CN103788272B - A kind of method of hydrotreating containing olefines unsaturated bond polymer - Google Patents
A kind of method of hydrotreating containing olefines unsaturated bond polymer Download PDFInfo
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Abstract
The invention provides a kind of method of hydrotreating containing olefines unsaturated bond polymer. Under hydrogenation catalyst exists, use successively annular-pipe reactor, tank reactor, the polymer solution that contains olefines unsaturated bond is contacted with hydrogen, carry out catalytic hydrogenation reaction; Afterwards product is carried out to flash separation, the polymer solution of liquid phase after as hydrogenation, gas phase is carried out condensation recovery, and the solvent obtaining and hydrogen are recycled. In the method, hydrogen can better be dissolved in polymer solution, has optimized mass transfer, has improved hydrogenation efficiency, and can stablize the reaction temperature of controlling the hydrogenation initial stage, improves efficiency and the stability of hydrogenation reaction.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to a kind of polymer containing olefines unsaturated bondMethod of hydrotreating.
Background technology
For improving heat resistance, oxidative stability and the resistance to ag(e)ing containing alkene unsaturated bond polymer, generally adoptGetting method of hydrotreating makes the unsaturated bond in polymer saturated. Conventionally require the degree of unsaturation of polymer after hydrogenationBe less than 2%(and be greater than 98% containing olefines unsaturated bond degree of hydrogenation), to obtain obvious improvement in performance.
US Patent No. 6,815,509B2 discloses a kind of method for hydrogenating polymer, and described method is included inThe polymer that hydrogenation catalyst makes to contain olefines unsaturated group under existing contacts with hydrogen and makes polymerOlefines unsaturated group hydrogenation, polymer after at least a portion that wherein circulates hydrogenation continues hydrogenation.In the method, applied reactor comprises two or two reactors that are connected in series above, reactionProcess is carried out continuously or intermittently, a part of reaction effluent warp of at least one reactor in course of reactionAfter heat exchanger heat exchange, recirculation is got back in this reactor or in upstream reactor, thereby carries by continuous circulationHigh product degree of hydrogenation.
The weak point of the method is: the first reactor of method of hydrotreating and/or later reactor are necessaryBand stirs, and needs constantly to consume and stir required mechanical energy, and ask with the sealing of mixing plant in course of reactionTopic make its manufacture and maintenance cost higher; And hydrogenation catalyst repeatedly adds, make the control of course of reactionComparatively complicated.
US Patent No. 3,696,088 discloses a kind of unsaturated polyester that adopts homogeneous hydrogenation catalyst systemCompound continously hydrogen adding method, wherein adopts trickle bed reactor, is mainly used in styrene-conjugated dieneAnalog copolymer hydrogenation, fills inert filler in reactor, the downward drip of polymer solution passes through hydrogen atmosphere,The degree of hydrogenation that reacts conjugated diene section in 4 minutes polymer is greater than 98%.
Although the method hydrogenation speed is fast, weak point is, hydrogenation catalyst consumption is large, reaction temperatureSpend high; The liquid holdup utilization rate little, unit volume reactor of trickle bed reactor is low; And trickle bedThe heat-transfer effect of reactor is bad, in the reaction starting stage when two key concentration in polymer solution is high, reactionWhen heat release is larger, reaction heat is difficult to withdraw from, and reaction temperature is difficult to steady control and even can significantly raises, and entersAnd can make hydrogenation catalyst inactivation cause hydrogenation cycle stretch-out or final products degree of hydrogenation to reduce.
Chinese patent CN101492513A discloses a kind of hydrogenation reactor and method for hydrogenating polymer, itsDescribed in the hydrogenation reactor combination that is two or more bubbling reactors, the first bubbling is wherein setReactor makes its Flow of Goods and Materials state approach complete mixing flow, and arrange second and later bubbling reactor make itFlow of Goods and Materials state approaches laminar flow.
The shortcoming of this method is to only depend on the more difficult Flow of Goods and Materials state that makes the first bubbling reactor of flow hydrogen gas to connectNearly complete mixing flow, and only depend on flow hydrogen gas and jacket for heat exchange to be difficult to steadily control reaction temperature, especially reactionBody long-pending large, exothermic heat of reaction is more, polymer solution viscosity is all the more so when larger, like this will shadowThereby the abundant contact and the catalyst activity that ring gas-liquid affect hydrogenation efficiency. The first reaction in the method in additionDevice hydrogen flow rate is large, needs the hydrogen flowing quantity of circulation just large, and the energy that circulating hydrogen consumes is also just many.
In prior art, US Patent No. 4,501,875, US4,673,714 and BP GB2,159,819A etc. all adopt stirred tank to carry out hydrogenation at intermittence, because two keys in reaction reaction solution in early stage are denseDegree height and hydrogenation speed cause thermal discharge large soon, make reaction temperature be difficult to control, and will make like this partThereby catalysqt deactivation affects the performance of hydrogenation efficiency and polymer.
Summary of the invention
In order better to control the temperature containing the reaction of olefines unsaturated bond hydrogenation of polymer, improve hydrogenation effectRate and stability, operation is controlled easy, the invention provides a kind of adding containing olefines unsaturated bond polymerHydrogen methods, this method of hydrotreating is achieved in that
Containing a method of hydrotreating for olefines unsaturated bond polymer, the method comprises the following steps successively:
(1) endless tube hydrogenation reaction: use the annular-pipe reactor (R1) of one or more series connection,Hydrogenation catalyst makes the polymer solution that contains olefines unsaturated bond contact with hydrogen under existing, and entersRow catalytic hydrogenation reaction;
(2) autoclave hydrogenation reaction: use tank reactor (R2), under hydrogenation catalyst exists,The product of endless tube hydrogenation reaction is contacted with hydrogen, carry out catalytic hydrogenation reaction;
(3) separate and reclaim: the product to described tank reactor (R2) carries out flash separation, described inThe liquid phase that flash separation obtains is the polymer solution after hydrogenation, and the gas phase that described flash separation is obtained is enteredRow condensation is reclaimed, and described condensation is reclaimed the condensate liquid that contains solvent obtaining and recycled, and described condensation is returnedThe fixed gas that what receipts obtained contain hydrogen is recycled.
In the specific implementation, described in contain olefines unsaturated bond polymer be: conjugated diene homopolymers,Preferably the copolymer of polyisoprene or polybutadiene or conjugated diene and vinyl-arene, preferably differentPentadiene or butadiene and cinnamic random copolymer or block copolymer, isoprene or butadiene andThe random copolymer of AMS or block copolymer; Solvent in described polymer solution is inertiaVarsol, is selected from one or more in alkane, cycloalkane and aromatic hydrocarbons, preferably hexane; 'inertia' withNot in disturbance reponse device hydrogenation reaction enter principle of conduct, described varsol can not with reactant or anti-Answer between product and react, can not be unfavorable for the performance of catalyst activity; The described alkene that containsThe concentration of the polymer of class unsaturated bond in solution is 5-40wt%, preferably 8-30wt%.
In the specific implementation, described hydrogenation catalyst can be any for hydrogenation of polymer in this areaSuitable hydrogenation catalyst. Described hydrogenation catalyst can be to contain periodic table of elements VIIIB family conventionallyThe organic compound of metal and the catalyst of organo-aluminium, described VIIIB family metal as iron, cobalt, nickel andPalladium, preferably nickel and cobalt; Described hydrogenation catalyst can be also metallocene catalyst, this metallocene catalystBe preferably metallocene-titanium catalyst, and optionally mix as lithium alkylide with organo-lithium compound, described lithium alkylide is preferredFor n-BuLi and triisobutyl lithium.
In the specific implementation, in step (1), described annular-pipe reactor R1 outer setting chuck, instituteThe medium of stating in chuck is refrigerant, and preferred water is as removing thermal medium, due to the heat transfer of annular-pipe reactor chuckArea is large, can control preferably reaction temperature, rationally regulates water temperature to be conducive to the length of catalytic hydrogenation reactionPhase stablizes and carries out; A circulator is at least set in described annular-pipe reactor R1, and described circulator is passablePump or other motor drives, so that the power of recycle stock in annular-pipe reactor to be provided; Anti-at endless tubeAnswer on device R1 multiple feed(raw material)inlets are set, the raw material entering from feed(raw material)inlet comprises: contain olefines notThe polymer of saturated bond, hydrogen, hydrogenation catalyst, diluent, co-catalyst, processing additive or itMixture; Wherein be provided with the entrance of described hydrogenation catalyst in the suction side of described circulator, in instituteThe outlet side of stating circulator is provided with entering of except described hydrogenation catalyst other catalytic hydrogenation reaction materialsMouthful, and at least one catalyst inlet and at least one feed(raw material)inlet are separately positioned on to same circulatorSuction side and outlet side; Before described annular-pipe reactor R1, hydrogen vacuum tank V1 is set, hydrogen is introduced intoAfter vacuum tank, V1 enters annular-pipe reactor R1 again, by regulating the pressure of flow-control vacuum tank of hydrogen,Be beneficial to the pressure stability of hydrogenation reactor.
In the specific implementation, in step (2), described tank reactor R2 outside be provided with chuck, inPortion arranges inner cool tube, and the medium in described chuck and described cold pipe is refrigerant, and preferred water is as removing thermal medium;Described tank reactor R2 is provided with one or more hydrogen feed mouth; Described tank reactor R2Be provided with mixing plant; Supplement and add described hydrogenation catalyst at described tank reactor R2. Owing to encirclingIn pipe reactor interpolymer, most of olefines unsaturated bond, by hydrogenation, is adding in tank reactorHydrogen catalyst does not exist and is not contacted mixed with hydrogen by the solution of the polymer containing olefines unsaturated bond of hydrogenationClose, further improve the degree of hydrogenation of olefines unsaturated bond. Hydrogenation catalyst can add endless tube anti-simultaneouslyAnswer device and tank reactor, for handled easily, also can only in annular-pipe reactor, add excessive urgingAgent, the discharging of annular-pipe reactor no longer adds catalyst after entering tank reactor, utilizes in material itRemaining hydrogenation catalyst can complete hydrogenation reaction.
In the specific implementation, the Matter Transfer of described endless tube hydrogenation reactor ratio is that 20 ~ 40(recycle ratio isThe flow of annular-pipe reactor circulating pump and the ratio of reactor feed, material in the time that recycle ratio is greater than 20Admixture close to complete mixing flow, for this technique, recycle ratio be 20 ~ 40 o'clock mix effectFruit better); The operating pressure of described endless tube hydrogenation reactor and described autoclave hydrogenation reactor is0.1-5.0MPa gauge pressure, preferred 0.5-4.0MPa gauge pressure, operating temperature is 30-150 DEG C, preferred 40-120 DEG C;The operating pressure of vacuum tank is 0.1-5.0MPa (gauge pressure), preferably 0.5-4.0MPa (gauge pressure); The behaviour of knockout drumBe 0.1-4.0MPa (gauge pressure) as pressure, be preferably 0.4-3.0MPa (gauge pressure).
In the specific implementation, in step (3), to the product of described tank reactor R2 carry out manyLevel flash separation, the liquid phase that afterbody flash distillation obtains is the polymer solution after hydrogenation, condensations at different levels are returnedThe condensate liquid that what receipts obtained contain solvent is recycled, condensations at different levels reclaim obtain contain the solidifying of hydrogenGas is recycled. For example two-stage flash, material is introduced into one-level knockout drum V2, and isolated one-level is dodgedVapor phase is collected after E1 condensation or partial condensation; One-level flash liquid enters the second knockout drum V3 and carries outTwo-stage flash, further isolates gas-liquid two-phase, and two-stage flash gas phase is solvent gas and unreacted hydrogenGas, two-stage flash liquid phase is the polymer solution after final hydrogenation, two-stage flash gas phase through E2 condensation orAfter partial condensation, collect, after the condensation of firsts and seconds flashed vapour, gained condensate liquid reclaims and uses after merging.
Method of hydrotreating of the present invention makes the polymer containing olefines unsaturated bond under hydrogenation catalyst existsSolution contact hydrogenation with hydrogen, comprise by containing the polymer of olefines unsaturated bond, hydrogenation catalyst,Hydrogen and selectable other co-catalysts, diluent or their mixture are sent into hydrogenation reactor,The hydrogenation reactor that wherein used comprises annular-pipe reactor and the band that one or more are connected in series, at least there is a circulator in the combination of stirred-tank reactor, described circulator can in annular-pipe reactorTo be pump or other motor drives, to increase the pressure of recycle stock in annular-pipe reactor, pass through thingThe circulation of material improves the rate of flow of fluid in endless tube, and guarantee polymer solution fully mixes and connects with hydrogenTouch, when annular-pipe reactor hydrogenation, in order to reach mixed effect better, requiring recycle ratio is circulating-pump outletThe ratio of flow and reactor feedstocks feed rate is greater than 20, now the mobile shape of annular-pipe reactor inner fluidState, close to complete mixing flow, therefore utilizes the circulating effect of annular-pipe reactor to improve hydrogenation from optimizing mass transfer aspectEfficiency, the material after annular-pipe reactor hydrogenation enters tank reactor, and tank reactor is band mixing plant,Hydrogen adds from reactor bottom, and tank reactor comprises one or more hydrogen inlet, autoclaveReactor, with chuck or while jacketed and inner cool tube, conducts heat by chuck and inner cool tube. Still reactionDevice also can further add hydrogenation catalyst, by the mixing of agitator, containing the polymer of unsaturated bond,Hydrogen further hydrogenation under the effect of hydrogenation catalyst, reaches after required time of staying still reactionThe discharging of device enters one or more flash separation tank and carries out one-level flash distillation or pressure reduction with classification flash distillation,Isolate gas-liquid two-phase, gas phase is diluent gas and unreacted hydrogen, and liquid phase is the polymerization after hydrogenationThing solution, flash distillation gas phase (partial condensation) after condensation is collected; If double flash evaporation, one-level flash liquid is enteredEnter the second knockout drum and carry out two-stage flash, further isolate gas-liquid two-phase, two-stage flash gas phase is dilutionAgent gas and unreacted hydrogen, two-stage flash liquid phase is the polymer solution after final hydrogenation, secondary dodgesVapor phase (partial condensation) after condensation is collected, and firsts and seconds flashed vapour obtains after condensate liquid merges and reclaims and makeWith, the fixed gas of firsts and seconds flashed vapour is hydrogen, can after compressor compression, recycle.
The inventive method can be for continued operation or intermittently operated, when intermittently operated, polymer solution, urgesThe charging of agent, auxiliary agent etc. is that batch (-type) adds, and hydrogen is continuous feed, when hydrogenation reaction material reactionA period of time, again product after hydrogenation is discharged after reaching the required time of staying of reaction.
The tank reactor that prior art generally adopts band to stir, because hydrogenation reaction initial stage thermal discharge is large,Tank reactor compared with annular-pipe reactor under the condition of same volume heat transfer area less, heat-transfer effectPoor, be unfavorable for heat transfer rapid moving to remove, thereby cause temperature to raise, and higher temperature can cause and urgesThe inactivation of agent and the degree of hydrogenation of benzene ring improve. Hydrogenation target of the present invention is in polymerConjugated alkene section hydrogenation, do not wish benzene ring hydrogenation, therefore the present invention is in hydrogenation reactionAt the initial stage, adopt annular-pipe reactor to control the temperature of hydrogenation reaction, makes the benzene ring hydrogenation degree in polymer mostPossible reduction, in the time that hydrogenation reaction proceeds to the middle and later periods, hydrogenation reaction heat release is less, and temperature is easily controlledSystem, now material enters the hydrogenation reactor of an autoclave again, further improves the conjugation alkene in polymerHydrocarbon section degree of hydrogenation. Aspect the continuity operation of device, annular-pipe reactor can be realized continuous adding in additionHydrogen operation, and the hydrogenation reactor that band of the prior art stirs is intermittent operation, therefore ring canal reactionDevice is easy to operate in hydrogenation process. Therefore temperature compared with other hydrogenation reaction forms that the present invention stirs with bandDegree is more easily controlled, also simpler aspect operability.
Hydrogenation reactor of the present invention comprises one or more annular-pipe reactor and tank reactorCarry out tandem compound. First reaction raw materials is introduced into annular-pipe reactor and carries out hydrogenation, can ensure like thisAbundant dissolving and the mixing of hydrogen in polymer solution, thus make gas-liquid contact more abundant, simultaneously canControl better reaction temperature at the hydrogenation reaction initial stage, may cause benzene ring to add because temperature is highHydrogen degree increases, and the hydrogenation of polymer is generally in order to ensure the performance of product, needs to reduce phenyl ring as far as possibleHydrogenation, (General Requirements benzene ring degree of hydrogenation is less than 2%). Adopt the present invention ensureing mass transferOn basis, reaction temperature be can also effectively control, and then hydrogenation efficiency and stability improved; Due to endless tubeThe time of staying of reactor is relatively short, in order further to improve the degree of hydrogenation of polymer, at ring canal reactionThe tank reactor with stirring of connecting after device, ensures time of staying of hydrogenation material, makes polymerReach eventually desirable degree of hydrogenation.
Brief description of the drawings
Fig. 1 is a kind of process flow diagram of the method for hydrogenating polymer containing olefines unsaturated bond.
Symbol description:
R1-endless tube hydrogenation reactor V1-vacuum tank
R2-autoclave hydrogenation reactor V2-the first knockout drum
E1-condenser V3-the second knockout drum
E2-condenser
Detailed description of the invention
Be described in further detail technical scheme of the present invention below in conjunction with drawings and Examples, protection model of the present inventionEnclose and be not limited to following detailed description of the invention.
Embodiment 1
Styrene-isoprene-block copolymer and hydrogen are under the catalytic action of hydrogenation catalyst, at ringIn pipe reactor and tank reactor, carry out catalytic hydrogenation.
The solution (hydrogenating materials 2) of styrene-isoprene-block copolymer and hexane is with 500L/h'sFlow velocity enters annular-pipe reactor R1 entrance, wherein styrene-isoprene-block copolymerization substrate concentration based onThe 10wt% of whole polymeric solution, the weight ratio of styrene and isoprene monomer unit is 3:7, polymerizationIn thing, the contents of ethylene of isoprene block is 30wt%.
Hydrogen (hydrogenating materials 1) enters annular-pipe reactor R1 entrance, hydrogen after vacuum tank V1Flow is 80Nm3/ h, arranges axial-flow pump in annular-pipe reactor R1, and hydrogenation material is circulated. HydrogenThe charging aperture of gas and hydrogenation copolymer is positioned at axial flow delivery side of pump, and the charging aperture of hydrogenation catalyst is positioned at axial flowThe entrance of pump.
The endless tube diameter of annular-pipe reactor R1 is 250mm, and the height of 2 straight lengths is 9 meters, spanIt is 1.2 meters; Axial-flow pump is arranged on the bottom of annular-pipe reactor R1, and the internal circulating load of axial-flow pump is 1000m3/h；Annular-pipe reactor R1 arranges chuck outward, and jacket for heat exchange area is 17m2, in chuck, medium is hot water. AddHydrogen reactor R1 uses in advance nitrogen replacement before charging, then uses hydrogen exchange.
Used catalyst preparation method is according to the method in CN1055294C: nickel naphthenate and triisobutylThe concentration (by metal) of aluminium is 2g/L, and aluminium nickel is 3:1 than (mol ratio); Catalyst amount is 8.33gNi/h。
The discharging of annular-pipe reactor R1 enters in tank reactor R2, catalysis in tank reactor R2The consumption of agent is 5.55gNi/h, and tank reactor R2 volume is 500L, and diameter is 800mm, cylinderHeight is 1200mm, and reaction time is 1 hour.
Vacuum tank V1 and annular-pipe reactor R1 operating pressure are 2.0MPa, and operating temperature is 100 DEG C;The operating pressure of tank reactor R2 is 1.9MPa, and operating temperature is 100 DEG C. Material after hydrogenation fromTank reactor R2 outlet enters the first knockout drum V2 and carries out flash distillation, and the pressure of knockout drum V2 is1.8MPa; It is own that the hydrogen dissolving in polymer after flash distillation and part hexane gas enter condenser E1 condensationAlkane, all the other polymer solutions enter the second knockout drum V3 and carry out flash distillation, and the pressure of knockout drum V3 is1.5MPa, the liquid phase that flash separation obtains is the polymer solution after hydrogenation, molten in polymer after flash distillationAll the other hydrogen and the part hexane gas separated enter condenser E2 by hexane condensation; Condenser E1 and E2The hexane that condensation is got off is 100L/h altogether, after collecting, reclaims and uses, and after not solidifying hydrogen collects, presses through compressorHydrogenation reactor is returned in contracting.
By polymer sampling its degree of hydrogenation of iodimetric analysis complete hydrogenation, isoprene section in polymerDegree of hydrogenation be 98.2%, wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 2
The consumption of annular-pipe reactor hydrogenation catalyst is 8.36gNi/h, tank reactor hydrogenation catalystConsumption is 5.57gNi/h, and other conditions are identical with embodiment 1. Different in polymer after hydrogenation reactionThe degree of hydrogenation of pentadiene section is 98.5%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 3
The consumption of annular-pipe reactor hydrogenation catalyst is 8.38gNi/h, tank reactor hydrogenation catalystConsumption is 5.59gNi/h, and other conditions are identical with embodiment 1. Different in polymer after hydrogenation reactionThe degree of hydrogenation of pentadiene section is 98.8%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 4
The consumption of annular-pipe reactor hydrogenation catalyst is 8.40gNi/h, tank reactor hydrogenation catalystConsumption is 5.60gNi/h, and other conditions are identical with embodiment 1. Different in polymer after hydrogenation reactionThe degree of hydrogenation of pentadiene section is 99.0%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 5
The consumption of annular-pipe reactor hydrogenation catalyst is 8.44gNi/h, tank reactor hydrogenation catalystConsumption is 5.63gNi/h, and other conditions are identical with embodiment 1. Different in polymer after hydrogenation reactionThe degree of hydrogenation of pentadiene section is 99.5%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 6
The consumption of annular-pipe reactor hydrogenation catalyst is 8.48gNi/h, tank reactor hydrogenation catalystConsumption is 5.65gNi/h, and other conditions are identical with embodiment 1. Different in polymer after hydrogenation reactionThe degree of hydrogenation of pentadiene section is 99.9%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 7
The charging that enters annular-pipe reactor R1 is styrene-butadiene-block copolymer, styrene and fourthThe weight ratio of diene monomers unit is 3:7, and in polymer, the contents of ethylene of butadiene block is 39wt%;The preparation method of catalyst is identical with embodiment 1, and the consumption of annular-pipe reactor R1 hydrogenation catalyst is 8.32GNi/h, the consumption of tank reactor R2 hydrogenation catalyst is 5.54gNi/h, other conditions and embodiment1 is identical. After hydrogenation reaction, in polymer, the degree of hydrogenation of butadiene block is 98.0%, in polymerBenzene ring hydrogenation degree is less than 1.8%.
Comparative example 1
In the tank reactor of 500L, carry out hydrogenation, by styrene-isoprene-block copolymer and hydrogenGas carries out intermittent reaction under the catalytic action of aluminium nickel hydrogenation catalyst, and catalyst amount is 13.88gNi,Reacting initial temperature is 70 DEG C, and reaction maximum temperature is 120 DEG C, and the reaction time is 2 hours, reactionPressure is 2.0MPa, and end reaction device outlet hydrogenation of polymer degree is 98.0%, benzene ring hydrogenationDegree is less than 2%.
Hydrogenation reaction result by above-described embodiment and comparative example can be found out: adopt ring canal reaction of the present inventionThe method of hydrotreating of device and tank reactor, adopts annular-pipe reactor and polymer solution circulation, anti-at hydrogenationShould can control more reposefully reaction temperature by initial stage annular-pipe reactor chuck, increase gas-liquid contact area, largeThe large hydrogenation reaction efficiency that improves, tank reactor has extended the time of hydrogenation reaction, the hydrogenation of final productsDegree also obviously improves, and benzene ring degree of hydrogenation obviously reduces, and has improved properties of product; Due to continuouslyEndless tube hydrogenation process in reaction pressure more steady, emptying amount is less, therefore material consumption is compared with autoclave hydrogenationCourse of reaction is few; Because continuous endless tube hydrogenation process has improved heat transfer efficiency, therefore energy consumption is compared with stillFormula hydrogenation process few (in embodiment 1, the consumption of continuous endless tube hydrogenation recirculated water is 694kg/h,In comparative example 1, the consumption of recirculated water is 809kg/h); And in the subsequent separation process of hydrogenation,To in hydrogen and partial solvent and hydrogenation polymer, separate by one-level or flash distillation more than one-level, willHydrogen and recycled solvent, flow process is simpler. Especially in the time of continued operation, the method can be long behaviourDo to obtain the polymeric articles with desirable degree of hydrogenation in the cycle, can reduce simultaneously course of reaction material consumption,Energy consumption and device operating cost.
Claims (10)
1. containing a method of hydrotreating for olefines unsaturated bond polymer, the method comprises the following steps successively:
(1) endless tube hydrogenation reaction: use the annular-pipe reactor (R1) of one or more series connection, addingHydrogen catalyst makes the polymer solution that contains olefines unsaturated bond contact with hydrogen under existing, and carries out catalysisHydrogenation reaction; A circulator is at least set in described annular-pipe reactor (R1);
(2) autoclave hydrogenation reaction: use tank reactor (R2), under hydrogenation catalyst exists, make ringThe product of pipe hydrogenation reaction contacts with hydrogen, carries out catalytic hydrogenation reaction;
(3) separate and reclaim: the product to described tank reactor (R2) carries out flash separation, described flash distillationThe liquid phase that separation obtains is the polymer solution after hydrogenation, and the gas phase that described flash separation is obtained is carried out condensationReclaim, described condensation is reclaimed the condensate liquid that contains solvent obtaining and is recycled, and described condensation recovery obtainsThe fixed gas that contains hydrogen is recycled.
2. method of hydrotreating according to claim 1, is characterized in that:
The described polymer that contains olefines unsaturated bond is: conjugated diene homopolymers or conjugated diene and etheneThe copolymer of base aromatic hydrocarbons; Solvent in described polymer solution is selected from the one in alkane, cycloalkane and aromatic hydrocarbonsOr several; The concentration of the described polymer that contains olefines unsaturated bond in solution is 5-40wt%.
3. method of hydrotreating according to claim 2, is characterized in that:
Described conjugated diene homopolymers is: polyisoprene or polybutadiene, described conjugated diene and vinylThe copolymer of aromatic hydrocarbons is: isoprene or butadiene and cinnamic random copolymer or block copolymer, orThe random copolymer of isoprene or butadiene and AMS or block copolymer; Described polymer is moltenSolvent in liquid is hexane; The concentration of the described polymer that contains olefines unsaturated bond in solution is8-30wt％。
4. method of hydrotreating according to claim 1, is characterized in that:
Described hydrogenation catalyst contains: the organic compound of iron, cobalt, nickel or palladium, and organo-aluminium; OrBe mixed with the metallocene catalyst of organo-lithium compound.
5. method of hydrotreating according to claim 4, is characterized in that:
Described hydrogenation catalyst contains: the organic compound of cobalt or nickel, and organo-aluminium; Or be mixed with positive fourthBase lithium is or/and the metallocene-titanium catalyst of triisobutyl lithium.
6. method of hydrotreating according to claim 1, is characterized in that:
In step (1), described annular-pipe reactor (R1) outer setting chuck, the medium in described chuckFor refrigerant; Be provided with the entrance of described hydrogenation catalyst in the suction side of described circulator, at described circulatorOutlet side be provided with the entrance of other catalytic hydrogenation reaction materials except described hydrogenation catalyst; Described endless tubeReactor (R1) arranges hydrogen vacuum tank (V1) before, and hydrogen is introduced into (V1) after vacuum tank and entersEnter annular-pipe reactor (R1).
7. method of hydrotreating according to claim 1, is characterized in that:
In step (2), described tank reactor (R2) outside is provided with chuck, inside arranges inner cool tube,Medium in described chuck and described cold pipe is refrigerant; Described tank reactor (R2) is provided with one or oneAbove hydrogen feed mouth; Described tank reactor (R2) is provided with mixing plant.
8. method of hydrotreating according to claim 1, is characterized in that:
In step (1) and step (2), described annular-pipe reactor (R1) and described tank reactor (R2)Operating pressure be that 0.1-5.0MPa gauge pressure, operating temperature are 30-150 DEG C; Described annular-pipe reactor (R1)Matter Transfer ratio be 20～40, described Matter Transfer is than flow and reaction for annular-pipe reactor circulating pumpThe ratio of device charging.
9. method of hydrotreating according to claim 8, is characterized in that:
The operating pressure of described annular-pipe reactor (R1) and described tank reactor (R2) is 0.5-4.0MPaGauge pressure, operating temperature are 40-120 DEG C.
10. method of hydrotreating according to claim 1, is characterized in that:
In step (3), the product of described tank reactor (R2) is being carried out to multistage flash evaporation separation,The liquid phase that rear one-level flash distillation obtains is the polymer solution after hydrogenation, and the solvent that contains obtaining is reclaimed in condensations at different levelsCondensate liquid recycle, the fixed gas that the contains hydrogen recycling obtaining is reclaimed in condensations at different levels.
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| CN105295021A (en) * | 2015-12-01 | 2016-02-03 | 王伟跃 | Process of continuously producing amine-terminated polyether and reactor design of process |
| CN114057911B (en) * | 2020-07-31 | 2023-08-15 | 中国石油化工股份有限公司 | Continuous hydrogenation method of nitrile rubber solution |
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| CN102399332B (en) * | 2010-09-16 | 2013-06-05 | 中国石油化工股份有限公司 | Propylene polymerization production technology by loop reactor batch liquid bulk method |
| CN102453125B (en) * | 2010-10-15 | 2013-06-05 | 中国石油化工股份有限公司 | Hydrogenation method for olefin unsaturated bond-containing polymer |
| CN102532379B (en) * | 2010-12-09 | 2014-05-07 | 中国石油化工股份有限公司 | Polymerization method for preparing rare earth isoprene rubber |
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