CN1053881C - Method for separation of cracking C5 fraction - Google Patents
Method for separation of cracking C5 fraction Download PDFInfo
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- CN1053881C CN1053881C CN96103569A CN96103569A CN1053881C CN 1053881 C CN1053881 C CN 1053881C CN 96103569 A CN96103569 A CN 96103569A CN 96103569 A CN96103569 A CN 96103569A CN 1053881 C CN1053881 C CN 1053881C
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Abstract
The present invention relates to a technological process for separating C5 diolefin from other components, such as alkane, olefin, etc. in C5 cracking distillate by using an extractive distillation method. The present invention is characterized in that at least two stripping towers are arranged in a first extraction system to eliminate water and dimer in the extraction system so as to enhance the quality of the circulation solvent; the dimer and the water can not be partially accumulated on the stripping towers so sa to improve the operation for the analytic tower and ensure that the whole separation process is normal and stable.
Description
The present invention relates to a kind of cracking c_5 (C
5) extraction separating method of fraction, more particularly, relate to a kind of C
5In extracting system, remove water and dimeric method in the separating technology.
C
5Fraction is one of by product of petroleum cracking system ethylene industry production equipment, and its boiling range is normally at 25～50 ℃, and the each component boiling point is close and can form multiple azeotrope, forms very complicated.Its separation and utilization, for the economic benefit that improves ethylene producing device, utilize resources synthetically all has very realistic meanings.
In order to make C
5Alkane in the fraction, monoolefine separate with diolefin, can adopt the method for extracting rectifying, promptly select for use suitable solvent as extraction agent, exist and keep under the certain density situation C at its
5The relative volatility of alkane, monoolefine and diolefin increases, thereby can with comparalive ease they be separated.Selective solvent commonly used has dimethyl formamide (DMF) and acetonitrile, and has produced some representative commercial runs therefrom, as JP63101338, JP74019245, JP74039644, US3, and 510,405, US3,535,260.Plurality of advantages such as wherein the DMF method is because the DMF solvent is good to the selectivity of T C 5 diene, solubleness big, be easy to separate with carbon five, and the low and toxicity of corrodibility is little and as if more people receive.US Patent specification 3,510 discloses in 405 a kind of from C
5The processing method of separating high-purity isoprene in the fraction mixture is exactly a kind of typical case and comparatively ideal DMF method technology, and it comprises following process: the C that will obtain by hydrocarbon steam cracking or other high-temperature cracking method
5Fraction is also therefrom isolated dicyclopentadiene (DCPD) through overheated dimerization reaction; With DMF is that solvent carries out the extractive distillation first time in the presence of stopper, and solvent is by a stripping tower recycling use; Material carries out rectifying through a weight-removing column, therefrom separates the heavy constituent that contain cyclopentadiene and m-pentadiene; With DMF is that solvent carries out the extracting rectifying second time in the presence of stopper, and solvent reclaims by stripping tower and uses; Material obtains highly purified isoprene product after a dehydrogenation tower carries out rectifying.
In above technological process, because C
5Bring the water of trace in raw material and the DMF solvent into, general C
5The dissolving water that contains 400～1000ppm in the fraction approximately contains the water of 500～1000ppm among the DMF.Under the situation of extracting system operate continuously, this part water can be in solvent, the particularly body of the tower of the stripping tower behind first extractive distillation column accumulation.We know solvent dimethyl formamide (DMF) and water effect meeting generation hydrolysis reaction, generate dimethylamine and formic acid, and its reaction formula is:
HCON (CH
3)
2+ H
2O NH (CH
3)
2It is high more that+HCOOH works as temperature, and hydrolysis reaction Shaoxing opera is strong.Therefore, be under 90～180 ℃ in the service temperature of stripping tower body of the tower, hydrolysis reaction very easily takes place in DMF, and the product dimethylamine of generation is C
5The detrimental impurity of diolefin, another product formic acid then can solvent slop.
In addition, C
5Cyclopentadiene in the fraction, isoprene, pentadiene-1, the 3rd, autohemagglutination and the dimerization reaction between them under the room temperature, especially at high temperature very easily take place and generate dimer in very active diolefin, the poly reaction takes place generate superpolymer.Owing in the charging of first extractive distillation column, contain a certain amount of cyclopentadiene component, be generally 1～5wt%.Cyclopentadiene is partially polymerized and generate dipolymer or polymer such as dicyclopentadiene, because dicyclopentadiene boiling point under normal pressure is 168 ℃, therefore they can not steam and accumulate circulating solvent from the stripping tower cat head, increase gradually along with recycling of solvent.There is following balance in the polyreaction of diolefin:
Along with dimeric increase, must cause polymeric increase, promptly gelationus increases in the circulating solvent, has so not only influenced the quality of solvent, but also can cause the obstruction of equipment.Their existence not only influenced solvent quality, reduced the concentration of solvent, and can expend certain energy.
Simultaneously, because water and dicyclopentadiene can generate azeotrope, its azeotropic temperature is between 150～180 ℃ of 40～50 ℃ of the tower top temperatures of stripping tower and tower still temperature, and this has just caused the body of the tower enrichment of moisture at stripping tower.Therefore above-mentioned technical process is after the long period operation, and water and dimer are not only accumulated in circulating solvent, and also can enrichment on the local column plate of first extraction distillation column and stripping tower, sees Table 1.
The Impurity Distribution of table 1 stripping tower
| Column plate number | Still | 6 | 16 | 22 (chargings) | 36 | 50 |
| Temperature ℃ | 154 | 149 | 124 | 77 | 43 | 38 |
| DCPDwt％ | 3.25 | 6.18 | 4.90 | 3.24 | ||
| X 3wt％ | 1.11 | 2.96 | 1.56 | 1.09 | ||
| H 2Oppm | 141 | 2921 | 6129 | 236 | 201 |
X
3---the polymkeric substance of other diolefins
In sum, no matter be the accumulation of water in solvent, or dimer or polymeric accumulation, solvent quality will be descended, operation of equipment is undesired.
The objective of the invention is to overcome the defective that exists in the above-mentioned prior art, a kind of improved C is provided
5Separation method is characterized in being provided with two stripping towers and removes water and dimer in the extracting system in first abstraction distillation system, make water and dimeric content in the circulating solvent all remain on lower level, guarantees that operation is normal stable.
The contriver has proposed a kind of cracking C through for many years further investigation
5The isolating method of fraction comprises following process:
Petroleum cracking C
5The fraction raw material carries out hot dimerization reaction in hot dipolymer reactor, make C
5Most of cyclopentadiene dimerization in the fraction generates dicyclopentadiene, and temperature of reaction is 60～150 ℃, and reaction pressure is 1.0～1.5MPa, and reactant removes dicyclopentadiene and other high boiling hydrocarbon through fractionation by distillation then;
The material that is obtained by said process enters first extractive distillation column by the middle part of tower, in the presence of solvent and stopper, carry out extracting rectifying, the tower internal pressure is 0.1～0.3MPa, tower still temperature is 100～140 ℃, the trim the top of column ratio is 4～10, get monoolefine, single alkane by cat head, must be rich in the solvent material of C 5 dienes such as isoprene by the tower still;
Above-mentioned tower still material enters stripping tower, isolates dicyclopentadiene, m-pentadiene and other heavy constituent by the tower still, obtains thick isoprene by cat head;
Weight-removing column cat head material enters second extractive distillation column by the tower middle part, in the presence of solvent and stopper to the further extracting rectifying of thick isoprene, the tower internal pressure is 0.1～0.3MPa, tower still temperature is 100～150 ℃, the trim the top of column ratio is 4～8, cat head gets qualified isoprene product, and its tower still material that contains a small amount of cyclopentadiene and other alkene and alkynes enters follow-up Analytic Tower, obtains the high purity isoprene product by precise distillation again;
It is characterized in that: two stripping towers are set behind first extractive distillation column remove water and dimer in the extracting system, the first extracting rectifying Tata still material enters first stripping tower by the top of tower, with C
5Component, dimer dicyclopentadiene and water are told from solvent, and tower top temperature is 85～130 ℃, and tower still temperature is 150～170 ℃, and the tower still obtains reclaiming solvent and returns first extractive distillation column and recycle;
The cat head material C of first stripping tower
5Component, dimer dicyclopentadiene and water enter second stripping tower, with C
5Hydrocarbon separates with high boiling material such as dicyclopentadiene, tower top temperature is 30～60 ℃, tower still temperature is 145～160 ℃, reflux ratio is 1～3, high boiling material such as tower bottoms dicyclopentadiene return the top charging of first stripping tower, wherein extract a part out and deliver to the solvent reclamation part to remove moisture and dipolymer such as dicyclopentadiene wherein, the thick isoprene of its cat head material enters follow-up weight-removing column and carries out rectifying separation.
In the present invention, two stripping towers are set after first abstraction distillation system at least remove water and dimer in the extracting system, the effect of first stripping tower is with C
5Component, dimer DCPD etc. tell from DMF with water, and the effect of second stripping tower is with C
5Hydrocarbon separates with high boiling material such as DCPD.
Describe the present invention in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 cracking C of the present invention
5The process flow sheet of the separation method of fraction
The schematic flow sheet of 2 two stripping towers of accompanying drawing
As shown in Figure 1, raw material C5Fraction at first enters acetylene removal tower 1, and with the removed overhead of alkynes from the acetylene removal tower, the number of plates of this tower is 80～140, and tower top temperature is 40～60 ℃, and the tower reactor temperature is 75～95 ℃, reflux ratio 20～180, and pressure is 0.11～0.13MPa. Remove the C of most of alkynes5Fraction enters hot dipolymer reactor 2, carries out the dimerization reaction of cyclopentadiene, generates dicyclopentadiene, and reaction temperature is 60～150 ℃, and reaction pressure is 1.0～1.5MPa, and the time of staying is 20～200 minutes. C through dimerization reaction5Fraction gives weight-removing column 3 entering, and removes dicyclopentadiene and C6The above restructuring of fraction divides, and the number of plates of this tower is 30～50, and charging aperture is between the 15th～20 block of column plate, and its technological parameter is: 50～70 ℃ of tower top temperatures, and 88～95 ℃ of tower reactor temperature, pressure is 0.11～0.2MPa, reflux ratio is 1.5～3.5.
The component that obtains from the cat head that gives weight-removing column 3 enters the first extractive distillation column 4, the number of plates of the first extracting rectifying is 90～140, charging aperture is between the 50th～60 block of column plate, its technological parameter is: the tower internal pressure is 0.1～0.3MPa, the tower reactor temperature is 100～140 ℃, and overhead reflux is than 4～10. Extractant can be selected a kind of in dimethyl formamide, the dimethylacetylamide, or their mixture, and the concentration of body of the tower solvent is controlled at 50～80%, and optimum value is 65～70%, can obtain larger relative volatility like this. In extraction separation process, the tower reactor temperature is higher, and diolefin is easy to polymerization reaction take place, causes the feed blocking e-quipment and pipe, makes loss of material, therefore must add polymerization inhibitor. In the present invention, used binary inhibition system, be preferably natrium nitrosum-monoethanolamine, weight ratio is 1: 2～1: 10, and the concentration expressed in percentage by weight in solvent is respectively 0.05～0.1wt% and 0.5～1wt%.
Be divided into single alkane, monoolefine from the cat head of the first extractive distillation column, the tower bottoms that has absorbed diolefin, alkynes enters two strippers 6,7, the water that accumulates in the circulating solvent and dimer are removed, steam diolefin, alkynes etc. from the cat head of stripper 7, obtain containing C from the tower reactor of stripper 65Hydrocarbon circulating solvent seldom returns the extraction part and recycles.
The C that the second stripper 7 cats head steam5Hydrocarbon enters the first extracting rectifying weight-removing column 5, removes boiling point greater than restructuring such as cyclopentadiene, pentadiene, cyclopentene and the pentamethylene of isoprene minute with rectification method, and the tower temperature is 45～65 ℃, and pressure is 0.1～0.2Mpa.
Thick isoprene product introduction the second extractive distillation column 8 that obtains from the first extracting rectifying weight-removing column 5 cats head, carry out again one-time extractive rectification with the solvent identical with the first extractive distillation column and polymerization inhibitor, remove the restructuring such as cyclopentadiene minute, the number of plates of the second extracting rectifying is 132～182, charging aperture is between the 100th～120 block of column plate, its technological parameter is: the tower internal pressure is 0.1～0.3MPa, and the tower reactor temperature is 100～150 ℃, and overhead reflux is than 4～8.
From the isoprene of the cat head of the second extractive distillation column 8, the C such as the isoprene containing of tower reactor extraction, cyclopentadiene, pentone5The solvent of hydrocarbon enters normal pressure Analytic Tower 9,100～170 ℃ of tower reactor temperature, and the overhead reflux ratio is 1～3, and its number of plates is 35～50, and charging aperture is between the 10th～20. At Ben Tanei with C5Hydrocarbon steams, and wherein a part of extraction obtains purity and be the isoprene product more than 99.3%, and a part is returned the second extractive distillation column.
The circulating solvent that normal pressure Analytic Tower 9 tower reactors obtain enters decompression Analytic Tower 10 further to remove the cyclopentadiene in the circulating solvent, its cat head material can partly send the solvent refining part except refluxing, refining solvent send the second extractive distillation column to recycle, its technological parameter is: the tower internal pressure is 0.01～0.03MPa, temperature is 80～130 ℃, the overhead reflux ratio is 70～90, and its number of plates is 30～50, and charging aperture is between the 5th～10 block of column plate.
We can be with the material that gives weight-removing column 3 and the first extracting rectifying weight-removing column 5 tower reactors the method by rectifying again, remove other carbon five hydrocarbon components and carbon six hydrocarbon components, obtain highly purified pentadiene and dicyclopentadiene product, this part equipment can not put into main flow.
In above-mentioned technological process, the first abstraction distillation system removes water and dimeric method as shown in Figure 2: C5 Charging 11 enters the first extractive distillation column 4, is told the components such as alkane and monoolefine by cat head, and tower reactor material 12 enters the first stripper 6, steams whole C by cat head5Hydrocarbon, the moisture in the solvent and part DCPD and DMF are also along with steaming simultaneously. These materials 15 enter the second stripper 7 together, obtain pure DMF solvent 14 turns back to the first extractive distillation column 4 as circulating solvent cat head by the tower reactor of the first stripper 6.
In the second stripper 7, tower reactor stays dimer and small part water such as whole DMF and DCPD, another part moisture content and whole C5Hydrocarbon is steamed by cat head, moisture content is removed C through behind the separatory5Hydrocarbon enters the weight-removing column of follow-up order operation to remove the high-boiling components such as cyclopentadiene, cyclopentene, pentamethylene and pentadiene-1,3. The tower bottoms 16 of the second stripper 7 returns the top charging of the first stripper 3, wherein extracts a part out and delivers to the solvent reclamation part to remove moisture and the dimer such as DCPD wherein. Because the C that the second stripper 7 cats head steam5Hydrocarbon 17 need be sent into the rectifying separator (weight-removing column) of next one, so this tower need to arrange the necessary number of plates and suitable reflux ratio to guarantee the C of this column overhead5Do not contain solvent DMF in the hydrocarbon, otherwise will cause the loss of solvent and will pollute C5The diolefin product.
Under normal pressure, the tower top temperature of first stripping tower is controlled at 85～130 ℃, and the best is 95～115 ℃; Tower top pressure is 0.02～0.1MPa; The temperature of tower still is controlled at 150～170 ℃, and the best is 150～160 ℃.The tower top temperature of second stripping tower is controlled at 30～60 ℃, and the best is 32～40 ℃; The temperature of tower still is controlled at 145～160 ℃, and the best is 150～155 ℃, and reflux ratio is 1～3.
Generally speaking, feed composition and the tower top temperature from first stripping tower is bigger to the removal effect influence of dimer and water.When the temperature of cat head was higher, removal effect was better.In the present invention, under the gentle different feeds in different tops was formed, the content of moisture content all was removed to below the 200ppm among the tower still DMF, makes the quality conformance with standard of the circulating solvent that returns first extractive distillation column, sees embodiment.
The cat head material of first stripping tower enters second stripping tower continuously, carries out C
5Hydrocarbon boils separating of component with dimer, DMF height, and the moisture content in its charging in this tower is and C
5Hydrocarbon forms azeotrope and is told by cat head, because C
5The mutual insolubility of hydrocarbon and water can fall water sepn by water trap, finally reaches the purpose that removes moisture content.Table 2 has provided through C behind the water trap
5The analytical data of hydrocarbon:
The composition of liquid of top of the tower behind minute water of table 2 second stripping tower
| Test | C 5(wt％) X 3 DCPD DMF H 2Oppm |
| 1 2 | 99.99 / / / 196 100.0 / / / 312 |
As can be seen from Table 2, C
5The moisture of hydrocarbon is deviate from substantially, only contains saturation water.
The present invention compared with prior art has the following advantages:
(1) the present invention has adopted two strippings behind first extractive distillation column, can remove dipolymer and water in first abstraction distillation system, has improved the quality of circulating solvent, and can not cause the localized accumulated of dipolymer and water on equipment configuration.Table 3 has provided under same processing condition, the correlation data of the present invention and prior art circulating solvent quality:
The correlation data of table 3 the present invention and prior art circulating solvent quality
| Content in the circulating solvent | Prior art the present invention's (stripping tower) (two stripping towers) |
| DCPDwt％ H 2Oppm | 1.43 0.38 700 100 |
(2) owing to the reduction of DCPD content in the circulating solvent, the gelationus accumulation reduces, and the viscosity of solvent is reduced, flowability improves, improve the operation of Analytic Tower, guaranteed the normal stable of whole separating technology, and this technology has also reduced the load of solvent regeneration system.
Embodiment
Example 1: with C
5After raw material removes most of alkynes, enter hot dipolymer reactor (R101) and give weight-removing column (T102) to remove high boiling point components such as dicyclopentadiene, enter the 56th block of column plate (by upwards counting at the bottom of the tower) of first extractive distillation column (T201) then with the flow of 0.53kg/h, contain 1500ppmNaNO with 114 column plates
2With the solvent of the dimethyl formamide of 1.0wt% thanomin the 104th block of column plate and 56 blocks of column plates, from up to down flow with the flow of 3.34kg/hr from tower.This tower is operated under following condition, tower still pressure 0.118MPa, and 125 ℃ of tower still temperature, trim the top of column 2.03kg/hr tower bottoms enters first stripping (T202).Enter the T203 tower by the T202 overhead product, the overhead product that obtains 0.48kg/hr is delivered to the weight-removing column (T204) with 120 blocks of column plates and is removed high boiling material.The operational condition of T204 tower: tower still pressure 0.102MPa, 62.5 ℃ of tower still temperature, reflux ratio 44.5.The overhead product of T204 tower enters second extractive distillation column (T301) with the flow of 0.29kg/hr by 22 blocks of column plates on the still, this tower has 132 blocks of column plates, add the solvent that contains with the same stopper of first extractive distillation column by the 122 blocks of column plates in tower top, from up to down mobile with the flow of 2.85kg/hr.The operational condition of this tower is: tower still pressure 0.10MPa, and 140 ℃ of tower still temperature, trim the top of column 1.18kg/hr obtains qualified isoprene product by cat head.In order to remove cyclopentadiene and the alkynes in the circulating solvent, the T301 tower bottoms enters normal pressure Analytic Tower (T303) and the decompression Analytic Tower (T304) with 52 blocks of column plates, and the cyclopentadiene in the circulating solvent is dropped to below the 1ppm.The analytical results of each tower is listed in table 4.
The analytical results of each tower in table 4 example 1
| Form wt% | T-101 advances | The T-101 top | At the bottom of the T-101 | T-201 advances | The T-201 top | The T-203 top | The T-204 top | At the bottom of the T-204 | T-301 advances | The T-301 top |
| | 11.46 | 0.06 | ||||||||
| Iso-pentane | 3.02 | 15.86 | 0.02 | 0.03 | 0.26 | |||||
| The trimethylammonium butene-1 | 3.91 | 15.09 | ||||||||
| Skellysolve A | 1.99 | 0.17 | 2.44 | 3.08 | 10.33 | |||||
| Amylene-1 | 6.88 | 25.20 | 1.91 | 4.82 | 22.96 | |||||
| Neohexene-1 | 4.71 | 11.20 | 2.85 | 5.81 | 21.19 | |||||
| Pentadiene-1,4 | 8.93 | 13.47 | 7.99 | 10.14 | 33.50 | |||||
| Neohexene-2 | 2.54 | 3.32 | 4.37 | 11.46 | 0.05 | 6.06 | 0.01 | |||
| Pentamethylene | 1.04 | 0.69 | 0.06 | 1.77 | ||||||
| Isoprene | 21.04 | 3.36 | 26.17 | 33.49 | 0.02 | 47.15 | 99.86 | 99.86 | 99.93 | |
| Crotonylene | 0.60 | 3.38 | 9.6ppm | |||||||
| Cyclopentenes | 4.50 | 5.73 | 6.54 | 9.12 | 17.68 | 0.03 | ||||
| Sow distrust among one's enemies pentadiene-1,3 | 12.10 | 14.45 | 17.80 | 24.30 | 45.18 | 0.02 | ||||
| Along m-pentadiene-1,3 | 6.03 | 8.39 | 9.31 | 13.31 | 24.43 | |||||
| Cyclopentadiene | 5.95 | 0.04 | 8.62 | 3.72 | 4.64 | 0.08 | 2.30 | 0.08 | 0.2ppm | |
| Total carbon six | 0.38 | 0.08 | 1.32 | 0.17 | 1.50 | 0.04 | 2.11 | 0.04 | ||
| Valylene | 0.11 | 0.64 | ||||||||
| X 2 | 0.49 | 0.74 | 0.06 | 0.03 | ||||||
| X 1 | 0.18 | 0.08 | 0.20 | 0.02 | 0.07 | 0.03 | ||||
| X 2 | 0.04 | 0.04 | ||||||||
| X 3 | 0.60 | 0.85 | 1.01 | |||||||
| Dicyclopentadiene | 11.62 | 14.90 | 0.23 | 0.04 | 5.32 |
Embodiment 2～8: with test 1 processing condition, change the feed composition and the tower top temperature of first stripping tower, obtain following test-results, see Table 5:
Table 5 different feeds form with different tower top temperatures under analytical data
| Embodiment | Warm ℃ of top | Feed composition (wt%) C 5 X 2 X 3 DCPD DMF H 2Oppm | The tower still is formed (wt%) C 5 X 3 DCPD DMF H 2Oppm | Overhead water ppm |
| Example 2 | 83+1 | 16.57 0.74 0.97 81.72 1600 | 0.02 0.02 0.16 99.80 130 0.02 0.11 0.28 99.59 155 | 1600 2400 |
| Example 3 | 112+1 | 16.43 0.2 0.91 1.06 81.78 1000 | 0.02 slight 99.98 125 0.05 0.10 0.17 99.68 108 | 4200 5000 |
| Example 4 | 120+1 | 15.53 0.91 1.31 82.26 1000 | 0.02 slight 99.98 161 0.04 0.05 0.06 99.85 122 | 3100 4000 |
| Example 5 | 120+1 | 15.16 0.75 1.00 83.15 62 | 0.06 0.13 0.26 99.55 20 0.03 0.10 0.20 96.68 108 | 2300 3800 |
| Example 6 | 93+3 | 14.06 0.73 3.03 81.13 3800 | 0.04 0.28 0.92 98.76 64 0.05 0.22 0.90 98.83 62 | 3300 is a large amount of |
| Example 7 | 125+2 | 12.56 0.72 2.33 84.39 2100 | 0.03 0.09 0.38 99.90 100 0.02 0.10 0.35 99.53 166 | 6400 8400 |
| Example 8 | 85+1 | 9.00 1.35 1.73 87.91 4100 | 0.16 0.33 0.99 98.53 112 0.07 0.15 0.61 99.18 128 | A large amount of |
X wherein
2, X
3Be C
5The dimer that generates between the diolefin.The correlation data of forming from the feed composition of table 5 and tower still as can be seen, first stripping tower is under different tower top temperatures and different feed composition situation, dimer and water can remove from DMF, the content of moisture content all is removed to below the 200ppm among the first stripping Tata still DMF, makes the quality conformance with standard of the circulating solvent that returns first extraction tower.
Example 9～11: with test 1 processing condition, the tower still temperature of first stripping tower is 155 ℃, and tower top temperature is 120 ℃, and the tower top temperature of second stripping tower is 34 ℃, changes the tower still temperature of second stripping tower, obtains following test-results, sees Table 5
The table 5 second stripping tower separate data
| Embodiment | Still temperature ℃ | Cat head analytical results (wt%) C 5 H 2Oppm | Tower still analytical results (wt%) C 5 X 2 X 3 DCPD DMF H 2Oppm |
| Example 9 | 150 | 99.99 250 | 0.03 0.27 6.22 8.75 84.73 61 |
| Example 10 | 151 | 99.99 237 | 0.05 0.17 7.05 9.40 83.34 98 |
| Example 11 | 152 | 100.0 165 | 0.05 0.22 7.16 8.99 83.57 90 |
Claims (4)
1, the isolating method of a kind of cracked, C 5 fraction comprises following process:
Petroleum cracking C
5The fraction raw material carries out hot dimerization reaction in hot dipolymer reactor, make C
5Most of cyclopentadiene dimerization in the fraction generates dicyclopentadiene, and temperature of reaction is 60～150 ℃, and reaction pressure is 1.0～1.5MPa, and reactant removes dicyclopentadiene and other high boiling hydrocarbon through fractionation by distillation then;
The material that is obtained by said process enters first extractive distillation column by the middle part of tower, in the presence of solvent and stopper, carry out extracting rectifying, the tower internal pressure is 0.1～0.3MPa, tower still temperature is 100～140 ℃, the trim the top of column ratio is 4～10, get monoolefine, single alkane by cat head, must be rich in the solvent material of C 5 dienes such as isoprene by the tower still;
Above-mentioned tower still material enters stripping tower and weight-removing column successively, to isolate dicyclopentadiene, m-pentadiene and other heavy constituent by weight-removing column tower still, obtains thick isoprene by the weight-removing column cat head;
Weight-removing column cat head material enters second extractive distillation column by the tower middle part, in the presence of solvent and stopper to the further extracting rectifying of thick isoprene, the tower internal pressure is 0.1～0.3MPa, tower still temperature is 100～150 ℃, the trim the top of column ratio is 4～8, cat head gets qualified isoprene product, and its tower still material that contains a small amount of cyclopentadiene and other alkene and alkynes enters follow-up Analytic Tower, obtains the high purity isoprene product by precise distillation again;
It is characterized in that: two stripping towers are set behind first extractive distillation column remove water and dimer in the extracting system, the first extracting rectifying Tata still material enters first stripping tower by the top of tower, with C
5Component, dimer dicyclopentadiene and water are told from solvent, and tower top temperature is 85～130 ℃, and tower still temperature is 150～170 ℃, and the tower still obtains reclaiming solvent and returns first extractive distillation column and recycle;
The cat head material C of first stripping tower
5Component, dimer dicyclopentadiene and water enter second stripping tower, with C
5Hydrocarbon separates with high boiling material such as dicyclopentadiene, tower top temperature is 30～60 ℃, tower still temperature is 145～160 ℃, reflux ratio is 1～3, high boiling material such as tower bottoms dicyclopentadiene return the top charging of first stripping tower, wherein extract a part out and deliver to the solvent reclamation part to remove moisture and dipolymer such as dicyclopentadiene wherein, the thick isoprene of its cat head material enters follow-up weight-removing column and carries out rectifying separation.
2, separation method according to claim 1 is characterized in that: the tower top temperature of first stripping tower is controlled at 95～115 ℃, and the temperature of tower still is controlled at 150～160 ℃.
3, separation method according to claim 1 is characterized in that: the tower top temperature of second stripping tower is controlled at 32～40 ℃, and the temperature of tower still is controlled at 150～155 ℃.
4, according to the described separation method of one of claim 1～3, it is characterized in that: the stopper in first extracting rectifying and the employing of the second extracting rectifying process can be ONP, oil of mirbane, furfural, NMP, thanomin, NaNO
2In a kind of or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103569A CN1053881C (en) | 1996-03-20 | 1996-03-20 | Method for separation of cracking C5 fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103569A CN1053881C (en) | 1996-03-20 | 1996-03-20 | Method for separation of cracking C5 fraction |
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| CN1160034A CN1160034A (en) | 1997-09-24 |
| CN1053881C true CN1053881C (en) | 2000-06-28 |
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| CN96103569A Expired - Lifetime CN1053881C (en) | 1996-03-20 | 1996-03-20 | Method for separation of cracking C5 fraction |
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| CN (1) | CN1053881C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348561C (en) * | 2004-05-20 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Process for preventing self-polymerization or co-polymerization of C5 diolefins in separation process of petroleum C5 distillate |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077561C (en) * | 1998-11-09 | 2002-01-09 | 化学工业部北京化工研究院 | Process for separating diolefin from C5 fraction |
| CN101053815B (en) * | 2006-04-13 | 2010-08-11 | 杨国华 | Hot reflux tower for producing carbon-13 |
| CN101805631B (en) * | 2010-05-07 | 2013-06-26 | 天津大学 | Variable pressure steam stripping method of C5 fraction extraction solvent |
| CN103143191B (en) * | 2013-01-25 | 2015-06-24 | 中国石油集团东北炼化工程有限公司吉林设计院 | Removal technology of cyclic solvent dipolymer in a C5 diolefin separation process by solvent method |
| CN106278782A (en) * | 2015-05-29 | 2017-01-04 | 汪上晓 | Carbon five product segregation apparatus |
| CN109679011B (en) * | 2017-10-18 | 2021-08-27 | 抚顺齐隆化工有限公司 | Production method of copolymerized petroleum resin |
| CN111320520B (en) * | 2018-12-14 | 2024-01-23 | 中国石油化工股份有限公司 | Extractive distillation tower for butadiene separation and separation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS494202B1 (en) * | 1970-03-17 | 1974-01-31 | ||
| US3851010A (en) * | 1972-01-28 | 1974-11-26 | Snam Progetti | Process for the separation of isoprene |
| SU571469A1 (en) * | 1971-08-02 | 1977-09-05 | Феб Лойна-Верке "Вальтер Ульбрихт" (Инопредприятие) | Method of purifying solvents |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS494202B1 (en) * | 1970-03-17 | 1974-01-31 | ||
| SU571469A1 (en) * | 1971-08-02 | 1977-09-05 | Феб Лойна-Верке "Вальтер Ульбрихт" (Инопредприятие) | Method of purifying solvents |
| US3851010A (en) * | 1972-01-28 | 1974-11-26 | Snam Progetti | Process for the separation of isoprene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348561C (en) * | 2004-05-20 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Process for preventing self-polymerization or co-polymerization of C5 diolefins in separation process of petroleum C5 distillate |
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| CN1160034A (en) | 1997-09-24 |
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