CN107099008A - A kind of hydrogenation of polymer reaction method of olefin-containing class unsaturated bond - Google Patents
A kind of hydrogenation of polymer reaction method of olefin-containing class unsaturated bond Download PDFInfo
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- CN107099008A CN107099008A CN201710400810.XA CN201710400810A CN107099008A CN 107099008 A CN107099008 A CN 107099008A CN 201710400810 A CN201710400810 A CN 201710400810A CN 107099008 A CN107099008 A CN 107099008A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Abstract
The invention discloses a kind of method of hydrotreating of the polymer of olefin-containing class unsaturated bond, this method is included under hydrogenation conditions, in the presence of a hydrogenation catalyst, the polymer solution and hydrogen of olefin-containing class unsaturated bond is set to contact in the reactor, it is characterized in that, the reactor is at least two reactors being connected in series, wherein first reactor is to be combined by tower reactor or stirred reactor with static mixer, by controlling the recycle ratio of the first reactor material in reactor is in close to complete mixing flow state, wherein, the recycle ratio of first reactor is 1~40：1；Second and later reactor be tower reactor, second and later reactor in material close to horizontal sliding stream mode.The method of this law invention, which can be better achieved, stably makes hydrogenation of polymer degree reach ideal value.
Description
Technical field
The present invention relates to a kind of hydrogenation of polymer reaction method of olefin-containing class unsaturated bond.More specifically, the present invention is related to
And make olefin-containing class unsaturated in the presence of hydrogenation catalyst and hydrogen using annular-pipe reactor and tower reactor tandem compound
The method of the polymer solution hydrogenation of key.
Background technology
The heat of polymer containing unsaturated bond, oxidative stability and resistance to ag(e)ing are poor, therefore make usually through method of hydrotreating to gather
The unsaturated bond saturation of compound, so as to greatly increase its stability.Usually require that in hydrogenation post-consumer polymer containing conjugated diene section
Degree of unsaturation be less than 2 weight % (i.e. degree of hydrogenation more than 98 weight %), to realize obvious performance improvement.Hydrogenation of polymer is usual
Carried out in the presence of metallic catalyst, used catalyst is the periodic table of elements group viii b metals such as Fe, Co, Ni and/or Pb
Organic compound or metallocene catalyst.
US 6,815,509B2 disclose a kind of method for hydrogenating polymer, and methods described is included in the presence of a hydrogenation catalyst
The polymer containing olefines unsaturated group is contacted with hydrogen and be hydrogenated with the olefines unsaturated group of polymer, wherein
Polymer solution after circulation at least a portion is hydrogenated with continues to be hydrogenated with.In the method, the reactor applied include two or
More than two reactors that are connected in series, course of reaction accomplished continuously or intermittently carries out, during the course of the reaction at least one reactor
A part of reaction effluent is recycled back into after being exchanged heat through external heat exchanger in the reactor or in upstream reactor, so as to pass through
Constantly circulation improves product degree of hydrogenation.The weak point of this method is as follows：The first reactor of the method for hydrotreating and/or later
To be stirred in reactor, mechanical energy constantly needed for consumption stirring is needed in course of reaction, and the sealing with mixing plant makes
It is manufactured and maintenance cost is higher；Furthermore, it is necessary to repeatedly add hydrogenation catalyst, make the control of course of reaction complex；
The method of hydrotreating is only applicable to be hydrogenated with as polymer hydrogenating catalyst with metallocene, is not suitable for other types of hydrogenation and urges
Agent such as Fe, Co, Ni etc. are hydrogenated with.
US3,696,088 discloses a kind of unsaturated polymer continuously hydrogen adding side of use homogeneous hydrogenation catalyst system
Method, this method uses trickle bed reactor, is mainly used in filling in styrene-conjugated diene analog copolymer hydrogenation, reactor
Inert filler, the downward drip of polymer solution reacts the hydrogenation of conjugated diene section in 4 minutes post-consumer polymers by hydrogen atmosphere
Degree is more than 98%.Although the inventive method hydrogenation rate is fast, have the following disadvantages：Hydrogenation catalyst consumption is big, reaction temperature
It is high；The liquid holdup of trickle bed reactor is small, unit volume reactor utilization rate is low；Further, since the biography of trickle bed reactor
Thermal effect is bad, is difficult in reaction starting stage reaction heat when double bond concentration is higher, exothermic heat of reaction is larger in polymer solution
Withdraw from, therefore, reaction temperature is difficult steady control or even reaction temperature is significantly raised, and then can inactivate hydrogenation catalyst
Cause hydrogenation cycle stretch-out or the reduction of final products degree of hydrogenation.
CN101492513A discloses a kind of hydrogenation reactor and method for hydrogenating polymer, wherein the hydrogenation reactor is
The combination of two or more bubbling reactors, being provided with the first bubbling reactor makes its Flow of Goods and Materials state be mixed close to complete
Stream, and setting second and later bubbling reactor make its Flow of Goods and Materials state close to laminar flow.The shortcoming of the method is only to lean on hydrogen
The more difficult Flow of Goods and Materials state for making the first bubbling reactor of flow of air only flows and jacket for heat exchange close to complete mixing flow by hydrogen
When relatively having much difficulty in healing that steady controlling reaction temperature, especially reactor volume are larger, exothermic heat of reaction is more, polymer solution viscosity is larger more
Be in this way, can thus influence gas-liquid abundant contact and catalyst activity so as to influenceing hydrogenation efficiency.The in other this method
One reactor hydrogen gas velocity is larger, accordingly, it would be desirable to which the hydrogen flowing quantity of circulation is larger, the energy of circulating hydrogen consumption is also more, causes
Make the expense of recycle unit also larger.
GB1,343,447 are related to a kind of method for carrying out gas-liquid contact reaction, wherein using special gas-liquid contact reaction
Device is hydrogenated with high-viscosity polymer, has in reactor and installs multiple in two Stirring axle stirring polymer solutions, rotary shaft
Retaining element, polymer solution is remained between rotate element, in the inner surface and the viscosity solution of rotate element of reactor wall
Between form certain space, solution-air surface is re-formed by shear-mixed, gas-liquid contact is realized, and constantly update gas-liquid
Contact surface, can be discharged with continuous feed, and when Hydrogen Vapor Pressure is 0.2MPa, Stirring rotating speed is 60 revs/min, hydrogenation temperature control
System is reacted 50 minutes, hydrogenation of polymer degree is up to 82% at 68 ± 30 DEG C.The shortcoming of the invention is that structure of reactor is complicated, manufactured
Cost is high and final products degree of hydrogenation is low.
CN102477111 is used for hydrogenation of polymer using two or more reactors being connected in series, although can make
Polymer is effectively hydrogenated with, but first reactor interlude is equipped with filler, and material only in packing section short stay, causes reactor to have
Effect volume greatly reduces, and greatly reduces the output of reactor unit volume, reduces reaction efficiency, and in the first reaction
Spray head is provided with the top of device, equipment Manufacture Process is become complex.
US 4,501,875, US 4,673,714 and GB 2,159,819A etc. carry out interval hydrogenation using stirred tank, by
Double bond concentration is high in reaction early stage reaction solution and hydrogenation rate causes thermal discharge big soon so that reaction temperature is difficult to control to,
Partial catalyst inactivation can be thus set to influence hydrogenation efficiency.In addition, intermittent reaction is also unfavorable for industrial amplification.
The content of the invention
It is not enough unsaturated there is provided a kind of olefin-containing class more than present in prior art the invention aims to overcome
The hydrogenation of polymer reaction method of key, can be such that hydrogen is fully contacted with polymer solution, so that within the longer operation cycle
Catalyst activity, preferable controlling reaction temperature are kept, and then improves hydrogenation efficiency, to reach comparatively ideal degree of hydrogenation.In view of on
The situation of prior art is stated, we have carried out extensive and in-depth study for conjugated diene polymer solution hydrogenation, found
Carry out hydrogenation of polymer by a kind of new hydrogenation reactor combination and mode of operation and hydrogenation process can be better achieved
Heat transfer, mass transfer, better control over reaction temperature, so as to keep catalyst activity within the longer operation cycle, and then improve
Hydrogenation reaction efficiency, especially after the hydrogenation reaction the phase by laminar flow operating procedure can with enhanced products degree of hydrogenation so that compared with
Hydrogenation of polymer degree is stably set to reach ideal value in the long operation cycle.
The invention provides a kind of method of hydrotreating of the polymer of olefin-containing class unsaturated bond, it is anti-that this method is included in hydrogenation
Under the conditions of answering, in the presence of a hydrogenation catalyst, the polymer solution and hydrogen of olefin-containing class unsaturated bond is set to connect in the reactor
Touch, wherein, the reactor is at least two reactors being connected in series, wherein, the first reactor is by tower reaction
Device or stirred reactor are combined with static mixer, second and later reactor be tower reactor, by controlling
Stating the recycle ratio of first reactor makes the material in reactor be in close to complete mixing flow state, wherein, the circulation of first reactor
Than for 1~40：1；And material is close to horizontal sliding stream mode in second and later reactor.
Brief description of the drawings
Fig. 1 describes a kind of process flow diagram of embodiment of the inventive method, which uses two series connection
Coupled reaction device, first reactor is is combined by tower reactor or stirred reactor with static mixer, the second reaction
Device is tower reactor.
Embodiment
The method of hydrotreating of the polymer of the olefin-containing class unsaturated bond provided according to the present invention, it is anti-that this method is included in hydrogenation
Under the conditions of answering, in the presence of a hydrogenation catalyst, the polymer solution and hydrogen of olefin-containing class unsaturated bond is set to connect in the reactor
Touch, wherein, the reactor is at least two reactors being connected in series, wherein, the first reactor is by tower reaction
Device or stirred reactor are combined with static mixer, second and later reactor be tower reactor, by controlling
Stating the recycle ratio of first reactor makes the material in annular-pipe reactor be in close to complete mixing flow state, wherein, first reactor
Recycle ratio is 1~40：1；And material is close to horizontal sliding stream mode in second and later reactor.
In the present invention, the recycle ratio refers to the ratio between flow of circular flow and outflow reactor in system.
In the present invention, it is described to refer to that the material in corresponding reactor lies substantially in laminar flow close to horizontal sliding stream mode
State, but also allow that slight back-mixing is present.
In the present invention, the annular-pipe reactor can be made up of one or more straight pipe type reaction tube, straight pipe type reaction tube
Connected between peripheral hardware chuck, straight pipe type reaction tube by bend pipe, first straight pipe type reaction tube and last root straight pipe type reaction tube
Closed-loop path is connected and composed with connecting tube, circulating pump is provided with the closed-loop path of annular-pipe reactor.By controlling circulating pump to follow
The flow of circular rector and outflow annular-pipe reactor makes material in annular-pipe reactor be in complete mixing flow state.The annular-pipe reactor straight tube
The draw ratio of section refers to the diameter ratio of the annular-pipe reactor length of the straight length of endless tube and straight length in the operating condition.
The method provided in the present invention, used hydrogenation reactor includes two or more reactors, and these are anti-
Device is answered to be connected in series each other, wherein the polymer solution flow state of olefin-containing unsaturated bond is approached in first reactor
Complete mixing flow is operated, and is hydrogenated with most of olefines unsaturated bond in polymer, and now hydrogenation reaction speed is fast, corresponding thermal discharge
Greatly, reaction temperature runaway is easily caused so that hydrogenation catalyst inactivation or activity reduction.The characteristics of annular-pipe reactor is unit volume
Heat transfer area is big, is not only stably controlled reaction temperature when polymer solution is fully circulated in a loop reactor, can also make
Hydrogen is fully contacted with polymer solution, reaches preferable mass transfer, heat-transfer effect.And polymerize in second and later reactor
Unsaturated double-bond concentration in thing solution is gradually reduced, and reaction speed is gradually reduced, and thermal discharge is gradually reduced, the heat exchange of reactor
Area can be gradually reduced, second and later reactor then take close to laminar flow operation, wherein by maintenance reaction device
Hydrogen pressure, utilizes reactant mixture（That is, the polymer solution and hydrogenation catalyst of olefin-containing class unsaturated bond）The hydrogen of middle dissolving and
The reactant mixture from first reactor is set to continue to be hydrogenated with.This hydrogenation of polymer with complete mixing flow and laminar flow combination operation
Method can realize more stable hydrogenation, while the degree of hydrogenation of final products can be strengthened by laminar flow operation, so as to
Reach required hydrogenation of polymer degree.
In the method that provides of the present invention, in order that the first reactor is in complete mixing flow state, and make described the
Two reactors are in close to horizontal sliding stream mode, it usually needs control the recycle ratio of the first reactor 1~40：1 model
In enclosing.Under preferable case, the recycle ratio of the first reactor is 5~20：1.
Specifically, in the method for the invention, hydrogen does not flow substantially in first reactor, as long as needed for keeping reaction
Pressure.The flow regime of reactant mixture can be made close to complete mixing flow by the circulation of polymer solution, and due to entering
Unsaturated double-bond concentration is of a relatively high in the polymer solution of one reactor, and reaction speed is relatively fast, can make wherein big portion
Divide unsaturated double-bond to be hydrogenated with, for example, degree of hydrogenation can be made to reach 90% or more, such hydrogenation reaction is more violent, reaction
Thermal discharge is relatively large, at this moment needs polymer solution largely to circulate i.e. recycle ratios in reactor and static mixer compared with great talent
Hydrogen can be made fully to be contacted with polymer solution, stability contorting reaction temperature, stabilizing catalyst activity, and enter second and after
Reactor olefin-containing unsaturated bond polymer solution in unsaturated double-bond concentration be gradually reduced the unsaturation, it is necessary to be hydrogenated with
Bond number amount is gradually decreased, and reaction speed is gradually reduced, and exothermic heat of reaction is also gradually reduced, can be relatively small using heat exchange area
Tower reactor, and polymer solution do not circulate substantially, its flow regime is close to laminar flow, so not only energy-saving, and
And the degree of hydrogenation of final products can be strengthened.
In the method for the invention, the gauge pressure of the hydrogen pressure in hydrogenation process in each reactor can with it is identical can not also
Together, respectively 0.2~10MPa, preferably 0.5~5MPa.Wherein, hydrogen can also be added from each reactor bottom, each anti-
Hydrogen in device is answered not flow substantially, as long as pressure needed for keeping normal reaction, regulating valve is passed through when reaction pressure is reduced
Give reaction system ftercompction.
In the method for the invention, the temperature in hydrogenation process in each reactor can be the same or different, point
Wei not be 30~130 DEG C, preferably 40~100 DEG C.Wherein, in first reactor, because exothermic heat of reaction is more, polymer is passed through
A large amount of circulations of solution and the collective effect of static mixer can not only be such that gas-liquid fully contacts, and improve hydrogenation reaction efficiency,
And can be with enhanced heat exchange efficiency, stable hydrogenation reaction temperature, so that stabilizing catalyst activity.Second and with post-reactor only
By keeping Hydrogen Vapor Pressure and dissolved hydrogen from first reactor to meet the demand of remaining double bond hydrogenation, it is not necessary to polymer
The circulation of solution, as long as keeping temperature needed for reaction.
Specifically, in the method for the invention, wherein the first reactor be tower reactor, its ratio of height to diameter be 1~
50：1, preferably 2~30：1.The form for the static mixer being applied in combination with first reactor does not have particular/special requirement, Ke Yiwei
One group can also be multigroup series connection, and the effect of static mixer is increase gas liquid interfacial area to improve hydrogenation reaction efficiency；
Second or using post-reactor as tower reactor, its ratio of height to diameter is 1~100：1, preferably 2~60：1.
The present invention method a kind of embodiment in, second and later reactor be void tower, the present invention side
In a kind of embodiment of method, second and later inside reactor be equipped with filler, the filler be inertia in bulk or regular
Filler, the material of the inert filler is stainless steel, ceramics or plastics.Second and later inside reactor be equipped with filler.Fill out
The presence of material can make polymer solution formed on filler liquid film increase contact area with hydrogen and beneficial to hydrogenation.
In the method for the invention, the solution of the hydrogenation catalyst and the polymer containing unsaturated bond enters in a continuous manner
Go out each reactor, polymer, hydrogenation catalyst and the hydrogen of the olefin-containing class unsaturated bond are needed before first reactor is entered
Static mixer combination is initially entered, static mixer combination is made up of 2 and above static mixer, wherein containing unsaturation
The polymer solution and hydrogenation catalyst of key initially enter the first static mixer obtain polymer solution containing unsaturated bond and
The pre-composition of hydrogenation catalyst, then the pre-composition together with hydrogen enter the second static mixer.Then first is continuously entered
Reactor, the polymer solution part into first reactor is used to circulate, and a part exits into the from first reactor
Two and with post-reactor, material is from second and reactor bottom charging later, and top overflow outflow can also its top feed, bottom
Portion flows out, preferably bottom feed, top overflow outflow.
In the method for the invention, the inlet flow rate and rate of discharge of polymer solution can be determined according to production scale,
And the size of the reactor can be determined therefrom that, so that it is determined that the residence time of polymer solution in the reactor, described
Residence time in one reactor is 10~120 minutes, preferably 20~60 minutes, second or during with stop in post-reactor
Between be 30~240 minutes, preferably 60~150 minutes.Residence time is too short, it is impossible to polymer solution is fully hydrogenated with, and stops
Time is oversize, although polymer solution can be made fully to be hydrogenated with, but it is too high to consume energy, uneconomical.
In the method for the invention, hydrogenation process can continuously also interval, but preferably hydrogenation process be continuous.
In the method for the invention, the concentration of the solution of the polymer of the olefin-containing class unsaturated bond can be 5~40
Weight %, preferably 8~30 weight %.Wherein, used solvent is inert hydrocarbon solvent, and the varsol is selected from alkane, ring
At least one of alkane and aromatic hydrocarbons.Here, 'inertia' enters principle of conduct with hydrogenation reaction in not disturbing reaction device, i.e., it is described
Varsol can not react between reactant or reaction product, can not be unfavorable for the performance of catalyst activity.
In the method for the invention, the polymer of the olefin-containing class unsaturated bond can be conjugated diene homopolymers or common
The copolymer of yoke diene and vinyl-arene.The conjugated diene homopolymers can be polybutadiene or polyisoprene.It is described
The copolymer of conjugated diene and vinyl-arene can be random copolymer and/or block copolymer, for example, can be butadiene
And/or the random copolymer and/or block copolymer of isoprene and styrene, or butadiene and/or isoprene
With the random copolymer and/or block copolymer of α-methylstyrene.
In the method for the invention, the hydrogenation catalyst can be used for hydrogenation of polymer in this area any suitable
Hydrogenation catalyst.The hydrogenation catalyst generally can be the organic compound containing periodic table of elements group VIII metal and
The mixture of alkyl aluminum, the group VIII metal such as iron, cobalt, nickel and palladium, preferably nickel and cobalt；The hydrogenation catalyst also may be used
To be metallocene catalyst, the metallocene catalyst is preferably metallocene-titanium catalyst, and optionally with organo-lithium compound such as lithium alkylide
Mixing, the lithium alkylide is preferably n-BuLi.
In one embodiment, the hydrogenation catalyst can be the catalyst containing organic acid nickel and alkyl aluminum, with
It can be 8 that the mol ratio of the alkyl aluminum of aluminium meter and the organic acid nickel in terms of nickel, which is,：1 to 1：1, preferably 6：1 to 3：1.Preferably,
The organic acid nickel is nickel naphthenate or nickel octoate, and the alkyl aluminum is triisobutyl aluminium or triethyl aluminum.
In another embodiment, the hydrogenation catalyst can be metallocene-titanium catalyst and for example positive fourth of optional lithium alkylide
The mol ratio of lithium and titanium can be 0 in the mixture of base lithium, this mixture：1 to 40：1, preferably 3：1 to 20：1.
In the method that the present invention is provided, the consumption of the hydrogenation catalyst can be in the conventional catalyst amount in this area
In the range of properly select.In the preferred case, when the hydrogenation catalyst is that the hydrogenation containing organic acid nickel and alkyl aluminum is urged
During agent, the consumption of the hydrogenation catalyst can be 0.01~0.1gNi/100g polymer, preferably 0.03~0.07gNi/
100g polymer；When the hydrogenation catalyst is the mixture of metallocene-titanium catalyst and optional lithium alkylide such as n-BuLi, institute
The consumption for stating hydrogenation catalyst can be 0.01~0.5mmolTi/100g polymer, preferably 0.05~0.3mmolTi/100g
Polymer.
The present invention is described in further detail by the following examples, but these embodiments are not considered as to the scope of the invention
Limitation.
Embodiment 1
The present embodiment is used for the method for hydrotreating for illustrating the polymer of olefin-containing class unsaturated bond.
500L jacketed stirred autoclaves are sufficiently displaced from purified nitrogen, and 250L hexamethylenes are added after displacement and are mixed with n-hexane
Bonding solvent (percentage by weight of the mixed solvent cyclohexane is 87 weight %) and 3.5L refined styrenes, continuously add 1.15L
Tetrahydrofuran, then adding 0.5M n-butyl lithium initiator solution 0.71L, (mol ratio of tetrahydrofuran and n-BuLi is 40：
1), reacted 30 minutes at 50~60 DEG C, continuously add 24L and refine butadiene reaction 40 minutes, then add 3.5L commercial benzenes
Ethylene reaction 30 minutes, adds 27ml isopropanol terminating reactions after the completion of reaction.Here, styrene-butadiene block copolymer
(S-B-S) concentration is about 10 weight % based on whole polymerization system, and the molecular weight of the block copolymer is 6.0 ten thousand, styrene with
The weight ratio of butadiene monomer unit is 29：71, the contents of ethylene of butadiene section is 41 weight % in polymer.（Using Switzerland
Bruker companies AVANCE DRX 400MHz nuclear magnetic resonance chemical analysers are determined）.
By nickel naphthenate (Beijing Yanshan Mountain synthetic rubber plant, 3gNi/L, technical grade) and triisobutyl aluminium (Beijing enlightening dragon chemical industry
Co., Ltd, 3gNi/L, technical grade) according to aluminium nickel mol ratio (based on metal) be 3：1 mixing, by the mixture in old at 50 DEG C
Change 30 minutes, be then added into styrene-butadiene block copolymer solution obtained above, and stir.Here,
The consumption of hydrogenation catalyst is 0.06gNi/100g polymer.
The hydrogenation operation is using the device shown in accompanying drawing 1, including two reactors being connected in series, wherein
First reactor is to include being combined with static mixer by tower reactor, and the ratio of height to diameter of tower reactor is 20, reaction
The volume of device is 100L, and static mixer internal diameter is 100mm, and model SX types are formed by four static mixer tandem compounds；
Second reactor is tower reactor, and its ratio of height to diameter is 30, and reactor volume is 320L, and inside is stainless equipped with 10 × 10mm of Ф
Steel filler.Wherein the first and second reactors use nitrogen displacement in advance, then are replaced with hydrogen.First, second reactor and quiet
State blender, which is carried, is connected with heat transferring medium water for giving reaction system heat exchange in chuck, chuck.
Material continuously enters first reactor and static mixer, and one section is stopped in first reactor and static mixer
Second reactor is continuously entered after time, is flowed out after being stayed for some time in second reactor from the outlet of tower reactor.
Intermittent reaction is carried out first in first reactor, 80L is squeezed into pump in the first reactor after being replaced to hydrogen
The pre- mixed styrene-butadiene block copolymer solution containing hydrogenation catalyst, wherein SB solution
Concentration is 10 weight %, and it is 65 DEG C to keep reaction temperature, and logical hydrogen simultaneously keeps Hydrogen Vapor Pressure 2.5MPa (gauge pressure), opens circulating pump,
Make polymer solution in the first reactor interior circulation, internal circulating load is to adjust by chuck and hydrogen in 800L/h, course of reaction
Valve controlling reaction temperature and pressure are saved, butadiene section in 30 minutes sampling its degrees of hydrogenation of iodimetric analysis, polymer is reacted
Degree of hydrogenation is 98.5%, reacts 1 hour degree of hydrogenation 99.4%.
Intermittent reaction completes to be continuously added to hydrogenation catalyst and benzene second in the static mixer 1 before backward first reactor
Alkene-butadiene block copolymer solution, copolymer solution feed rate is 160L/h, to the static mixer before first reactor
2 logical hydrogen, the continuous first reactor of styrene-butadiene block copolymer solution containing hydrogenation catalyst, while opening circulation
Pump, makes a part of polymer solution containing hydrogenation catalyst in first reactor and static mixing by adjusting the flow of circulating pump
Device interior circulation, another part solution outflow first reactor enters in second reactor, course of reaction to be polymerize in first reactor
The amount retained of thing solution keeps constant, and it is 65 DEG C that the temperature in reactor is controlled by chuck, passes through governor valve control hydrogen
Addition, maintains Hydrogen Vapor Pressure 2.5MPa (gauge pressure), internal circulating load of the circulating pump in first reactor and outflow first reactor
The recycle ratio of amount is 10：1, residence time of the polymer solution in first reactor is 30 minutes.
Next, the polymer solution of outflow first reactor is from the bottom feed of second reactor, and from top overflow
Outflow, controls the temperature of second reactor to be 70 DEG C by chuck, by the addition of governor valve control hydrogen, maintains hydrogen pressure
Power is 2.5MPa (gauge pressure), and residence time of the polymer solution in second reactor is 120 minutes.
React after a period of time, per every other hour from the hydrogenation of the upper, middle and lower position sampling analysis sample point of first reactor
Degree, degree of hydrogenation is respectively 96.3%, 96.5% and 96.7%, it is possible thereby to think that Flow of Goods and Materials state is close to entirely in first reactor
Mixed flow.And successively under second reactor, in, upper bit sampling analysis, resulting polymers degree of hydrogenation raises successively（Under：
97.2%, in：98.7%, on：99.5%）, it is thus regarded that Flow of Goods and Materials state is close to laminar flow in second reactor.
Reaction continue for 300 hours, sample and use respectively iodimetric analysis hydrogenation of polymer from first and second reactor outlet
Degree, the average hydrogenation reaction of each reactor the results are shown in Table 1.
Embodiment 2
Except the ratio between the circular flow in first reactor and the flow for flowing out the annular-pipe reactor are 20：1, with embodiment 1
In the same method carry out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 3
Except the ratio between the circular flow in first reactor and the flow for flowing out the annular-pipe reactor are 5：1, with embodiment 1
The same method carries out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 4
Except residence time of the polymer solution in first reactor is 20 minutes, the residence time in second reactor is
80 minutes, the hydrogenation reaction of the solution containing conjugated diene polymer is carried out with method the same in embodiment 1,1 is the results are shown in Table.
Embodiment 5
Except residence time of the polymer solution in first reactor is 60 minutes, the residence time in second reactor is
240 minutes, the hydrogenation reaction of the solution containing conjugated diene polymer is carried out with method the same in embodiment 1,1 is the results are shown in Table.
Embodiment 6
Except the ratio of height to diameter 30 of first reactor straight length：1, the ratio of height to diameter 2 of second reactor：1, with the same in embodiment 1
Method carries out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 7
Except the ratio of height to diameter 50 of first reactor straight length：1, the ratio of height to diameter 60 of second reactor：1, with the same in embodiment 1
Method carries out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 8
Except first reactor is in addition to reactor and speed of agitator with stirring are 300rpm, with method the same in embodiment 1
The hydrogenation reaction of the solution containing conjugated diene polymer is carried out, 1 is the results are shown in Table.
Embodiment 9
Except hydrogenation catalyst consumption is 0.04gNi/100g polymer, carried out with method the same in embodiment 1 containing conjugation two
The hydrogenation reaction of olefin polymer solution, the results are shown in Table 1.
Embodiment 10
Except hydrogenation catalyst consumption is 0.03gNi/100g polymer, carried out with method the same in embodiment 1 containing conjugation two
The hydrogenation reaction of olefin polymer solution, the results are shown in Table 1.
Embodiment 11
In addition to the static mixer combined with first reactor is connected for the static mixer of 3 model SV types, with implementation
The same method carries out the hydrogenation reaction of the solution containing conjugated diene polymer in example 1, the results are shown in Table 1.
Embodiment 12
Except adding 0.1M n-BuLis in the styrene-butadiene block copolymer solution containing active group that is obtained to polymerization
Cyclohexane solution, then terminated 10 minutes with hydrogen, then add the toluene solution of the titanocenes containing di-p-tolyl, mixing is equal
First reactor is added after even, catalyst amount is 0.2mmolTi/100g polymer, and Li/Ti mol ratios are 8：1, simply first
Reactor interior reaction temperature is 75 DEG C, and the reaction temperature in second reactor is 80 DEG C, is entered with method the same in embodiment 1
The hydrogenation reaction of row solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 13
Except first reactor interior reaction temperature is 70 DEG C, the reaction temperature in second reactor is 90 DEG C, with embodiment 17
In the same method carry out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.
Embodiment 14
Except in polymerisation, styrene is added with butadiene simultaneously, resulting polymer is styrene-butadiene random
Copolymer, molecular weight, styrene and the butadiene unit weight of resulting polymers contain than the vinyl of butadiene section in, polymer
Amount etc. is same as Example 1, and polymer solution concentration is 15 weight %, is carried out with method the same in embodiment 1 containing conjugation two
The hydrogenation reaction of olefin polymer solution, the results are shown in Table 1.Hydrogenation reaction the results are shown in Table 1.
Embodiment 15
Except substituting butadiene with isoprene in polymerisation, resulting polymer is styrene-isoprene block
Copolymer (S-I-S), SIS molecular weight number-average molecular weight is 100,000, is carried out containing conjugated diene with method the same in embodiment 1
The hydrogenation reaction of hydrocarbon polymer solution, the results are shown in Table 1.
Embodiment 16
In addition to being not added with filling material in second reactor, carried out containing conjugated diene polymer with method the same in embodiment 1
The hydrogenation reaction of solution, the results are shown in Table 1.
Embodiment 17
It is basic to repeat embodiment 1, except hydrogenation process is including 3 reactors being connected in series, wherein the 3rd reaction
Device is identical with second reactor, and residence time of the polymer solution in 3 reactors is respectively 20,80,80 minutes, and reaction is held
200 hours are continued, from three reactor outlets samplings and have used its degree of hydrogenation of iodimetric analysis afterwards, with as in embodiment 1
Method carries out the hydrogenation reaction of the solution containing conjugated diene polymer, the results are shown in Table 1.As a result three reactor outlet polymerizations are shown
The last degree of hydrogenation of thing is followed successively by 96.2%.98.7% and 99.9%.
Comparative example 1
Except the ratio between the circular flow in the first annular-pipe reactor and the flow for flowing out the annular-pipe reactor are 2：1, with implementation
The same method carries out the hydrogenation reaction of the solution containing conjugated diene polymer in example 1, the results are shown in Table 1.
In continuously hydrogen adding course of reaction, it is 2.5MPa (gauge pressure) to keep the Hydrogen Vapor Pressure in the first and second reactors.
Each inside reactor temperature, but the more difficult stability contorting of first reactor internal temperature are controlled by chuck in course of reaction, and
Reactor different parts sampling analysis degree of hydrogenation, mean error about 15% shows that Flow of Goods and Materials state is not complete in first reactor
Mixed flow.Reaction continue for 30 hours, and the average degree of hydrogenation of first reactor outlet sample is 90.0%, second reactor outlet sample
The degree of hydrogenation of product is 95.5%.As a result show during continuous operation, when first reactor recycle ratio is smaller, material is first
Flow regime in reactor is not complete mixing flow, and the more difficult stability contorting of hydrogenation reaction temperature, gas-liquid contact is insufficient, final products
Degree of hydrogenation is undesirable.
Comparative example 2
Except polymer solution, the residence time is 5 minutes in first reactor, and the residence time in second reactor is 20 points
Clock, the hydrogenation reaction of the solution containing conjugated diene polymer is carried out with method the same in embodiment 1,1 is the results are shown in Table.
Reaction continue for 50 hours, and the degree of hydrogenation of first reactor outlet sample is 92.3%, second reactor outlet sample
Degree of hydrogenation be 96.0%.As a result show during continuous operation, residence time of the polymer solution in second reactor is too
The short degree of hydrogenation for making final products is relatively low, undesirable.
Comparative example 3
Except the ratio between the circular flow in first reactor and the flow for flowing out the annular-pipe reactor are 0, with one in embodiment 1
The method of sample carries out the hydrogenation reaction of the solution containing conjugated diene polymer, as a result finds that reaction temperature can not be steady in course of reaction
Fixed control, first reactor outlet sampling analysis degree of hydrogenation is 78.2%, and second reactor outlet sampling analysis degree of hydrogenation is
93.5%, degree of hydrogenation can not meet requirement, the results are shown in Table 1.
Comparative example 4
Except the first reactor only tower reactor used, not including static mixer outside, remaining be the same as Example 1, first
Reactor outlet sampling analysis degree of hydrogenation is 92.0, and second reactor outlet sampling analysis degree of hydrogenation is 96.5, and degree of hydrogenation can not
Meet require, and course of reaction temperature can not stability contorting, the results are shown in Table 1.
Claims (18)
1. a kind of method of hydrotreating of the polymer of olefin-containing class unsaturated bond, this method is included under hydrogenation conditions, added
In the presence of hydrogen catalyst, the polymer solution and hydrogen of olefin-containing class unsaturated bond is set to contact in the reactor, it is characterised in that
The reactor is at least two reactors being connected in series, wherein, first reactor is by tower reactor or stirring reaction
Device is combined with static mixer, second and later reactor be tower reactor, by controlling the first reactor
Recycle ratio material in reactor is in close to complete mixing flow state, the recycle ratio of first reactor is 1~40：1；And second
And in later reactor material close to horizontal sliding stream mode.
2. method according to claim 1, it is characterised in that polymer, the hydrogenation catalyst of the olefin-containing class unsaturated bond
And hydrogen needs to initially enter static mixer combination before first reactor is entered, static mixer combination by 2 and more than
Static mixer is constituted, and is obtained wherein polymer solution and hydrogenation catalyst containing unsaturated bond initially enter the first static mixer
To polymer solution and the pre-composition of hydrogenation catalyst containing unsaturated bond, then the pre-composition is quiet into second together with hydrogen
State blender.
3. method according to claim 1, it is characterised in that the recycle ratio of first reactor is 5~20：1.
4. method according to claim 1 or 2, it is characterised in that the ratio of height to diameter of the first reactor is 1~50：1,
Preferably 2~30：1.
5. according to the method described in claim 1, it is characterised in that described second and the ratio of height to diameter of later tower reactor be
1~100：1, preferably 2~60：1.
6. according to the method described in claim 1, it is characterised in that described second and later reactor be void tower.
7. according to the method described in claim 1, it is characterised in that described second and later inside reactor filler is housed,
The filler is inert filler in bulk or regular, and the material of the inert filler is stainless steel, ceramics or plastics.
8. according to the method described in claim 1, it is characterised in that during stop of the polymer solution in first reactor
Between be 10~120 minutes, preferably 20~60 minutes；Second and using the residence time in post-reactor as 30~240 minutes,
Preferably 60~150 minutes.
9. according to the method described in claim 1, it is characterised in that in hydrogenation process, hydrogenation catalyst, containing unsaturated bond
Polymer solution and hydrogen continuously enter first reactor after being mixed through static mixer, second and later reactor be bottom
Portion's charging, top overflow outflow.
10. according to the method described in claim 1, it is characterised in that in hydrogenation process, the hydrogen pressure in each reactor can be with
It is identical or different, respectively 0.2~10MPa, preferably 0.5~5MPa.
11. the temperature according to the method described in claim 1, it is characterised in that in hydrogenation process, in each reactor it is identical or
Difference, preferably respectively 20~120 DEG C, 30~100 DEG C.
12. according to the method described in claim 1, it is characterised in that the polymer solution of the olefin-containing class unsaturated bond
Concentration is 5~40 weight %, preferably 8~30 weight %, wherein used solvent is in alkane, cycloalkane and aromatic hydrocarbons
At least one inert hydrocarbon solvent.
13. according to the method described in claim 1, it is characterised in that the polymer of the olefin-containing class unsaturated bond is conjugation
The copolymer of diene homopolymer and/or conjugated diene and vinyl-arene, the conjugated diene homopolymers be polybutadiene and/or
The copolymer of polyisoprene, the conjugated diene and vinyl-arene is the nothing of butadiene and/or isoprene and styrene
Advise copolymer and/or block copolymer or butadiene and/or isoprene and the random copolymer or embedding of α-methylstyrene
Section copolymer.
14. according to the method described in claim 1, it is characterised in that the hydrogenation catalyst is nickel containing organic acid and alkyl aluminum
Mixture, the mol ratio of the alkyl aluminum counted using aluminium and the organic acid nickel counted using nickel is 1~8:1, preferably 2~6:1, it is described to add
The consumption of hydrogen catalyst is 0.01~0.1gNi/100g polymer, preferably 0.03~0.07gNi/100g polymer.
15. method according to claim 14, it is characterised in that the organic acid nickel is nickel naphthenate, nickel octoate or 2-
Thylhexoic acid nickel, the alkyl aluminum is triisobutyl aluminium or triethyl aluminum.
16. according to the method described in claim 1, it is characterised in that the hydrogenation catalyst contains metallocene-titanium catalyst and optional
Lithium alkylide, the mol ratio of lithium and titanium is 0：1 to 40：1, preferably 3：1 to 20：1；The consumption of the hydrogenation catalyst is 0.01
~0.5mmolTi/100g polymer, preferably 0.05~0.3mmolTi/100g polymer.
17. method according to claim 16, it is characterised in that the lithium alkylide is n-BuLi.
18. method according to claim 1, it is characterised in that the hydrogenation process is interval, hydrogenation reactor is only wrapped
Include first reactor.
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| CN110016092A (en) * | 2018-01-08 | 2019-07-16 | 中国科学院化学研究所 | A kind of polyolefin for continuously preparing the method for polyolefin and its being prepared |
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