CN104109071B - The method of cracked C 5 fraction propylene - Google Patents
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Abstract
A kind of method that the present invention relates to cracked C 5 fraction propylene, the problem that mainly present in solution prior art, propylene weight yield is low.The present invention is by a kind of method using cracked C 5 fraction propylene, with cracking c_5 and ethylene as raw material, comprise the following steps: cracked C 5 fraction is sent into decylization pentadiene unit, selective hydrogenation reaction device is sent in carbon five logistics of the removing cyclopentadiene obtained after Reaction Separation, under conditions of hydrogenation catalyst and hydrogen exist, diolefin selective hydrogenation is monoolefine, monoolefine carbon five material obtained and ethylene mixing, then through sorbent treatment, after the absorption obtained, logistics and disproportionation catalyst haptoreaction obtain containing product propylene, unreacted ethylene and the logistics of carbon five, the technical scheme of propylene is obtained after separation, preferably solve this problem, can be used for the commercial production of cracked C 5 fraction propylene.
Description
Technical field
A kind of method that the present invention relates to cracked C 5 fraction propylene.
Background technology
The present invention relates to a kind of method comprehensively utilizing cracked, C 5 fraction, specifically, the present invention relates to a kind of method comprehensively utilizing cracked, C 5 fraction ethylene, propylene.
By-product about 15～the C 5 fraction of 20% in petroleum cracking process of producing ethylene.Continuous along with ethylene unit expands, improving constantly of production capacity, and the cracked, C 5 fraction of by-product is also on the increase, and the most synthetically effectively utilizing this part fraction is current each Petroleum & Petrochemical Enterprises question of common concern.And along with being gradually reduced of benefit room for promotion of ethylene unit, also force each enterprise sight to be turned in the comprehensive utilization of this part fraction rather than only reside within and do fuel and use.
The component that cracked, C 5 fraction is close by more than 20 kinds of boiling points, be easily formed azeotropic mixture to each other forms, its constituent classification is summarized as: the content of isoprene, pentadiene and cyclopentadiene (dicyclopentadiene) is respectively about 20%, the content of branched monoolefins and straight chain mono-olefins is respectively about near 15～20%, possibly together with a small amount of alkane, alkene and carbon four thereof, carbon six component.But isolating the C 5 diene that comprehensive utilization value is higher from cracked, C 5 fraction, need to take extraction rectifying method, its complex process, equipment investment is many, is the approach of people's avoidance as far as possible.
On the other hand, the demand of propylene is greatly increased in the market, occurs in that propylene breach, needs to find various method and solves this problem.The most at home and abroad studying a ardentest method is that olefin(e) disproportionation converts ethylene, the method for propylene, the most all has numerous patents application.But alkene converts and mostly uses c4 fraction, cracked, C 5 fraction is seldom used to do raw material.Analyzing its reason mainly has be in cracked, C 5 fraction containing substantial amounts of diolefin at two: one, directly carries out alkene conversion and can produce burnt matter, causes catalysqt deactivation；Two is the branched monoolefins in cracked, C 5 fraction containing 10-20%, and this part monoolefine can not be converted into ethylene, propylene.It is, thus, sought for cracked, C 5 fraction is converted into the raw material that alkene converts by a kind of suitable method, could be that the real cracked, C 5 fraction of comprehensive utilization efficiently finds an effective method.
It is known that, the a considerable amount of C5 fraction of by-product in petroleum hydrocarbon thermal cracking process of producing ethylene, Main Components be 3-methyl-1-butene, isopentane, 1,4-pentadiene, valerylene, 1-amylene, 2-methyl-1-butene alkene, pentane, isoprene, trans-2-amylene, cis-2-amylene, 2-methyl-2-butene, trans-1,3-pentadiene, cyclopentadiene, cis-1,3-pentadiene, cyclopentenes, Pentamethylene. and a small amount of carbon four and carbon six fraction.At present, the utilization of cracking c_5 mainly has a following two aspect:
One is the separation and purification of one pack system, from cracking c_5, i.e. isolate the alkadienes such as isoprene, cyclopentadiene, pentadiene as industrial chemicals, owing to cracking c_5 each component boiling point is close, it is difficult to separate by conventional method, the general method using chemistry or extractive distillation in addition separation and purification, therefore, the investment of these methods is big, cost is high；Two is the utilization of blending ingredients, hydrofinishing therein is to use most technology (such as CN1145891), C5 fraction after hydrogenation is containing pentane, isopentane and Pentamethylene., can be as the blend component of gasoline or the raw material of cracking of ethylene, this method technique is simple but hydrogen consumption is big, and C5 fraction is owing to containing substantial amounts of isopentane, the yield of ethene therefore obtained as cracking stock cracking is relatively low；The technique that USP5352846 discloses the comprehensive utilization of a kind of cracking c_5, it is characterized in that first cracking c_5 is carried out hydrogenation and isomery processes, it is then fed into methyltertiarvbutyl ether reactor and carries out reaction generation tert amyl methyl ether(TAME) (TAME) with methanol, then obtain the fraction rich in pentane and the fraction rich in TAME by distillation.
The active component of described selective hydrogenation catalyst be the metal of VIII, preferably active component be palladium, active component both can be used alone, it is also possible to is used in conjunction with other modifying agent that it is known in the art that especially VIB, IB race；The carrier of catalyst is aluminium oxide, silicon oxide or its mixture, preferential oxidation aluminum；Metal Palladium content in the catalyst is 0.1～1% (weight), and the specific surface area of catalyst is 5～200cm2/g；In described fixed bed, the selective hydrogenation catalyst of filling can be column, spherical, trilobes etc., in described catalytic distillation tower, the selective hydrogenation catalyst of filling can be column, spherical, trilobes, preferably itself there is fractionation and catalytic action bifunctional filler shape
CN1242410 discloses the preparation method of double-functional packing shape catalyst, and carries out, with catalytic distillation reactor, the method that C5 fraction selects hydrogenation.
Olefin disproportionation is the conversion process of a kind of alkene.By under the effect of transition metal compound catalyst, the fracture of C=C double bond and re-forming in alkene, thus obtain new olefin product.
Utilize the disproportionation of amylene, can be by relative surplus, C that added value is relatively low5Olefin feedstock is converted into high added value propylene product, and olefin disproportionation catalyst is the key realizing this technique.
US5898091 and US6166279 reports C4、C5Olefin treated.Wherein during preparing propylene through olefin disproportionation, the catalyst used is Re2O7/Al2O3, reactor is moving bed.
US5300718 reports the technique of butene-2 and ethylene generation dismutation reaction propylene, and the catalyst of use is MgO and WO3/SiO2 mixed bed.
CN102372573A reports a kind of carbon four and the method for ethylene propylene after ether, the problem that mainly present in solution conventional art, target product selectivity is low, raw material availability is the highest.
CN1182069A discloses the method preparing propylene and 1-butylene and the method preparing propylene, 2-amylene and ethylene reaction is made in the presence of being included in metathesis catalyst, above-mentioned catalyst contains the VIth b at least one periodic table of elements, VII b or the compound of VIII group 4 transition metal, including: a) in the presence of metathesis catalyst, 1-butylene is made to react with 2-butylene, generate propylene and 2-amylene, b) propylene and the 2-amylene of generation are then separated, c) in the presence of metathesis catalyst, 2-amylene is made to react with ethylene, generate propylene and 1-butylene, d) propylene generated and 1-butylene are separated, e) 1-butylene of generation is sent back in step a).
CN1852878A discloses the processing method of a kind of C4 olefin stream for maximum production of propylene, in order to be supplied with maximum production of propylene in limited time in the outside of ethylene, before any isobutylene removal step and in the case of without any ethylene, first the C 4 fraction from hydrocarbon cracking processes is carried out automatic double decomposition.This is conducive to generating propylene and the reaction of amylene class.Then remove the ethylene generated and propylene, leave C4 and the stream of more heavy constituent.Then removing C5 and more heavy constituent, leave 1-butylene, 2-butylene, isobutene. and the different and mixture of normal butane class.The most preferably remove isobutene. by catalytic distillation hydrogenation isomerization Deisobutenizer.C4 stream without isobutene. then should mix with product ethylene and the required any fresh external ethylene removed from automatic metathesis product, and carry out conventional metathesis, generate other propylene.
CN1810743A discloses a kind of method ethylene utilizing cracked, C 5 fraction and the method for propylene, carbon five material after being converted by alkene or after alkene conversion etherificate again is hydrogenated with entirely, generate pentane and isopentane, main pyrolysis furnace cracking ethylene preparation, propylene can be sent as cracking stock, pentane and isopentane can also be separated into sell as product
When reacting for cracked C 5 fraction propylene, there is the problem that propylene weight yield is low in the method in document above.
Summary of the invention
The technical problem to be solved is the problem that propylene weight yield is low present in prior art, it is provided that a kind of method of new cracked C 5 fraction propylene.The method, when cracked C 5 fraction propylene reacts, has the advantage that propylene weight yield is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of method of cracked C 5 fraction propylene, with cracking c_5 and ethylene as raw material, comprise the following steps: cracked C 5 fraction is sent into decylization pentadiene unit by (a), after separation, obtain removing carbon five logistics I of cyclopentadiene;B carbon five logistics I is sent into selective hydrogenation reaction device by (), under conditions of hydrogenation catalyst and hydrogen exist, it is monoolefine by the diolefin selective hydrogenation including isoprene and pentadiene therein, obtains comprising monoolefine carbon five logistics II of tertiary amylene, 1-amylene, 2-amylene；Logistics III is obtained through sorbent treatment after (c) carbon five logistics II and fresh ethylene mixing；D () logistics III and disproportionation catalyst haptoreaction obtain containing product propylene, unreacted ethylene and carbon five logistics IV；E () logistics IV enters de-ethylene column, tower top obtains ethylene, and tower reactor obtains the logistics V containing propylene, carbon four and carbon five；F () logistics V enters depropenizer, tower top obtains product propylene, and tower reactor obtains carbon four and carbon five.
In technique scheme, the preferred version of decylization pentadiene unit includes polymer reactor and distillation column, after cracked C 5 fraction enters polymer reactor, make cyclopentadiene from being polymerized to dicyclopentadiene, reacting rear material enters back into distillation column, discharging at the bottom of described distillation column tower is thick dicyclopentadiene, and tower top discharging is carbon five logistics of removing cyclopentadiene；The preferred operating condition of polymer reactor is reaction pressure 0.2～3.0MPa, reaction temperature 50～150 DEG C, weight space velocity 0.1～1.0h-1, the time of staying is 30～120 minutes；The de-dicyclopentadiene tower of distillation column, number of theoretical plate is 15～60 pieces, and reflux ratio is 0.5～10, tower top pressure is 0.06～0.5MPa, and tower reactor pressure is 0.08～0.6MPa, and tower top temperature is 20～80 DEG C, bottom temperature is 80～130 DEG C, and feed entrance point is at the middle part of tower；The preferred version of selective hydrogenation reaction device is fixed bed reactors, and preferred operating condition is reaction pressure 0.1～5Mpa, reaction temperature 30～130 DEG C, the mol ratio 1～10 of hydrogen and alkadienes, liquid phase volume air speed 1～8h-1；The preferred version using catalyst activity component in selective hydrogenation reaction device is nickel, cobalt and/or palladium, the preferred version of carrier is aluminium oxide or silicon oxide, the more preferably scope of reaction temperature is 50～120 DEG C, the more preferably scope of reaction pressure is 0.5～3.0MPa, the more preferably scope of the mol ratio of hydrogen and diolefin is 1～4, and the more preferably scope of liquid phase volume air speed is 1～8h-1；Adsorbent described in step (c) is seated in adsorption tower, and preferred version is for include following components in terms of adsorbent weight number: 1) 0～20 part of at least one metal in Li, Cs, Fe, Cu, Hg, Co, Cd, Au, Au or Ag；2) 80～100 parts of at least one molecular sieves in A type, X-type, Y type, modenite, ZSM type zeolite or beta molecular sieve；The preferred version of disproportionation catalyst described in step (d) is for including following components in terms of parts by weight: 1) 2～20 parts of tungsten oxides, molybdenum oxide or rheium oxide；2) 80～98 parts of one in MCM series, SBA series, HMS series or MSU Series Molecules sieve；Preferably operating condition is: reaction temperature 250 ~ 350 DEG C, reaction pressure in terms of absolute pressure 1～4MPa, the weight space velocity 1～10h of carbon five logistics-1；Isomerization reactor reaction first sent into by monoolefine carbon five material II that step (b) obtains, and obtains entering back into step (c) reaction rich in the logistics of 2-methyl-2-butene and 2-amylene；In isomerization reactor the preferred version of isomerization catalyst be specific surface area be 200～500m2The alkaline earth oxide of/g, the preferred scope of reaction temperature is 200～400 DEG C, and the reaction pressure preferred scope in terms of absolute pressure is 0.1～4MPa, and the preferred scope of weight space velocity is 1～50 hour-1；The preferred version of de-ethylene column operating condition is: theoretical cam curve 100～120 pieces, tower pressure 1.8～2.2MPa, tower top temperature-35～-30 DEG C, bottom temperature-10～-5 DEG C；The preferred version of the operating condition of depropenizer is: theoretical cam curve 160～180 pieces, tower pressure 1.7～1.9MPa, tower top temperature 40～45 DEG C, bottom temperature 50～55 DEG C.
Etherificate unit removing tertiary amylene can first be sent into by carbon five material II, wherein the 2-methyl-2-butene in tertiary amylene and 2-methyl-1-butene alkene and methanol reaction generate tert amyl methyl ether(TAME), described etherificate unit includes methyltertiarvbutyl ether reactor and rectifying column, and after etherificate, rectification obtains removing carbon five material of tertiary amylene；It is sent to adsorption tower and olefin reactor again, in described methyltertiarvbutyl ether reactor, catalyst for etherification used is acid-exchange resin, reaction bed is fixed bed, etherification temperature is 40～90 DEG C, etherificate pressure is 0.5～3.0MPa, and material liquid phase volume air speed in methyltertiarvbutyl ether reactor is 0.4～8h-1, tertiary amylene and the mol ratio of methanol in material are 1: 1～1.3；The number of theoretical plate of the rectifying column of described etherificate unit is 20～40 pieces, and tower top temperature is 20～80 DEG C, and tower top pressure is 0.06～0.5MPa, and bottom temperature is 50～110 DEG C, and feed entrance point is at the middle part of tower.
The preparation method of isomerization catalyst, in air or the atmosphere inert to catalyst, under the conditions of sintering temperature is 300～1200 DEG C, by alkali salt roasting 2～24 hours, obtaining specific surface area was 200～500m2The alkaline earth oxide of/g.At least one in the acylate or inorganic acid salt of alkaline-earth metal of alkali salt preferred version, more preferably scheme is selected from the acylate of alkaline-earth metal.Isomerization catalyst can select spin, tabletting, is squeezed into the method molding such as bar, can add water, sesbania powder etc. in forming process.
The preparation method of selective hydrogenation catalyst is: the solution impregnation being made into the desired amount of nickel, cobalt and/or palladium compound by carrier, and carrier drying after dipping, in atmosphere 350～500 DEG C of roastings i.e. obtain oxidative catalyst finished product.Repeatable above-mentioned steps prepares required nickel, cobalt and/or palladium content.Finished catalyst needs to use hydrogen reducing before use.
The solid absorbent prepared is seated in ADSORPTION IN A FIXED BED tower, at N2In atmosphere, anticipate at 200～350 DEG C 4～12 hours, be cooled to room temperature, preferably pretreatment temperature is 250～300 DEG C, and the preferred process time is 6～10 hours, and the operation pressure of adsorption tower is 2.0～4.0MPa, temperature is 20～60 DEG C, and the weight space velocity of raw material is 1～10 hour-1。
The preparation method of adsorbent comprises the following steps: 1) aequum being selected from metal ion is Li+、Cs+、Fe2+、Cu2 +、Hg2+、Co2+、Cd2+、Au3+、Au2+Or Ag+In oxalates, citrate or acetate at least one be made into the solution that a kind of mass concentration is 1～50%；2) at 20～180 DEG C, with above-mentioned metal salt solution, molecular sieve is carried out ion and exchange 1～120h；3) by the desired amount of above-mentioned Ion exchange-Size exclusion and binding agent mixed-forming, dry or be dried, then roasting at 300～700 DEG C, preparing formation solid adsorbent；4) by the desired amount of above-mentioned Ion exchange-Size exclusion and binding agent mixed-forming, dry or be dried, then roasting at 300～700 DEG C, preparing formation solid adsorbent.
Olefin disproportionation catalyst inactivation is to hinder its commercial Application greatest problem, causes the reason of catalysqt deactivation to have: in reactant, in impurities, polar substances (such as water etc.) can make catalyst poisoning；In course of reaction, transiting metal oxidation state changes；A large amount of poly state byproduct of reaction has been adsorbed at catalyst surface；Concentration reduction of metal carbene etc. in course of reaction.Wherein the concentration of metal carbene is reduced to topmost deactivation cause.So needing reaction raw materials is carried out purified treatment before disproportionation reactor, exchange the duct to molecular sieve by the ion of different radii to modify, remove for specific oxygenatedchemicals impurity, purify the degree of depth and be significantly improved, also improve adsorptive selectivity simultaneously.The metal cation charge density exchanged due to ion used is different, the electrostatic field distribution in molecular sieve is changed after ion exchange, improve the selectivity of adsorbent so that the adsorption capacity of the materials such as alkene and heat of adsorption are reduced while absorption oxygenatedchemicals impurity by molecular sieve
The method of the present invention can obtain dicyclopentadiene product.Dicyclopentadiene product at home and abroad has good market, is important fine chemicals raw material, and can be as the raw material of high-quality resin.The method of the present invention needs less amounts of hydrogen.The present invention uses selective hydrogenation technology that the diolefin in carbon five material of removing dicyclopentadiene is hydrogenated to monoolefine, straight chain mono-olefins the most therein can be converted into ethylene, propylene in olefin process, compare as cracking stock with full hydrogenation, save a large amount of hydrogen, even and if branched monoolefins is hydrogenated with entirely, ethylene, propylene can not be cracked into.
The method of the present invention can be that comprehensive utilization cracked, C 5 fraction, the economic benefit of raising ethylene unit and social benefit provide an approach the most effective.The present invention adds adsorption tower by using before disproportionation reactor, can effectively remove the impurity in carbon five logistics, improve the activity of disproportionation catalyst, thus improve the weight yield of target product propylene, compare the reaction not adding adsorption tower, and propene yield can improve 6%；Using ethylene as raw material simultaneously, can be effectively improved the yield of propylene, compare the reaction not using ethylene as raw material, propene yield can improve 6%, achieves preferable technique effect.
Accompanying drawing explanation
Fig. 1 is the techniqueflow chart of the present invention of the cracked C 5 fraction for producing propylene.
In Fig. 1,1 is cracked C 5 fraction, the cyclopentadiene that 2 is removing, 3 is carbon five logistics without cyclopentadiene, and 4 is monoolefine carbon five logistics, 5 fresh ethylene, 6 is mixing raw material, and 7 is the impurity removed, and 8 is material feed stream, 9 is product, 10 is ethylene tail gas, and 11 is propylene product, and 12 is carbon four by-product, 13 is cyclic carbon five, 14 is cyclic ethylene, and 21 is decylization pentadiene unit, and 22 is selective hydrogenation reaction device, 23 is adsorption tower, 24 is disproportionation reactor, and 25 is de-ethylene column, and 26 is depropenizer.
With reference to Fig. 1, the method for the present invention is briefly stated in flow charts.
nullAs shown in Figure 1，Carbon five logistics 3 without cyclopentadiene is obtained after the cracked C 5 fraction 1 cyclopentadiene in decylization pentadiene unit removes raw material，Logistics 3 and selective hydrogenation catalyst haptoreaction obtain monoolefine carbon five logistics 4，Mixing raw material 6 is formed after fresh ethylene 5 mixing outside material 4 and battery limit (BL)，Mixing raw material removes the impurity 7 in raw material after the sorbent treatment in adsorption tower 23，Impurity includes water、Alcohol、Ether isopolarity material，Material 8 after process and the disproportionation catalyst haptoreaction in disproportionation reactor 24，Reaction obtains target product propylene、Unreacted ethylene and C_5 olefins，Product 9 is through de-ethylene column，Most ethylene that tower top obtains reuse as reaction raw materials with the form of cyclic ethylene 14，Remaining is with ethylene exhaust emissions，The component that tower reactor obtains enters depropenizer and processes，Tower top obtains polymerization-grade propylene，The carbon five that tower reactor obtains mainly reuses as reaction raw materials with the form of cyclic carbon 5 13，Remaining carbon four side-product 12 can use as liquefied gas.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Technological process as shown in Figure 1, the component of cracked C 5 fraction is as shown in table 1, the C5 fraction without cyclopentadiene is obtained after the cyclopentadiene in decylization pentadiene unit removing raw material, the C5 fraction component of removing dicyclopentadiene is as shown in table 1, monoolefine carbon five logistics is obtained again with selective hydrogenation catalyst haptoreaction, its component is as shown in table 1, mixing raw material is formed after fresh ethylene mixing outside monoolefine carbon five logistics and battery limit (BL), mixing raw material removes the impurity in raw material after the sorbent treatment in adsorption tower, material after process and the disproportionation catalyst haptoreaction in disproportionation reactor, reaction obtains target product propylene, unreacted ethylene and C_5 olefins, product separates with depropenizer through de-ethylene column, obtain carbon five and carbon four logistics of polymerization-grade propylene and reaction capable of circulation.
The component of selective hydrogenation catalyst, adsorbent and disproportionation catalyst is as shown in table 2, the operating condition of decylization pentadiene unit is as shown in table 3, the operating condition of selective hydrogenation reaction device and disproportionation reactor is as shown in table 4, the operating condition of de-ethylene column and depropenizer is as shown in table 5, and reaction result is as shown in table 6.
Table 1
[embodiment 2～6]
React with step by each condition of embodiment 1, simply change different operating parameters, the component of selective hydrogenation catalyst, adsorbent and disproportionation catalyst is as shown in table 2, the operating condition of decylization pentadiene unit is as shown in table 3, the operating condition of selective hydrogenation reaction device and disproportionation reactor is as shown in table 4, the operating condition of de-ethylene column and depropenizer is as shown in table 5, and reaction result is as shown in table 6.
[embodiment 7]
Technological process as shown in Figure 1, simply with the addition of isomerization reactor between 22 and 23.nullThe component of cracked C 5 fraction is as shown in table 1，Cracked C 5 fraction obtains the C5 fraction without cyclopentadiene after the cyclopentadiene in decylization pentadiene unit removing raw material，The C5 fraction component of removing dicyclopentadiene is as shown in table 1，Monoolefine carbon five logistics is obtained again with selective hydrogenation catalyst haptoreaction，Its component is as shown in table 1，Isomerization reactor is first sent in monoolefine carbon five logistics，Reaction obtains rich in 2-methyl-2-butene and the logistics of 2-amylene，This logistics again with battery limit (BL) outside fresh ethylene mixing after formed mixing raw material，Mixing raw material removes the impurity in raw material after the sorbent treatment in adsorption tower，Material after process and the disproportionation catalyst haptoreaction in disproportionation reactor，Reaction obtains target product propylene、Unreacted ethylene and C_5 olefins，Product separates with depropenizer through de-ethylene column，Obtain carbon five and carbon four logistics of polymerization-grade propylene and reaction capable of circulation.Wherein isomerization catalyst be specific surface be 300m2The magnesium oxide of/g, reaction temperature is 300 DEG C, and reaction pressure is calculated as 3MPa with absolute pressure, and weight space velocity is 4 hours-1。
The component of selective hydrogenation catalyst, adsorbent and disproportionation catalyst is same as in Example 1, and the operating condition of decylization pentadiene unit, selective hydrogenation reaction device, disproportionation reactor, de-ethylene column and depropenizer is with embodiment 1, and reaction result is as shown in table 7.
[embodiment 8～10]
With the reaction process of embodiment 7, simply isomerization catalyst is different with the operating condition of isomerization reactor, as shown in table 6.
The component of selective hydrogenation catalyst, adsorbent and disproportionation catalyst is same as in Example 1, and the operating condition of decylization pentadiene unit, selective hydrogenation reaction device, disproportionation reactor, de-ethylene column and depropenizer is with embodiment 1.
[comparative example 1]
Technological process as shown in Figure 1, does not the most process through adsorption tower.The component of selective hydrogenation catalyst and disproportionation catalyst is same as in Example 1, and the operating condition of decylization pentadiene unit, selective hydrogenation reaction device, disproportionation reactor, de-ethylene column and depropenizer is with embodiment 1, and reaction result is as shown in table 7.
[comparative example 2]
Technological process as shown in Figure 1, raw material only has monoolefine carbon five logistics, does not has fresh ethylene.The component of selective hydrogenation catalyst, adsorbent and disproportionation catalyst is same as in Example 3, and the operating condition of decylization pentadiene unit, selective hydrogenation reaction device, disproportionation reactor, de-ethylene column and depropenizer is with embodiment 3, and reaction result is as shown in table 7.
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Note: weight of material percentage ratio is on the basis of cracked C 5 fraction.
Claims (6)
1. a method for cracked C 5 fraction propylene, with cracking c_5 and ethylene as raw material, comprises the following steps:
A cracked C 5 fraction is sent into decylization pentadiene unit by (), obtain removing carbon five logistics I of cyclopentadiene after separation；
B carbon five logistics I is sent into selective hydrogenation reaction device by (), under conditions of hydrogenation catalyst and hydrogen exist, it is monoolefine by the diolefin selective hydrogenation including isoprene and pentadiene therein, obtains comprising monoolefine carbon five logistics II of tertiary amylene, 1-amylene, 2-amylene；
Logistics III is obtained through sorbent treatment after (c) carbon five logistics II and fresh ethylene mixing；
D () logistics III and disproportionation catalyst haptoreaction, obtain containing product propylene, unreacted ethylene and carbon five logistics IV；
E () logistics IV enters de-ethylene column, tower top obtains ethylene, and tower reactor obtains the logistics V containing propylene, carbon four and carbon five；
F () logistics V enters depropenizer, tower top obtains product propylene, and tower reactor obtains carbon four and carbon five；
Adsorbent described in step (c) is in terms of parts by weight, including following components: 1) 80～100 parts of at least one molecular sieves in A type, Y type, modenite, ZSM type zeolite or beta molecular sieve；And it is loaded in thereon: 2) 0～20 part of at least one metal in Li, Cs, Fe, Cu, Hg, Co, Cd, Au, Au or Ag；
Decylization pentadiene unit includes polymer reactor and distillation column, after cracked C 5 fraction enters polymer reactor, cyclopentadiene is from being polymerized to dicyclopentadiene, reacting rear material enters back into distillation column, discharging at the bottom of described distillation column tower is thick dicyclopentadiene, and tower top discharging is carbon five logistics of removing cyclopentadiene；
The operating condition of described polymer reactor is reaction pressure 0.2～3.0MPa, reaction temperature 50～150 DEG C, weight space velocity 0.1～1.0h-1, the time of staying is 30～120 minutes；Described distillation column is de-dicyclopentadiene tower, and number of theoretical plate is 15～60 pieces, and reflux ratio is 0.5～10, and tower top pressure is 0.06～0.5MPa, and tower reactor pressure is 0.08～0.6MPa, and tower top temperature is 20～80 DEG C, and bottom temperature is 80～130 DEG C；Described selective hydrogenation reaction device is fixed bed reactors, and operating condition is reaction pressure 0.1～5MPa, reaction temperature 30～130 DEG C, the mol ratio 1～10 of hydrogen and alkadienes, liquid phase volume air speed 1～8h-1。
The method of cracked C 5 fraction propylene the most according to claim 1, it is characterized in that the catalyst activity component used in described selective hydrogenation reaction device is nickel, cobalt and/or palladium, carrier is aluminium oxide or silicon oxide, reaction temperature is 50～120 DEG C, reaction pressure is 0.5～3.0MPa, the mol ratio of hydrogen and diolefin is 1～4, and liquid phase volume air speed is 1～5h-1。
The method of cracked C 5 fraction propylene the most according to claim 1, it is characterised in that described in step (d), disproportionation catalyst is in terms of parts by weight, including following components: 1) 2～20 parts of tungsten oxides, molybdenum oxide or rheium oxide；2) 80～98 parts of one in MCM series, SBA series, HMS series or MSU Series Molecules sieve；Operating condition is: reaction temperature 250～350 DEG C, reaction pressure in terms of absolute pressure 1～4MPa, the weight space velocity 1～10h of carbon five logistics IV-1。
The method of cracked C 5 fraction propylene the most according to claim 1, it is characterized in that isomerization reactor reaction first sent into by monoolefine carbon five material II that step (b) obtains, the logistics rich in 2-methyl-2-butene and 2-amylene obtained enters back into step (c).
The method of cracked C 5 fraction propylene the most according to claim 4, it is characterised in that in isomerization reactor isomerization catalyst be specific surface area be 200～500m2The alkaline earth oxide of/g, reaction temperature is 200～400 DEG C, and reaction pressure is calculated as 0.1～4MPa with absolute pressure, and weight space velocity is 1～50 hour-1。
The method of cracked C 5 fraction propylene the most according to claim 1, it is characterised in that the operating condition of de-ethylene column: theoretical cam curve 100～120 pieces, tower pressure 1.8～2.2MPa, tower top temperature-35～-30 DEG C, bottom temperature-10～-5 DEG C；The operating condition of depropenizer: theoretical cam curve 160～180 pieces, tower pressure 1.7～1.9MPa, tower top temperature 40～45 DEG C, bottom temperature 50～55 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| MY174443A (en) * | 2015-01-29 | 2020-04-19 | Lummus Technology Inc | Producing c5 olefins from steam cracker c5 feeds |
| CN107970927B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating |
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| CN1810743A (en) * | 2005-01-28 | 2006-08-02 | 中国石油化工股份有限公司 | Method of utilizing cracked, C5 fraction |
| US20090105512A1 (en) * | 2005-08-15 | 2009-04-23 | China Petroleum & Chemical Corporation | Process for producing lower olefins under negative pressure |
| CN102372573A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing propylene by using etherified C4 and ethylene |
| CN103030507A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
| CN103030508A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
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| CN1810743A (en) * | 2005-01-28 | 2006-08-02 | 中国石油化工股份有限公司 | Method of utilizing cracked, C5 fraction |
| US20090105512A1 (en) * | 2005-08-15 | 2009-04-23 | China Petroleum & Chemical Corporation | Process for producing lower olefins under negative pressure |
| CN102372573A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing propylene by using etherified C4 and ethylene |
| CN103030507A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
| CN103030508A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
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