.61 | ??5.57 | |
| The 2-methyl-2-butene | ??11.29 | ??12.99 | ??7.24 | ??12.99 | ??16.21 | |
| The 1-amylene | ??6.87 | ??8.60 | ??0.56 | ??8.60 | ??7.24 | ??9.09 |
| 2-methyl-1-butene alkene | ??3.37 | ??3.77 | ??3.29 | ??3.77 | ??4.60 | |
| 2-butyne | ??0.90 | ??1.12 | ??0.00 | ??1.12 | ??5.78 | ??0.01 |
| 1.4-pentadiene | ??0.29 | ??0.36 | ??0.00 | ??0.36 | ??1.21 | ??0.03 |
| 2-methyl-pentane | ??0.08 | ??0.02 | ??0.39 | ??0.02 | ??0.02 | |
| 3-methyl-pentane | ??0.10 | ??0.06 | ??0.46 | ??0.06 | ??0.06 | |
| Isoprene | ??30.21 | ??40.31 | ??2.54 | ??40.31 | ??0.56 | ??50.24 |
| Cyclopentadiene | ??4.13 | ??2.07 | ??2.54 | ??2.07 | ??2.63 |
| Feed composition | Cat head is formed | The tower still is formed | Feed composition | Cat head is formed | The tower still is formed | |
| ??X1 | ??0.05 | ??0.02 | ??0.24 | ??0.02 | ??0.03 | |
| Along the 1.3-pentadiene | ??5.60 | ??0.50 | ??24.86 | ??0.50 | ??0.72 | |
| Anti-1.3-pentadiene | ??12.17 | ??0.22 | ??51.06 | ??0.22 | ??0.26 | |
| ??X2 | ??0.04 | ??0.02 | ??0.09 | ??0.02 | ??0.05 | |
| ??X3 | ??0.14 | ??0.08 | ??0.51 | ??0.08 | ??0.07 | |
| Benzene | ??0.58 | ??3.37 |
Continuous table 5
Continuous table 5
Continuous table 5
Continuous table 5
Claims (2)
1. an acetonitrile separates the method for diolefin in the five fractions of petroleum cracked carbon, it is characterized in that: may further comprise the steps:
(1) the cracked C 5 fraction a that will remove cyclopentadiene sends into rough segmentation tower 1 middle part, and cat head obtains being rich in the material b of isoprene, and the tower still obtains being rich in the material c of m-pentadiene; The operational condition of rough segmentation tower 1: stage number is 60～90, and tower still temperature is 45～65 ℃, and tower top temperature is 27～40 ℃, and reflux ratio is 2～8, and working pressure is 100～300KPa;
(2) material b enters acetylene removal tower 2 middle and lower parts, and cat head obtains being rich in the material d of alkynes, and the tower still obtains the Materialien of enrichment isoprene; The operational condition of acetylene removal tower 2: stage number is 40～80, and tower still temperature is 38～60 ℃, and tower top temperature is 24～38 ℃, and reflux ratio is 2～8, and working pressure is 100～300KPa;
(3) Materialien enters first extractive distillation column, 3 middle and lower parts, and the extraction agent that enters with tower top contacts, and carries out extracting rectifying, and cat head obtains containing the light constituent material I of alkane and monoolefine; The tower still obtains being rich in the solvent material f of isoprene; The operational condition of first extractive distillation column 3: stage number is 90～120, and tower still temperature is 80～130 ℃, and tower top temperature is 30～50 ℃, and reflux ratio is 2～15, and working pressure is 100～300KPa, and the weight ratio of solvent and material c is 2～10;
(4) material f enters solvent Analytic Tower 11, solvent is resolved top of tower and is connected with second extractive distillation column, 5 bottoms, the material that is rich in isoprene that parses directly enters second extractive distillation column 5, contact with the solvent that enters from tower top and to carry out extracting rectifying, cat head obtains being rich in the material g of isoprene; Solvent is resolved the Tata still and is obtained solvent h, solvent Analytic Tower middle and lower part material, and approaching side is cut tower 12, and cat head obtains containing the material II of anti--2-amylene, isoprene, cyclopentadiene and alkynes, and the tower still obtains the material i of enrichment acetonitrile, returns solvent Analytic Tower 11; The operational condition of second extractive distillation column 5: stage number is 90～160, and tower top temperature is 34～50 ℃, and reflux ratio is 2～12, and working pressure is 100～400KPa, and the weight ratio of solvent and material f is 2～10; The operational condition of solvent Analytic Tower 11: stage number is 50～80, and tower still temperature is 80～140 ℃, and working pressure is 100～300KPa; Side is cut the operational condition of tower 12: stage number is 15～30, and tower still temperature is 80～140 ℃, and tower top temperature is 30～70 ℃, and working pressure is 100～350KPa;
(5) material g enters isoprene water wash column 6 middle parts, and the acetonitrile that contains among the material g is washed off, and the tower still obtains containing the washing water III of minor amounts of acetonitrile, and cat head obtains the material j of enrichment isoprene; The operational condition of isoprene water wash column 6: stage number is 20～40, and tower still temperature is 50～70 ℃, and tower top temperature is 30～50 ℃, and working pressure is 100～300KPa;
(6) material j enters isoprene lightness-removing column 7 middle parts, and cat head obtains containing the isoprene of a small amount of light constituent, and the tower still obtains further spissated isoprene material k; The operational condition of isoprene lightness-removing column 7: stage number is 70～120, and tower still temperature is 40～60 ℃, and tower top temperature is 30～40 ℃, and reflux ratio is 3～6, and working pressure is 100～300KPa;
(7) material k enters isoprene weight-removing column 8 middle parts, and the tower still obtains carbon five and raffinates oil, and cat head obtains purity at 99.3～99.8% isoprene product; The operational condition of isoprene weight-removing column 8: stage number is 60～120, and tower still temperature is 50～90 ℃, and tower top temperature is 35～50 ℃, and reflux ratio is 5～15, and working pressure is 100～400KPa;
(8) material I, II enter raffinate carbon-5 water wash column 4 middle parts, and material III enters raffinate carbon-5 water wash column 4 tops, and the water-containing solvent n that the tower still obtains, cat head obtain carbon five and raffinate oil; The operational condition of raffinate carbon-5 water wash column 4: stage number is 20～40, and tower still temperature is 50～70 ℃, and tower top temperature is 30～65 ℃, and working pressure is 100～220KPa;
(9) water-containing solvent n enters solvent recovery tower 10 middle parts, and cat head obtains the azeotrope of acetonitrile and water, and retrieval system recycles, tower still discharge of wastewater; The operational condition of solvent recovery tower 10: stage number is 15～50, and tower still temperature is 85～120 ℃, and tower top temperature is 60～85 ℃, and reflux ratio is 2～6, and working pressure is 80～130KPa;
(10) material h enters solvent treatment tower 13 middle parts, and cat head obtains that solvent acetonitrile is back to first extractive distillation column 3 and second extractive distillation column 5 recycles, and the tower still is the raffinate that contains polymkeric substance; The operational condition of solvent treatment tower 13: stage number is 25～55, and tower still temperature is 90～150 ℃, and tower top temperature is 70～90 ℃, and reflux ratio is 2～5, and working pressure is 100～200KPa;
(11) material c enters m-pentadiene rectifying tower 9 middle parts, the tower still obtains purity greater than 80% m-pentadiene product, the operational condition of m-pentadiene treating tower 9: stage number is 40～65, tower still temperature is 60～110 ℃, tower top temperature is 45～70 ℃, reflux ratio is 5～20, and working pressure is 100～300KPa;
In first extracting rectifying, second extracting rectifying, extraction agent is acetonitrile and at least a mixture of dimethyl formamide, N-Methyl pyrrolidone or water; At least wherein a kind of of ethane nitrile content 80～95%, dimethyl formamide, N-Methyl pyrrolidone or water, content 5～20%;
Rough segmentation tower, first extractive distillation column, second extractive distillation column, isoprene lightness-removing column and isoprene weight-removing column use stopper, the stopper that adopts is Sodium Nitrite, p-ten.-butylcatechol, diethyl hydroxylammonium or/and o-NP, and stopper is 50～1000ppm by mass concentration in material.
2. acetonitrile according to claim 1 separates the method for diolefin in the five fractions of petroleum cracked carbon, it is characterized in that: the composite polymerzation inhibitor that the stopper that first extracting rectifying and second extracting rectifying adopt is made up of p-ten.-butylcatechol, diethyl hydroxylammonium and o-NP, wherein the mass ratio of p-ten.-butylcatechol, diethyl hydroxylammonium and o-NP is 1: 3～5: 0.6～4.
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| CN113999100A (en) * | 2021-10-29 | 2022-02-01 | 万华化学集团股份有限公司 | Preparation of methyl heptenone and method for mechanically applying raw materials |
| CN113999100B (en) * | 2021-10-29 | 2023-10-13 | 万华化学集团股份有限公司 | Method for preparing methyl heptenone and applying raw materials |
| CN116730791A (en) * | 2023-08-14 | 2023-09-12 | 淄博鲁华同方化工有限公司 | Continuous extraction process in carbon five separation |
| CN116730791B (en) * | 2023-08-14 | 2023-11-07 | 淄博鲁华同方化工有限公司 | Continuous extraction process in carbon five separation |
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