CN103788272A - Hydrogenation method of polymer containing olefin unsaturated bonds - Google Patents
Hydrogenation method of polymer containing olefin unsaturated bonds Download PDFInfo
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Abstract
The invention provides a hydrogenation method of polymer containing olefin unsaturated bonds. The method comprises the following steps: in the presence of a hydrogenation catalyst, contacting a polymer solution containing olefin unsaturated bonds with hydrogen by a loop reactor and a tank reactor in order to carry out a catalytic hydrogenation reaction; then performing flash evaporation separation of the reaction product with the liquid phase being used as a hydrogenated polymer solution, performing condensation and recovery of the gas phase, and recycling the obtained solvent and hydrogen. The method realizes better dissolution of hydrogen in the polymer solution, optimizes the mass transfer, improves hydrogenation efficiency, realizes stable control of the reaction temperature at the initial stage of the hydrogenation, and improves the efficiency and stability of the hydrogenation reaction.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to a kind of method of hydrotreating of the polymkeric substance containing olefines unsaturated link(age).
Background technology
For improving thermotolerance, oxidative stability and the ageing resistance containing alkene unsaturated link(age) polymkeric substance, generally take method of hydrotreating to make the unsaturated link(age) in polymkeric substance saturated.Conventionally require the degree of unsaturation of hydrogenation post polymerization thing to be less than 2%(and be greater than 98% containing olefines unsaturated link(age) degree of hydrogenation), to obtain obvious improvement in performance.
U.S. Pat 6,815,509B2 discloses a kind of method for hydrogenating polymer, described method is included in that polymkeric substance that hydrogenation catalyst makes to contain olefines unsaturated group under existing contacts with hydrogen and the olefines unsaturated group hydrogenation that makes polymkeric substance, the polymkeric substance continuation hydrogenation after at least a portion that wherein circulates hydrogenation.In the method, applied reactor comprises two or two reactors that are connected in series above, reaction process is carried out continuously or intermittently, in reaction process, the recirculation after interchanger heat exchange of a part of reaction effluent of at least one reactor is got back in this reactor or in upstream reactor, thereby improves product degree of hydrogenation by constantly circulating.
The weak point of the method is: the first reactor of method of hydrotreating and/or later reactor must be with stirring, in reaction process, need constantly to consume to stir required mechanical energy, and with the sealing problem of whipping device make its manufacture and maintenance cost higher; And hydrogenation catalyst repeatedly adds, make the control of reaction process comparatively complicated.
U.S. Pat 3,696,088 discloses a kind of unsaturated polymer continously hydrogen adding method that adopts homogeneous hydrogenation catalyst system, wherein adopt trickle-bed reactor, be mainly used in styrene-conjugated diene analog copolymer hydrogenation, in reactor, fill inert filler, the downward drip of polymers soln is by hydrogen atmosphere, and the degree of hydrogenation that reacts conjugated diene section in 4 minutes polymkeric substance is greater than 98%.
Although the method hydrogenation speed is fast, weak point is, hydrogenation catalyst consumption is large, temperature of reaction is high; The liquid holdup utilization ratio little, unit volume reactor of trickle-bed reactor is low; And the heat-transfer effect of trickle-bed reactor is bad, in the reaction starting stage when pair key concentration in polymers soln is high, exothermic heat of reaction when larger reaction heat be difficult to withdraw from, temperature of reaction is difficult to steady control and even can significantly raises, and then can make hydrogenation catalyst inactivation cause hydrogenation cycle stretch-out or the finished product degree of hydrogenation to reduce.
Chinese patent CN101492513A discloses a kind of hydrogenator and method for hydrogenating polymer, wherein said hydrogenator is the combination of two or more bubbling reactors, the first bubbling reactor is wherein set and makes its Flow of Goods and Materials state approach complete mixing flow, and arrange second and later bubbling reactor make its Flow of Goods and Materials state approach plug 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 approach complete mixing flow, and only depend on flow hydrogen gas and jacket for heat exchange to be difficult to steadily control temperature of reaction, especially reactor volume is large, exothermic heat of reaction is more, polymer solution viscosity is all the more so when larger, thereby abundant contact and the catalyst activity that will affect like this gas-liquid affect hydrogenation efficiency.In the method, the first reactor hydrogen gas velocity is large in addition, needs the hydrogen flowing quantity of circulation just large, and the energy that circulating hydrogen consumes is also just many.
In prior art, U.S. Pat 4,501,875, US 4,673,714 and English Patent GB2,159,819A etc. all adopt stirring tank to carry out hydrogenation at intermittence, because two key concentration in reaction reaction soln in early stage is high and hydrogenation speed causes thermal discharge large soon, make temperature of reaction be difficult to control, thereby will make like this partially catalyzed agent inactivation affect the performance of hydrogenation efficiency and polymkeric substance.
Summary of the invention
In order better to control the temperature containing the reaction of olefines unsaturated link(age) hydrogenation of polymer, improve hydrogenation efficiency and stability, operation is controlled easy, the invention provides a kind of method of hydrotreating containing olefines unsaturated link(age) polymkeric substance, and this method of hydrotreating is achieved in that
Containing a method of hydrotreating for olefines unsaturated link(age) polymkeric substance, the method comprises the following steps successively:
(1) endless tube hydrogenation reaction: use the annular-pipe reactor (R1) of one or more series connection, under hydrogenation catalyst exists, the polymers soln that contains olefines unsaturated link(age) is contacted with hydrogen, carry out 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) Separation and Recovery: the product to described tank reactor (R2) carries out flash separation, the liquid phase that described flash separation obtains is the polymers soln after hydrogenation, the gas phase that described flash separation is obtained is carried out condensation recovery, described condensation is reclaimed the phlegma that contains solvent obtaining and is recycled, and described condensation is reclaimed the non-condensable gas that contains hydrogen obtaining and recycled.
In the specific implementation, the described polymkeric substance that contains olefines unsaturated link(age) is: conjugated diene homopolymers, the preferably multipolymer of polyisoprene or polyhutadiene or conjugated diolefine and vinyl-arene, preferably random copolymers or the segmented copolymer of isoprene or divinyl and cinnamic random copolymers or segmented copolymer, isoprene or divinyl and alpha-methyl styrene; Solvent in described polymers soln is inert hydrocarbon solvent, is selected from one or more in alkane, naphthenic hydrocarbon and aromatic hydrocarbons, preferably hexane; 'inertia' is with the principle of conduct that enters of hydrogenation reaction in disturbance reponse device not, described varsol can not and reactant or reaction product between react, can not be unfavorable for the performance of catalyst activity; The concentration of the described polymkeric substance that contains olefines unsaturated link(age) in solution is 5-40wt%, preferably 8-30wt%.
In the specific implementation, described hydrogenation catalyst can be any suitable hydrogenation catalyst for hydrogenation of polymer in this area.Described hydrogenation catalyst can be the organic compound that contains periodic table of elements VIIIB family metal and the catalyzer of organoaluminum conventionally, and described VIIIB family metal is as iron, cobalt, nickel and palladium, preferably nickel and cobalt; Described hydrogenation catalyst can be also metallocene catalyst, and this metallocene catalyst is preferably metallocene-titanium catalyst, and optionally mixes as lithium alkylide with organolithium compound, and described lithium alkylide is preferably n-Butyl Lithium and triisobutyl lithium.
In the specific implementation, in step (1), described annular-pipe reactor R1 outer setting chuck, medium in described chuck is refrigerant, preferably water is as removing thermal medium, because the heat transfer area of annular-pipe reactor chuck is large, can control preferably temperature of reaction, the long-term stability that rationally regulates water temperature to be conducive to catalytic hydrogenation reaction is carried out; A circulator is at least set in described annular-pipe reactor R1, and described circulator can be pump or other motor drives, so that the power of recycle stock in annular-pipe reactor to be provided; Multiple feed(raw material)inlets are set on annular-pipe reactor R1, and the raw material entering from feed(raw material)inlet comprises: the polymkeric substance, hydrogen, hydrogenation catalyst, thinner, promotor, processing additive or their mixture that contain olefines unsaturated link(age); Wherein be provided with the entrance of described hydrogenation catalyst in the suction side of described circulator, be provided with the entrance of other catalytic hydrogenation reaction materials except described hydrogenation catalyst at the outlet end of described circulator, and at least one catalyst inlet and at least one feed(raw material)inlet be separately positioned on to suction side and the outlet end of same circulator; Hydrogen buffer tank V1 is set before described annular-pipe reactor R1, after hydrogen is introduced into buffer tank, V1 enters annular-pipe reactor R1 again, by regulating the pressure of flow control buffer tank of hydrogen, is beneficial to the pressure-stabilisation of hydrogenator.
In the specific implementation, in step (2), described tank reactor R2 outside is provided with chuck, inside arranges inner cool tube, and the medium in described chuck and described cold pipe is refrigerant, and preferably water is as removing thermal medium; Described tank reactor R2 is provided with one or more hydrogen feed mouth; Described tank reactor R2 is provided with whipping device; Supplement and add described hydrogenation catalyst at described tank reactor R2.Because most of olefines unsaturated link(age) in annular-pipe reactor interpolymer is by hydrogenation, in tank reactor, do not exist and do not contacted mixing with hydrogen by the solution of the polymkeric substance containing olefines unsaturated link(age) of hydrogenation at hydrogenation catalyst, further improve the degree of hydrogenation of olefines unsaturated link(age).Hydrogenation catalyst can add annular-pipe reactor and tank reactor simultaneously, for handled easily, also can only in annular-pipe reactor, add excessive catalyzer, the discharging of annular-pipe reactor no longer adds catalyzer after entering tank reactor, utilizes remaining hydrogenation catalyst in material can complete hydrogenation reaction.
In the specific implementation, the Matter Transfer ratio of described endless tube hydrogenator is that 20 ~ 40(recycle ratio is the flow of annular-pipe reactor recycle pump and the ratio of reactor feed, in the time that recycle ratio is greater than 20, the admixture of material is close to complete mixing flow, for this technique, recycle ratio is that 20 ~ 40 o'clock mixed effects are better); The working pressure of described endless tube hydrogenator and described autoclave hydrogenator is 0.1-5.0MPa gauge pressure, preferred 0.5-4.0MPa gauge pressure, and service temperature is 30-150 ℃, preferred 40-120 ℃; The working pressure of buffer tank is 0.1-5.0MPa (gauge pressure), preferably 0.5-4.0MPa (gauge pressure); The working pressure of separating tank is 0.1-4.0MPa (gauge pressure), is preferably 0.4-3.0MPa (gauge pressure).
In the specific implementation, in step (3), the product of described tank reactor R2 is being carried out to multistage flash evaporation separation, the liquid phase that last step flash distillation obtains is the polymers soln after hydrogenation, condensations at different levels are reclaimed the phlegma that contains solvent obtaining and are recycled, and condensations at different levels are reclaimed the non-condensable gas that contains hydrogen obtaining and recycled.For example two-stage flash, material is introduced into flash trapping stage tank V2, and isolated one-level flash distillation gas phase is collected after E1 condensation or partial condensation; One-level flash liquid enters the second separating tank V3 and carries out two-stage flash, further isolate gas-liquid two-phase, two-stage flash gas phase is solvent gas and unreacted hydrogen, two-stage flash liquid phase is the polymers soln after final hydrogenation, two-stage flash gas phase is collected after E2 condensation or partial condensation, and after the condensation of firsts and seconds flashed vapour, gained phlegma reclaims and uses after merging.
Method of hydrotreating of the present invention, under existing, hydrogenation catalyst make the solution of the polymkeric substance that contains olefines unsaturated link(age) contact hydrogenation with hydrogen, comprise the polymkeric substance containing olefines unsaturated link(age), hydrogenation catalyst, hydrogen and selectable other promotors, thinner or their mixture are sent into hydrogenator, the hydrogenator that wherein used comprises annular-pipe reactor that one or more are connected in series and the combination of stirred-tank reactor, in annular-pipe reactor, at least there is a circulator, described circulator can be pump or other motor drives, to increase the pressure of recycle stock in annular-pipe reactor, circulation by material improves the rate of flow of fluid in endless tube, the abundant mixing that guarantees polymers soln and hydrogen with contact, when annular-pipe reactor hydrogenation in order to reach mixed effect better, requirement recycle ratio is that the ratio of circulating-pump outlet flow and reactor feedstocks feed rate is greater than 20, now the flow state of annular-pipe reactor inner fluid is close to complete mixing flow, therefore utilize the circulating effect of annular-pipe reactor to improve hydrogenation efficiency from optimizing mass transfer aspect, material after annular-pipe reactor hydrogenation enters tank reactor, tank reactor is band whipping device, hydrogen adds from reactor bottom, tank reactor comprises one or more hydrogen inlet, tank reactor is with chuck or while jacketed and inner cool tube, conduct heat by chuck and inner cool tube.Tank reactor also can further add hydrogenation catalyst, by the mixing of agitator, containing polymkeric substance, hydrogen further hydrogenation under the effect of hydrogenation catalyst of unsaturated link(age), reach after required residence time, the discharging of tank reactor 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, liquid phase is the polymers soln after hydrogenation, and flash distillation gas phase (partial condensation) after condensation is collected; If double flash evaporation, one-level flash liquid enters the second separating tank and carries out two-stage flash, further isolate gas-liquid two-phase, two-stage flash gas phase is diluent gas and unreacted hydrogen, two-stage flash liquid phase is the polymers soln after final hydrogenation, and two-stage flash gas phase (partial condensation) after condensation is collected, and firsts and seconds flashed vapour obtains after phlegma merges and reclaims and use, the non-condensable gas of firsts and seconds flashed vapour is hydrogen, can after compressor compression, recycle.
The inventive method can be operate continuously or periodical operation, when periodical operation, the charging of polymers soln, catalyzer, auxiliary agent etc. is that intermittent type adds, and hydrogen is continuously feeding, when hydrogenation reaction material reaction for some time, again product after hydrogenation is discharged after reaching the required residence time 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 effect is poor, be unfavorable for heat transfer rapid moving to remove, thereby cause temperature to raise, and higher temperature can cause the inactivation of catalyzer and the degree of hydrogenation of benzene ring to improve.Hydrogenation target of the present invention is the conjugated alkene section hydrogenation in polymkeric substance, do not wish benzene ring hydrogenation, therefore the present invention is at the initial stage in hydrogenation reaction, adopt annular-pipe reactor to control the temperature of hydrogenation reaction, the benzene ring hydrogenation degree in polymkeric substance is reduced as much as possible, in the time that hydrogenation reaction proceeds to the middle and later periods, hydrogenation reaction heat release is less, easy control of temperature, now material enters the hydrogenator of an autoclave again, further improves the conjugated alkene section degree of hydrogenation in polymkeric substance.Aspect the continuity operation of device, annular-pipe reactor can be realized continuous hydroprocessing in addition, and the hydrogenator that band of the prior art stirs is batch operation, and therefore annular-pipe reactor is easy to operate in hydrogenation process.Therefore compared with other hydrogenation reaction forms that the present invention stirs with band, temperature is more easily controlled, also simpler aspect operability.
Hydrogenator of the present invention comprises that one or more annular-pipe reactor and tank reactor carry out series combination.First reaction raw materials is introduced into annular-pipe reactor and carries out hydrogenation, can guarantee so abundant dissolving and the mixing of hydrogen in polymers soln, thereby make gas-to-liquid contact more abundant, can control better temperature of reaction at the hydrogenation reaction initial stage simultaneously, may cause benzene ring degree of hydrogenation to increase because temperature is high, and the hydrogenation of polymkeric substance is generally in order to guarantee the performance of product, need to reduce benzene ring hydrogenation (general requirement benzene ring degree of hydrogenation is less than 2%) as far as possible.Adopt the present invention can also effectively control temperature of reaction on the basis that guarantees mass transfer, and then improved hydrogenation efficiency and stability; Because the residence time of annular-pipe reactor is relatively short, in order further to improve the degree of hydrogenation of polymkeric substance, the tank reactor with stirring of connecting after annular-pipe reactor, the residence time of assurance hydrogenation material, makes polymkeric substance finally reach desirable degree of hydrogenation.
Accompanying drawing explanation
Fig. 1 is a kind of process flow diagram of the method for hydrogenating polymer containing olefines unsaturated link(age).
Nomenclature:
R1-endless tube hydrogenator V1-buffer tank
R2-autoclave hydrogenator V2-the first separating tank
E1-condenser V3-the second separating tank
E2-condenser
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with drawings and Examples, protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Styrene-isoprene-segmented copolymer and hydrogen, under the katalysis of hydrogenation catalyst, carry out shortening in annular-pipe reactor and tank reactor.
The solution (hydrogenating materials 2) of styrene-isoprene-segmented copolymer and hexane enters annular-pipe reactor R1 entrance with the flow velocity of 500L/h, the wherein 10wt% of styrene-isoprene-block copolymerization substrate concentration based on whole polymeric solution, the weight ratio of vinylbenzene and isoprene monomer unit is 3:7, and in polymkeric substance, the contents of ethylene of isoprene block is 30wt%.
Hydrogen (hydrogenating materials 1) enters annular-pipe reactor R1 entrance after buffer tank V1, and the flow of hydrogen is 80Nm
3/ h, arranges propeller pump in annular-pipe reactor R1, and hydrogenation material is circulated.The opening for feed of hydrogen and hydrogenation multipolymer is positioned at axial flow pump outlet, and the opening for feed of hydrogenation catalyst is positioned at the entrance of propeller pump.
The endless tube diameter of annular-pipe reactor R1 is 250mm, and the height of 2 straight lengths is 9 meters, and span is 1.2 meters; Propeller pump is arranged on the bottom of annular-pipe reactor R1, and the internal circulating load of propeller pump is 1000m
3/ h; Annular-pipe reactor R1 arranges chuck outward, and jacket for heat exchange area is 17m
2, in chuck, medium is hot water.Hydrogenator R1 uses in advance nitrogen replacement before charging, then uses hydrogen exchange.
Used catalyst preparation method is according to the method in CN1055294C: the concentration (by metal) of nickel naphthenate and triisobutyl aluminium is 2g/L, and aluminium nickel is 3:1 than (mol ratio); Catalyst levels is 8.33g Ni/h.
The discharging of annular-pipe reactor R1 enters in tank reactor R2, and in tank reactor R2, the consumption of catalyzer is 5.55g Ni/h, and tank reactor R2 volume is 500L, and diameter is 800mm, and cylindrical shell height is 1200mm, and reaction time is 1 hour.
Buffer tank V1 and annular-pipe reactor R1 working pressure are 2.0MPa, and service temperature is 100 ℃; The working pressure of tank reactor R2 is 1.9MPa, and service temperature is 100 ℃.Material after hydrogenation enters the first separating tank V2 from tank reactor R2 outlet and carries out flash distillation, and the pressure of separating tank V2 is 1.8MPa; The hydrogen dissolving in flash distillation post polymerization thing and part hexane gas enter condenser E1 condensation hexane, all the other polymers solns enter the second separating tank V3 and carry out flash distillation, the pressure of separating tank V3 is 1.5MPa, the liquid phase that flash separation obtains is the polymers soln after hydrogenation, and all the other hydrogen that dissolve in flash distillation post polymerization thing and part hexane gas enter condenser E2 by hexane condensation; The hexane that condenser E1 and E2 condensation are got off is 100L/h altogether, after collecting, reclaims and uses, and after not solidifying hydrogen collects, returns to hydrogenator through compressor compresses.
By polymkeric substance sampling its degree of hydrogenation of iodimetric analysis complete hydrogenation, in polymkeric substance, the degree of hydrogenation of isoprene section is 98.2%, and wherein benzene ring degree of hydrogenation is less than 1.8%.
Embodiment 2
The consumption of annular-pipe reactor hydrogenation catalyst is 8.36g Ni/h, and the consumption of tank reactor hydrogenation catalyst is 5.57g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of isoprene 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 8.38g Ni/h, and the consumption of tank reactor hydrogenation catalyst is 5.59g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of isoprene 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 8.40g Ni/h, and the consumption of tank reactor hydrogenation catalyst is 5.60g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of isoprene 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 8.44g Ni/h, and the consumption of tank reactor hydrogenation catalyst is 5.63g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of isoprene 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 8.48g Ni/h, and the consumption of tank reactor hydrogenation catalyst is 5.65g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of isoprene 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-segmented copolymer, and the weight ratio of vinylbenzene and butadiene monomer unit is 3:7, and in polymkeric substance, the contents of ethylene of butadiene block is 39wt%; The preparation method of catalyzer is identical with embodiment 1, and the consumption of annular-pipe reactor R1 hydrogenation catalyst is 8.32g Ni/h, and the consumption of tank reactor R2 hydrogenation catalyst is 5.54g Ni/h, and other conditions are identical with embodiment 1.After hydrogenation reaction, in polymkeric substance, the degree of hydrogenation of butadiene block is 98.0%, and benzene ring degree of hydrogenation is less than 1.8%.
Comparative example 1
In the tank reactor of 500L, carry out hydrogenation, styrene-isoprene-segmented copolymer and hydrogen are carried out to rhythmic reaction under the katalysis of aluminium nickel hydrogenation catalyst, catalyst levels is 13.88g Ni, reacting initial temperature is 70 ℃, reaction top temperature is 120 ℃, and the reaction times is 2 hours, and reaction pressure is 2.0MPa, end reaction device outlet hydrogenation of polymer degree is 98.0%, and benzene ring degree of hydrogenation is less than 2%.
Hydrogenation reaction result by above-described embodiment and comparative example can be found out: the method for hydrotreating that adopts annular-pipe reactor of the present invention and tank reactor, adopt annular-pipe reactor and polymers soln circulation, can control more reposefully temperature of reaction at hydrogenation reaction initial stage annular-pipe reactor chuck, increase gas-to-liquid contact area, greatly improve hydrogenation reaction efficiency, tank reactor has extended the time of hydrogenation reaction, the degree of hydrogenation of the finished product also obviously improves, benzene ring degree of hydrogenation obviously reduces, and has improved product performance; Because reaction pressure in continuous endless tube hydrogenation process is more steady, emptying amount is less, and therefore material consumption is few compared with autoclave hydrogenation process; Because continuous endless tube hydrogenation process has improved heat transfer efficiency, therefore energy consumption is compared with autoclave hydrogenation process few (in embodiment 1, the consumption of continuous endless tube hydrogenation recirculated water is 694kg/h, and in comparative example 1, the consumption of recirculated water is 809kg/h); And in the subsequent separation process of hydrogenation, will in hydrogen and partial solvent and hydrogenation polymkeric substance, separate by one-level or flash distillation more than one-level, by hydrogen and recycled solvent, flow process is simpler.Especially in the time of operate continuously, the method can obtain the polymeric articles with desirable degree of hydrogenation within the longer operational cycle, can reduce material consumption, energy consumption and the device process cost of reaction process simultaneously.
Claims (10)
1. containing a method of hydrotreating for olefines unsaturated link(age) polymkeric substance, the method comprises the following steps successively:
(1) endless tube hydrogenation reaction: use the annular-pipe reactor (R1) of one or more series connection, under hydrogenation catalyst exists, the polymers soln that contains olefines unsaturated link(age) is contacted with hydrogen, carry out 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) Separation and Recovery: the product to described tank reactor (R2) carries out flash separation, the liquid phase that described flash separation obtains is the polymers soln after hydrogenation, the gas phase that described flash separation is obtained is carried out condensation recovery, described condensation is reclaimed the phlegma that contains solvent obtaining and is recycled, and described condensation is reclaimed the non-condensable gas that contains hydrogen obtaining and recycled.
2. method of hydrotreating according to claim 1, is characterized in that:
The described polymkeric substance that contains olefines unsaturated link(age) is: the multipolymer of conjugated diene homopolymers or conjugated diolefine and vinyl-arene; Solvent in described polymers soln is selected from one or more in alkane, naphthenic hydrocarbon and aromatic hydrocarbons; The concentration of the described polymkeric substance that contains olefines unsaturated link(age) in solution is 5-40wt%.
3. method of hydrotreating according to claim 2, is characterized in that:
Described conjugated diene homopolymers is: polyisoprene or polyhutadiene, the multipolymer of described conjugated diolefine and vinyl-arene is: isoprene or divinyl and cinnamic random copolymers or segmented copolymer, or random copolymers or the segmented copolymer of isoprene or divinyl and alpha-methyl styrene; Solvent in described polymers soln is hexane; The concentration of the described polymkeric substance that contains olefines unsaturated link(age) in solution is 8-30wt%.
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 organoaluminum; Or be mixed with the metallocene catalyst of organolithium 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 organoaluminum; Or be mixed with n-Butyl Lithium 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 chuck is refrigerant; A circulator is at least set in described annular-pipe reactor (R1); Be provided with the entrance of described hydrogenation catalyst in the suction side of described circulator, be provided with the entrance of other catalytic hydrogenation reaction materials except described hydrogenation catalyst at the outlet end of described circulator; Described annular-pipe reactor (R1) arranges hydrogen buffer tank (V1) before, and hydrogen is introduced into (V1) after buffer tank and enters annular-pipe reactor (R1) again.
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, and the medium in described chuck and described cold pipe is refrigerant; Described tank reactor (R2) is provided with one or more hydrogen feed mouth; Described tank reactor (R2) is provided with whipping device.
8. method of hydrotreating according to claim 1, is characterized in that:
In step (1) and step (2), the working pressure of described annular-pipe reactor (R1) and described tank reactor (R2) is that 0.1-5.0MPa gauge pressure, service temperature are 30-150 ℃; The Matter Transfer ratio of described annular-pipe reactor (R1) is 20 ~ 40.
9. method of hydrotreating according to claim 8, is characterized in that:
The working pressure of described annular-pipe reactor (R1) and described tank reactor (R2) is that 0.5-4.0MPa gauge pressure, service temperature are 40-120 ℃.
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 last step flash distillation obtains is the polymers soln after hydrogenation, condensations at different levels are reclaimed the phlegma that contains solvent obtaining and are recycled, and condensations at different levels are reclaimed the non-condensable gas that contains hydrogen obtaining and recycled.
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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 |
| CN105542842A (en) * | 2014-11-03 | 2016-05-04 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction apparatus, system thereof, and continuous liquid phase hydrogenation method |
| CN114057911A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Continuous hydrogenation method of nitrile butadiene rubber solution |
| CN114437397A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Foaming device of foaming beads, production method and application thereof, and foaming beads |
| CN114539446A (en) * | 2020-11-26 | 2022-05-27 | 沈阳化工研究院有限公司 | Hydrogenation reaction method of conjugated diene-containing polymer |
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| CN105542842A (en) * | 2014-11-03 | 2016-05-04 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction apparatus, system thereof, and continuous liquid phase hydrogenation method |
| CN105295021A (en) * | 2015-12-01 | 2016-02-03 | 王伟跃 | Process of continuously producing amine-terminated polyether and reactor design of process |
| CN114057911A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Continuous hydrogenation method of nitrile butadiene rubber solution |
| 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 |
| CN114437397A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Foaming device of foaming beads, production method and application thereof, and foaming beads |
| CN114539446A (en) * | 2020-11-26 | 2022-05-27 | 沈阳化工研究院有限公司 | Hydrogenation reaction method of conjugated diene-containing polymer |
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