CN102453125B - Hydrogenation method for olefin unsaturated bond-containing polymer - Google Patents
Hydrogenation method for olefin unsaturated bond-containing polymer Download PDFInfo
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Abstract
The invention discloses a continuous hydrogenation method for olefin unsaturated bond-containing polymer. The method comprises a step of contacting a solution of the olefin unsaturated bond-containing polymer with hydrogen for hydrogenation in the presence of a hydrogenation catalyst, wherein a hydrogenation reactor used comprises two or more than two serially connected reactors; in the hydrogenation process, reaction effluent of a first reactor is divided into two parts, one part enters a second reactor, and the other part exchanges heat with a heat exchanger and is recycled to return the first reactor; by controlling the apparent velocity of hydrogen bubbles flowing through a reaction mixture and the circulating flow of the reaction effluent, the first reactor approaches full-Francis operation, and the second and subsequent reactors approach piston flow operation; and the reaction mixture is continuously hydrogenated through hydrogen dissolved in the reaction mixture by maintaining the hydrogen pressure in the reactor. By the method, the hydrogen and the polymer solution are fully contacted uniformly, so the hydrogenation efficiency is improved; and the temperature in the hydrogenation process can be stably controlled, so the catalyst is prevented from being deactivated due to high temperature; therefore, products with an ideal hydrogenation degree are stably obtained in a long operating period. Meanwhile, material consumption, energy consumption and operating cost in the reaction process are reduced.
Description
Technical field
The present invention relates to a kind of continously hydrogen adding method that contains the polymkeric substance of olefines unsaturated link(age), the method is included under the hydrogenation catalyst existence and makes the solution of the polymkeric substance that contains the olefines unsaturated link(age) contact hydrogenation with hydrogen.
Background technology
The thermotolerance, oxidative stability and the ageing resistance that contain the polymkeric substance of alkene unsaturated link(age) for improvement, hydrogenation makes the alkene unsaturated link(age) of polymkeric substance saturated usually.Usually require the degree of unsaturation of hydrogenation post polymerization thing less than 2% (being that degree of hydrogenation is greater than 98%), to realize obvious improvement in performance.
US Patent No. 6,815,509B2 discloses a kind of method for hydrogenating polymer, described method is included in the olefines unsaturated group hydrogenation that under the hydrogenation catalyst existence, the polymkeric substance that contains the olefines unsaturated group is contacted with hydrogen and make polymkeric substance, and the polymers soln after at least a portion that wherein circulates hydrogenation continues hydrogenation.In the method, applied reactor comprises the reactor that is connected in series more than two or two, reaction process is carried out continuously or intermittently, the recirculation after the interchanger heat exchange of a part of reaction effluent of at least one reactor is got back in this reactor or in upstream reactor, is improved the product degree of hydrogenation thereby pass through constantly to circulate in reaction process.The weak point of the method is as follows: generally to stir in the first reactor of this method of hydrotreating and/or later reactor, need in reaction process constantly to consume and stir required mechanical energy, and with the sealing of whipping device make its make and maintenance cost all higher; Repeatedly add with 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 such as Fe, Co, the Ni etc. that are not suitable for other type carry out hydrogenation.
US Patent No. 3,696,088 discloses a kind of unsaturated polymer continously hydrogen adding method that adopts the homogeneous hydrogenation catalyst system, wherein adopt trickle-bed reactor, be mainly used in styrene-conjugated diene analog copolymer hydrogenation, fill inert filler in reactor, the downward drip of polymers soln is by hydrogen atmosphere, reacts the degree of hydrogenation of conjugated diene section in 4 minutes polymkeric substance greater than 98%.Although this inventive method hydrogenation speed is fast, weak point is as follows: the hydrogenation catalyst consumption is large, temperature of reaction is high; The liquid holdup of trickle-bed reactor is little, the utilization ratio of unit volume reactor is low; Bad with the heat-transfer effect of trickle-bed reactor, reacting the starting stage when in polymers soln, two key concentration are higher, when exothermic heat of reaction is larger, reaction heat is difficult to withdraw from, therefore, temperature of reaction is difficult to steady control even makes temperature of reaction significantly raise, and then can make the hydrogenation catalyst inactivation cause hydrogenation cycle stretch-out or the finished product degree of hydrogenation to reduce.
Chinese patent CN101492513A discloses a kind of hydrogenator and method for hydrogenating polymer, wherein said hydrogenator is the combination of two or more bubbling reactors, the first bubbling reactor wherein is set makes its Flow of Goods and Materials state near complete mixing flow, and arrange second and later bubbling reactor make its Flow of Goods and Materials state near plug flow.The shortcoming of this method is to only depend on the more difficult Flow of Goods and Materials state of the first bubbling reactor that makes of flow hydrogen gas near 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, all the more so when polymer solution viscosity is 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.
English Patent GB1, 343, 447 relate to a kind of method of carrying out gas-liquid contact reaction, wherein adopt special gas-liquid contact reactor to make the high-viscosity polymer hydrogenation, there are two Stirring axles to stir polymers soln in reactor, a plurality of retaining elements are installed on turning axle, polymers soln remains between spinner member, form certain space between the viscous soln of the internal surface of reactor wall and spinner member, again form the solution-air surface by shear-mixed, realize gas-to-liquid contact, and continuous renewal gas-to-liquid contact face, can continuous feeding and discharging, when hydrogen pressure is 0.2MPa, Stirring axle rotating speed is 60 rev/mins, hydrogenation temperature is controlled at 68 ± 30 ℃, reacted 50 minutes, hydrogenation of polymer Du Keda 82%.The shortcoming of this patent is that structure of reactor is complicated, manufacturing cost is high and the finished product degree of hydrogenation is low.
In prior art, US Patent No. 4,501,875, US 4,673,714 and English Patent GB2,159,819A etc. all adopt stirring tank to carry out the hydrogenation at intermittence, because two key concentration height and hydrogenation speed in reaction reaction soln in early stage cause 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 also is unfavorable for the industry amplification.
Present situation in view of prior art, the inventor has carried out extensive and deep research for the polymers soln hydrogenation that contains unsaturated link(age), discovery is carried out hydrogenation of polymer by a kind of new hydrogenator Combination Operation Modes can control temperature of reaction better, thereby keep catalyst activity within the long operational cycle, and then the raising hydrogenation efficiency, to reach desirable degree of hydrogenation.
Summary of the invention
the invention provides a kind of polymkeric substance continously hydrogen adding method, be specially the continously hydrogen adding method of the polymkeric substance that contains the olefines unsaturated link(age), the method is included under the hydrogenation catalyst existence and makes the solution of the polymkeric substance that contains the olefines unsaturated link(age) contact hydrogenation with hydrogen, the hydrogenator that wherein uses comprises the reactor that two or more are connected in series, reaction effluent with the first reactor in hydrogenation process is divided into two portions, a part enters the second reactor, another part after the interchanger heat exchange recirculation get back to the first reactor, wherein cross the superfacial velocity of reaction mixture and the circular flow of reaction effluent by controlling the hydrogen bubble flow in the first reactor, make the first reactor operate near complete mixing flow, second and later reactor operate near plug flow, wherein utilize the hydrogen that dissolves in reaction mixture to make reaction mixture continue hydrogenation by the hydrogen pressure of keeping in reactor.
In the method for the invention, the hydrogenator that uses comprises two or more reactors, these reactors are connected in series each other, wherein operate near complete mixing flow in the first reactor, make the most of olefines unsaturated link(age) hydrogenation in polymkeric substance, second and later reactor near the plug flow operation, wherein the residual olefin class unsaturated link(age) in reaction mixture is continued hydrogenation.This method for hydrogenating polymer with complete mixing flow and plug flow combination operation can be realized more stable hydrogenation, thereby can reach needed hydrogenation of polymer degree.
particularly, in the method for the invention, the circulation of crossing reaction mixture and reaction effluent by the hydrogen bubble flow in the first reactor makes the flow state of reaction mixture near complete mixing flow, hydrogenation reaction is acutely carried out therein, make the most of olefines unsaturated link(age) hydrogenation in polymkeric substance, for example can reach 90% or above degree of hydrogenation, second and later reactor in utilize the hydrogen that dissolves in reaction mixture to make reaction mixture continue hydrogenation by the hydrogen pressure of keeping in reactor, wherein hydrogen basically no longer bubbling pass through reaction mixture, do not have the circulation of reaction effluent to cause mixing effect yet, thereby make second and later reactor in the flow state of reaction mixture near plug flow.
More specifically, in the method for the invention, in the first reactor, for the flow state that makes reaction mixture near complete mixing flow, the superfacial velocity that control hydrogen bubble flow is crossed reaction mixture is 0.005-0.10m/s, be preferably 0.01-0.05m/s, and the weight ratio of controlling feed of polymer solution amount and reaction effluent internal circulating load is 1: 60 to 60: 1, is preferably 1: 30 to 30: 1.
In the method for the invention, the hydrogen pressure in hydrogenation process in each reactor can be the same or different, and is respectively 0.5-10.0MPa (gauge pressure), is preferably 0.5-5.0MPa (gauge pressure).Wherein, in the first reactor, thereby hydrogen makes most of olefines unsaturated link(age) hydrogenation polymkeric substance with certain speed bubbling by reaction mixture after reactor bottom adds, unreacted hydrogen separates and collects on reactor top, and then after compressed machine compression, recirculation is got back to and further participated in reaction in the first reactor; Second and later reactor in, maintain during enough hydrogen is dissolved in reaction mixture by keep hydrogen pressure in reactor in the reactor bottom hydrogen make-up, thereby make the olefines unsaturated link(age) of the remainder in polymkeric substance continue hydrogenation.
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, the circulation of reaction effluent not only can be regulated the flow state of internal-response mixture, also can regulate the temperature of internal-response mixture, because reaction effluent recirculation after the interchanger heat exchange.Therefore, the temperature of reaction effluent can be regulated by interchanger, and then the temperature in the first reactor can be regulated by circular flow and the temperature of reaction effluent, thereby be beneficial to its internal reaction temperature of steady control, the long-term stability that is beneficial to catalytic hydrogenation reaction is carried out.
In the method for the invention, wherein said two or more reactors can for being used for any suitable reactor of hydrogenation of polymer in this area, for example can for reactor, tower reactor and tubular reactor, be preferably tower reactor.
Particularly, in the method for the invention, wherein the aspect ratio of the first reactor can be 50: 1 to 1: 2, is preferably 30: 1 to 1: 1, and second and the aspect ratio of later reactor can be 100: 1 to 1: 1, be preferably 50: 1 to 2: 1; Can be furnished with water cooler on the first reactor top, for separating of with collect unreacted hydrogen with its recycle; The outside of all reactors all can be furnished with chuck, and further regulating its internal reaction temperature by hot water or water coolant, thereby the long-term stability that is conducive to catalytic hydrogenation reaction is carried out; In addition, second and later inside reactor filler can be housed, filler used can be in bulk or regular inert filler, the material of described inert filler can be stainless steel, pottery or plastics, under the effect of filler, can further increase the contact area of polymkeric substance and hydrogen, and the flow state that is conducive to keep reaction mixture is plug flow.
In the method for the invention, the chuck of circulation that can be by hydrogen bubbling, reaction effluent, reactor outside and the filler combination of inside reactor get up flow state and the temperature of reaction of conditioned reaction device inside, thereby be conducive to keep the activity of hydrogenation catalyst within the longer operating time, and then can improve the efficient of the inventive method and reduce running cost.
In the method for the invention, the described solution that contains the polymkeric substance of olefines unsaturated link(age) passes in and out each reactor in a continuous manner, described polymers soln can enter the top overflow from each reactor bottom and flow out, (said top is near reactor head here also can to enter the bottom outflow from each reactor head, when reactor top is furnished with water cooler, polymers soln enters between water cooler and reactor, and is lower same).
In the method for the invention, the concentration of the solution of the described polymkeric substance that contains the olefines unsaturated link(age) can be 5-40wt%, is preferably 8-30wt%.Wherein, the solvent that uses is inert hydrocarbon solvent, and this varsol is selected from alkane, naphthenic hydrocarbon and aromatic hydrocarbons.At this, 'inertia' in the disturbance reponse device not hydrogenation reaction as principle, namely described varsol can not and reactant or reaction product between react, can not be unfavorable for the performance of catalyst activity.For the first reactor, at the water cooler on reactor top also cooling described varsol in cooling unreacted hydrogen, therefore, also reclaim described varsol in recover hydrogen, thereby avoided hot hydrogen to take away varsol in reaction mixture.
In the method for the invention, the described polymkeric substance that contains the olefines unsaturated link(age) can be the multipolymer of conjugated diene homopolymers or conjugated diolefine and vinyl-arene, described conjugated diene homopolymers can be polyhutadiene or polyisoprene, comprise random copolymers and segmented copolymer with the multipolymer of described conjugated diolefine and vinyl-arene, divinyl or isoprene and cinnamic random copolymers or segmented copolymer can be, also random copolymers or the segmented copolymer of divinyl or isoprene and alpha-methyl styrene can be.
In the method for the invention, described hydrogenation catalyst can be to be used for any suitable hydrogenation catalyst of hydrogenation of polymer in this area.Described hydrogenation catalyst can be to contain the organic compound of periodic table of elements VIIIB family metal and the catalyzer of organoaluminum usually, and described VIIIB family's metal such as iron, cobalt, nickel and palladium are preferably nickel and cobalt; Described hydrogenation catalyst can be also metallocene catalyst, and this metallocene catalyst is preferably metallocene-titanium catalyst, and chooses wantonly and mix with organolithium compound such as lithium alkylide, and described lithium alkylide is preferably n-Butyl Lithium.
Particularly, in the method for the invention, described hydrogenation catalyst can be the mixture of organic acid nickel such as nickel naphthenate and aluminum alkyls such as 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, the consumption of described hydrogenation catalyst can be the 0.01-0.10gNi/100g polymkeric substance with this moment, is preferably the 0.03-0.08gNi/100g polymkeric substance.
In addition, in the method for the invention, described hydrogenation catalyst also can be metallocene-titanium catalyst and the lithium alkylide of choosing wantonly such 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, the consumption of described hydrogenation catalyst can be the 0.01-0.5mmolTi/100g polymkeric substance with this moment, is preferably the 0.05-0.3mmolTi/100g polymkeric substance.
In the method for the invention, described hydrogenation catalyst can be independent of described polymers soln and adds in each reactor.particularly, described hydrogenation catalyst can add the top overflow to flow out from each reactor bottom, also can add the bottom to flow out from each reactor head, but preferred described hydrogenation catalyst with after described polymers soln mixes together with add in each reactor, thereby and further preferred described hydrogenation catalyst with after described polymers soln mixes together with add the bottom to flow out from the first reactor head to carry out hydrogenation reaction with the hydrogen counter current contact, with from second and the bottom of later reactor add the top overflow to flow out, be beneficial to control second and later reactor in liquid level.
Description of drawings
Further describe the present invention referring to accompanying drawing, wherein:
Fig. 1 has described the process flow diagram of a kind of embodiment of the inventive method, has wherein used two reactors that are connected in series, and is furnished with water cooler on the first reactor top; With
Fig. 2 has described the process flow diagram of the another embodiment of the inventive method, has wherein used three reactors that are connected in series, and is furnished with water cooler on the first reactor top.
Embodiment
The present invention is described in further detail by the following examples, but these embodiment should not think limitation of the scope of the invention.
Embodiment 1
500L jacketed stirred autoclave is fully replaced with refining nitrogen, add 250L hexanaphthene and hexane mixed solvent (in this mixed solvent, the weight percent of hexanaphthene is 87wt%) and 3.6L commercial benzene ethene after displacement, the mixture (in this mixture, the mol ratio of tetrahydrofuran (THF) and n-Butyl Lithium is 37: 1) that adds n-Butyl Lithium and tetrahydrofuran (THF), 50-60 ℃ of reaction 30 minutes, continue to add the refining divinyl reaction of 25L 30 minutes, and then added 3.6L commercial benzene ethylene reaction 30 minutes, after completing, reaction adds 30ml Virahol termination reaction.At this, the concentration of styrene-butadiene block copolymer (S-B-S) is about 10wt% based on whole polymerization system, the molecular weight of this segmented copolymer is 6.5 ten thousand, and the weight ratio of vinylbenzene and butadiene monomer unit is 3: 7, and in polymkeric substance, the contents of ethylene of divinyl section is 39wt%.
With nickel naphthenate (synthetic rubber plant, the Yanshan Mountain, Beijing, 3gNi/L, technical grade) and triisobutyl aluminium (synthetic rubber plant, the Yanshan Mountain, Beijing, 4gNi/L, technical grade) be mixing in 4: 1 according to aluminium nickel mol ratio (by metal), this mixture in 50 ℃ of lower ageings 30 minutes, then is added to it in styrene-butadiene block copolymer solution obtained above, and stirs.At this, the consumption of hydrogenation catalyst is the 0.07gNi/100g polymkeric substance.
This hydrogenation operation adopts the device shown in accompanying drawing 1, comprising two reactors that are connected in series, the first reactor inside diameter is 200mm, total reactor height is 6m (height of its middle and upper part water cooler is 3m), the second reactor inside diameter is 200mm, and height for reactor is 6m, and the Stainless Steel Helices of Φ 10 * 10 is equipped with in inside, wherein the first and second reactors are all used nitrogen replacement in advance, then use hydrogen exchange.
To with adding 60L to contain the styrene-butadiene block copolymer solution of hydrogenation catalyst in the first reactor after hydrogen exchange, keeping temperature of reaction is 55 ℃, then pass into hydrogen and keep hydrogen pressure 4.0MPa (gauge pressure) in reactor, and the control hydrogen flow rate is 0.03m/s.In reaction process, a part of reaction effluent of the first reactor by the interchanger heat exchange after continuous circulation get back in the first reactor, circular flow is 540L/h.React and begin sampling after 30 minutes and with its degree of hydrogenation of iodimetric analysis, when result shows 30 minutes, degree of hydrogenation is 97.8%, and 1 hour degree of hydrogenation is 98.5%.
After above-mentioned rhythmic reaction, add continuously the styrene-butadiene block copolymer solution that contains hydrogenation catalyst in the first reactor, polymers soln from the first reactor middle part (apart from reactor bottom 3m, be between water cooler and reactor) enter, with flow out from the bottom, feed rate is 60L/h, and keeping temperature of reaction is 55 ℃, and the control hydrogen flow rate is 0.03m/s.In reaction process, the reaction effluent of the first reactor flows out from reactor bottom, this reaction effluent is divided into two portions, a part is entered by the second reactor bottom and wherein continues reaction, another part after volume pump metering and interchanger heat exchange recirculation get back in the first reactor, circular flow is 540L/h (weight ratio of charging and recycle stream is 1: 9), keeps simultaneously reaction mixture constancy of volume in the first reactor.Temperature of reaction in the second reactor is 65 ℃, and hydrogen pressure is 4.0MPa (gauge pressure), and liquid level is 6m, and reaction effluent flows out from the reactor head overflow.After reaction for some time, every two hours respectively from the sampling of first and second reactor outlet with its degree of hydrogenation of iodimetric analysis.Reaction has continued 60 hours, and hydrogenation reaction the results are shown in Table 1.
Embodiment 2
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor and the weight ratio of reaction effluent circular flow are 1: 19, hydrogenation reaction the results are shown in Table 1.
Embodiment 3
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor and the weight ratio of reaction effluent circular flow are 1: 29, hydrogenation reaction the results are shown in Table 1.
Embodiment 4
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor and the weight ratio of reaction effluent circular flow are 1: 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 5
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor and the weight ratio of reaction effluent circular flow are 5: 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 6
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor and the weight ratio of reaction effluent circular flow are 10: 1, hydrogenation reaction the results are shown in Table 1.
Embodiment 7
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor is 30L/h, hydrogenation reaction the results are shown in Table 1.
Embodiment 8
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor is 90L/h, hydrogenation reaction the results are shown in Table 1.
Embodiment 9
The basic embodiment 1 that repeats, just the feed of polymer solution flow of the first reactor is 120L/h, hydrogenation reaction the results are shown in Table 1.
Embodiment 10
The basic embodiment 1 that repeats, just the second in-built filler of reactor is the ceramic packing of Φ 10 * 10, hydrogenation reaction the results are shown in Table 1.
Embodiment 11
The basic embodiment 1 that repeats, just the second in-built filler of reactor is the stainless steel structured packing of Φ 200 * 10, hydrogenation reaction the results are shown in Table 1.
Embodiment 12
The basic embodiment 1 that repeats, just the hydrogen flow rate in the first reactor is 0.01m/s, hydrogenation reaction the results are shown in Table 1.
Embodiment 13
The basic embodiment 1 that repeats, just the hydrogen flow rate in the first reactor is 0.05m/s, hydrogenation reaction the results are shown in Table 1.
Embodiment 14
The basic embodiment 1 that repeats does not just load material in the second reactor, and hydrogenation reaction the results are shown in Table 1.
Embodiment 15
The basic embodiment 1 that repeats, just the hydrogenation catalyst consumption is the 0.05gNi/100g polymkeric substance, hydrogenation reaction the results are shown in Table 1.
Embodiment 16
The basic embodiment 1 that repeats, just the hydrogenation catalyst consumption is the 0.03gNi/100g polymkeric substance, hydrogenation reaction the results are shown in Table 1.
Embodiment 17
The basic embodiment 1 that repeats, just the first reactor reaction section is highly 2.0m, and internal diameter is 1.0m, and hydrogenation reaction the results are shown in Table 1.
Embodiment 18
The basic embodiment 1 that repeats, just the second reactor reaction section is highly 3.0m, and internal diameter is 0.5m, and hydrogenation reaction the results are shown in Table 1.
Embodiment 19
The basic embodiment 1 that repeats, just the second reactor reaction section is highly 10m, and internal diameter is 200mm, and hydrogenation reaction the results are shown in Table 1.
Embodiment 20
The basic embodiment 1 that repeats, just polymers soln and hydrogenation catalyst agent solution join respectively in the first reactor, and the polymers soln flow is 60L/h, and the hydrogenation catalyst solution flow is 2L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 21
The basic embodiment 1 that repeats, the cyclohexane solution that adds the 0.1M n-Butyl Lithium in the styrene-butadiene block copolymer solution that contains active group that just obtains to polymerization, then stop 10 minutes with hydrogen, then add the toluene solution that contains cyclopentadienyl titanium dichloride, add the first reactor after mixing, catalyst levels is the 0.2mmolTi/100g polymkeric substance, and the Li/Ti mol ratio is 20: 1, temperature of reaction in first and second reactor is 70 ℃, and hydrogenation reaction the results are shown in Table 1.
Embodiment 22
The basic embodiment 19 that repeats, just the temperature of reaction in first and second reactor is 90 ℃, and hydrogenation reaction the results are shown in Table 1.
Embodiment 23
The basic embodiment 1 that repeats, just polymer solution concentration is 15wt%, hydrogenation reaction the results are shown in Table 1.
Embodiment 24
The basic embodiment 1 that repeats, just vinylbenzene and divinyl add simultaneously when polyreaction, resulting polymkeric substance is styrene butadiene random copolymer, in the molecular weight of resulting polymers, vinylbenzene and butadiene unit weight ratio, polymkeric substance, contents of ethylene of divinyl section etc. is all identical with embodiment 1, and hydrogenation reaction the results are shown in Table 1.
Embodiment 25
The basic embodiment 1 that repeats just substitutes divinyl with isoprene when polyreaction, resulting polymkeric substance is styrene-isoprene block copolymer (S-I-S), and hydrogenation reaction the results are shown in Table 1.
Embodiment 26
The basic embodiment 1 that repeats, just hydrogenation process adopts the device shown in accompanying drawing 2, comprising 3 reactors that are connected in series, the 3rd reactor is identical with the second reactor, and all do not load material in second and third reactor, reaction has continued 30 hours, and 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 97.2%, 98.5% and 99.5% afterwards.
Comparative Examples 1
The basic embodiment 1 that repeats, just in the continuous hydrogenation reaction process, keeping the hydrogen pressure in the first and second reactors is 4.0MPa (gauge pressure), hydrogen and reaction effluent all do not circulate.Control each inside reactor temperature by chuck in reaction process, but each inside reactor temperature is difficult to stable control.Reaction has continued 10 hours, and the degree of hydrogenation of the first reactor outlet sample is that the degree of hydrogenation of 85.0%, the second reactor outlet sample is 92.0%.Result shows in the operate continuously process, and all the circulation time hydrogenation efficiency is not lower for hydrogen and reaction effluent.
Comparative Examples 2
The basic embodiment 1 that repeats, just in the continuous hydrogenation reaction process, the reaction effluent of the first reactor does not circulate.Control each inside reactor temperature by chuck in reaction process, but each inside reactor temperature is difficult to stable control.Reaction has continued 10 hours, and the degree of hydrogenation of the first reactor outlet sample is that the degree of hydrogenation of 92.5%, the second reactor outlet sample is 95.5%.Result shows that during hydrogen recycle, hydrogenation efficiency slightly is improved in the operate continuously process.
Comparative Examples 3
The basic embodiment 1 that repeats, just in the continuous hydrogenation reaction process, keeping the hydrogen pressure in the first and second reactors is 4.0MPa (gauge pressure), hydrogen does not circulate.Control each inside reactor temperature by chuck in reaction process, but each inside reactor temperature is difficult to stable control.Reaction has continued 10 hours, and the degree of hydrogenation of the first reactor outlet sample is that the degree of hydrogenation of 93.8%, the second reactor outlet sample is 96.5%.Result shows in the operate continuously process, and reaction effluent circulation time hydrogenation efficiency slightly is improved.
Hydrogenation reaction result by above each embodiment and Comparative Examples can be found out, for method of the present invention, cross in the hydrogen bubble flow under the acting in conjunction of reaction mixture and reaction effluent circulation and can control more reposefully the hydrogenation reaction temperature, and hydrogenation reaction efficient is had a more substantial increase.
Can be found out by Comparative Examples 1-3, cross reaction mixture and reaction effluent circulation or only have the hydrogen bubble flow to cross reaction mixture or reaction effluent circulation time in the no hydrogen bubble flow, temperature of reaction is steady relatively not, and hydrogenation reaction efficient slightly reduces, and final hydrogenation of net product degree is also lower.
Therefore, adopt the method for hydrogenating polymer of complete mixing flow of the present invention and plug flow combination, not only can control more reposefully temperature of reaction, further improve reaction efficiency, make the degree of hydrogenation of the finished product obviously higher, and can obtain to have the polymeric articles of desirable degree of hydrogenation within the longer operational cycle, can reduce material consumption, energy consumption and the device process cost of reaction process simultaneously.
Claims (24)
1. continously hydrogen adding method that contains the polymkeric substance of olefines unsaturated link(age), the method is included under the hydrogenation catalyst existence and makes the solution of the polymkeric substance that contains the olefines unsaturated link(age) contact hydrogenation with hydrogen, the hydrogenator that wherein uses comprises the reactor that two or more are connected in series, reaction effluent with the first reactor in hydrogenation process is divided into two portions, a part enters the second reactor, another part after the interchanger heat exchange recirculation get back to the first reactor, wherein cross the superfacial velocity of reaction mixture and the circular flow of reaction effluent by controlling the hydrogen bubble flow in the first reactor, make the first reactor operate near complete mixing flow, second and later reactor operate near plug flow, wherein utilize the hydrogen that dissolves in reaction mixture to make reaction mixture continue hydrogenation by the hydrogen pressure of keeping in reactor.
2. the process of claim 1 wherein that the superfacial velocity that in the first reactor hydrogen bubble flow is crossed reaction mixture is 0.005-0.10m/s.
3. the method for claim 2, the superfacial velocity that wherein the hydrogen bubble flow is crossed reaction mixture in the first reactor is 0.01-0.05m/s.
4. the method for claim 1-3 any one, wherein the weight ratio of feed of polymer solution amount and reaction effluent internal circulating load is 1: 60 to 60: 1 in the first reactor.
5. the method for claim 4, wherein the weight ratio of feed of polymer solution amount and reaction effluent internal circulating load is 1: 30 to 30: 1 in the first reactor.
6. the method for claim 1-3 any one, wherein the hydrogen pressure in each reactor is identical or different in hydrogenation process, is respectively the 0.5-10.0MPa gauge pressure.
7. the method for claim 6, wherein the hydrogen pressure in each reactor is identical or different in hydrogenation process, is respectively the 0.5-5.0MPa gauge pressure.
8. the method for claim 1-3 any one, wherein the temperature in each reactor is identical or different in hydrogenation process, is respectively 30-130 ℃.
9. the method for claim 8, wherein the temperature in each reactor is identical or different in hydrogenation process, is respectively 40-100 ℃.
10. the method for claim 1-3 any one, wherein the aspect ratio of the first reactor is 50: 1 to 1: 2, and second and the aspect ratio of later reactor be 100: 1 to 1: 1.
11. the method for claim 10, wherein the aspect ratio of the first reactor is 30: 1 to 1: 1, and second and the aspect ratio of later reactor be 50: 1 to 2: 1.
12. the method for claim 1-3 any one, wherein be furnished with on the first reactor top water cooler for separating of with collect unreacted hydrogen, and unreacted hydrogen then after compressed machine compression recirculation get back to and further participate in reaction in the first reactor.
13. the method for claim 1-3 any one, wherein the first reactor outside is furnished with chuck, by hot water or its internal reaction temperature of chilled water modulation, and second and later reactor outside also be furnished with chuck, by hot water or its internal reaction temperature of chilled water modulation.
14. the method for claim 1-3 any one, wherein second and later inside reactor filler is housed, filler used is in bulk or regular inert filler, the material of described inert material is stainless steel, pottery or plastics.
15. the method for claim 1-3 any one, the concentration of the solution of the wherein said polymkeric substance that contains the olefines unsaturated link(age) is 5-40wt%, and the solvent that wherein uses is inert hydrocarbon solvent, is selected from alkane, naphthenic hydrocarbon and aromatic hydrocarbons.
16. the method for claim 15, the wherein said concentration that contains the polymkeric substance of olefines unsaturated link(age) is 8-30wt%.
17. the method for claim 1-3 any one, the wherein said polymkeric substance that contains the olefines unsaturated link(age) is the multipolymer of conjugated diene homopolymers or conjugated diolefine and vinyl-arene, described conjugated diene homopolymers is polyhutadiene or polyisoprene, and the multipolymer of described conjugated diolefine and vinyl-arene is random copolymers or the segmented copolymer of divinyl or isoprene and cinnamic random copolymers or segmented copolymer or divinyl or isoprene and alpha-methyl styrene.
18. the method for claim 1-3 any one enters the bottom from the first reactor head continuously after wherein hydrogenation catalyst and polymers soln mix in hydrogenation process and flows out, and from second and later reactor bottom enter the top overflow and flow out.
19. the method for claim 1-3 any one, wherein said hydrogenation catalyst are the mixture of organic acid nickel and aluminum alkyls, in this mixture, the mol ratio of aluminium and nickel is 8: 1 to 1: 1, and the consumption of described hydrogenation catalyst is the 0.01-0.10gNi/100g polymkeric substance.
20. the method for claim 19, wherein said hydrogenation catalyst are the mixture of organic acid nickel and aluminum alkyls, in this mixture, the mol ratio of aluminium and nickel is 6: 1 to 3: 1, and the consumption of described hydrogenation catalyst is the 0.03-0.08gNi/100g polymkeric substance.
21. the method for claim 19, wherein said organic acid nickel is nickel naphthenate, and described aluminum alkyls is triisobutyl aluminium or triethyl aluminum.
22. the method for claim 1-3 any one, wherein said hydrogenation catalyst is metallocene-titanium catalyst and the mixture of optional lithium alkylide, in this mixture, the mol ratio of lithium and titanium is 0: 1 to 40: 1, and the consumption of described hydrogenation catalyst is the 0.01-0.5mmolTi/100g polymkeric substance.
23. the method for claim 22, wherein said hydrogenation catalyst is metallocene-titanium catalyst and the mixture of optional lithium alkylide, in this mixture, the mol ratio of lithium and titanium is 3: 1 to 20: 1, and the consumption of described hydrogenation catalyst is the 0.05-0.3mmolTi/100g polymkeric substance.
24. the method for claim 22, wherein said lithium alkylide are n-Butyl Lithium.
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| CN103788238B (en) * | 2012-10-30 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of hydrogenation of polymer reaction method containing olefines unsaturated link(age) |
| CN103788272B (en) * | 2012-10-31 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method of hydrotreating containing olefines unsaturated bond polymer |
| CN104178242A (en) * | 2013-05-28 | 2014-12-03 | 西安艾姆高分子材料有限公司 | Method for preparation of food-grade general fully synthetic lubricating oil |
| CN104277873A (en) * | 2013-07-03 | 2015-01-14 | 西安艾姆高分子材料有限公司 | New polyolefin synthesis lubricating oil hydrogenation technology |
| CN105085724B (en) * | 2015-09-14 | 2017-11-21 | 山东聚圣科技有限公司 | A kind of hydrogenation plant and method of hydrotreating for polymer continuously hydrogen adding |
| CN107674166B (en) * | 2016-08-01 | 2020-11-13 | 浙江众立合成材料科技股份有限公司 | Hydrogenated styrene thermoplastic elastomer and synthesis method and application thereof |
| CN107674137B (en) * | 2016-08-01 | 2020-11-13 | 浙江众立合成材料科技股份有限公司 | Hydrogenated styrene thermoplastic elastomer and synthesis method and application thereof |
| CN107099008A (en) * | 2017-05-31 | 2017-08-29 | 苏州双湖化工技术有限公司 | A kind of hydrogenation of polymer reaction method of olefin-containing class unsaturated bond |
| CN113698511A (en) * | 2020-05-21 | 2021-11-26 | 中国石油化工股份有限公司 | Device and method for nitrile rubber hydrogenation |
| CN112940155A (en) * | 2021-01-21 | 2021-06-11 | 张宇 | Preparation process of petroleum resin with high reaction rate and low softening point |
| CN113278119B (en) * | 2021-07-08 | 2022-09-30 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
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