CN103788317B - A kind of hydrogenation of polymer reaction method containing olefines unsaturated bond - Google Patents
A kind of hydrogenation of polymer reaction method containing olefines unsaturated bond Download PDFInfo
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- CN103788317B CN103788317B CN201210424424.1A CN201210424424A CN103788317B CN 103788317 B CN103788317 B CN 103788317B CN 201210424424 A CN201210424424 A CN 201210424424A CN 103788317 B CN103788317 B CN 103788317B
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Abstract
The invention discloses a kind of method of hydrotreating of the polymer containing olefines unsaturated bond, the method is included under hydrogenation conditions, under hydrogenation catalyst exists, solution, the hydrogen of the polymer that contains olefines unsaturated bond are contacted in reactor, wherein, described reactor is two or more annular-pipe reactors that are connected in series, make the material in reactor approach complete mixing flow state by controlling the recycle ratio of described annular-pipe reactor, wherein, the recycle ratio of the first reactor is 10-200, and the recycle ratio of the second reactor and later reactor is 10-100. Method of the present invention can be controlled reaction temperature better, thereby keeps catalyst activity within the longer operation cycle, and then improves hydrogenation efficiency, thereby reaches desirable degree of hydrogenation.
Description
Technical field
The present invention relates to a kind of process for selective hydrogenation of the polymer containing olefines unsaturated bond. More specificallyGround, adopts two or more annular-pipe reactors that are connected in series to exist at hydrogenation catalyst and hydrogenUnder make the method containing the polymer continously hydrogen adding of unsaturated bond.
Background technology
Heat, oxidative stability and resistance to ag(e)ing containing the polymer of unsaturated bond are poor, therefore often pass through hydrogenationMethod makes the unsaturated bond of polymer saturated, thereby increases its stability. Conventionally require polymerization after hydrogenationThe degree of unsaturation of thing is less than 2% (being that degree of hydrogenation is greater than 98%), significantly changes to realize polymer performanceEnter. Hydrogenation of polymer conventionally metallic catalyst exist under carry out, used catalyst can be Fe, Co,The organic compound of the periodic table of elements such as Ni and/or Pb VIIIB family metal can be also that metallocene is urgedAgent.
US6,815,509B2 discloses a kind of method for hydrogenating polymer, and described method is included in hydrogenationThe polymer that catalyst makes to contain olefines unsaturated group under existing contacts with hydrogen and makes polymerOlefines unsaturated group hydrogenation, the polymer solution after at least a portion that wherein circulates hydrogenation continuesContinuous hydrogenation. In the method, applied reactor comprises that two or two are connected in series aboveReactor, course of reaction is carried out continuously or intermittently, in course of reaction one of at least one reactorPartial reaction effluent recycles and gets back in this reactor or upstream reaction after external heat exchanger heat exchangeIn device, thereby improve product degree of hydrogenation by constantly circulating. The weak point of the method is as follows: shouldIn the first reactor of method of hydrotreating and/or later reactor, to stir, in course of reaction, needTo constantly consume and stir required mechanical energy, and make its manufacture and maintenance cost with the sealing of mixing plantAll higher; In addition, need to repeatedly add hydrogenation catalyst, make the control of course of reaction comparatively complicated;This method of hydrotreating is only applicable to carry out hydrogenation with metallocene as polymer hydrogenating catalyst, is not suitable forThe hydrogenation catalyst of other type carries out hydrogenation as Fe, Co, Ni etc.
US3,696,088 disclose a kind of unsaturated polymer that adopts homogeneous hydrogenation catalyst systemContinously hydrogen adding method, the method 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 hydrogenAtmosphere, reacts after 4 minutes the degree of hydrogenation of conjugated diene section in polymer and is greater than 98%. This inventionAlthough method hydrogenation speed is fast, has the following disadvantages: hydrogenation catalyst consumption is large, reaction temperatureHigh; The liquid holdup utilization rate little, unit volume reactor of trickle bed reactor is low; In addition, byHeat-transfer effect in trickle bed reactor is bad, works as two keys in polymer solution in the reaction starting stageConcentration is higher, exothermic heat of reaction when larger reaction heat be difficult to withdraw from, therefore, reaction temperature is difficult to steadilyControl and even make reaction temperature significantly raise, and then can make hydrogenation catalyst inactivation cause hydrogenation weekPhase extends or final products degree of hydrogenation reduces.
CN101492513A discloses a kind of hydrogenation reactor and method for hydrogenating polymer, wherein saidHydrogenation reactor is the combination of two or more bubbling reactors, the first bubbling is wherein set anti-Answer device to make its Flow of Goods and Materials state approach complete mixing flow, and arrange second and later bubbling reactor makeIts Flow of Goods and Materials state approaches laminar flow. The shortcoming of this method is to only depend on more difficult first drum that makes of flow hydrogen gasThe Flow of Goods and Materials state of bubble reactor approaches complete mixing flow, and only depends on flow hydrogen gas and jacket for heat exchange alsoHaving much difficulty in healing, steady control reaction temperature, especially reactor volume are large, exothermic heat of reaction is more, polymerAll the more so when solution viscosity is larger, will affect so abundant contact and the catalyst activity of gas-liquidThereby affect hydrogenation efficiency. In the method, the first reactor hydrogen gas velocity is larger in addition, therefore, needsThe hydrogen flowing quantity circulating is larger, and the energy that circulating hydrogen consumes is also more, causes recycle unitExpense is also larger.
GB1,343,447 relate to a kind of method of carrying out gas-liquid contact reaction, wherein adopt special gasLiquid contact reactor makes high-viscosity polymer hydrogenation, has two Stirring axles to stir poly-in reactorCompound solution, installs multiple retaining elements on rotating shaft, polymer solution remain in spinner member itBetween, between the inner surface of reactor wall and the viscosity solution of spinner member, form certain space,Again form solution-air surface by shear-mixed, realize gas-liquid contact, and constantly update gas-liquid contactFace, can continuous feed discharging, and when Hydrogen Vapor Pressure is 0.2MPa, Stirring axle rotating speed is 60Rev/min, hydrogenation temperature is controlled at 68 ± 30 DEG C, reacts hydrogenation of polymer Du Keda 82% 50 minutes.The shortcoming of this invention is that structure of reactor complexity, manufacturing cost are high and final products degree of hydrogenation is low.
US4,501,875, US4,673,714 and GB2,159,819A etc. all adopt stirred tank to carry outIntermittently hydrogenation, because two key concentration in reaction reaction solution in early stage is high and hydrogenation speed causes heat release soonAmount is large, makes reaction temperature be difficult to control, thereby will make like this impact of partially catalyzed agent inactivation addHydrogen efficiency. In addition, intermittent reaction is also unfavorable for industry amplification.
In sum, need at present one badly and can control better reaction temperature, thereby in longer operationKeep catalyst activity in cycle, and then improve hydrogenation efficiency, with reach desirable degree of hydrogenation containing alkeneThe method of hydrotreating of the polymer of class unsaturated bond.
Summary of the invention
To the object of the invention is the above deficiency of leaving in prior art in order overcoming, to provide the one can be moreControl well reaction temperature, thereby keep catalyst activity within the longer operation cycle, and then raising addsHydrogen efficiency, to reach the method for hydrotreating of the polymer containing olefines unsaturated bond of desirable degree of hydrogenation.
In view of the situation of above-mentioned prior art, the inventor adds for the polymer solution containing unsaturated bondHydrogen has carried out extensive and deep research, finds in the annular-pipe reactor of at least two series connection, logicalCrossing the recycle ratio of controlling reactor makes polymer solution material in annular-pipe reactor in complete mixing flow shapeState, makes hydrogenation of polymer, thereby can realize better heat transfer, the mass transfer of hydrogenation process,Control better reaction temperature, and within the longer operation cycle, keep catalyst activity, Jin ErtiHigh hydrogenation reaction efficiency, stably to make hydrogenation of polymer degree reach desirable within the longer operation cycleValue.
The invention provides a kind of process for selective hydrogenation of the polymer containing olefines unsaturated bond, the method bagDraw together under hydrogenation conditions, under hydrogenation catalyst exists, make containing the polymer of olefines unsaturated bondSolution, hydrogen contact in reactor, and wherein, described reactor is connected in series for two or moreAnnular-pipe reactor, controlling the recycle ratio of the first reactor is 10-200, the second reactor and laterThe recycle ratio of reactor is 10-100, makes the material in reactor approach complete mixing flow state.
Method provided by the invention, can realize heat transfer, the mass transfer of hydrogenation process, more betterControl well reaction temperature, thereby within the longer operation cycle, keep catalyst activity, Jin ErtiHigh hydrogenation reaction efficiency, stably to make hydrogenation of polymer degree reach desirable within the longer operation cycleValue.
Brief description of the drawings
Fig. 1 has described the process flow diagram of a kind of embodiment of the inventive method, wherein usesTwo annular-pipe reactors that are connected in series.
Detailed description of the invention
The invention provides a kind of process for selective hydrogenation of the polymer containing olefines unsaturated bond, the method bagDraw together the method under hydrogenation conditions, under hydrogenation catalyst exists, make gathering containing olefines unsaturated bondSolution, the hydrogen of compound contact in reactor, make by the recycle ratio of controlling described annular-pipe reactorMaterial in reactor approaches complete mixing flow state, and the recycle ratio of the first reactor is 10-200, and second is anti-Answering the recycle ratio of device and later reactor is 10-100, makes the material in reactor approach complete mixing flowState.
In the present invention, described recycle ratio refers to the circular flow and the described ring canal reaction of outflow of axial-flow pumpThe ratio of the flow of device.
In the present invention, described complete mixing flow state refers in corresponding reactor, due to strong in reactorStirring action, make just to enter in the material infinitesimal of reactor and device instantaneous reaching between original material infinitesimalFully mix, each point concentration is equated and temporal evolution not, reactor outlet fluid composition and the interior phase of deviceDeng state.
In the present invention, described annular-pipe reactor is made up of one or more straight pipe type reaction tube, and straight pipe type is anti-Should pipe peripheral hardware chuck, between straight pipe type reaction tube, connected first straight pipe type reaction tube and last by bend pipeA straight pipe type reaction tube connects and composes closed-loop path with tube connector, on the closed-loop path of annular-pipe reactorBe provided with circulating pump. Flow by controlled circulation pump internal circulating load and outflow annular-pipe reactor makes annular-pipe reactorInterior material is in complete mixing flow state. The draw ratio of described annular-pipe reactor straight length refers to that annular-pipe reactor is straightThe length of pipeline section and the diameter ratio of straight length.
The first reactor of the present invention can from second or later reactor is identical also can be different, its behaviourThe condition of doing also can be identical or different.
In the method for the invention, the hydrogenation reactor using comprises that two or more endless tubes are anti-Answer device, these reactors are connected in series each other, and in all reactors, polymer solution is all locatedIn complete mixing flow state, wherein enter the unsaturated double-bond relative concentration in the polymer solution of the first reactorEnter second or large with the unsaturated double-bond concentration of post-reactor, need the unsaturated double-bond concentration of hydrogenationAlso large, it is fast that reaction speed is wanted relatively, and it is large that corresponding thermal discharge is also wanted, and therefore requires the heat exchange of the first reactorArea relative second or large with the heat exchange area of post-reactor, the recycle ratio of material in the first reactorRelative second or also large with post-reactor. Enter second or with in the polymer solution of post-reactor notSaturated pair of key relative concentration the first reactor is little, and reaction speed reduces relatively, and thermal discharge reduces gradually,The heat exchange area of reactor can reduce gradually. This complete mixing flow reactor with different operating conditional combinationMethod for hydrogenating polymer can realize the temperature of more stable control hydrogenation process, betterRealize contacting of polymer solution and hydrogen, thereby more stable control hydrogenation process is stableCatalyst activity, thus reach the object that improves catalyst activity and hydrogenation reaction efficiency.
Particularly, in the method for the invention, in the first reactor, hydrogen does not flow, as long as keepReact required pressure, can make the flow regime of reactant mixture by the circulation of polymer solutionApproach complete mixing flow, and owing to entering unsaturated double-bond concentration phase in the polymer solution of the first reactorTo higher, reaction speed is relatively very fast, can make wherein most of unsaturated double-bond obtain hydrogenation,For example can make degree of hydrogenation reach 90% or more than, comparatively violent, the exothermic heat of reaction of hydrogenation reaction like thisMeasure relatively large, at this moment need polymer solution a large amount of circulations in annular-pipe reactor be recycle ratioThe large control reaction temperature of could stablizing, stabilizing catalyst activity, preferably, the following of the first reactorChain rate is 20-150; And enter second and later reactor polymer solution in unsaturated double-bondConcentration reduces gradually, needs the unsaturated bond quantity of hydrogenation to reduce gradually, and reaction speed reduces gradually,Exothermic heat of reaction also reduces gradually, second or the recycle ratio of later reactor be 10-60. Course of reactionMiddle recycle ratio is too little, and polymer solution can not fully contact with hydrogen, and hydrogenation reaction efficiency is low, andHeat-transfer effect is bad, can not control hydrogenation reaction temperature, and recycle ratio is too large, although can improve hydrogenationReaction efficiency, but it is high to consume energy, uneconomical.
In the method for the invention, in hydrogenation process, the hydrogen pressure in each reactor can identically also canWith difference, be respectively 0.2-10MPa (gauge pressure), be preferably 0.5-5MPa (gauge pressure). Wherein, hydrogenAdd from each reactor bottom, in each reactor, hydrogen does not flow substantially, as long as keep normal anti-Should required pressure, in the time that reaction pressure reduces by control valve to reaction system ftercompction.
In the method for the invention, in hydrogenation process, the temperature in each reactor can identically also canWith difference, be respectively 30-130 DEG C, be preferably 40-100 DEG C. Wherein, in the first reactor,Because exothermic heat of reaction is more, not only can make gas-liquid fully connect by a large amount of circulations of polymer solutionTouch, improve hydrogenation reaction efficiency, and can enhanced heat exchange efficiency, stable hydrogenation reaction temperature,Thereby stabilizing catalyst activity, and second or later reactor in due to exothermic heat of reaction relativelyLittle, do not need very large heat exchange area just can stablize reaction temperature, but still require gas-liquid fully to connectTouch.
Particularly, in the method for the invention, the length of the straight length of wherein said first ring pipe reactorFootpath, than for 3-200, is preferably 6-150, more preferably 10-120, second or annular-pipe reactor laterStraight length draw ratio is 2-150, is preferably 4-100, more preferably 8-80. Described annular-pipe reactorBe provided with charging aperture and discharging opening in bottom.
In the method for the invention, described hydrogenation catalyst and molten containing the polymer of olefines unsaturated bondLiquid passes in and out each reactor in a continuous manner, hydrogenation catalyst can with polymer solution premix after enter, alsoCan enter from identical or different entrance respectively, preferably after hydrogenation catalyst and polymer solution premix, enterOr the two enters from same entrance.
In the method for the invention, can determine the inlet flow rate of polymer solution and go out according to production scaleMouthful flow, and can determine accordingly size for example definite described annular-pipe reactor of described annular-pipe reactorThe draw ratio of straight length part, thus determine the time of staying of polymer solution in reactor, described theMean residence time in one annular-pipe reactor is 10-120min, is preferably 20-60min, second or withMean residence time in rear annular-pipe reactor is 20-240min, is preferably 30-150min. The time of stayingToo short, can not make the abundant hydrogenation of polymer solution, the time of staying is oversize, although can make polymer solution fillDivide hydrogenation, but power consumption is too high, uneconomical.
In the method for the invention, hydrogenation process can be continuous, also can be intermittently, but preferably addH-H reaction process is continuous.
In the method for the invention, the concentration of the solution of the described polymer containing olefines unsaturated bond canThink 5-40 % by weight, be preferably 8-30 % by weight. Wherein, the solvent using is inertia hydro carbonsSolvent, this varsol is selected from alkane, cycloalkane and aromatic hydrocarbons. At this, 'inertia' is with disturbance reponse notIn device hydrogenation reaction enter principle of conduct, described varsol can not with reactant or productBetween react, can not be unfavorable for the performance of catalyst activity.
In the method for the invention, the described polymer containing olefines unsaturated bond can be described containing alkeneThe polymer of hydro carbons unsaturated bond is conjugated diolefin homopolymerization thing and/or conjugated diene and vinyl aromatic (co)The copolymer of hydrocarbon, described conjugated diene homopolymers is polybutadiene and/or polyisoprene; Described commonThe copolymer of yoke diene and vinyl-arene is butadiene and/or isoprene and cinnamic random commonPolymers and/or butadiene and/or isoprene and cinnamic block copolymer and/or butadiene and/Or the random copolymer of isoprene and AMS and/or butadiene and/or isoprene andAlpha-methylstyrene block copolymer.
In the method for the invention, described hydrogenation catalyst can be for hydrogenation of polymer in this areaAny suitable hydrogenation catalyst. Described hydrogenation catalyst can be to contain the periodic table of elements conventionallyThe organic compound of VIIIB family metal and the mixture of alkyl aluminum, described VIIIB family metal asIron, cobalt, nickel and palladium, be preferably nickel and cobalt; Described hydrogenation catalyst can be also metallocene catalysisAgent, this metallocene catalyst is preferably metallocene-titanium catalyst, and optional and organo-lithium compound is as alkylLithium mixes, and described lithium alkylide is preferably n-BuLi.
What in the method for the invention, the consumption of wherein said hydrogenation catalyst should be based on industrial economy is formerSuitably select, can not be too small or excessive, be unfavorable for normally carrying out of hydrogenation process because too small,And final products degree of hydrogenation cannot reach requirement, the excessive cost that not only can increase hydrogenation process, andAnd can increase the follow-up cost that removes hydrogenation catalyst, improve the production cost of product.
Particularly, in the method for the invention, described hydrogenation catalyst can be that organic acid nickel is as cycloalkanesAcid nickel or nickel octoate and alkyl aluminum are as the mixture of triisobutyl aluminium or triethyl aluminum, in this mixtureThe mol ratio of aluminium and nickel can be 8:1 to 1:1, is preferably 6:1 to 3:1, and now described hydrogenation is urgedThe consumption of agent can be 0.01-0.10gNi/100g polymer, is preferably 0.03-0.07gNi/100gPolymer.
In addition, in the method for the invention, described hydrogenation catalyst can be also metallocene-titanium catalyst and appointThe lithium alkylide of choosing is as the mixture of n-BuLi, and in this mixture, the mol ratio of lithium and titanium can be 0:1To 40:1, be preferably 3:1 to 20:1, and now the consumption of described hydrogenation catalyst can be0.01-0.5mmolTi/100g, containing the polymer of olefines unsaturated bond, is preferably0.05-0.3mmolTi/100g is containing the polymer of olefines unsaturated bond.
Embodiment 1
The present embodiment is for illustrating the method for hydrotreating containing the polymer of olefines unsaturated bond.
500L jacketed stirred autoclave is fully replaced with refining nitrogen, adds 250L hexamethylene after displacementAlkane and hexane mixed solvent (in this mixed solvent, the percentage by weight of cyclohexane is 87 % by weight) and3.5L commercial benzene ethene, continues to add 1.15L oxolane, then adds 0.5M n-BuLi to drawSend out agent solution 0.71L (mol ratio of oxolane and n-BuLi is 40:1), 50-60 DEG C of reaction30 minutes, continue to add the refining butadiene reaction of 24L 30 minutes, and then add 3.5L refiningStyrene reaction 30 minutes, adds 27ml isopropyl alcohol cessation reaction after having reacted. At this, benzeneThe concentration of ethene-butadiene block polymer (S-B-S) is about 10 % by weight based on whole polymerization system,The molecular weight of this block polymer is 6.0 ten thousand, and the weight ratio of styrene and butadiene monomer unit is29:71, in polymer, the contents of ethylene of butadiene section is that 41 % by weight (adopt Switzerland BrukerThe AVANCEDRX400MHz of company nuclear magnetic resonance chemical analyser is measured).
By nickel naphthenate (Yanshan Mountain, Beijing synthetic rubber plant, 3gNi/L, technical grade) and triisobutyl aluminium (northFlycatcher mountain synthetic rubber plant, 4gNi/L, technical grade) according to aluminium nickel mol ratio (by metal) for 4:1 mixedClose, by the ageing 30 minutes at 50 DEG C of this mixture, be then added to styrene obtained aboveIn-butadiene block polymer solution, and stir. At this, the consumption of hydrogenation catalyst is0.06gNi/100g polymer.
This hydrogenation operation adopts the device shown in Fig. 1, comprising two rings that are connected in seriesPipe reactor, wherein the draw ratio of first ring pipe reactor straight length is 60, the volume of reactor is100L; Draw ratio in the second annular-pipe reactor straight length is 40, and reactor volume is 300L. ItsIn the first and second reactors all use in advance nitrogen replacement, then use hydrogen exchange. Material enters first continuouslyAnnular-pipe reactor, continuously enters second annular-pipe reactor after staying for some time in the first reactor,After staying for some time in the second reactor, flow out continuously from the outlet of the second annular-pipe reactor.
First in the first reactor, carry out intermittent reaction, in the first reactor after hydrogen exchangeSqueeze into the pre-mixed styrene-butadiene block polymer solution containing hydrogenation catalyst of 80L with pump, keepReaction temperature is 60 DEG C, and logical hydrogen also keeps Hydrogen Vapor Pressure 2.5MPa (gauge pressure), opens axial-flow pump, makesPolymer solution circulates in described the first reactor, and internal circulating load is 2000L/h, in course of reaction, passes throughChuck and hydrogen regulating valve control reaction temperature and pressure, react 30 minutes sampling iodimetric analysisesIts degree of hydrogenation, in polymer, the degree of hydrogenation of butadiene section is 98.5%, reacts 1 hour degree of hydrogenation99.4%。
Intermittent reaction completes and in backward the first reactor, adds continuously the styrene-Ding bis-containing hydrogenation catalystAlkene block polymer solution, feed rate is 160L/h, opens axial-flow pump simultaneously, by regulating axial-flow pumpFlow a part is circulated in the first reactor containing the polymer solution of hydrogenation catalyst, make polymerThe circular flow of solution in described first ring pipe reactor and the flow that flows out described annular-pipe reactorRatio (that is, and the internal circulating load of axial-flow pump in the first reactor with flow out the first ratio that reacts tolerance, alsoBe called recycle ratio) be 60, in course of reaction, keeping reaction temperature is 55 DEG C, by control valve controlThe addition of hydrogen, maintains Hydrogen Vapor Pressure 2.5MPa (gauge pressure). First ring pipe reactor adopts outside folderCover heat exchange, the time of staying of polymer solution in first ring pipe reactor is 30 minutes. Reaction oneAfter the section time, every one hour degree of hydrogenation from the different parts sample analysis sample point of the first reactor,The position of sample analysis is respectively the flow direction according to material, taking the entrance of the first reactor as starting point, and firstThe outlet of reactor is terminal, on average every a segment distance, a sample point is set, and 5 samplings are set altogetherPoint, the result of 5 sample point resulting polymers degrees of hydrogenation is very approaching, degree of hydrogenation is respectively 96.8%,96.9%, 96.9%, 96.9% and 97.0%, can think thus Flow of Goods and Materials state in the first reactorApproach complete mixing flow.
Next, the polymer solution of outflow first ring pipe reactor enters the second annular-pipe reactor continuationCarry out hydrogenation reaction, wherein make the circular flow of polymer solution in described the second annular-pipe reactorThe temperature that is 40, the second annular-pipe reactors with the ratio of flow that flows out described annular-pipe reactor is 65 DEG C,Hydrogen Vapor Pressure is 2.5MPa (gauge pressure), the time of staying of polymer solution in the second annular-pipe reactorIt is 90 minutes. After reaction a period of time, every the sampling point of the different parts from the second reactor in a hourAnalyse, the position of sample analysis is respectively the flow direction according to material, taking the entrance of the second reactor as starting point,The outlet of the second reactor is terminal, on average every a segment distance, a sample point is set, and sampling is set altogether5 of points, test result shows that the result of 5 sample point test resulting polymers degrees of hydrogenation is very approaching,Degree of hydrogenation is respectively 98.8%, 98.9%, 98.7%, 98.8% and 98.8%, can think second thusIn reactor, Flow of Goods and Materials state approaches complete mixing flow,
After reaction a period of time, sampled and used iodine from first and second reactor outlet respectively every one hourAmount method analyzing polymers degree of hydrogenation. Reaction has continued 80 hours, the average hydrogenation reaction knot of each reactorFruit is in table 1.
Embodiment 2
Except the circular flow in first ring pipe reactor with flow out described annular-pipe reactor flow itThan be circular flow in 100, the second annular-pipe reactors with flow out described annular-pipe reactor flow itThan being beyond 40, contain the polymer of olefines unsaturated bond by method the same in embodiment 1Hydrogenation reaction, the results are shown in Table 1.
Embodiment 3
Except the circular flow in first ring pipe reactor with flow out described annular-pipe reactor flow itThan be circular flow in 150, the second annular-pipe reactors with flow out described annular-pipe reactor flow itThan being beyond 40, contain olefines unsaturated double-bond polymer by method the same in embodiment 1The hydrogenation reaction of solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 4
Except the circular flow in first ring pipe reactor with flow out described annular-pipe reactor flow itThan be circular flow in 20, the second annular-pipe reactors with flow out described annular-pipe reactor flow itThan being beyond 40, contain olefines unsaturated double-bond polymer by method the same in embodiment 1The hydrogenation reaction of solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 5
Except the circular flow in first ring pipe reactor and the ratio of the flow of the described annular-pipe reactor of outflowBe that circular flow in 60, the second annular-pipe reactors is with the ratio of the flow that flows out described annular-pipe reactorBeyond 60, contain adding of olefines unsaturated double-bond polymer solution by method the same in embodiment 1H-H reaction, hydrogenation reaction the results are shown in Table 1.
Embodiment 6
Except the circular flow in first ring pipe reactor and the ratio of the flow of the described annular-pipe reactor of outflowBe that circular flow in 60, the second annular-pipe reactors is with the ratio of the flow that flows out described annular-pipe reactorBeyond 10, contain adding of olefines unsaturated double-bond polymer solution by method the same in embodiment 1H-H reaction, hydrogenation reaction the results are shown in Table 1.
Embodiment 7
Except the time of staying of polymer solution in first ring pipe reactor is 20 minutes, at the second ringThe time of staying in pipe reactor is beyond 90 minutes, contains alkene by method the same in embodiment 1The hydrogenation reaction of hydro carbons unsaturated double-bond polymer solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 8
Except the time of staying of polymer solution in first ring pipe reactor is 40 minutes, at the second ringThe time of staying in pipe reactor is beyond 90 minutes, contains alkene by method the same in embodiment 1The hydrogenation reaction of hydro carbons unsaturated double-bond polymer solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 9
Except the time of staying of polymer solution in first ring pipe reactor is 60 minutes, at the second ringThe time of staying in pipe reactor is beyond 90 minutes, contains alkene by method the same in embodiment 1The hydrogenation reaction of hydro carbons unsaturated double-bond polymer solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 10
Except the time of staying of polymer solution in first ring pipe reactor is 30 minutes, at the second ringThe time of staying in pipe reactor is beyond 60 minutes, contains alkene by method the same in embodiment 1The hydrogenation reaction of hydro carbons unsaturated double-bond polymer solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 11
Except the time of staying of polymer solution in first ring pipe reactor is 30 minutes, secondThe time of staying in annular-pipe reactor is beyond 120 minutes, enters by method the same in embodiment 1Row is containing the hydrogenation reaction of olefines unsaturated double-bond polymer solution, and hydrogenation reaction the results are shown in Table 1.
Embodiment 12
Except the time of staying of polymer solution in first ring pipe reactor is 30 minutes, secondThe time of staying in annular-pipe reactor is beyond 150 minutes, enters by method the same in embodiment 1Row is containing the hydrogenation reaction of olefines unsaturated double-bond polymer solution, and hydrogenation reaction the results are shown in Table 1.
Embodiment 13
Except draw ratio 10, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactorDraw ratio 40 beyond, contain olefines unsaturated double-bond by method the same in embodiment 1 and gatherThe hydrogenation reaction of compound solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 14
Except draw ratio 120, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactorDraw ratio 40 beyond, contain olefines unsaturated double-bond by method the same in embodiment 1 and gatherThe hydrogenation reaction of compound solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 15
Except draw ratio 60, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactorDraw ratio 8 beyond, contain olefines unsaturated double-bond by method the same in embodiment 1 and gatherThe hydrogenation reaction of compound solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 16
Except draw ratio 60, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactorDraw ratio 80 beyond, contain olefines unsaturated double-bond by method the same in embodiment 1 and gatherThe hydrogenation reaction of compound solution, hydrogenation reaction the results are shown in Table 1.
Embodiment 17
Except hydrogenation catalyst consumption is 0.04gNi/100g polymer, with in embodiment 1 oneThe method of sample contains the hydrogenation reaction of olefines unsaturated double-bond polymer solution, hydrogenation reaction knotFruit is in table 1.
Embodiment 18
Except hydrogenation catalyst consumption is 0.03gNi/100g polymer, with in embodiment 1 oneThe method of sample contains the hydrogenation reaction of olefines unsaturated double-bond polymer solution, hydrogenation reaction knotFruit is in table 1.
Embodiment 19
Except polymer solution and hydrogenation catalyst agent solution join respectively in first ring pipe reactor withContain adding of olefines unsaturated double-bond polymer solution by method the same in embodiment 1 outward,H-H reaction, hydrogenation reaction the results are shown in Table 1.
Embodiment 20
Except adding containing in the styrene-butadiene block polymer solution of active group that polymerization obtainsThe cyclohexane solution of 0.1M n-BuLi, then stops 10 minutes with hydrogen, then adds containing two pairsThe toluene solution of tolyl two luxuriant titaniums, adds first ring pipe reactor after mixing, catalyst is usedAmount is 0.2mmolTi/100g polymer, and Li/Ti mol ratio is 8:1, anti-in first ring pipe reactorAnswering temperature is 70 DEG C, and the reaction temperature in the second annular-pipe reactor is 75 DEG C, hydrogenation reaction resultIn table 1.
Embodiment 21
The basic embodiment 20 that repeats, just first ring pipe reactor interior reaction temperature is 70 DEG C, secondReaction temperature in annular-pipe reactor is 90 DEG C, and hydrogenation reaction the results are shown in Table 1.
Embodiment 22
The basic embodiment 1 that repeats, just in the time of polymerisation, styrene and butadiene add simultaneously, instituteThe polymer obtaining is styrene-butadiene atactic polymer, the molecular weight of resulting polymers, benzene secondIn alkene and butadiene unit weight ratio, polymer contents of ethylene of butadiene section etc. all with embodiment 1Identical, polymer solution concentration is 15 % by weight, and hydrogenation reaction the results are shown in Table 1.
Embodiment 23
The basic embodiment 1 that repeats just substitutes butadiene, gained with isoprene in the time of polymerisationTo polymer be styrene-isoprene block polymer (S-I-S), hydrogenation reaction the results are shown in Table 1.
Embodiment 24
The basic embodiment 1 that repeats, just hydrogenation process is comprising 3 reactions that are connected in seriesDevice, wherein the 3rd reactor is identical with the second annular-pipe reactor, and polymer solution is at 3 reactorsIn the time of staying be respectively 20,60,60 minutes, reaction continued 30 hours, afterwards from threeIndividual reactor outlet sampling and with its degree of hydrogenation of iodimetric analysis, result shows that three reactorsBack end hydrogenation degree is followed successively by 96.0%, 98.1% and 99.5%.
In embodiment 1-24, all after reaction a period of time, every one hour from the first reactor notWith the degree of hydrogenation of position sample analysis sample point, the position of sample analysis is respectively the flow direction according to material,Taking the entrance of the first reactor as starting point, the outlet of the first reactor is terminal, on average every a segment distanceIf a sample point, arranges 5 sample points altogether. In embodiment 1-24,5 sample point resulting polymersThe result of degree of hydrogenation is all very approaching.
Comparative example 1
The basic embodiment 1 that repeats, the just circular flow in first ring pipe reactor and the described ring of outflowThe ratio of the flow of pipe reactor is the circular flow and the described endless tube of outflow in 5, the second annular-pipe reactorsThe ratio of the flow of reactor is 3, and hydrogenation reaction the results are shown in Table 1.
In continously hydrogen adding course of reaction, keep the Hydrogen Vapor Pressure in the first and second annular-pipe reactors to be2.5MPa (gauge pressure). In course of reaction by the each inside reactor temperature of chuck control, but each reactorThe especially more difficult stable control of first ring pipe reactor internal temperature of interior temperature. Reaction has continued 10 littleTime, the degree of hydrogenation of first ring pipe reactor outlet sample is 85.0%, the second annular-pipe reactor outlet sampleThe degree of hydrogenation of product is 93.5%. Result shows that, in continued operation process, first and second reactor followsHour, the flow regime of material in two reactors is not all complete mixing flow to chain rate, hydrogenation reaction temperatureMore difficult stable control, gas-liquid contact is insufficient, and final products degree of hydrogenation is undesirable.
Comparative example 2
The basic embodiment 1 that repeats, the just circular flow in first ring pipe reactor and the described ring of outflowThe ratio of the flow of pipe reactor is the circular flow and the described ring of outflow in 60, the second annular-pipe reactorsThe ratio of the flow of pipe reactor is 3. Reaction has continued 10 hours, first ring pipe reactor outlet sampleThe degree of hydrogenation of product is that the degree of hydrogenation of 96.9%, the second annular-pipe reactor outlet sample is 97.7%. ResultShow in continued operation process, the recycle ratio of the second annular-pipe reactor too hour, gas-liquid mass transfer effectFruit is bad, and hydrogenation reaction efficiency is lower, and final products degree of hydrogenation is lower. Can find out, pass through simultaneouslyThe recycle ratio hydrogenation reaction efficiency that improves first ring pipe reactor improves to some extent compared with comparative example 1.
Comparative example 3
Except the circular flow in first ring pipe reactor with flow out described annular-pipe reactor flow itThan being circular flow in 5, the second annular-pipe reactors and the ratio of flow that flows out described annular-pipe reactorBe 40, all the other are with embodiment 1. In course of reaction by the each inside reactor temperature of chuck control,But the more difficult stable control of first ring pipe reactor temperature. Reaction has continued 10 hours, and the first endless tube is anti-The degree of hydrogenation of answering device outlet sample is that the degree of hydrogenation of 85.0%, the second annular-pipe reactor outlet sample is97.2%. Result shows in continued operation process, when the recycle ratio of first ring pipe reactor is lower,The hydrogenation reaction efficiency of first ring pipe reactor is lower, can find out, by improving the second endless tube simultaneouslyThe recycle ratio hydrogenation reaction efficiency of reactor improves to some extent compared with comparative example 1.
The impact of table 1 operating condition on hydrogenation reaction
* degree of hydrogenation result is the degree of hydrogenation of alkadienes section in polymer, surveys the degree of unsaturation (being iodine number) before and after hydrogenation in polymer determine by iodimetric titration. Benzene ring hydrogenation degree is all less than 2%, by nmr for the determination. This embodiment 24 of * applies three stringsThe reactor that connection connects, which reactor bracket inner digital represents. 100g polymer refers to containing the polymer containing olefines unsaturated bond.
As can be seen from Table 1, can be found out by the hydrogenation reaction result of above each embodiment and comparative example,According to method of the present invention, the Efficient Cycle by polymer solution in hydrogenation reactor can make polymerizationThing solution fully contacts with hydrogen, improves gas-liquid mass transfer effect, can steadily control reaction temperature simultaneously,Can make hydrogenation reaction efficiency have a more substantial increase.
Can be found out by comparative example 1-3, when the first reactor or/and polymer solution in the second reactorRecycle ratio hour, can not make polymer solution fully contact with hydrogen, and gas-liquid mass transfer effect is undesirable,Hydrogenation reaction temperature also has much difficulty in healing and surely controls, and hydrogenation reaction efficiency is relatively low, final hydrogenation of net product degreeAlso lower.
Therefore, adopt annular-pipe reactor combination of the present invention and process conditions, not only can be more steadyReaction temperature is controlled on ground, further improves reaction efficiency, and the degree of hydrogenation of final products is obviously improved, andCan within the longer operation cycle, obtain the polymeric articles with desirable degree of hydrogenation, can reduce and react simultaneouslyMaterial consumption, energy consumption and device operation and the maintenance cost of journey.
Claims (21)
1. a process for selective hydrogenation that contains the polymer of olefines unsaturated bond, the method is included in and addsUnder hydroformylation reaction condition, under hydrogenation catalyst exists, make polymer solution, hydrogen containing olefines unsaturated bondGas contacts in reactor, it is characterized in that, described reactor is that two or more are connected in seriesAnnular-pipe reactor, controlling the recycle ratio of the first reactor is 10-200, the second reactor and later anti-Answering the recycle ratio of device is 10-100, makes the material in reactor approach complete mixing flow state.
2. method according to claim 1, wherein, the recycle ratio of the first reactor is 20-150.
3. method according to claim 1, wherein, the second reactor and later reactorRecycle ratio be 10-60.
4. according to the method described in any one in claim 1-3, wherein, in each reactorHydrogen pressure is identical or different, is 0.2-10MPa independently of one another.
5. method according to claim 4, wherein, hydrogen pressure in each reactor is identical or notWith, be 0.5-5MPa independently of one another.
6. according to the method described in any one in claim 1-3, wherein, in each reactorTemperature is identical or different, is 30-130 DEG C independently of one another.
7. method according to claim 6, wherein, temperature in each reactor is identical or notWith, be 40-100 DEG C independently of one another.
8. according to the method described in any one in claim 1-3, wherein, the first reactorThe draw ratio of straight length is 3-200, and the draw ratio of the second reactor and later reactor straight length is 2-150。
9. method according to claim 8, wherein, the major diameter of the straight length of the first reactorThan for 6-150, the draw ratio of the second reactor and later reactor straight length is 4-100.
10. method according to claim 9, wherein, the major diameter of the straight length of the first reactorThan for 10-120, the draw ratio of the second reactor and later reactor straight length is 8-80.
11. according to the method described in any one in claim 1-3, wherein, described the first reactorIn mean residence time be 10-120min, the average stop in the second reactor and later reactorTime is 20-240min.
12. methods according to claim 11, wherein, on average stopping in described the first reactorStaying the time is 20-60min, and the mean residence time in the second reactor and later reactor is30-150min。
13. methods according to claim 1, wherein, described gathering containing olefines unsaturated bondThe concentration of the solution of compound is 5-40 % by weight, the described polymer containing olefines unsaturated bond moltenThe solvent using in liquid is at least one the inertia hydro carbons being selected from alkane, cycloalkane and aromatic hydrocarbonsSolvent.
14. methods according to claim 13, wherein, described containing olefines unsaturated bondThe concentration of the solution of polymer is 8-30 % by weight,
15. according to the method described in claim 13 or 14, wherein, described unsaturated containing olefinesThe polymer of key is the copolymerization of conjugated diolefin homopolymerization thing and/or conjugated diene and vinyl-areneThing, described conjugated diene homopolymers is polybutadiene and/or polyisoprene; Described conjugated diene withThe copolymer of vinyl-arene be butadiene and/or isoprene and cinnamic random copolymer and/Or butadiene and/or isoprene and cinnamic block copolymer and/or butadiene and/or isoamylThe random copolymer of diene and AMS and/or butadiene and/or isoprene and Alpha-MethylStyrene block copolymer.
16. according to the method described in any one in claim 1, wherein, and described hydrogenation catalystAgent contains organic acid nickel and alkyl aluminum, in the alkyl aluminum of aluminium with in the organic acid nickel of nickel moleThan being 8:1 to 1:1; The consumption of described hydrogenation catalyst is 0.01-0.10gNi/100g polymer.
17. methods according to claim 16, wherein, in the alkyl aluminum of aluminium and in nickelThe mol ratio of organic acid nickel be 6:1 to 3:1; The consumption of described hydrogenation catalyst is0.03-0.08gNi/100g polymer.
18. methods according to claim 16, wherein, described organic acid nickel is nickel naphthenate,Described alkyl aluminum is triisobutyl aluminium or triethyl aluminum.
19. methods according to claim 1, wherein, described hydrogenation catalyst contains luxuriant titanium urgesAgent and optional lithium alkylide, the mol ratio of lithium and titanium is 0:1 to 40:1; Described hydrogenation catalystConsumption is 0.01-0.5mmolTi/100g polymer.
20. methods according to claim 19, wherein, described hydrogenation catalyst contains luxuriant titaniumCatalyst and optional lithium alkylide, the mol ratio of lithium and titanium is 3:1 to 20:1; Described hydrogenation catalystConsumption be 0.05-0.3mmolTi/100g polymer.
21. according to the method described in claim 19 or 20, and wherein, described lithium alkylide is normal-butylLithium.
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