CN1162380C - Separation method of cracked C5 fraction - Google Patents
Separation method of cracked C5 fraction Download PDFInfo
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- CN1162380C CN1162380C CNB011363835A CN01136383A CN1162380C CN 1162380 C CN1162380 C CN 1162380C CN B011363835 A CNB011363835 A CN B011363835A CN 01136383 A CN01136383 A CN 01136383A CN 1162380 C CN1162380 C CN 1162380C
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Abstract
The present invention relates to a technological method for separating C5 diolefin and other components in petroleum cracking C5 fractions by removing alkyne with a selective catalytic hydrogenation technology, which comprises the following technological processes: dicyclopentadiene removal by thermal dimerisation, extractive rectification, heavy component removal, etc. The present invention is characterized in that before the C5 fractions are treated with extraction separation, alkyne is removed by using a selective catalytic hydrogenation technology; after reaction rectification, a small amount of cyclopentadiene, etc. is removed. By using the technology, the flows of the prior art are simplified, the second-segment extractive rectification is omitted, a solvent recovering unit is simplified, the investment cost, operating cost and the energy consumption are reduced, the solvent consumption and the production cost are reduced, and the problem that devices are plugged by black residue generated by solvent hydrolyzation is solved.
Description
Technical field
The present invention relates to a kind of separation method of five fractions of petroleum cracked carbon, more particularly, relate to a kind of separation method that removes the cracked C 5 fraction of alkynes before the process for selective hydrogenation that adopts.
Background technology
Diolefins such as isoprene, cyclopentadiene and m-pentadiene are rich in a considerable amount of C5 fractions of by-product in the C5 fraction in the petroleum cracking process of producing ethylene.These diolefin chemical property are active, are important chemical material.Because the difference on raw material, cracking severity and the separation degree of petroleum hydrocarbon cracking, the diolefin content in the C5 fraction is different, but total content is between 40-60Wt%.Therefore, separate and utilize C5 fraction for the economic benefit that improves ethylene unit, the comprehensive utilization petroleum resources have profound significance.
Cracked C 5 fraction is close by more than 20 kinds of boiling points, and the component that easily forms azeotrope is to each other formed, and therefrom isolates the higher C 5 diene of comprehensive utilization value, and its technology is comparatively complicated.The a small amount of four carbon atom that contains in the C5 fraction and the alkynes of five carbon atoms, as crotonylene, pentyne-1, pentyne-2, pseudoallyl acetylene (hereinafter to be referred as valylene) etc., wherein total alkynes content is greatly in the 0.1-2Wt% scope, because their chemical property is active, be the main detrimental impurity of reaction of C 5 diene product and polymerization process, so effective elimination alkynes become the important step of cracked C 5 fraction separating technology.
In order to produce highly purified C 5 diene, generally adopt the method for extracting rectifying in the prior art, the advantage of this method is when removing micro-cyclopentadiene the total alkynes in the isoprene finished product to be removed to below the 50ppm, its shortcoming is to need higher energy consumption, and alkynes can concentrate in some equipment in sepn process.Selective solvent commonly used has dimethyl formamide (DMF) and acetonitrile, as disclosed processing methodes such as patent JP63101338, JP74019245, US3510405, US3535260.
Nippon Zeon Co., Ltd. in US3510405, disclose a kind of from C5 fraction the processing method of separating high-purity isoprene, it comprises following process: the C5 fraction that will obtain by hydrocarbon steam cracking or other high-temperature cracking method, through overheated dimerization reaction and therefrom isolate dicyclopentadiene; 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 component that contains cyclopentadiene and m-pentadiene; With DMF is that solvent carries out the extractive distillation second time in the presence of stopper, and solvent reclaims by stripping tower and uses; Material obtains highly purified isoprene product after a lightness-removing column carries out rectifying.
Domestic unique carbon five separation process scheme can be divided into 5 unit.First module is the raw materials pretreatment unit, and purpose is to remove light component such as carbon four and most of alkynes, amylene, pentane and isolate by heavy components such as the dicyclopentadiene of cyclopentadiene dimerization and carbon six, and Unit second is delivered in other C5 fraction.Unit second is the first extracting rectifying unit, purpose is to adopt solvent dimethylformamide to extract diolefin and alkynes, monoolefine and alkane separation are gone out, and isolate the heavy component based on m-pentadiene again from diolefin and alkynes, obtain chemical grade isoprene and deliver to Unit the 3rd.Unit the 3rd is the second extracting rectifying unit, and purpose is to adopt solvent dimethylformamide to extract alkynes and cyclopentadiene, obtains polymerization grade isoprene.The heavy component based on m-pentadiene that heavy components such as dicyclopentadiene of separating from first module and carbon six and Unit second are separated is mixed into Unit the 4th, i.e. m-pentadiene, dicyclopentadiene separating unit, and purpose is that the two is separated.The used solvent in first module and Unit second needs reclaim to the 5th unit solvent recovering system refining, makes that system is coal-tar middle oil, impurity level reaches balance.At first remove burnt matter and residue, remove water and the dicyclopentadiene that accumulates in the solvent through treating tower again.
Disclose a kind of reaction rectification technique among the patent CN1253130, directly carried out in reaction fractionating tower without dimerization reaction but raw material is C5 fraction, cat head cyclopentadiene content is higher, and not easy to operate.A kind of method by rectifying is disclosed before extracting and separating is carried out in C5 fraction, the method that alkynes is removed among the patent CN1056823.These two technology all need and the supporting use of domestic carbon five separation process, and the material that this tower is separated need carry out two-section extraction, two sections strippings and two sections rectifying and isoprene could be separated.
It is the external C of extensive employing that acetonitrile method carbon five dienes separate
5One of cut separation method.The flow process of U.S. Esso company exploitation is only produced a kind of product of isoprene, and three water wash columns are arranged in the flow process, and the processing of solvent recovery unit load is bigger.The technology of Japan SYnthetic Rubber Co. Ltd's exploitation is made up of three parts, and first part carries out the pre-treatment of carbon Wuyuan material, removes most of cyclopentadiene and heavier component through overheated dimerization redistillation; Second section is two-section extraction rectifying, and alkane and the alkene in the C5 fraction is told in first section extractive distillation, and cyclopentadiene and alkynes are removed in second section extractive distillation; Third part is aftertreatment, and thick isoprene washes with water removes a small amount of solvent, sloughs light component through lightness-removing column again, removes heavy components such as cyclopentadiene and m-pentadiene through weight-removing column, and cat head obtains polymerization grade isoprene.
From the prior art, domestic or external carbon five separation process generally all will pass through two-section extraction rectifying, two sections and steam and two sections rectifying, just can obtain polymerization grade isoprene; And solvent need arrive the solvent recuperation refined unit and reclaim refining.Long flow process has increased energy consumption, investment cost and process cost.With domestic carbon five separation process, exist subject matter to have: one, long flow path, project equipment is many, the investment cost height, correspondingly process cost and energy consumption all can increase; Two, there is black bits latch up phenomenon in equipment in the flow process, needs the parking cleaning equipment every year at least twice, and solvent recovery unit has a large amount of burnt matter, and is difficult to cleaning, needs manual handling; Three, solvent-oil ratio is big, and product per ton need consume 20 kilograms of DMF, makes production cost improve; Four, because m-pentadiene mainly removes at the last and product of flow process, the load of whole flow process is increased, the processing power of production equipment is lower.
Summary of the invention
At having the problem that exists in carbon five isolation technique both at home and abroad now, the contriver has proposed a kind of C5 fraction separation method that adopts process for selective hydrogenation to remove alkynes, just perhaps make its residual content reach the separation method of several ppm (by weight) at least by being hydroconverted into isoprene, 2-butylene, 1-amylene etc. in alkynes such as valylene, 2-butyne, 1-pentyne in the C5 fraction.
The separation method of cracked C 5 fraction of the present invention comprises following process:
1) the five fractions of petroleum cracked carbon raw material enters lightness-removing column 1 by the middle part of tower, removed overhead carbon four light component and part alkynes, and the tower still gets carbon five materials;
2) the tower still material that obtains of said process enters hot dipolymer reactor 2 and carries out hot dimerization reaction, and making the most of cyclopentadiene dimerization in the C5 fraction is dicyclopentadiene, and temperature of reaction is 60-150 ℃, and reaction pressure is 1.0-1.5MPa; Reactant enters pre-weight-removing column 3 then, separation removal dicyclopentadiene and other heavy component;
3) the cat head material that is obtained by said process enters catalytic hydrogenation reaction device 4, and alkynes such as valylene, crotonylene that will be wherein by selective hydrogenation remove; Filling alkynes selective hydrogenation catalyst in the reactor 4; Service temperature is 20-80 ℃, and pressure is 0.3-1.2MPa, and liquid air speed is 2-15m
3/ m
3Hr, hydrogen usage is advisable so that outlet alkynes is lower than required value;
4) material that comes out of hydrogenator 4 enters extractive distillation column 5 by the middle part of tower, solvent and stopper are added by the top of tower, carry out extracting rectifying, stage number is the 70-150 piece, and working pressure is 0.01-0.3MPa, tower still temperature is 100-150 ℃, tower top temperature is 40-80 ℃, and reflux ratio is 4-15, and solvent ratio is 5-11, get monoolefine and alkane by cat head, must be rich in the solvent material of C 5 dienes such as isoprene by the tower still;
5) above-mentioned solvent material enters stripping tower 6, must reclaim solvent by the tower still returns extractive distillation column 5 and recycles, the material that its cat head obtains enters weight-removing column 7 and carries out rectifying separation, obtain polymerization grade isoprene by cat head, the discharging of tower still is cyclopentadiene, dicyclopentadiene, isoprene and other heavy component;
6) enter decarburization five towers 8 together by pre-weight-removing column 3 tower still dischargings and weight-removing column 7 tower still dischargings, tower top temperature is 40-55 ℃, and tower still temperature is 95-120 ℃, and tower top pressure is 0.01-0.03MPa, and tower still pressure is 0.02-0.07MPa, and reflux ratio is 0.5-3; Decarburization five towers 8 cats head get carbon five hydrocarbon, delivering to m-pentadiene treating tower 9 makes with extra care, tower top temperature is 40-60 ℃, tower still temperature is 50-70 ℃, tower top pressure is 0.02-0.1MPa, and tower still pressure is 0.07-0.15MPa, and reflux ratio is 30-70, the tower still gets the m-pentadiene product, and the cat head discharging turns back to the C5 fraction pipeline; Dicyclo treating tower 10 is delivered in the 8 tower still dischargings of decarburization five towers, and tower top temperature is 20-50 ℃, and tower still temperature is 90-120 ℃, and the tower internal pressure is-0.05--0.12MPa that reflux ratio is 1-5.
The feeding temperature of described lightness-removing column 1 is 30-75 ℃, and the still temperature is 75-96 ℃, and the top temperature is 40-60 ℃, and roof pressure is 0.1-0.3MPa, and still is pressed and is 0.2-0.4MPa, and reflux ratio is 15-32.
Described pre-weight-removing column 3 is a reaction fractionating tower, in tower, the unreacted cyclopentadiene of part is further reacted the generation dicyclopentadiene, isolate m-pentadiene, dicyclopentadiene and other heavy component by the tower still, cat head is isolated isoprene, monoolefine, alkane, alkynes and cyclopentadiene etc., and cyclopentadiene content is lower than 2% in the overhead fraction, and stage number is the 30-80 piece, tower still temperature is 50-110 ℃, tower top temperature is 35-70 ℃, and reflux ratio is 0.5-35, and working pressure is 0.01-0.06MPa.
The alkynes selective hydrogenation catalyst of filling can use at Al in the described catalytic hydrogenation reaction device 4
2O
3, SiO
2, on the carrier such as ZnO, be the loaded catalyst of active constituent with the precious metal; Preferred catalyzer is to be carrier with the aluminum oxide, is benchmark with the gross weight of catalyzer, comprises the I B-group metal at least a periodic table of elements, and its weight content is 0.1%-10%; Group VIII metal at least a periodic table of elements, its weight content are 0.008%-1%; At least a basic metal, its weight content are 0.01%-5%; More preferably I B-group metal is at least a in copper and the silver, and wherein copper accounts for 90% of I B-group metal at least; The group VIII metal is a palladium; Basic metal is potassium.
Described hydrogenation catalyst can prepare by following method: at first use the salpeter solution oxide impregnation alumina supporter of the salt of the salpeter solution of salt of I B-group metal and group VIII metal, then with the aqueous solution dipping of alkali metal compound; Drying is carried out in each step dipping back in 50-200 ℃ temperature range, carry out roasting in 250-650 ℃ temperature range.
Described technical process the 4th) the used solvent of extracting rectifying can be selected from least a in dimethyl formamide, N,N-DIMETHYLACETAMIDE, acetonitrile, the n-formyl sarcolysine base pyrrolidone in the step.
Described weight-removing column 7 is a reaction fractionating tower, cyclopentadiene carries out dimerization reaction generation dicyclopentadiene in weight-removing column 7, make it be easy to separate with isoprene, its stage number is the 100-200 piece, tower top temperature is 40-55 ℃, and tower still temperature is 60-90 ℃, and tower top pressure is 0.01-0.15MPa, tower still pressure is 0.15-0.25MPa, and reflux ratio is 15-60.
Described technical process the 6th) step, it is the material method by rectifying again of the tower still of pre-weight-removing column 3 and weight-removing column 7, remove other carbon five hydrocarbon components and carbon six hydrocarbon components, obtain highly purified m-pentadiene and dicyclopentadiene product, this part equipment can not put into main flow.
In technical process of the present invention, when pre-weight-removing column 3 and weight-removing column 7 were reaction fractionating tower, the material that pre-weight-removing column 3 cats head obtain directly entered extractive distillation column 5, can obtain chemical grade isoprene by weight-removing column 7 cats head.
The present invention compares with prior art, has simplified existing technical process greatly, has saved second section extracting rectifying unit, has reduced solvent loss, and has simplified solvent recovery unit; Solved the problem that produces black bits occluding device because of the solvent hydrolysis; Saved construction cost and process cost, reduced energy consumption, made investment and production cost reduce 15-20% at least.
Description of drawings
Accompanying drawing 1 is the process flow sheet of the separation method of cracked C 5 fraction of the present invention.
Reference numeral: 1 lightness-removing column, 2 dipolymer reactors, 3 pre-weight-removing columns, 4 hydrogenators, 5 extractive distillation columns, 6 stripping towers, 7 weight-removing columns, 8 decarburizations, five towers, 9 m-pentadiene treating towers, 10 dicyclo treating towers
Embodiment
Embodiment 1
At ambient temperature, use salpeter solution (PH=1.0) oxide impregnation alumina supporter (the BET surface-area: 287m of cupric nitrate and Silver Nitrate
2/ g), drying is 4 hours under 120 ℃, calcines 4 hours down at 500 ℃ then, and take out and be cooled to room temperature; Use salpeter solution (PH=1.0) dipping of Palladous nitrate again, again drying and calcining; The aqueous solution with potassium hydroxide floods drying and calcining at last.The amount of dipping solution is the adsorbable maximum volume amount of employed carrier, and the setting of the concentration of metal compound solution should make catalyzer finally contain 3% bronze medal, 0.04% silver medal, 0.04% palladium and 0.3% potassium (all being weight percentage) in dipping solution.
The five fractions of petroleum cracked carbon raw material enters lightness-removing column 1 by the middle part of tower, removed overhead carbon four light component and part alkynes, and the tower still gets carbon five materials.Feeding temperature is 65 ℃, and the still temperature is 82 ℃, and the top temperature is 50 ℃, and roof pressure is 0.20MPa, and still is pressed and is 0.24MPa, and reflux ratio is 19.
The tower still material of lightness-removing column 1 enters dipolymer reactor 2, and to make the hot dimerization of cyclopentadiene be dicyclopentadiene.Temperature of reaction is 80 ℃, and reaction pressure is 1.2MPa; Material through dimerization enters pre-weight-removing column 3, stage number is 75, tower still temperature is 101 ℃, tower top temperature is 52 ℃, reflux ratio is 0.95, working pressure is 0.06MPa, and the tower still is isolated m-pentadiene, dicyclopentadiene and other heavy component, and cat head is isolated isoprene, monoolefine, alkane and alkynes.
The material that pre-weight-removing column 3 cats head come out enters catalytic hydrogenation reaction device 4, by selective hydrogenation alkynes is removed.The hydrogenation catalyst Cu-Ag-Pd-K/Al that filling embodiment 1 obtains in the reactor
2O
3Service temperature is 40 ℃, and pressure is 0.8MPa, and liquid air speed is 8m
3/ m
3Hr.
The material that hydrogenator 4 comes out enters extractive distillation column 5 by the middle part, in the presence of solvent and stopper, carry out extracting rectifying, stage number is 114, and tower top pressure is 0.19MPa, and tower still pressure is 0.20MPa, tower still temperature is 138 ℃, tower top temperature is 65 ℃, and reflux ratio is 8.4, and solvent ratio is 7.2, obtain monoolefine and alkane by cat head, obtain being rich in the solvent material of isoprene by the tower still;
Above-mentioned solvent material enters stripping tower 6, and the solvent that the tower still obtains returns extractive distillation column and recycles, and the isoprene that cat head obtains enters weight-removing column 7.
The tower top temperature of weight-removing column 7 is 50 ℃, and tower still temperature is 62.5 ℃, and tower top pressure is 0.09MPa, and tower still pressure is 0.10MPa, and reflux ratio is 44.5, and stage number is 120.This tower further reacts cyclopentadiene wherein to the generation dicyclopentadiene, makes it be easy to separate, and cat head obtains polymerization grade isoprene, and the discharging of tower still is isoprene, cyclopentadiene, dicyclopentadiene and other heavy component.
Enter decarburization five towers 8 together by pre-weight-removing column tower still discharging and the discharging of weight-removing column tower still, tower top temperature is 47 ℃, and tower still temperature is 105 ℃, and tower top pressure is 0.02MPa, and tower still pressure is 0.04MPa, and reflux ratio is 2.0.Decarburization five column overhead obtain carbon five hydrocarbon, are sent to m-pentadiene treating tower 9 and make with extra care, and tower top temperature is 52 ℃, and tower still temperature is 65 ℃, and tower top pressure is 0.05MPa, and tower still pressure is 0.11MPa, and reflux ratio is 40.Refining Tata still obtains m-pentadiene, and the cat head discharging turns back to the C5 fraction pipeline.Dicyclo treating tower 10 is delivered in decarburization five Tata still dischargings, and tower top temperature is 37 ℃, and tower still temperature is 106 ℃, and the tower internal pressure is-0.08MPa that reflux ratio is 2.5.
Show each supplies of unit proximate analysis (%)
| Component | Lightness-removing column | Dipolymer reactor | Pre-weight-removing column | Hydrogenator | Extractive distillation column | |||||||
| Charging | Eject material | The still discharging | Charging | Discharging | Charging | Eject material | The still discharging | Charging | Discharging | Charging | Eject material | |
| Carbon four | 4.60 | 28.41 | 0.06 | 0.06 | 0.06 | 0.06 | 0.09 | |||||
| Iso-pentane | 1.07 | 8.32 | 0.10 | 0.10 | 0.10 | 0.49 | 0.49 | 0.49 | 0.49 | 0.34 | ||
| 3-methyl butene-1 | 4.64 | 27.42 | 0.02 | 0.02 | 0.22 | 0.22 | 0.77 | |||||
| Skellysolve A | 1.74 | 0.07 | 2.10 | 2.10 | 2.13 | 2.13 | 3.19 | 1.53 | 3.19 | 3.19 | 3.19 | 8.27 |
| Amylene-1 | 7.69 | 12.76 | 6.59 | 6.59 | 6.11 | 6.11 | 30.13 | 3.68 | 9.26 | 9.26 | 9.26 | 28.04 |
| 2-methyl butene-1 anti-amylene-2 | 4.49 | 2.55 | 4.80 | 4.80 | 4.87 | 4.87 | 7.37 | 8.17 | 8.17 | 20.15 | ||
| Pentadiene-1,4 is along amylene-2 | 9.16 | 16.52 | 7.83 | 7.83 | 8.26 | 8.26 | 12.52 | 12.55 | 12.55 | 25.30 | ||
| 2-methyl butene-2 | 2.56 | 0.01 | 2.97 | 2.97 | 2.88 | 2.88 | 5.43 | 1.86 | 5.43 | 6.20 | 6.20 | 15.76 |
| Pentamethylene | 0.98 | 1.27 | 1.27 | 20.91 | 20.91 | 3.81 | 0.05 | |||||
| Isoprene | 16.70 | 0.57 | 19.29 | 19.29 | 53.31 | 53.31 | 52.11 | 52.11 | 1.12 | |||
| Cyclopentenes | 4.29 | 5.14 | 5.14 | 5.10 | 5.10 | 2.85 | 4.27 | 2.85 | 2.85 | 2.85 | 0.01 | |
| Crotonylene | 0.31 | 2.16 | 0.02 | 0.02 | 9ppm | 9ppm | ||||||
| Anti-pentadiene-1,3 | 11.70 | 0.12 | 14.01 | 14.01 | 13.81 | 13.81 | 2.39 | 23.23 | 2.39 | 2.37 | 2.37 | 0.05 |
| Along pentadiene-1,3 | 5.99 | 0.07 | 7.14 | 7.14 | 7.14 | 7.14 | 0.23 | 14.03 | 0.23 | 0.22 | 0.22 | 0.01 |
| Cyclopentadiene | 12.45 | 0.04 | 13.40 | 13.40 | 3.40 | 3.40 | 1.88 | 1.50 | 1.88 | 1.88 | 1.88 | 0.04 |
| Valylene | 0.47 | 0.08 | 10ppm | 10ppm | ||||||||
| Carbon six | 5.89 | 0.51 | 5.36 | 5.36 | 5.94 | 5.94 | 9.28 | |||||
| Dicyclopentadiene | 4.80 | 7.97 | 7.97 | 17.29 | 17.29 | 33.77 | ||||||
| X2’ | 0.25 | 0.37 | 0.37 | 0.32 | 0.32 | 0.50 | ||||||
| X 1 | 0.12 | 0.21 | 0.21 | 0.20 | 0.20 | 0.31 | 0.11 | 0.11 | ||||
| X 2 | 0.17 | 0.25 | 0.25 | 0.15 | 0.15 | 0.23 | 0.21 | 0.21 | ||||
| X 3 | 0.40 | 0.70 | 0.70 | 1.39 | 1.39 | 2.17 | 0.11 | 0.11 | ||||
From table data as can be seen, the content of valylene and crotonylene is respectively 0.08% and 0.02% in hydrogenator 4 chargings, in discharging after the hydrogenation reaction, their content is reduced to 9ppm and 10ppm respectively.
Each the supplies of unit proximate analysis (%) of continuous table
| Component | Stripping tower | Weight-removing column | Decarburization five towers | The m-pentadiene treating tower | The dicyclo treating tower | ||||||
| Eject material | Charging | Eject material | The still discharging | Charging | Eject material | The still discharging | Eject material | The still discharging | Eject material | The still discharging | |
| Carbon four | |||||||||||
| Iso-pentane | |||||||||||
| 3-methyl butene-1 | |||||||||||
| Skellysolve A | 0.06 | 0.12 | 0.92 | ||||||||
| Amylene-1 | 0.02 | 0.03 | 0.15 | 0.01 | |||||||
| 2-methyl butene-1 | 0.04 | 0.09 | 0.27 | 0.06 | |||||||
| Anti-amylene-2 pentadiene-1,4 is along amylene-2 | 0.15 | 0.30 | 2.23 | 0.02 | |||||||
| 2-methyl butene-2 | 0.28 | 0.55 | 3.72 | 0.10 | |||||||
| Pentamethylene | 0.03 | 2.17 | 3.28 | 1.06 | 3.75 | 6.11 | |||||
| Isoprene | 88.74 | 88.74 | 99.88 | 5.67 | 2.21 | 4.42 | 34.46 | 0.13 | |||
| Cyclopentenes | 4.56 | 4.56 | 0.10 | 16.87 | 9.19 | 18.01 | 0.37 | 6.35 | 19.67 | 8.03 | 1.72 |
| Crotonylene | 20.2pp m | 20.2pp m | 24ppm | ||||||||
| Anti-pentadiene-1,3 | 3.11 | 3.11 | 0.005 | 30.5 | 22.52 | 42.80 | 2.24 | 37.42 | 43.57 | 11.96 | |
| Along pentadiene-1,3 | 0.21 | 0.21 | 2.43 | 13.06 | 23.77 | 2.35 | 1.68 | 26.92 | 20.18 | ||
| Cyclopentadiene | 2.80 | 2.80 | ＜1ppm | 8.04 | 2.38 | 2.34 | 2.42 | 12.37 | 0.91 | 10.99 | |
| Valylene | 18ppm | 18ppm | 20ppm | ||||||||
| Carbon six | 10.80 | 2.55 | 19.05 | 1.04 | 2.77 | 38.80 | |||||
| Dicyclopentadiene | 29.10 | 33.07 | 1.58 | 64.56 | 0.10 | 1.79 | 0.04 | 81.53 | |||
| X 2’ | 0.02 | 0.72 | 0.03 | 1.41 | 0.03 | 3.84 | 1.75 | ||||
| X 1 | 0.18 | 0.18 | 0.01 | 1.23 | 0.52 | 0.09 | 0.95 | 0.29 | 0.06 | 0.05 | 2.81 |
| X 2 | 0.29 | 0.29 | 3.74 | 0.32 | 0.08 | 0.56 | 0.09 | 2.44 | |||
| X 3 | 0.18 | 0.18 | 2.37 | 2.57 | 0.11 | 5.03 | 0.12 | 9.75 | |||
Can find out that by continuous table data the content of cyclopentadiene is 2.80% in weight-removing column 7 chargings, behind reaction fractionating tower, the cat head discharging obtains polymerization grade isoprene, and wherein cyclopentadiene content is less than 1ppm, and total alkynes content is less than 50ppm.
Claims (8)
1. the separation method of a cracked C 5 fraction comprises following process:
The five fractions of petroleum cracked carbon raw material enters lightness-removing column 1 by the middle part of tower, gets carbon four light component and part alkynes by cat head, gets carbon five materials by the tower still;
The tower still material that is obtained by said process enters hot dipolymer reactor 2 and carries out hot dimerization reaction, makes the most of cyclopentadiene dimerization in the C5 fraction generate dicyclopentadiene, and temperature of reaction is 60-150 ℃, and reaction pressure is 1.0-1.5MPa; Material enters pre-weight-removing column 3 then, and separation removal comprises the heavy component of dicyclopentadiene, m-pentadiene;
The cat head material that is obtained by said process enters catalytic hydrogenation reaction device 4, by selective hydrogenation alkynes is wherein removed; Filling alkynes selective hydrogenation catalyst in the reactor 4, its service temperature is 20-80 ℃, and pressure is 0.3-1.2MPa, and liquid air speed is 2-15m
3/ m
3Hr, hydrogen usage is advisable so that outlet alkynes is lower than required value;
The material that is obtained by said process enters extractive distillation column 5 by the middle part of tower, in the presence of solvent and stopper, carry out extracting rectifying, working pressure is 0.01-0.3MPa, tower still temperature is 100-150 ℃, tower top temperature is 40-80 ℃, reflux ratio is 4-15, obtains monoolefine and alkane by cat head, must be rich in the solvent material of the C 5 diene of isoprene by the tower still;
Above-mentioned solvent material enters stripping tower 6, the recovery solvent that is obtained by the tower still returns extractive distillation column 5 and recycles, the material that its cat head obtains enters weight-removing column 7 and carries out rectifying separation, isolate the heavy component that comprises dicyclopentadiene, m-pentadiene by weight-removing column 7 tower stills, obtain the isoprene product of polymerization-grade by cat head.
2. separation method according to claim 1, it is characterized in that described pre-weight-removing column 3 is reaction fractionating tower, unreacted cyclopentadiene further carries out dimerization reaction generation dicyclopentadiene in pre-weight-removing column 3, the heavy component that must comprise m-pentadiene, dicyclopentadiene by the tower still, get isoprene, monoolefine, alkane, alkynes and cyclopentadiene by cat head, wherein cyclopentadiene is lower than 2%; Stage number is the 30-80 piece, and tower still temperature is 50-110 ℃, and tower top temperature is 35-50 ℃, and reflux ratio is 0.5-35, and working pressure is 0.01-0.06MPa.
3. separation method according to claim 1, it is characterized in that described weight-removing column 7 is reaction fractionating tower, cyclopentadiene carries out dimerization reaction generation dicyclopentadiene in weight-removing column 7, get polymerization grade isoprene by cat head, must comprise the heavy component of isoprene, cyclopentadiene, dicyclopentadiene by the tower still; Stage number is the 100-200 piece, and tower still temperature is 60-90 ℃, and tower top temperature is 40-55 ℃, and reflux ratio is 15-60, and tower top pressure is 0.01-0.15MPa, and tower still pressure is 0.15-0.25MPa.
4. separation method according to claim 1, it is characterized in that described pre-weight-removing column 3 tower still dischargings and weight-removing column 7 tower still dischargings enter decarburization five towers 8 together, enter m-pentadiene treating tower 9 by the 8 cat head dischargings of decarburization five towers, get the m-pentadiene product by the tower still, the cat head discharging turns back to the C5 fraction pipeline; Dicyclo treating tower 10 is delivered in the 8 tower still dischargings of decarburization five towers, gets the dicyclopentadiene product by the tower still.
5. separation method according to claim 1 is characterized in that described solvent is selected from least a in dimethyl formamide, N,N-DIMETHYLACETAMIDE, acetonitrile, the n-formyl sarcolysine base pyrrolidone.
6. separation method according to claim 1, it is characterized in that described alkynes selective hydrogenation catalyst is carrier with the aluminum oxide, gross weight with catalyzer is a benchmark, comprises following component: the I B-group metal at least a periodic table of elements, its weight content are 0.1%-10%; Group VIII metal at least a periodic table of elements, its weight content are 0.008%-1%; At least a basic metal, its weight content are 0.01%-5%.
7. separation method according to claim 6, it is characterized in that described alkynes selective hydrogenation catalyst can prepare by following method: at first use the salpeter solution oxide impregnation alumina supporter of the salt of the salpeter solution of salt of I B-group metal and group VIII metal, then with the aqueous solution dipping of alkali metal compound; Drying is carried out in each step dipping back in 50-200 ℃ temperature range, carry out roasting in 250-650 ℃ temperature range.
8. separation method according to claim 6 is characterized in that I B-group metal in the described alkynes selective hydrogenation catalyst is at least a in copper and the silver, and wherein copper accounts for 90% of I B-group metal at least; The group VIII metal is a palladium; Basic metal is potassium.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
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| CNB011363835A CN1162380C (en) | 2001-10-12 | 2001-10-12 | Separation method of cracked C5 fraction |
| TW091122409A TW583178B (en) | 2001-09-29 | 2002-09-27 | Process for separating C5 cuts obtained from a petroleum cracking process |
| US10/255,628 US6958426B2 (en) | 2001-09-29 | 2002-09-27 | Process for separating C5 cuts obtained from a petroleum cracking process |
| KR1020020059101A KR100869156B1 (en) | 2001-09-29 | 2002-09-28 | Process for separating c5 cuts obtained from a petroleum cracking process |
| JP2002286554A JP4346294B2 (en) | 2001-09-29 | 2002-09-30 | Method for separating C5 fractions obtained from petroleum cracking process |
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| CNB011363835A CN1162380C (en) | 2001-10-12 | 2001-10-12 | Separation method of cracked C5 fraction |
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| CN1412165A CN1412165A (en) | 2003-04-23 |
| CN1162380C true CN1162380C (en) | 2004-08-18 |
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Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101053815B (en) * | 2006-04-13 | 2010-08-11 | 杨国华 | Hot reflux tower for producing carbon-13 |
| CN100412040C (en) * | 2006-06-29 | 2008-08-20 | 山东玉皇化工有限公司 | Chemical grade isoprene recovery method |
| CN101209948B (en) * | 2006-12-31 | 2010-10-06 | 淄博鲁华泓锦化工股份有限公司 | Method for modifying heat dimerization effect of cyclopentadiene |
| CN101244973B (en) * | 2007-02-15 | 2010-05-19 | 中国石油化工股份有限公司 | Method for removing alkyne in high purity isoprene |
| CN101397232B (en) * | 2007-09-24 | 2012-05-30 | 中国石油化工股份有限公司 | Method for separating cracked carbon 5 fraction by using one section extraction of reaction rectification |
| CN101423450B (en) * | 2007-10-31 | 2012-11-21 | 中国石油化工股份有限公司 | Method for separating carbon 5 fraction by NMP method and one-stage extraction and rectification |
| CN101450887B (en) * | 2007-12-07 | 2011-08-03 | 中国石油化工股份有限公司 | Method for separating and cracking cyclopentadienyl from carbon 5 fraction |
| CN101798255B (en) * | 2009-02-11 | 2013-04-24 | 中国石油天然气股份有限公司 | Method for separating diolefin from petroleum cracking carbon five fraction by acetonitrile |
| CN102234543A (en) * | 2010-04-20 | 2011-11-09 | 中国石油化工股份有限公司 | Method for prolonging service life of pyrolysis gas mixed phase hydrogenation catalyst |
| CN103183579B (en) * | 2011-12-28 | 2015-05-13 | 中国石油化工集团公司 | Separation system and separation method for piperylene and dicyclopentadiene |
| CN103864555B (en) * | 2012-12-12 | 2016-09-14 | 中国石油化工股份有限公司 | A kind of method separating C5 fraction |
| 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 |
| CN104058915B (en) * | 2013-03-20 | 2016-09-21 | 中国石油化工股份有限公司 | The method of hydrogenation distillation separation cracking C 5 fraction |
| AR101431A1 (en) * | 2013-06-05 | 2016-12-21 | Gtc Technology Us Llc | PROCESS AND APPARATUS TO SEPARATE DI-OLEFINS C₅ FROM PIRÓISIS NAFTAS |
| CN104761428A (en) * | 2014-01-03 | 2015-07-08 | 抚顺伊科思新材料有限公司 | Prepolymerization method for separating cracking C5 |
| CN105481631B (en) * | 2014-09-19 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of process for purification of pentadiene |
| SG11201706157TA (en) * | 2015-01-29 | 2017-08-30 | Lummus Technology Inc | Producing c5 olefins from steam cracker c5 feeds |
| CN106588553A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Method for removing 2-butyne by conducting selective hydrogenation on C5 fractions |
| EP3371131A4 (en) * | 2015-11-04 | 2018-10-17 | ExxonMobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
| CN108017500A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | The removal methods of pentone in C5 fraction |
| CN108017503A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of 2- butine and pentone in removing C5 fraction |
| SG11201907708QA (en) * | 2017-03-08 | 2019-09-27 | Zeon Corp | Hydrocarbon production method and production apparatus |
| CN109721452A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The removal methods of pentone in C5 fraction |
| CN114276834B (en) * | 2021-12-24 | 2023-03-14 | 宁波甬华树脂有限公司 | Preparation method of refined C5 fraction |
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