CN105585401A - Method for producing propylene - Google Patents
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Abstract
The invention relates to a method for producing propylene. The invention mainly aims at solving a problem of low propylene weight yield in prior arts. According to the propylene production method, cracked C5, C4 and ethylene are adopted as raw materials. The method comprises the following steps: a cracked C5 fraction is delivered into a de-cyclopentadiene unit; after reaction separation, a C5 material flow with cyclopentadiene removed is delivered into a selective hydrogenation reactor; under the existences of a hydrogenation catalyst and hydrogen, diolefin is selectively hydrogenated into monoolefine; the obtained monoolefine C5, C4 material and ethylene are mixed; the mixture is treated with an adsorbent; a material flow obtained after adsorption is subjected to a contact reaction with an isomerization catalyst and a disproportionation catalyst, such that a material flow containing a product propylene and unreacted ethylene, C5 and C4 is obtained; and propylene is obtained after separation. With the method, the problem is well solved. The method can be used in industrial production of propylene.
Description
Technical field
The present invention relates to a kind of method of producing propylene.
Background technology
The present invention relates to a kind of method that fully utilizes cracked, C 5 fraction, specifically, the present invention relates to a kind of comprehensive utilizationThe method of cracked, C 5 fraction ethene processed, propylene.
The C 5 fraction of by-product approximately 15～20% in petroleum cracking process of producing ethylene. Along with the continuous expansion of ethylene unit, rawImproving constantly of production capacity power, the cracked, C 5 fraction of by-product is also on the increase, and how synthetically to effectively utilize this part fractionIt is current each Petroleum & Petrochemical Enterprises question of common concern. And along with dwindling gradually of the benefit room for promotion of ethylene unit,Also force each enterprise that sight is turned in the comprehensive utilization of this part fraction, instead of only rest on do fuel use on.
Cracked, C 5 fraction is made up of more than 20 kinds of boiling point components close, that easily form to each other azeotropic mixture, by its constituent classificationBe summarized as: the content of isoprene, pentadiene and cyclopentadiene (dicyclopentadiene) is respectively in 20% left and right side chain monoeneThe content difference of hydrocarbon and straight chain mono-olefins near 15～20%, also contains a small amount of alkane, alkene and carbon four thereof, carbon greatlySix components. But from cracked, C 5 fraction, isolate the C 5 diene that comprehensive utilization value is higher, need to take extraction essenceHeat up in a steamer method, its complex process, equipment investment is many, is the approach that people avoid as far as possible.
On the other hand, the demand of propylene increases greatly in the market, has occurred propylene breach, need to find the whole bag of tricksAddress this problem. Wherein at home and abroad a comparatively ardent method of research is the method that olefin(e) disproportionation transforms ethene, propylene,All there are at present many sections of patent applications at home and abroad. But alkene transforms and mostly adopts c4 fraction, seldom adopts cracking c_5 to heat up in a steamerPart is done raw material. Analyze its reason and mainly contain two: one, in cracked, C 5 fraction, contain a large amount of diolefins, directly carry out alkeneTransform and can produce burnt matter, cause catalysqt deactivation; The 2nd, in cracked, C 5 fraction, contain the side chain monoolefine of 10-20%, thisPart monoolefine can not be converted into ethene, propylene. Therefore, need to find a kind of suitable method transforms cracked, C 5 fractionFor the raw material that alkene transforms, could find an effective method for really fully utilizing efficiently cracked, C 5 fraction.
As everyone knows, a considerable amount of C5 fractions of by-product in petroleum hydrocarbon thermal cracking process of producing ethylene, Main Components is 3-methyl-1-butylene, isopentane, Isosorbide-5-Nitrae-pentadiene, valerylene, 1-amylene, 2-methyl-1-butene alkene, pentane, isoprene, anti--2-amylene, cis-2-amylene, 2-methyl-2-butene, trans-1,3-pentadiene, cyclopentadiene, cis-1,3-pentadiene, ring pentaAlkene, pentamethylene and a small amount of carbon four and carbon six cuts. At present, the utilization of cracking c_5 mainly contains following two aspects:
The one, the separation and purification of one pack system is isolated isoprene, cyclopentadiene, pentadiene etc. two from cracking c_5Alkene, as industrial chemicals, because the each component boiling point of cracking c_5 is close, is difficult to separate by conventional method general employingizationLearn or in addition separation and purification of the method for extractive distillation, therefore, these methods investments are large, cost is high; The 2nd, the profit of blending ingredientsWith, hydrofinishing is wherein to adopt maximum technology (as CN1145891), the C5 fraction after hydrogenation is containing pentane, differentPentane and pentamethylene, can be used as the blend component of gasoline or the raw material of cracking of ethylene, the simple but hydrogen consumption of this method techniqueGreatly, and C5 fraction is owing to containing a large amount of isopentane, and the yield of ethene that therefore cracking obtains as cracking stock is lower;USP5352846 discloses a kind of technique of cracking c_5 comprehensive utilization, it is characterized in that first cracking c_5 being carried out to hydrogenation and differentStructure processing, then sends into methyltertiarvbutyl ether reactor and reacts generation tert amyl methyl ether(TAME) (TAME) with methyl alcohol, then by distillationAcquisition is rich in the cut of pentane and is rich in the cut of TAME.
The active component of described selective hydrogenation catalyst is the metal of VIII family, and preferably active component is palladium, and active component both canTo use separately, also can be well known in the art with other, especially the modifier of VIB, IB family uses jointly; CatalystCarrier be aluminium oxide, silica or its mixture, preferential oxidation aluminium; The content of Metal Palladium in catalyst is 0.1～1%(weight), the specific area of catalyst is 5～200cm2/ g; The selective hydrogenation catalyst loading in described fixed bed can beColumn, spherical, clover shape etc., the selective hydrogenation catalyst loading in described catalytic distillation tower can for column, spherical,Clover shape, is preferably and itself has fractionation and the bifunctional filler shape of catalytic action,
CN1242410 discloses the preparation method of double-functional packing shape catalyst, and carries out carbon five with catalytic distillation reactor and heat up in a steamerThe method of component selections hydrogenation.
Olefin disproportionation is a kind of conversion of olefines process. By under the effect of transition metal compound catalyst, alkeneThe fracture of the two keys of middle C=C and again formation, thus new olefin product obtained.
Utilize the disproportionation of amylene, can be by C relative surplus, that added value is lower5Olefin feedstock is converted into high added valuePropylene product, and olefin disproportionation catalyst is the key that realizes this technique.
US5300718 has reported the technique of butene-2 and ethene generation disproportionated reaction propylene processed, and the catalyst of use is MgOWith WO3/SiO2 mixed bed.
CN102372573A has reported a kind of method of carbon four and ethene propylene processed after ether, mainly solves in conventional art and existsThe problem that target product selectivity is low, raw material availability is not high.
CN1182069A discloses the method for preparing propylene and 1-butylene and the method for preparing propylene, is included in double decomposition and urgesAgent makes 2-amylene and ethylene reaction under existing, and above-mentioned catalyst contains VI b, VII b or VIII at least one periodic table of elementsThe compound of group 4 transition metal, comprising: a), under metathesis catalyst exists, 1-butylene is reacted with 2-butylene, generate thirdAlkene and 2-amylene, b) then separate the propylene and the 2-amylene that generate, c), under metathesis catalyst exists, makes 2-amylene and etheneReact, generate propylene and 1-butylene, d) separate the propylene and the 1-butylene that generate, e) send the 1-butylene of generation back to stepA) in.
US5898091 and US6166279 have reported C4、C5Olefin treated. Wherein in preparing propylene through olefin disproportionation process, instituteThe catalyst adopting is Re2O7/Al2O3, reactor is moving bed.
CN1852878A discloses a kind of processing method of the C4 olefin stream for maximum production of propylene, in secondThe outside of alkene is supplied with maximum production of propylene in limited time, before any isobutene removes step and do not adding any etheneSituation under, first the C 4 fraction from hydrocarbon cracking processes is carried out to automatic double decomposition. This is conducive to generate propylene and amylene classReaction. Then remove generated ethene and propylene, leave C4 and the material stream of heavy constituent more. Then remove C5 and heavierComponent, leaves 1-butylene, 2-butylene, isobutene and mixture different and normal butane class. Next preferably pass through catalytic distillationHydroisomerization Deisobutenizer is removed isobutene. This does not flow then with from automatic metathesis product containing the C4 material of isobuteneThe product ethene removing and required any fresh external ethene mix, and carry out conventional double decomposition, generate other propylene.
CN1810743A discloses a kind of method ethene processed of cracked, C 5 fraction and method of propylene utilized, and alkene is transformedCarbon five materials rear or that alkene transforms after etherificate again carry out full hydrogenation, generate pentane and isopentane, can be used as cracking stockSend main pyrolysis furnace cracking ethylene preparation, propylene, also can be separated into pentane and isopentane is sold as product,
When for propylene reaction processed, there is the problem that propylene weight yield is not high in the method in above document.
Summary of the invention
Technical problem to be solved by this invention is the low problem of propylene weight yield existing in prior art, provides a kind of newThe method of production propylene. When the method is reacted for the production of propylene, have advantages of that propylene weight yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing propylene, and with cracking carbonFive, carbon four and ethene are raw material, comprise the following steps:
(a) cracked C 5 fraction is sent into decylization pentadiene unit, after separation, obtained removing the carbon five logistics I of cyclopentadiene;
(b) carbon five logistics I and carbon four raw materials are sent into selective hydrogenation reaction device, in the condition of hydrogenation catalyst and hydrogen existenceUnder, be monoolefine by the diolefin selective hydrogenation that comprises isoprene, pentadiene and butadiene wherein, comprisedThe monoolefine logistics II of tertiary amylene, 1-amylene, 2-amylene, 1-butylene and 2-butylene;
(c) monoolefine material II and fresh ethylene obtain logistics III through adsorption tower processing after mixing;
(d) logistics III is sent into isomerization reactor, the thing that is rich in 2-methyl-2-butene, 2-amylene and 2-butylene that reaction obtainsStream IV;
(e) logistics IV is sent into disproportionation reactor, and reaction obtains containing product propylene, unreacted ethene, carbon four and carbon five logistics Ⅴ；
(f) logistics V enters separative element, separates the logistics VI that obtains ethene, propylene, carbon four and carbon five.
In technique scheme, the preferred version of decylization pentadiene unit comprises polymer reactor and destilling tower, and cracking c_5 heats up in a steamerDivide and enter after polymer reactor, make cyclopentadiene from being polymerized to dicyclopentadiene, reacting rear material enters destilling tower again, describedAt the bottom of destilling tower tower, discharging is thick dicyclopentadiene, and tower top discharging is to remove five logistics of the carbon of cyclopentadiene; Polymer reactor is preferredOperating condition be reaction pressure 0.2～3.0MPa, 50～150 DEG C of reaction temperatures, weight space velocity 0.1～1.0h-1, when stopBetween be 30～120 minutes; The de-dicyclopentadiene tower of destilling tower, number of theoretical plate is 15～60, 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, tower reactor temperatureBe 80～130 DEG C, feed entrance point is at the middle part of tower; The preferred version of selective hydrogenation reaction device is fixed bed reactors, preferablyOperating condition be reaction pressure 0.1～5Mpa, 30～130 DEG C of reaction temperatures, the mol ratio 1～10 of hydrogen and alkadienes,Liquid phase volume air speed 1～8h-1。
In in technique scheme, preferably, the catalyst activity component using in selective hydrogenation reaction device for nickel, cobalt and/Or palladium, carrier is aluminium oxide or silica, and reaction temperature is 50～130 DEG C, and reaction pressure is 0.5～3.0MPa, hydrogenWith the mol ratio of diolefin be 1～4, liquid phase volume air speed is 1～5h-1。
In in technique scheme, preferably, in the adsorption tower described in step (c), be filled with adsorbent, preferred version be withAdsorbent weight umber meter comprises following component: 1) 0～20 part be selected from Li, Cs, Fe, Cu, Hg, Co, Cd, Au,At least one metal in Au or Ag; 2) 80～100 parts are selected from A type, X-type, Y type, modenite, ZSM typeAt least one molecular sieve in zeolite or beta molecular sieve.
In in technique scheme, preferably, in isomerization reactor, isomerization catalyst is alkaline earth oxide, reactionTemperature is 200～400 DEG C, and reaction pressure is 1～4MPa, and weight space velocity is 1～20 hour-1。
In in technique scheme, preferably, described in step (d), in disproportionation reactor, be filled with disproportionation catalyst, catalystIn parts by weight, comprise following component: 1) 2～20 parts of tungsten oxides; 2) 1～5 part of lithia; 3) 0～5 part be selected from Ga,At least one oxide in In and Tl; 3) 70～97 parts of silica; Operating condition is: 250～350 DEG C of reaction temperatures,Reaction pressure is 1～4MPa, the weight space velocity 1～20h of logistics IV-1；
More preferably, silica is MSU-x molecular sieve or MCM-48 molecular sieve; Isomerization catalysis in isomerization reactorThe preferred version of agent is that specific area is 200～500m2The alkaline earth oxide of/g.
In technique scheme, in the material of carbon four raw materials and carbon Wuyuan, the mol ratio of butylene is (10:1)～(1:10); Preferably,In the material of carbon four raw materials and carbon Wuyuan, the mol ratio of butylene is (5:1)～(1:5); More preferably, carbon four raw materials and carbon Wuyuan materialThe mol ratio of middle butylene is (2:1)～(1:2).
In in technique scheme, preferably, separative element comprises de-ethylene column and depropenizer, unreacted carbon four, carbonFive and ethene capable of circulation to steps d) continue reaction; The preferred version of de-ethylene column operating condition is: theoretical cam curve 100～120, tower is pressed 1.8～2.2MPa, tower top temperature-35～-30 DEG C, tower reactor temperature-10～-5 DEG C; The operation bar of depropenizerThe preferred version of part is: 160～180 of theoretical cam curves, tower is pressed 1.7～1.9MPa, 40～45 DEG C of tower top temperatures, tower50～55 DEG C of still temperature.
Carbon five material II can first be sent into etherificate unit and remove tertiary amylene, the wherein 2-methyl-2-butene in tertiary amylene and 2-methyl isophthalic acid-Butylene and methyl alcohol reaction generate tert amyl methyl ether(TAME), and described etherificate unit comprises methyltertiarvbutyl ether reactor and rectifying column, essence after etherificateHeat up in a steamer carbon five materials that obtain removing tertiary amylene; Sent into again adsorption tower and olefin reactor, described methyltertiarvbutyl ether reactorIn, catalyst for etherification used is acid-exchange resin, and reaction bed is fixed bed, and etherification temperature is 40～90 DEG C, etherChange pressure is 0.5～3.0MPa, and the liquid phase volume air speed of material in methyltertiarvbutyl ether reactor is 0.4～8h-1, the uncle penta in materialThe mol ratio of alkene and methyl alcohol is 1: 1～1.3; The number of theoretical plate of the rectifying column of described etherificate unit is 20～40, tower topTemperature is 20～80 DEG C, and tower top pressure is 0.06～0.5MPa, and tower reactor temperature is 50～110 DEG C, and feed entrance point is in towerPortion.
The preparation method of isomerization catalyst, at air or catalyst is in the atmosphere of inertia, sintering temperature isUnder 300～1200 DEG C of conditions, by alkali salt roasting 2～24 hours, obtaining specific area was 200～500m2The alkali of/gSoil metal oxide. Alkali salt preferred version is selected from least one in the acylate of alkaline-earth metal or inorganic acid saltKind, more preferably scheme is selected from the acylate of alkaline-earth metal. Isomerization catalyst can be selected spin, compressing tablet, extruding sliveringEtc. method moulding, in forming process, can add water, sesbania powder etc.
The preparation method of selective hydrogenation catalyst is: carrier is soaked with the solution that nickel, cobalt and/or the palladium compound of aequum are made intoStain, carrier drying after dipping, in air, 350～500 DEG C of roastings obtain oxidative catalyst finished product. Can repeat above-mentionedStep makes required nickel, cobalt and/or palladium content. Finished catalyst needs to use hydrogen reducing before use.
The solid absorbent preparing is seated in ADSORPTION IN A FIXED BED tower, at N2In atmosphere, locate in advance at 200～350 DEG CManage 4～12 hours, be cooled to room temperature, preferred pretreatment temperature is 250～300 DEG C, and the preferred processing time is 6～10Hour, the operating pressure of adsorption tower is 2.0～4.0MPa, and temperature is 20～60 DEG C, and the weight space velocity of raw material is 1～10 littleTime-1。
The preparation method of adsorbent comprises the following steps: 1) aequum being selected to metal ion is Li+、Cs+、Fe2+、Cu2+、Hg2+、Co2+、Cd2+、Au3+、Au2+Or Ag+In oxalates, citrate or acetate at least one be made intoA kind of mass concentration is 1～50% solution; 2) at 20～180 DEG C, with above-mentioned metal salt solution to molecular sieve carry out fromSon exchange 1～120h; 3) by the above-mentioned Ion exchange-Size exclusion of aequum and binding agent mixed-forming, dry or dry,Then roasting at 300～700 DEG C, makes formation solid adsorbent; 4) by the above-mentioned Ion exchange-Size exclusion of aequum withBinding agent mixed-forming, dry or dry, then roasting at 300～700 DEG C, makes formation solid adsorbent.
Olefin disproportionation catalyst inactivation is to hinder its commercial Application greatest problem, causes the reason of catalysqt deactivation to have: reactionImpurities Semi-polarity material in thing (as water etc.) can make catalyst poisoning; In course of reaction, transiting metal oxidation state becomesChange; A large amount of poly state byproducts of reaction are adsorbed at catalyst surface; In course of reaction, the concentration of metal carbene reduces etc.Wherein the concentration of metal carbene is reduced to topmost deactivation cause. So need reaction raw materials to carry out only before disproportionation reactorChange and process, by the ion-exchange of different radii, the duct of molecular sieve is modified, for specific oxygenatedchemicals impurityRemove, purify the degree of depth and be significantly improved, also improved adsorptive selectivity simultaneously. Due to the metal of ion-exchange usedCationic charge density difference, has changed the electrostatic field in molecular sieve and has distributed after ion-exchange, improved the selective of adsorbent,Molecular sieve adsorption capacity and heat of adsorption to materials such as alkene in absorption oxygenatedchemicals impurity reduced.
Method of the present invention can obtain dicyclopentadiene product. Dicyclopentadiene product has good market at home and abroad,Be important fine chemicals raw material, and can be used as the raw material of high-quality resin. Method of the present invention needs less hydrogenTolerance. The present invention adopts selective hydrogenation technology that the diolefin removing in carbon five materials of dicyclopentadiene is hydrogenated to monoeneHydrocarbon, straight chain mono-olefins so wherein can be converted into ethene, propylene in olefin process, and full hydrogenation is as crackingRaw material is compared, and has saved a large amount of hydrogen, even and the full hydrogenation of side chain monoolefine, can not be cracked into ethene, propylene.
Method of the present invention can be comprehensive utilization cracked, C 5 fraction, carbon four, economic benefit and the society of improving ethylene unitBenefit provides a rationally effective approach. The present invention adds and inhales by adopting before isomerization reactor and disproportionation reactorAttached tower, can effectively remove the impurity in carbon elimination five, carbon four logistics, improves the activity of disproportionation catalyst, thereby improves target productThe weight yield of propylene, compares the reaction that does not add adsorption tower, and propene yield can improve more than 10%; Use ethene conduct simultaneouslyRaw material, can effectively improve the yield of propylene, compare do not use the reaction of ethene as raw material, propene yield can improve 10% withUpper, it is active better that disproportionation catalyst of the present invention is compared conventional catalyst, by auxiliary agent Ga, In, Tl and main active component WBetween synergy, obtained unforeseeable technique effect, compare conventional catalyst reaction propene yield and can improve 10%,Obtain good technique effect.
Brief description of the drawings
Fig. 1 be for the production of propylene techniqueflow chart of the present invention.
In Fig. 1,1 is cracked C 5 fraction, and 2 is the cyclopentadiene removing, and 3 is not carbon five logistics containing cyclopentadiene, 4For monoolefine carbon five, carbon four logistics, 5 fresh ethylene, 6 is mixed material, and 7 is the impurity of removing, and 8 is adsorption tower processingAfter logistics, 9 is raw material feed stream, 10 is product, 11 is propylene product, 12 is carbon fourth officer product, 13For cyclic carbon five, carbon four and ethene, 14 is that material carbon four, 21 is decylization pentadiene unit, and 22 is selective hydrogenation reaction device,23 is adsorption tower, and 24 is isomerization reactor, and 25 is disproportionation reactor, and 26 is separative element.
With reference to Fig. 1, method of the present invention is briefly expressed in flow chart.
As shown in Figure 1, cracked C 5 fraction 1 after removing the cyclopentadiene in raw material, decylization pentadiene unit is not containedCarbon five logistics 3 of cyclopentadiene, logistics 3, logistics 14 obtain monoolefine carbon four, carbon with selective hydrogenation catalyst haptoreactionFive logistics 4, the fresh ethylene 5 outside material 4 and battery limit (BL) forms mixed material 6 after mixing, and mixed material is through adsorption tower 23In sorbent treatment after remove the impurity 7 in raw material, impurity comprises water, alcohol, ether isopolarity material, material after treatment8 enter isomerization reactor 24 reacts, and obtains being rich in the raw material charging of 2-methyl-2-butene, 2-amylene and 2-butyleneLogistics 9, the disproportionation catalyst haptoreaction in logistics 9 and disproportionation reactor 25, reaction obtains containing propylene, unreacted secondThe product 10 of alkene, carbon five and carbon four logistics, product 10 separates through separative element, obtains polymerization-grade propylene product11, carbon fourth officer product 12 and the carbon five can be recycled, carbon four and ethene.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Press the technological process shown in Fig. 1, the component of cracked C 5 fraction is as shown in table 1, removes former through decylization pentadiene unitAfter cyclopentadiene in material, obtain the not C5 fraction containing cyclopentadiene, remove the C5 fraction component of dicyclopentadiene as table 1Shown in, then enter selective hydrogenation catalyst haptoreaction with carbon four raw materials and obtain monoolefine carbon four, carbon five logistics, its componentAs shown in table 1, the fresh ethylene outside monoolefine carbon five, carbon four logistics and battery limit (BL) forms mixed material, mixed material after mixingAfter the sorbent treatment in adsorption tower, remove the impurity in raw material, material after treatment is through isomerization reactor and disproportionated reactionAfter device, reaction obtains target product propylene, unreacted ethene and carbon five, C 4 olefin, and product obtains through separative elementCarbon five, carbon four and the ethylene streams of polymerization-grade propylene and reaction capable of circulation.
The component of selective hydrogenation catalyst, adsorbent is as shown in table 2, and the component of isomerization catalyst and disproportionation catalyst is as tableShown in 3, the operating condition of decylization pentadiene unit is as shown in table 4, the operating condition of selective hydrogenation reaction device, adsorption tower asShown in table 5, the operating condition of isomerization reactor and disproportionation reactor is as shown in table 6, and reaction result is as shown in table 7.
Table 1
[embodiment 2～12]
React with step by each condition of embodiment 1, just change different operating parameters, selective hydrogenation catalyst,The component of adsorbent is as shown in table 2, and the component of isomerization catalyst and disproportionation catalyst is as shown in table 3, decylization pentadiene listThe operating condition of unit is as shown in table 4, and the operating condition of selective hydrogenation reaction device, adsorption tower is as shown in table 5, isomerization reactionThe operating condition of device and disproportionation reactor is as shown in table 6, and reaction result is as shown in table 7.
[comparative example 1]
Press the technological process shown in Fig. 1, just do not pass through adsorption tower processing. Selective hydrogenation catalyst, isomerization catalystIdentical with embodiment 2 with the component of disproportionation catalyst, decylization pentadiene unit, selective hydrogenation reaction device, isomerization reactorWith embodiment 2, reaction result is as shown in table 7 with the operating condition of disproportionation reactor.
[comparative example 2]
Press the technological process shown in Fig. 1, raw material only has monoolefine carbon four, carbon five logistics, there is no fresh ethylene. Select hydrogenationThe component of catalyst, adsorbent, isomerization catalyst and disproportionation catalyst is identical with embodiment 6, decylization pentadiene unit,The operating condition of selective hydrogenation reaction device, adsorption tower, isomerization reactor and disproportionation reactor is with embodiment 6, reaction resultAs shown in table 7.
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
| Product distribution (% by weight) | 1-amylene | 2-amylene | Butylene | 2-methyl-2-butene | Propylene |
| Example 1 | 2.4 | 5.2 | 9.1 | 10.3 | 35.6 |
| Example 2 | 2.6 | 5.4 | 9.2 | 10.3 | 34.7 |
| Example 3 | 2.0 | 5.2 | 7.1 | 10.5 | 36.6 |
| Example 4 | 1.9 | 4.8 | 7.0 | 10.0 | 37.4 |
| Example 5 | 2.6 | 5.8 | 8.0 | 11.2 | 31.7 |
| Example 6 | 2.2 | 5.0 | 7.8 | 10.5 | 34.8 |
| Example 7 | 1.6 | 4.1 | 6.9 | 10.0 | 38.2 |
| Example 8 | 1.4 | 4.4 | 6.8 | 10.0 | 38.0 |
| Example 9 | 1.5 | 4.2 | 6.6 | 10.0 | 37.8 |
| Example 10 | 1.0 | 3.0 | 6.0 | 9.0 | 41.0 |
| Example 11 | 2.4 | 5.0 | 7.2 | 10.5 | 34.8 |
| Example 12 | 2.4 | 5.5 | 7.0 | 10.1 | 34.4 |
| Comparative example 1 | 2.7 | 7.5 | 9.2 | 18.9 | 23.0 |
| Comparative example 2 | 5.0 | 8.2 | 8.8 | 20.5 | 21.3 |
Claims (10)
1. produce a method for propylene, taking cracking c_5, carbon four and ethene as raw material, comprise the following steps:
(a) cracked C 5 fraction is sent into decylization pentadiene unit, after separation, obtained removing the carbon five logistics I of cyclopentadiene;
(b) carbon five logistics I and carbon four raw materials are sent into selective hydrogenation reaction device, in the condition of hydrogenation catalyst and hydrogen existenceUnder, be monoolefine by the diolefin selective hydrogenation that comprises isoprene, pentadiene and butadiene wherein, comprisedThe monoolefine logistics II of tertiary amylene, 1-amylene, 2-amylene, 1-butylene and 2-butylene;
(c) monoolefine material II and fresh ethylene obtain logistics III through adsorption tower processing after mixing;
(d) logistics III is sent into isomerization reactor, the thing that is rich in 2-methyl-2-butene, 2-amylene and 2-butylene that reaction obtainsStream IV;
(e) logistics IV is sent into disproportionation reactor, and reaction obtains containing product propylene, unreacted ethene, carbon four and carbon five logisticsⅤ；
(f) logistics V enters separative element, separates the logistics VI that obtains ethene, propylene, carbon four and carbon five.
2. the method for production propylene according to claim 1, is characterized in that decylization pentadiene unit comprises polymerisationDevice and destilling tower, cracked C 5 fraction enters after polymer reactor, and cyclopentadiene is from being polymerized to dicyclopentadiene, reacting rear materialEnter destilling tower, at the bottom of described destilling tower tower, discharging is thick dicyclopentadiene again, and tower top discharging is to remove the carbon of cyclopentadiene fiveLogistics.
3. the method for production propylene according to claim 2, is characterized in that: the operating condition of described polymer reactorFor reaction pressure 0.2～3.0MPa, 50～150 DEG C of reaction temperatures, weight space velocity 0.1～1.0h-1, the time of staying is 30～120 minutes; Described destilling tower is de-dicyclopentadiene tower, and number of theoretical plate is 15～60, and reflux ratio is 0.5～10, towerPressure on top surface is 0.06～0.5MPa, and tower reactor pressure is 0.08～0.6MPa, and tower top temperature is 20～80 DEG C, and tower reactor temperature is80～130℃。
4. the method for production propylene according to claim 1, is characterized in that described selective hydrogenation reaction device is for solidFixed bed reactor, operating condition is reaction pressure 0.1～5MPa, 30～150 DEG C of reaction temperatures, the rubbing of hydrogen and alkadienesThat ratio 1～10, liquid phase volume air speed 1～8h-1。
5. the method for production propylene according to claim 1, is characterized in that using in described selective hydrogenation reaction deviceCatalyst activity component be nickel, cobalt and/or palladium, carrier is aluminium oxide or silica, reaction temperature is 50～130 DEG C, anti-Answering pressure is 0.5～3.0MPa, and the mol ratio of hydrogen and diolefin is 1～4, and liquid phase volume air speed is 1～5h-1。
6. the method for production propylene according to claim 1, is characterized in that filling in the adsorption tower described in step (c)Be filled with adsorbent, adsorbent, in parts by weight, comprises following component: 1) 80～100 parts be selected from A type, X-type, Y type,At least one molecular sieve in modenite, ZSM type zeolite or beta molecular sieve; And carry thereon: 2) 0～20 partBe selected from least one metal in Li, Cs, Fe, Cu, Hg, Co, Cd, Au, Au or Ag.
7. the method for production propylene according to claim 1, is characterized in that isomerization catalysis in isomerization reactorAgent is alkaline earth oxide, and reaction temperature is 200～400 DEG C, and reaction pressure is 1～4MPa, and weight space velocity is 1～20Hour-1。
8. the method for production propylene according to claim 1, is characterized in that described in step (d) in disproportionation reactorBe filled with disproportionation catalyst, catalyst, in parts by weight, comprises following component: 1) 2～20 parts of tungsten oxides; 2) 1～5 partLithia; 3) 0～5 part of at least one oxide being selected from Ga, In and Tl; 4) 70～97 parts of silica; Operation barPart is: 250～350 DEG C of reaction temperatures, reaction pressure is 1～4MPa, the weight space velocity 1～20h of logistics IV-1。
9. the method for production propylene according to claim 1, is characterized in that separative element comprises de-ethylene column and de-Propylene tower.
10. the method for production propylene according to claim 1, is characterized in that unreacted carbon five, carbon four and ethene followEncircle to steps d) continue to react.
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| CN107970914A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Disproportionation catalyst and application thereof |
| CN107970915A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst and its application method |
| CN107970916A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst and application thereof |
| CN112759500A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for producing propylene by using carbon tetrahydrocarbon |
| CN114456030A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Comprehensive utilization method of mixed carbon four-carbon five-material |
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| CN112759500B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Method for producing propylene by using carbon tetrahydrocarbon |
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