CN101798255B - Method for separating diolefin from petroleum cracking C5 fraction by acetonitrile - Google Patents
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Abstract
The invention relates to a method for separating diolefin from petroleum cracking C5 fraction by an acetonitrile method. The method comprises the following steps: sending the C5 fraction into a crude separation tower; processing materials through an acetylene removal tower, a first extraction rectifying tower, a solvent desorption tower, a second extraction rectifying tower side cutting tower, a second extraction rectifying tower, an isoprene water washing tower, an isoprene light component removal tower, an isoprene heavy component removal tower, a residual C5 pumping water washing tower, a solvent recovering tower solvent refining tower and an m-pentadiene rectifying tower. An extracting agent is a mixture of acetonitrile and at least one kind of materials in dimethylformamide, N-methylpyrrolidone or water, the content of the acetonitrile is between 80 and 95 percent, the content of at least one kind of materials in dimethylformamide, N-methylpyrrolidone or water is between 5 and 20percent, an adopted polymerization inhibitor is sodium nitrite, para-tert-butylcatechol, 2-hydroxyethyl or o-nitrophenol, the concentration of the polymerization inhibitor in the materials is between50 and 1000 ppm, the isoprene with the purity between 99.3 and 99.8 percent and the m-pentadiene with the purity higher than 80 percent can be obtained.
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 forms each other, therefrom isolating purity, to meet the C 5 diene difficulty of application requiring larger, 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), such as patent US2993841, the 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 a small amount of components such as dimethyl formamide, dimethyl sulfoxide (DMSO), morpholine and N-Methyl pyrrolidone in acetonitrile solution.US Patent No. 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; Then take with the acetonitrile of a small amount of water as solvent carries out the extracting rectifying first time, remove alkane and monoolefine, solvent uses by solvent recovery cycle; Take with the acetonitrile of a small amount of water as solvent carries out the second extracting rectifying, remove the alkene such as alkynes, cyclopentadiene and m-pentadiene, solvent recycles by solvent recovery tower; Pass through the operations such as water wash column, cat head obtains highly purified isoprene product again.Chinese patent CN100999434A discloses a kind of C5 fraction separation of acetonitrile solvent method and the method for comprehensive utilization, its technique 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, the dicyclopentadiene that obtains making with extra care, the component that obtains in decarburization five column overhead enters the isoprene system, enter the first extractive distillation column after the pre-separation of carrying out first expecting the carbon Wuyuan, obtained being rich in the solvent material of the C 5 dienes such as isoprene, alkynes by tower reactor; Then enter the second extractive distillation column, operational condition and quantity of solvent by control tower, mainly carry out the extracting rectifying of alkynes, the tower reactor material enters flashing tower, then enters water wash system, and the 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 at last highly purified isoprene.Carbon five separation process are long, are comprised of a plurality of rectifying tower, extractive distillation column and solvent recovery tower, and energy consumption is large; Isoprene and m-pentadiene in the separating carbon 5 fraction adopt extracting rectifying more, its solvent ratio is large, the internal circulating load of solvent is large, energy expenditure is also large, liquid load is high in the tower simultaneously, 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 extractive distillation column tower reactor material is directly entered the solvent analysis tower top, the solvent analysis system of the first extractive distillation column and the second extractive distillation column is merged into a cover.Between the second extractive distillation column and the solvent analysis tower, adopt hot integrated technology, reduce energy consumption, saving equipment; Circulating solvent is refining, the polymkeric substance in the desolvation, the long-period stable operation of assurance carbon five tripping devices.
The technical solution used in the present invention comprises the steps:
The cracked C 5 fraction a that (1) will remove cyclopentadiene sends into rough segmentation tower 1 middle part, and cat head obtains being rich in the material b of isoprene, and tower reactor 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 tower reactor obtains the Materialien of enrichment isoprene;
(3) Materialien enters the 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; Tower reactor obtains being rich in the solvent material f of isoprene;
(4) material f enters the solvent analysis tower 11, the solvent analysis top of tower is connected with the second extractive distillation column 5 bottoms, the material that is rich in isoprene that parses directly enters the 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; The solvent analysis Tata still obtains solvent h, the solvent analysis 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 material i that tower reactor obtains the enrichment acetonitrile returns the solvent analysis 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 tower reactor obtains containing the washing water III of a small amount 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, the isoprene material k that tower reactor is further concentrated;
(7) material k enters isoprene weight-removing column 8 middle parts, and tower reactor 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 tower reactor 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, the tower reactor discharge of wastewater;
(10) material h enters solvent treatment tower 13 middle parts, and cat head obtains that solvent acetonitrile is back to the first extractive distillation column 3 and the second extractive distillation column 5 recycles, and tower reactor is the raffinate that contains polymkeric substance;
(11) material c enters m-pentadiene rectifying tower 9 middle parts, and tower reactor obtains purity greater than 80% m-pentadiene product.
Rough segmentation tower, the first extractive distillation column, the 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 the 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the tower reactor 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 the solvent analysis tower 11: stage number is 50～80, and the tower reactor 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 the tower reactor 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 the tower reactor 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 the first extracting rectifying and the second extracting rectifying adopt is the composite polymerzation inhibitor that is comprised 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 for isoprene, has avoided isoprene in sepn process, and the loss that autohemagglutination or copolymerization cause occurs, and can improve 2～8% isoprene yield; By process optimization, reduce solvent ratio, can greatly reduce the solvent usage quantity, also can reduce solvent recovery tower and the solvent analysis tower load; Adopt hot integrated technology that twice the solvent analysis synthesized in a tower and carry out, simultaneously the second extractive distillation column and the solvent analysis tower are advanced series connection, effectively reduce energy consumption; Adopt first acetylene removal hydrocarbon technique, can remove first most of alkynes, 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 the solvent analysis 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 the solvent analysis 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 the first extractive distillation column 3 middle and lower parts at the bottom of acetylene removal tower 2 towers.
The first extractive distillation column 3 cats head are connected with water wash column 4 middle parts; Be connected with the solvent analysis tower 11 at the bottom of the tower, the solvent analysis top of tower is connected with the second extractive distillation column 5 bottoms, and the 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 the solvent analysis tower 11 towers.
The solvent analysis 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; Tower reactor is connected with the solvent analysis tower 11.
Isoprene water wash column 6 cats head are connected with isoprene lightness-removing column 7 middle parts; Tower reactor 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 reactors are connected with carbon five water wash columns 4 tops, and carbon five water wash columns 4 tower reactors 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; Tower reactor 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; Tower reactor obtains the Materialien of enrichment isoprene, enters the 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 the first extractive distillation column 3 cats head enters water wash column 4 middle parts; The solvent material f that tower reactor obtains being rich in isoprene enters the solvent analysis tower 11, the solvent analysis top of tower is connected with the second extractive distillation column 5 bottoms, the material that is rich in isoprene that parses directly enters the 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; The solvent analysis Tata still obtains solvent h and enters solvent treatment tower 13 middle parts.
The solvent analysis 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 tower reactor obtains the enrichment acetonitrile returns the solvent analysis 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 tower reactor contains a small amount 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 isoprene material k that tower reactor is further concentrated enters isoprene weight-removing column 8 middle parts.
Isoprene weight-removing column 8 tower reactors 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 the 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 reactors enters raffinate carbon-5 water wash column 4 tops, and the water-containing solvent n that is obtained by tower reactor 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, the tower reactor discharge of wastewater;
Enter solvent treatment tower 13 middle parts from the material h of the solvent analysis tower 11 tower reactors with from the material i that side is cut tower 12 tower reactors, obtained by cat head that solvent acetonitrile is back to the first extractive distillation column 3 and the second extractive distillation column 5 recycles, tower reactor 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 tower reactor obtains the material c of enrichment m-pentadiene.The feeding temperature of rough segmentation tower 1 is 50 ℃, and stage number is 60, and the tower reactor temperature is 61 ℃, and tower top temperature is 37 ℃, and tower top pressure is 130KPa, and tower reactor 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 tower reactor obtains the Materialien of enrichment isoprene.35 ℃ of the feeding temperatures of acetylene removal tower 2, stage number are 70, and the tower reactor temperature is 47 ℃, and tower top temperature is 32 ℃, and tower top pressure is 120KPa, and tower reactor pressure is 138KPa, and reflux ratio is 4.
Materialien enters the 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; Tower reactor obtains being rich in the solvent material f of isoprene; The feeding temperature of the first extractive distillation column is 50 ℃, and stage number is 120, and the tower reactor temperature is 116 ℃, and tower top temperature is 39 ℃, and tower top pressure is 203KPa, and tower reactor 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 the 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 the solvent analysis tower 11 and carries out the solvent analysis, the solvent analysis top of tower is connected with the second extractive distillation column 5 bottoms, the material that is rich in isoprene that parses directly enters the 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; The solvent analysis Tata still obtains solvent h; The solvent analysis tower 11, the tower reactor temperature is 118 ℃, tower reactor pressure is 212KPa.The stage number of the 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 the 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.
The solvent analysis 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 tower reactor obtains the material i of enrichment acetonitrile; The stage number that side is cut tower 12 is 30, and 103 ℃ of tower reactor temperature, tower top temperature are 69 ℃, and tower top pressure is 101KPa, and tower reactor 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; Tower reactor obtains containing the wash water III of a small amount of acetonitrile; The stage number of isoprene water wash column 6 is 40, and the tower reactor temperature is 50 ℃, and tower top temperature is 35 ℃, and tower top pressure is 233KPa, and tower reactor 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 tower reactor obtains the material k of enrichment isoprene; The stage number of isoprene lightness-removing column is 100,42 ℃ of tower reactor temperature, tower top temperature is 34 ℃, tower top pressure is 99KPa, tower reactor 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 tower reactor 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 reactor temperature, tower top temperature is 39 ℃, tower top pressure is 115KPa, tower reactor pressure is 138KPa, and reflux ratio is 5.6, and stopper is 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 tower reactor 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 the tower reactor temperature is 55 ℃, and tower top temperature is 42 ℃, and tower top pressure is 178KPa, and tower reactor pressure is 202KPa.The stage number of solvent recovery tower is 50, and the tower reactor temperature is 98 ℃, and tower top temperature is 76 ℃, and tower top pressure is 99KPa, and tower reactor 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 the first extractive distillation column and the second extractive distillation column recycles, and tower reactor is raffinate; The stage number of solvent treatment tower 13 is 50, and the tower reactor temperature is 119 ℃, and tower top temperature is 82 ℃, and tower top pressure is 99KPa, and tower reactor 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 the tower reactor temperature is 92 ℃, and tower top temperature is 50 ℃, and tower top pressure is 110KPa, and tower reactor pressure is 135KPa, and reflux ratio is 5.7, and stopper is o-NP.
The weight percent composition of raw material and each unit component sees Table 1.
Table 1
Continued 1
Continued 1
Continued 1
Continued 1
Embodiment 2
By the technical process of [embodiment 1], the solvent of the first extractive distillation column and the 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%.The operational condition of each unit sees Table 2, and the weight percent composition of raw material and each unit component sees Table 3.
Table 2
| Operational condition | The first rectifying tower 1 | Acetylene removal tower 2 | The first extractive distillation column 3 | Water wash column 4 | The second extractive distillation column 5 | 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 |
| The tower reactor temperature (℃) | 63 | 50 | 120 | 60 | 51 | |
| Tower top temperature (℃) | 36 | 33 | 33 | 40 | 48 | 34 |
| Tower reactor 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 |
Continued 2
| Operational condition | Isoprene lightness-removing column 7 | Isoprene weight-removing column 8 | M-pentadiene rectifying tower 9 | Solvent recovery tower 10 | The solvent analysis tower 11 | Side is cut tower 12 | Solvent treatment tower 13 |
| Feeding temperature (℃) |
| Charging place stage number (piece) | 65 | 80 | 36 | 28 | |||
| Total stage number (piece) | 110 | 110 | 62 | 50 | 28 | 55 | |
| The tower reactor temperature (℃) | 43 | 60 | 93 | 101 | 123 | 107 | 122 |
| Tower top temperature (℃) | 35 | 39 | 49 | 77 | 68 | 83 | |
| Tower reactor 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
Continued 3
Continued 3
Continued 3
Continued 3
Embodiment 3
Press the technical process of embodiment 1, the solvent of the first extractive distillation column and the 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 the mass ratio of its 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%.The operational condition of each unit sees Table 4, and the weight percent composition of raw material and each unit component sees Table 5.
Table 4
| Operational condition | The first rectifying tower 1 | Acetylene removal tower 2 | The first extractive distillation column 3 | Take out in carbon five water wash columns 4 | The second extractive distillation column 5 | 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 |
| The tower reactor temperature (℃) | 60 | 48 | 122 | 60 | 51 | |
| Tower top temperature (℃) | 36 | 34 | 40 | 42 | 48 | 35 |
| Tower reactor 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 |
Continued 4
| Operational condition | Isoprene lightness-removing column 7 | Isoprene weight-removing column 8 | M-pentadiene rectifying tower 9 | Solvent recovery tower 10 | The solvent analysis tower 11 | Side is cut tower 12 | Solvent treatment tower 13 |
| Feeding temperature (℃) | |||||||
| Charging place stage number (piece) | 60 | 70 | 34 | 25 | |||
| Total stage number (piece) | 100 | 100 | 60 | 48 | 26 | 50 | |
| The tower reactor temperature (℃) | 44 | 59 | 92 | 105 | 125 | 108 | 122 |
| Tower top temperature (℃) | 34 | 38 | 49 | 76 | 69 | 82 | |
| Tower reactor 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
Continued 5
Continued 5
Continued 5
Continued 5
Claims (2)
1. an acetonitrile separates the method for diene hydrocarbon in five fractions of petroleum cracked carbon, it is characterized in that: may further comprise the steps:
The cracked C 5 fraction a that (1) will remove cyclopentadiene sends into rough segmentation tower 1 middle part, and cat head obtains being rich in the material b of isoprene, and tower reactor obtains being rich in the material c of m-pentadiene; The operational condition of rough segmentation tower 1: stage number is 60～90, and the tower reactor 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 tower reactor obtains the Materialien of enrichment isoprene; The operational condition of acetylene removal tower 2: stage number is 40～80, and the tower reactor 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 the 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; Tower reactor obtains being rich in the solvent material f of isoprene; The operational condition of the first extractive distillation column 3: stage number is 90～120, and the tower reactor 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 the solvent analysis tower 11, the solvent analysis top of tower is connected with the second extractive distillation column 5 bottoms, the material that is rich in isoprene that parses directly enters the 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; The solvent analysis Tata still obtains solvent h, the solvent analysis 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 material i that tower reactor obtains the enrichment acetonitrile returns the solvent analysis tower 11; The operational condition of the 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 the solvent analysis tower 11: stage number is 50～80, and the tower reactor 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 the tower reactor 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 tower reactor obtains containing the washing water III of a small amount 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 the tower reactor 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, the isoprene material k that tower reactor is further concentrated; The operational condition of isoprene lightness-removing column 7: stage number is 70～120, and the tower reactor 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 tower reactor 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 the tower reactor 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 tower reactor 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 the tower reactor 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, the tower reactor discharge of wastewater; The operational condition of solvent recovery tower 10: stage number is 15～50, and the tower reactor 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 the first extractive distillation column 3 and the second extractive distillation column 5 recycles, and tower reactor is the raffinate that contains polymkeric substance; The operational condition of solvent treatment tower 13: stage number is 25～55, and the tower reactor 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, tower reactor obtains purity greater than 80% m-pentadiene product, the operational condition of m-pentadiene treating tower 9: stage number is 40～65, the tower reactor temperature is 60～110 ℃, tower top temperature is 45～70 ℃, reflux ratio is 5～20, and working pressure is 100～300KPa;
In the first extracting rectifying, the 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, the first extractive distillation column, the 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 diene hydrocarbon in five fractions of petroleum cracked carbon, it is characterized in that: the composite polymerzation inhibitor that the stopper that the first extracting rectifying and the second extracting rectifying adopt is comprised 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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| CN102452883A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Method of separating C5 fraction by using DMF mixed solvent |
| CN102485708B (en) * | 2010-12-03 | 2014-04-02 | 中国石油化工股份有限公司 | C5 fraction separation method employing hypergravity extractive distillation apparatus |
| CN103570486A (en) * | 2012-07-27 | 2014-02-12 | 抚顺伊科思新材料有限公司 | Method for obtaining isoprene from C5 fraction |
| DE102013204950A1 (en) | 2013-03-20 | 2014-09-25 | Evonik Industries Ag | Process and composition for inhibiting the polymerization of cyclopentadiene compounds |
| CN103724227B (en) * | 2013-12-25 | 2016-03-30 | 天津大学 | Acetonitrile method isoprene extraction circulating solvent refining system and method |
| CN105622327B (en) * | 2014-11-28 | 2019-01-18 | 中国石油天然气股份有限公司 | A kind of method of acetonitrile method separation five fractions of petroleum cracked carbon |
| CN107501028B (en) * | 2017-07-28 | 2020-12-22 | 北京万邦达环保技术股份有限公司 | Treatment process of carbon five raw material |
| CN110498726A (en) * | 2018-05-18 | 2019-11-26 | 抚顺伊科思新材料有限公司 | The extractant modified technique of acetonitrile method light dydrocarbon separation |
| 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 |
| 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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