CN103788317A - Olefines unsaturated bond-containing polymer hydrogenation reaction method - Google Patents
Olefines unsaturated bond-containing polymer hydrogenation reaction method Download PDFInfo
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Abstract
The invention discloses an olefines unsaturated bond-containing polymer hydrogenation reaction method. The method comprises the following steps: under a hydrogenation reaction condition and existence of a hydrogenation catalyst, an olefines unsaturated bond-containing polymer solution and hydrogen are contacted in a reactor, wherein the reactors are two or more loop reactors connected in series, the cycle ratio of the loop reactors can be controlled so that the material in the reactor is close to a complete mixing flow state, wherein the cycle ratio of a first reactor is 10-200, and the cycle ratio of a second reactor and other reactor is 10-100. The method can better control the reaction temperature, the catalyst activity can be kept in a long operation period, hydrogenation efficiency is increased, and ideal hydrogenation degree can reached.
Description
Technical field
The present invention relates to a kind of process for selective hydrogenation of the polymkeric substance containing olefines unsaturated link(age).More specifically, adopt two or more annular-pipe reactors that are connected in series to make the method containing the polymkeric substance continuous hydrogenation of unsaturated link(age) under hydrogenation catalyst and hydrogen existence.
Background technology
Heat, oxidative stability and ageing resistance containing the polymkeric substance of unsaturated link(age) are poor, therefore often make the unsaturated link(age) of polymkeric substance saturated by method of hydrotreating, thereby increase its stability.Conventionally require the degree of unsaturation of hydrogenation post polymerization thing to be less than 2% (being that degree of hydrogenation is greater than 98%), significantly improve to realize polymer performance.Hydrogenation of polymer carries out conventionally under metal catalyst exists, and used catalyst can be the organic compound of the periodic table of elements VIIIB family metals such as Fe, Co, Ni and/or Pb, can be also metallocene catalyst.
US 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 polymers soln 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 external heat exchanger 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 as follows: in the first reactor of this method of hydrotreating and/or later reactor, to stir, in reaction process, need constantly to consume and stir required mechanical energy, and with the sealing of whipping device make its manufacture and maintenance cost all higher; In addition, need to repeatedly add hydrogenation catalyst, make the control of reaction process comparatively complicated; This method of hydrotreating is only applicable to carry out hydrogenation with metallocene as polymer hydrogenating catalyst, and the hydrogenation catalyst that is not suitable for other type carries out hydrogenation as Fe, Co, Ni etc.
US 3,696,088 discloses a kind of unsaturated polymer continously hydrogen adding method that adopts homogeneous hydrogenation catalyst system, the method adopts 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 post polymerization things is greater than 98%.Although this inventive method hydrogenation speed is fast, has the following disadvantages: 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; In addition, because the heat-transfer effect of trickle-bed reactor is bad, in the reaction starting stage when pair key concentration in polymers soln is higher, exothermic heat of reaction when larger reaction heat be difficult to withdraw from, therefore, temperature of reaction is difficult to steady control even makes temperature of reaction significantly raise, and then can make hydrogenation catalyst inactivation cause hydrogenation cycle stretch-out or the finished product degree of hydrogenation to reduce.
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, surely control temperature of reaction and only depend on flow hydrogen gas and jacket for heat exchange also to have much difficulty in healing, 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 larger in addition, therefore, needs the hydrogen flowing quantity of circulation larger, and the energy that circulating hydrogen consumes is also more, causes the expense of recycle unit also larger.
GB 1, 343, 447 relate to a kind of method of carrying out gas-liquid contact reaction, wherein adopt special gas-liquid contact reactor to make high-viscosity polymer hydrogenation, in reactor, there are two Stirring axles to stir polymers soln, multiple retaining elements are installed on turning axle, polymers soln remains between spinner member, between the internal surface of reactor wall and the viscous soln of spinner member, form certain space, again form solution-air surface by shear-mixed, realize gas-to-liquid contact, and constantly update gas-to-liquid contact face, can continuously feeding discharging, when hydrogen pressure is 0.2MPa, Stirring axle rotating speed is 60 revs/min, hydrogenation temperature is controlled at 68 ± 30 ℃, react 50 minutes, hydrogenation of polymer Du Keda 82%.The shortcoming of this invention is that structure of reactor complexity, manufacturing cost are high and the finished product degree of hydrogenation is low.
US 4,501,875, US 4,673,714 and GB 2,159,819A 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 hydrogenation efficiency.In addition, rhythmic reaction is also unfavorable for industry amplification.
In sum, need at present one badly and can control better temperature of reaction, thereby keep catalyst activity within the longer operational cycle, and then improve hydrogenation efficiency, to reach the method for hydrotreating of the polymkeric substance containing olefines unsaturated link(age) of desirable degree of hydrogenation.
Summary of the invention
The object of the invention is the above deficiency of leaving in prior art in order to overcome, provide one can control better temperature of reaction, thereby keep catalyst activity within the longer operational cycle, and then raising hydrogenation efficiency, to reach the method for hydrotreating of the polymkeric substance containing olefines unsaturated link(age) of desirable degree of hydrogenation.
In view of the situation of above-mentioned prior art, the inventor has carried out extensive and deep research for the polymers soln hydrogenation containing unsaturated link(age), find in the annular-pipe reactor of at least two series connection, make polymers soln material in annular-pipe reactor in complete mixing flow state by controlling the recycle ratio of reactor, make hydrogenation of polymer, thereby can realize better the heat transfer of hydrogenation process, mass transfer, control better temperature of reaction, and keep catalyst activity within the longer operational cycle, and then raising hydrogenation reaction efficiency, stably to make hydrogenation of polymer degree reach ideal value within the longer operational cycle.
The invention provides a kind of process for selective hydrogenation of the polymkeric substance containing olefines unsaturated link(age), the method is included under hydrogenation conditions, under hydrogenation catalyst exists, solution, the hydrogen of the polymkeric substance that contains olefines unsaturated link(age) are contacted in reactor, wherein, described reactor is two or more annular-pipe reactors that are connected in series, the recycle ratio of controlling the first reactor is 10-200, the recycle ratio of the second reactor and later reactor is 10-100, makes the material in reactor approach complete mixing flow state.
Method provided by the invention, can realize better heat transfer, the mass transfer of hydrogenation process, control better temperature of reaction, thereby keep catalyst activity within the longer operational cycle, and then improve hydrogenation reaction efficiency, stably to make hydrogenation of polymer degree reach ideal value within the longer operational cycle.
Accompanying drawing explanation
Fig. 1 has described the process flow diagram of a kind of embodiment of the inventive method, has wherein used two annular-pipe reactors that are connected in series.
Embodiment
The invention provides a kind of process for selective hydrogenation of the polymkeric substance containing olefines unsaturated link(age), the method comprises that the method is under hydrogenation conditions, under hydrogenation catalyst exists, solution, the hydrogen of the polymkeric substance that contains olefines unsaturated link(age) are contacted in reactor, make the material in reactor approach complete mixing flow state by controlling the recycle ratio of described annular-pipe reactor, the recycle ratio of the first reactor is 10-200, the recycle ratio of the second reactor and later reactor is 10-100, makes the material in reactor approach complete mixing flow state.
In the present invention, described recycle ratio refers to the circular flow of propeller pump and the ratio of the flow of the described annular-pipe reactor of outflow.
In the present invention, described complete mixing flow state refers in corresponding reactor, due to stirring action strong in reactor, between the material infinitesimal that makes just to enter reactor and original material infinitesimal in device, instantaneous reaching fully mixed, each point concentration is equated and temporal evolution not, reactor outlet fluid composition and the interior state equating of device.
In the present invention, described annular-pipe reactor is made up of one or more straight pipe type reaction tubes, straight pipe type reaction tubes peripheral hardware chuck, between straight pipe type reaction tubes, connected by bend pipe, first straight pipe type reaction tubes and last root straight pipe type reaction tubes connect and compose loop line with pipe connecting, on the loop line of annular-pipe reactor, are provided with recycle pump.By controlled circulation pump internal circulating load and flow out the flow of annular-pipe reactor and make in annular-pipe reactor material in complete mixing flow state.The length-to-diameter ratio of described annular-pipe reactor straight length refers to the length of annular-pipe reactor straight length 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 operational condition also can be identical or different.
In the method for the invention, the hydrogenator using comprises two or more annular-pipe reactors, these reactors are connected in series each other, in all reactors, polymers soln is all in complete mixing flow state, wherein enter unsaturated double-bond relative concentration in the polymers soln of the first reactor and enter second or want large with the unsaturated double-bond concentration of post-reactor, need the unsaturated double-bond concentration of hydrogenation also large, it is fast that speed of response is wanted relatively, it is large that corresponding thermal discharge is also wanted, therefore require the heat interchanging area relative second of the first reactor or want large with the heat interchanging area of post-reactor, the recycle ratio of material in the first reactor relative second or also large with post-reactor.Enter second or little with unsaturated double-bond relative concentration the first reactor in the polymers soln of post-reactor, speed of response reduces relatively, and thermal discharge reduces gradually, and the heat interchanging area of reactor can reduce gradually.The method for hydrogenating polymer of this complete mixing flow reactor with different operating conditional combination can be realized the temperature of more stable control hydrogenation process, realize contacting of polymers soln and hydrogen better, thereby more stable control hydrogenation process, stabilizing catalyst 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 keep the required pressure of reaction, can make the flow state of reaction mixture approach complete mixing flow by the circulation of polymers soln, and higher owing to entering in the polymers soln of the first reactor unsaturated double-bond relative concentration, speed of response 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, hydrogenation reaction is comparatively violent like this, exothermic heat of reaction amount is relatively large, at this moment needing polymers soln a large amount of circulations in annular-pipe reactor is the stable temperature of reaction of controlling of the larger ability of recycle ratio, stabilizing catalyst activity, preferably, the recycle ratio of the first reactor is 20-150, and enter second and later reactor polymer solution in unsaturated double-bond concentration reduce gradually, need the unsaturated link(age) quantity of hydrogenation to reduce gradually, speed of response reduces gradually, and exothermic heat of reaction also reduces gradually, second or the recycle ratio of later reactor be 10-60.In reaction process, recycle ratio is too little, and polymers soln can not fully contact with hydrogen, and hydrogenation reaction efficiency is low, and heat-transfer effect is bad, can not control hydrogenation reaction temperature, and recycle ratio is too large, although can improve hydrogenation reaction efficiency, consumes energy high, uneconomical.
In the method for the invention, the hydrogen pressure in hydrogenation process in each reactor can be the same or different, and is respectively 0.2-10MPa (gauge pressure), is preferably 0.5-5MPa (gauge pressure).Wherein, hydrogen adds from each reactor bottom, and in each reactor, hydrogen substantially flows, as long as keep normal reaction required pressure, in the time that reaction pressure reduces by variable valve to reactive system ftercompction.
In the method for the invention, the temperature in hydrogenation process in each reactor can be the same or different, and is respectively 30-130 ℃, is preferably 40-100 ℃.Wherein, in the first reactor, because exothermic heat of reaction is more, not only can make gas-liquid fully contact by a large amount of circulations of polymers soln, improve hydrogenation reaction efficiency, and can enhanced heat exchange efficiency, stable hydrogenation temperature of reaction, thereby stabilizing catalyst activity, and second or later reactor in because exothermic heat of reaction is relatively little, do not need very large heat interchanging area just can stablize temperature of reaction, but still require gas-liquid fully to contact.
Particularly, in the method for the invention, the length-to-diameter ratio of the straight length of wherein said first ring pipe reactor is 3-200, be preferably 6-150, more preferably 10-120, second or later annular-pipe reactor straight length length-to-diameter ratio be 2-150, be preferably 4-100, more preferably 8-80.Described annular-pipe reactor is provided with opening for feed and discharge port in bottom.
In the method for the invention, described hydrogenation catalyst and pass in and out in a continuous manner each reactor containing the solution of the polymkeric substance of olefines unsaturated link(age), hydrogenation catalyst can with polymers soln premix after enter, also can enter from identical or different entrance respectively, preferably after hydrogenation catalyst and polymers soln premix, enter or the two enters from same entrance.
In the method for the invention, can determine according to industrial scale inlet flow rate and the rate of discharge of polymers soln, and the size that can determine accordingly described annular-pipe reactor is for example determined the length-to-diameter ratio of the straight length part of described annular-pipe reactor, thereby determine the residence time of polymers soln in reactor, mean residence time in described first ring pipe reactor is 10-120min, be preferably 20-60min, second or later the mean residence time in annular-pipe reactor be 20-240min, be preferably 30-150min.The residence time is too short, can not make the abundant hydrogenation of polymers soln, and the residence time is oversize, although can make the abundant hydrogenation of polymers soln, consumes energy too high, uneconomical.
In the method for the invention, hydrogenation process can be continuous, also can be intermittently, but preferably hydrogenation process is continuous.
In the method for the invention, the concentration of the solution of the described polymkeric substance containing olefines unsaturated link(age) can be 5-40 % by weight, is preferably 8-30 % by weight.Wherein, the solvent using is inert hydrocarbon solvent, and this varsol is selected from alkane, naphthenic hydrocarbon and aromatic hydrocarbons.At this, '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.
In the method for the invention, the described polymkeric substance containing olefines unsaturated link(age) can be the multipolymer of conjugated diolefin homopolymerization thing and/or conjugated diene and vinyl-arene for the described polymkeric substance containing olefines unsaturated link(age), and described conjugated diene homopolymers is polyhutadiene and/or polyisoprene; The multipolymer of described conjugated diolefine and vinyl-arene is random copolymers and/or divinyl and/or isoprene and the alpha-methylstyrene block copolymer of divinyl and/or isoprene and cinnamic random copolymers and/or divinyl and/or isoprene and cinnamic segmented copolymer and/or divinyl and/or isoprene and alpha-methyl styrene.
In the method for the invention, 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 mixture of aluminum alkyls conventionally, and described VIIIB family metal, as iron, cobalt, nickel and palladium, is 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.
In the method for the invention, the consumption of wherein said hydrogenation catalyst should the principle based on industrial economy suitably be selected, can not be too small or excessive, be unfavorable for normally carrying out of hydrogenation process because too small, and the finished product degree of hydrogenation cannot reach requirement, the excessive cost that not only can increase hydrogenation process, and 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 organic acid nickel if nickel naphthenate or nickel octoate and aluminum alkyls are as the mixture of triisobutyl aluminium or triethyl aluminum, in this mixture, the mol ratio of aluminium and nickel can be 8:1 to 1:1, be preferably 6:1 to 3:1, now the consumption of described hydrogenation catalyst can be 0.01-0.10gNi/100g polymkeric substance, is preferably 0.03-0.07gNi/100g polymkeric substance.
In addition, in the method for the invention, described hydrogenation catalyst can be also that metallocene-titanium catalyst and optional lithium alkylide are as the mixture of n-Butyl Lithium, in this mixture, the mol ratio of lithium and titanium can be 0:1 to 40:1, be preferably 3:1 to 20:1, now the consumption of described hydrogenation catalyst can, for 0.01-0.5mmolTi/100g is containing the polymkeric substance of olefines unsaturated link(age), be preferably the polymkeric substance of 0.05-0.3mmolTi/100g containing olefines unsaturated link(age).
Embodiment 1
The present embodiment is for illustrating the method for hydrotreating containing the polymkeric substance of olefines unsaturated link(age).
500L jacketed stirred autoclave is fully replaced with refining nitrogen, after displacement, add 250L hexanaphthene and hexane mixed solvent (in this mixed solvent, the weight percent of hexanaphthene is 87 % by weight) and 3.5L commercial benzene ethene, continue to add 1.15L tetrahydrofuran (THF), then add 0.5M n-butyl lithium initiator solution 0.71L (mol ratio of tetrahydrofuran (THF) and n-Butyl Lithium is 40:1), 50-60 ℃ of reaction 30 minutes, continue to add the refining divinyl reaction of 24L 30 minutes, and then add 3.5L commercial benzene ethylene reaction 30 minutes, after having reacted, add 27ml Virahol termination reaction.At this, the concentration of styrene 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, the weight ratio of vinylbenzene and butadiene monomer unit is 29:71, and in polymkeric substance, the contents of ethylene of divinyl section is 41 % by weight (adopting the Switzerland AVANCE DRX 400MHz of Bruker company nuclear magnetic resonance spectrometer to measure).
By the nickel naphthenate (Yanshan Mountain, Beijing synthetic rubber plant, 3gNi/L, technical grade) and the triisobutyl aluminium (Yanshan Mountain, Beijing synthetic rubber plant, 4gNi/L, technical grade) be 4:1 mixing according to aluminium nickel mol ratio (by metal), by the ageing 30 minutes at 50 ℃ of this mixture, be then added in styrene butadiene block polymer solution obtained above, and stirred.At this, the consumption of hydrogenation catalyst is 0.06gNi/100g polymkeric substance.
This hydrogenation operation adopts the device shown in Fig. 1, and comprising two annular-pipe reactors that are connected in series, wherein the length-to-diameter ratio of first ring pipe reactor straight length is 60, and the volume of reactor is 100L; Length-to-diameter ratio in the second annular-pipe reactor straight length is 40, and reactor volume is 300L.Wherein the first and second reactors are all used nitrogen replacement in advance, then use hydrogen exchange.Material enters first ring pipe reactor continuously, after staying for some time, enters continuously the second annular-pipe reactor in the first reactor, after staying for some time, flows out continuously from the outlet of the second annular-pipe reactor in the second reactor.
First in the first reactor, carry out rhythmic reaction, to squeezing into the pre-mixed styrene butadiene block polymer solution containing hydrogenation catalyst of 80L with pump in the first reactor after hydrogen exchange, keeping temperature of reaction is 60 ℃, logical hydrogen also keeps hydrogen pressure 2.5MPa (gauge pressure), open propeller pump, make polymers soln at described the first reactor internal recycle, internal circulating load is 2000L/h, in reaction process by chuck and hydrogen regulating valve control temperature of reaction and pressure, react 30 minutes its degrees of hydrogenation of sampling iodimetric analysis, in polymkeric substance, the degree of hydrogenation of divinyl section is 98.5%, react 1 hour degree of hydrogenation 99.4%.
Rhythmic reaction completes and in backward the first reactor, adds continuously the styrene butadiene block polymer solution containing hydrogenation catalyst, feed rate is 160L/h, open propeller pump simultaneously, by regulating the flow of propeller pump to make a part of polymers soln containing hydrogenation catalyst at the first reactor internal recycle, make the circular flow of polymers soln in described first ring pipe reactor with flow out described annular-pipe reactor flow ratio (, the internal circulating load of propeller pump in the first reactor reacted the ratio of tolerance with outflow first, also be called recycle ratio) be 60, in reaction process, keeping temperature of reaction is 55 ℃, by the add-on of variable valve control hydrogen, maintain hydrogen pressure 2.5MPa (gauge pressure).First ring pipe reactor adopts external jacket heat exchange, and the residence time of polymers soln in first ring pipe reactor is 30 minutes.After reaction for some time, every one hour degree of hydrogenation from the different sites sampling analysis sampling spot of the first reactor, the position of sampling analysis is respectively the flow direction according to material, take the entrance of the first reactor as starting point, the outlet of the first reactor is terminal, on average every a segment distance, a sampling spot is set, 5 sampling spots are set altogether, the result of 5 sampling spot 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 in the first reactor that Flow of Goods and Materials state approaches complete mixing flow.
Next, the polymers soln that flows out first ring pipe reactor enters the second annular-pipe reactor and proceeds hydrogenation reaction, wherein making the circular flow of polymers soln in described the second annular-pipe reactor and the ratio of the flow that flows out described annular-pipe reactor is 40, the temperature of the second annular-pipe reactor is 65 ℃, hydrogen pressure is 2.5MPa (gauge pressure), and the residence time of polymers soln in the second annular-pipe reactor is 90 minutes.After reaction for some time, every one hour different sites sampling analysis from the second reactor, the position of sampling analysis is respectively the flow direction according to material, take the entrance of the second reactor as starting point, the outlet of the second reactor is terminal, on average every a segment distance, a sampling spot is set, 5 of sampling spots are set altogether, test result shows that the result of 5 sampling spot 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 thus in the second reactor that Flow of Goods and Materials state approaches complete mixing flow
After reaction for some time, every one hour respectively from the sampling of first and second reactor outlet with iodimetric analysis hydrogenation of polymer degree.Reaction has continued 80 hours, and the average hydrogenation reaction of each reactor the results are shown in Table 1.
Embodiment 2
Except the circular flow in first ring pipe reactor is 100 with the ratio of the flow that flows out described annular-pipe reactor, circular flow in the second annular-pipe reactor and the ratio of flow that flows out described annular-pipe reactor are beyond 40, the hydrogenation reaction that contains the polymkeric substance of olefines unsaturated link(age) by method the same in embodiment 1, the results are shown in Table 1.
Embodiment 3
Except the circular flow in first ring pipe reactor is 150 with the ratio of the flow that flows out described annular-pipe reactor, circular flow in the second annular-pipe reactor and the ratio of flow that flows out described annular-pipe reactor are beyond 40, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 4
Except the circular flow in first ring pipe reactor is 20 with the ratio of the flow that flows out described annular-pipe reactor, circular flow in the second annular-pipe reactor and the ratio of flow that flows out described annular-pipe reactor are beyond 40, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 5
Except the circular flow in first ring pipe reactor is 60 with the ratio of the flow that flows out described annular-pipe reactor, circular flow in the second annular-pipe reactor and the ratio of flow that flows out described annular-pipe reactor are beyond 60, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 6
Except the circular flow in first ring pipe reactor is 60 with the ratio of the flow that flows out described annular-pipe reactor, circular flow in the second annular-pipe reactor and the ratio of flow that flows out described annular-pipe reactor are beyond 10, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 7
Except the residence time of polymers soln in first ring pipe reactor is 20 minutes, the residence time in the second annular-pipe reactor is beyond 90 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 8
Except the residence time of polymers soln in first ring pipe reactor is 40 minutes, the residence time in the second annular-pipe reactor is beyond 90 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 9
Except the residence time of polymers soln in first ring pipe reactor is 60 minutes, the residence time in the second annular-pipe reactor is beyond 90 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 10
Except the residence time of polymers soln in first ring pipe reactor is 30 minutes, the residence time in the second annular-pipe reactor is beyond 60 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 11
Except the residence time of polymers soln in first ring pipe reactor is 30 minutes, the residence time in the second annular-pipe reactor is beyond 120 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 12
Except the residence time of polymers soln in first ring pipe reactor is 30 minutes, the residence time in the second annular-pipe reactor is beyond 150 minutes, the hydrogenation reaction that contains olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 13
Beyond length-to-diameter ratio 40 except length-to-diameter ratio 10, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactor, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 14
Beyond length-to-diameter ratio 40 except length-to-diameter ratio 120, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactor, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 15
Beyond length-to-diameter ratio 8 except length-to-diameter ratio 60, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactor, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 16
Beyond length-to-diameter ratio 80 except length-to-diameter ratio 60, the second annular-pipe reactor straight lengths of straight length in first ring pipe reactor, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 17
Except hydrogenation catalyst consumption is 0.04gNi/100g polymkeric substance, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 18
Except hydrogenation catalyst consumption is 0.03gNi/100g polymkeric substance, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 19
Except polymers soln and hydrogenation catalyst agent solution join respectively in first ring pipe reactor, contain the hydrogenation reaction of olefines unsaturated double-bond polymers soln by method the same in embodiment 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 20
Except polymerization obtain containing the cyclohexane solution that adds 0.1M n-Butyl Lithium in the styrene butadiene block polymer solution of active group, then stop 10 minutes with hydrogen, then add the toluene solution containing di-p-tolyl two luxuriant titaniums, after mixing, add first ring pipe reactor, catalyst levels is 0.2mmol Ti/100g polymkeric substance, Li/Ti mol ratio is 8:1, first ring pipe reactor interior reaction temperature is 70 ℃, temperature of reaction in the second annular-pipe reactor is 75 ℃, and hydrogenation reaction the results are shown in Table 1.
Embodiment 21
The basic embodiment 20 that repeats, just first ring pipe reactor interior reaction temperature is 70 ℃, and the temperature of reaction in the second annular-pipe reactor is 90 ℃, and hydrogenation reaction the results are shown in Table 1.
Embodiment 22
The basic embodiment 1 that repeats, just in the time of polyreaction, vinylbenzene and divinyl add simultaneously, the polymkeric substance obtaining is styrene butadiene unregulated polymer, contents of ethylene of the molecular weight of resulting polymers, vinylbenzene and divinyl section in butadiene unit weight ratio, polymkeric substance etc. is all identical with embodiment 1, 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 divinyl with isoprene in the time of polyreaction, and the polymkeric substance obtaining is styrene-isoprene block polymer (S-I-S), and hydrogenation reaction the results are shown in Table 1.
Embodiment 24
The basic embodiment 1 that repeats, just hydrogenation process is comprising 3 reactors that are connected in series, wherein the 3rd reactor is identical with the second annular-pipe reactor, the residence time of polymers soln in 3 reactors is respectively 20,60,60 minutes, reaction continued 30 hours, from the sampling of three reactor outlets with its degree of hydrogenation of iodimetric analysis, result shows that the last degree of hydrogenation of three reactors is followed successively by 96.0%, 98.1% and 99.5% afterwards.
In embodiment 1-24, all after reaction for some time, every one hour degree of hydrogenation from the different sites sampling analysis sampling spot of the first reactor, the position of sampling analysis is respectively the flow direction according to material, take the entrance of the first reactor as starting point, the outlet of the first reactor is terminal, on average establishes a sampling spot every a segment distance, and 5 sampling spots are set altogether.In embodiment 1-24, the result of 5 sampling spot resulting polymers degrees of hydrogenation is all very approaching.
Comparative example 1
The basic embodiment 1 that repeats, just the circular flow in first ring pipe reactor and the ratio of flow that flows out described annular-pipe reactor are that the circular flow in 5, the second annular-pipe reactors is 3 with the ratio of the flow that flows out described annular-pipe reactor, hydrogenation reaction the results are shown in Table 1.
In continuous hydrogenation reaction process, keeping the hydrogen pressure in the first and second annular-pipe reactors is 2.5MPa (gauge pressure).In reaction process by the each inside reactor temperature of chuck control, but the especially more difficult stable control of first ring pipe reactor internal temperature of each reactor temperature.Reaction has continued 10 hours, and the degree of hydrogenation of first ring pipe reactor outlet sample is that the degree of hydrogenation of 85.0%, the second annular-pipe reactor outlet sample is 93.5%.Result shows in operate continuously process, when first and second reactor cycles is smaller, the flow state of material in two reactors is not all complete mixing flow, the more difficult stable control of hydrogenation reaction temperature, gas-to-liquid contact is insufficient, and the finished product degree of hydrogenation is undesirable.
Comparative example 2
The basic embodiment 1 that repeats, just the circular flow in first ring pipe reactor and the ratio of flow that flows out described annular-pipe reactor are that the circular flow in 60, the second annular-pipe reactors is 3 with the ratio of the flow that flows out described annular-pipe reactor.Reaction has continued 10 hours, and the degree of hydrogenation of first ring pipe reactor outlet sample is that the degree of hydrogenation of 96.9%, the second annular-pipe reactor outlet sample is 97.7%.Result shows in operate continuously process, and too hour, gas-liquid mass transfer effect is bad for the recycle ratio of the second annular-pipe reactor, and hydrogenation reaction efficiency is lower, and the finished product degree of hydrogenation is lower.Can find out, improve to some extent compared with comparative example 1 by the recycle ratio hydrogenation reaction efficiency that improves first ring pipe reactor simultaneously.
Comparative example 3
Except the circular flow in first ring pipe reactor and the ratio of flow that flows out described annular-pipe reactor are that circular flow in 5, the second annular-pipe reactors is 40 with the ratio of the flow that flows out described annular-pipe reactor, all the other are with embodiment 1.In reaction process 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 degree of hydrogenation of first ring pipe reactor outlet sample is that the degree of hydrogenation of 85.0%, the second annular-pipe reactor outlet sample is 97.2%.Result shows in operate continuously 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 simultaneously, improves to some extent compared with comparative example 1 by the recycle ratio hydrogenation reaction efficiency that improves the second annular-pipe reactor.
The impact of table 1 operational condition on hydrogenation reaction
* degree of hydrogenation result is the degree of hydrogenation of diolefine section in polymkeric substance, surveys the degree of unsaturation (being iodine number) before and after hydrogenation in polymkeric substance determine by iodimetry,iodometry.Benzene ring hydrogenation degree is all less than 2%, by nmr for the determination.This embodiment 24 of * applies three reactors that are connected in series, and which reactor bracket inner digital represents.100g polymkeric substance refers to containing the polymkeric substance containing olefines unsaturated link(age).
As can be seen from Table 1, hydrogenation reaction result by above each embodiment and comparative example can be found out, according to method of the present invention, Efficient Cycle by polymers soln in hydrogenator can make polymers soln fully contact with hydrogen, improve gas-liquid mass transfer effect, can steadily control temperature of reaction, can make hydrogenation reaction efficiency have a more substantial increase simultaneously.
Can be found out by comparative example 1-3, when the first reactor or/and in the second reactor the recycle ratio of polymers soln is hour, can not make polymers soln fully contact with hydrogen, gas-liquid mass transfer effect is undesirable, hydrogenation reaction temperature also has much difficulty in healing and surely controls, hydrogenation reaction efficiency is relatively low, and final hydrogenation of net product degree is also lower.
Therefore, adopt annular-pipe reactor array mode of the present invention and processing condition, not only can control more reposefully temperature of reaction, further improve reaction efficiency, the degree of hydrogenation of the finished product is obviously improved, and can within the longer operational cycle, obtain the polymeric articles with desirable degree of hydrogenation, can reduce material consumption, energy consumption and device operation and the maintenance cost of reaction process simultaneously.
Claims (13)
1. the process for selective hydrogenation containing the polymkeric substance of olefines unsaturated link(age), the method is included under hydrogenation conditions, under hydrogenation catalyst exists, make to contact in reactor containing polymers soln, the hydrogen of olefines unsaturated link(age), it is characterized in that, described reactor is two or more annular-pipe reactors that are connected in series, the recycle ratio of controlling the first reactor is 10-200, the recycle ratio of the second reactor and later reactor 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 recycle ratio of the second reactor and later reactor is 10-60.
4. according to the method described in any one in claim 1-3, wherein, the hydrogen pressure in each reactor is identical or different, is 0.2-10MPa independently of one another, is preferably 0.5-5MPa.
5. according to the method described in any one in claim 1-4, wherein, the temperature in each reactor is identical or different, is 30-130 ℃ independently of one another, is preferably 40-100 ℃.
6. according to the method described in any one in claim 1-5, wherein, the length-to-diameter ratio of the straight length of the first reactor is 3-200, be preferably 6-150, more preferably 10-120, the length-to-diameter ratio of the second reactor and later reactor straight length is 2-150, be preferably 4-100, more preferably 8-80.
7. according to the method described in any one in claim 1-5, wherein, the mean residence time in described the first reactor is 10-120min, is preferably 20-60min, mean residence time in the second reactor and later reactor is 20-240min, is preferably 30-150min.
8. according to the method described in any one in claim 1-7, wherein, the concentration of the solution of the described polymkeric substance containing olefines unsaturated link(age) is 5-40 % by weight, be preferably 8-30 % by weight, the solvent using in the solution of the described polymkeric substance containing olefines unsaturated link(age) is at least one the inert hydrocarbon solvent being selected from alkane, naphthenic hydrocarbon and aromatic hydrocarbons.
9. according to the method described in any one in claim 1-8, wherein, the described polymkeric substance containing olefines unsaturated link(age) is the multipolymer of conjugated diolefin homopolymerization thing and/or conjugated diene and vinyl-arene, and described conjugated diene homopolymers is polyhutadiene and/or polyisoprene; The multipolymer of described conjugated diolefine and vinyl-arene is random copolymers and/or divinyl and/or isoprene and the alpha-methylstyrene block copolymer of divinyl and/or isoprene and cinnamic random copolymers and/or divinyl and/or isoprene and cinnamic segmented copolymer and/or divinyl and/or isoprene and alpha-methyl styrene.
10. according to the method described in any one in claim 1-9, wherein, described hydrogenation catalyst contains organic acid nickel and aluminum alkyls, in the aluminum alkyls of aluminium with the mol ratio take the organic acid nickel of nickel as 8:1 to 1:1, be preferably 6:1 to 3:1; The consumption of described hydrogenation catalyst is 0.01-0.10gNi/100g polymkeric substance, is preferably 0.03-0.08gNi/100g polymkeric substance.
11. methods according to claim 10, wherein, described organic acid nickel is nickel naphthenate, described aluminum alkyls is triisobutyl aluminium or triethyl aluminum.
12. according to the method described in any one in claim 1-9, and wherein, described hydrogenation catalyst contains metallocene-titanium catalyst and optional lithium alkylide, and the mol ratio of lithium and titanium is 0:1 to 40:1, is preferably 3:1 to 20:1; The consumption of described hydrogenation catalyst is 0.01-0.5mmolTi/100g polymkeric substance, is preferably 0.05-0.3mmolTi/100g polymkeric substance.
13. methods according to claim 12, wherein, described lithium alkylide is n-Butyl Lithium.
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| 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 |
| CN114752015A (en) * | 2022-03-30 | 2022-07-15 | 安徽凯泽新材料有限公司 | Tubular continuous production process of butyronitrile latex |
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