CN101492513B - Hydrogenator and polymer hydrogenation method - Google Patents
Hydrogenator and polymer hydrogenation method Download PDFInfo
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- CN101492513B CN101492513B CN2008100568758A CN200810056875A CN101492513B CN 101492513 B CN101492513 B CN 101492513B CN 2008100568758 A CN2008100568758 A CN 2008100568758A CN 200810056875 A CN200810056875 A CN 200810056875A CN 101492513 B CN101492513 B CN 101492513B
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Abstract
The invention relates to a hydrogenation reactor which is the combination of two or more bubbling reactors, wherein, a first bubbling reactor is arranged for causing the material flow state thereof to be close to totally mixed flow, and a second and the other bubbling reactors are arranged for causing the material flow states thereof to be close to laminar flow. The invention also relates to a method for utilizing the hydrogenation reactor to cause polymers with unsaturated bonds to be continuously hydrogenized. According the method, the temperature of the process of the hydrogenation can be stably controlled, the material consumption, energy consumption and operation cost of the reaction process are greatly reduced, the hydrogenation reaction efficiency is improved, the production cost is reduced, and simultaneously, products with ideal hydrogenation degree can be stably obtained within a longer operation period.
Description
Technical field
The hydrogenation of polymer method that the present invention relates to a kind of built-up type hydrogenator and utilize described built-up type hydrogenator.More specifically, according to the present invention, adopt continuous processing to hydrogenation of polymer, wherein used hydrogenator is the combination of two or more bubbling reactors.
Background technology
The heat, oxidative stability and the ageing resistance that contain the polymkeric substance of unsaturated link(age) are relatively poor, therefore often make the unsaturated link(age) of polymkeric substance saturated by method of hydrotreating, thereby increase its stability greatly, and make it have good thermostability.Hydrogenation of polymer carries out in the presence of metal catalyst usually, and catalyst system therefor is the organic compound of periodic table of elements VIIIB family metals such as Fe, Co, Ni and/or Pb, and organoaluminum or organolithium compound, also can be metallocene catalyst.
In the prior art as U.S. Pat P 6,815,509 have introduced a kind of hydrogenator, this reactor is combined by two or more stirred reactors, reaction process can be that successive also can be intermittently, be recycled in the reactor after the heat exchange of process interchanger but a part of material in the reactor must be extracted into outside the reactor with pump in reaction process, interchanger can cool off or the heating cycle material, thus the control reaction temperature and the raising hydrogenation of net product degree that passes through constantly to circulate.This method advantage is control reaction temperature also can obtain the degree of hydrogenation high product, weak point is that this method adopts stirred reactor to carry out hydrogenation reaction, need in the reaction process constantly to consume and stir required mechanical energy, the polymers soln of reaction process must could guarantee that than playing circulation reacting balance carries out with systemic circulation very, like this need be in circulation with a large amount of energy expenditures, and the sealing of band whipping device makes its manufacturing cost higher, hydrogenation catalyst needs to add several times in addition, this makes the control of reaction process become more complicated, and all these all can increase the cost of hydrogenation of polymer process.
U.S. Pat P 3,696,088 adopts the trickle bed flow reactor to be used for vinylbenzene-conjugated diene copolymer hydrogenation, fill inert filler in the reactor, polymers soln enters tower bottom flow from cat head and goes out, hydrogen does not flow in tower, and the degree of hydrogenation that reacts conjugated diolefine section in 4 minutes polymkeric substance is greater than 98%.Though this inventive method hydrogenation reaction speed is fast, its weak point one is that the hydrogenation catalyst consumption is big, temperature of reaction is high; The 2nd, the liquid holdup of trickle-bed reactor is little, the utilization ratio of unit volume reactor is low; The 3rd, the heat-transfer effect of trickle-bed reactor is bad, because containing the hydrogenation of polymer of unsaturated link(age) is strong exothermal reaction, reaction starting stage, exothermic heat of reaction higher when unsaturated link(age) concentration in the polymers soln greatly the time reaction heat be difficult to withdraw from, temperature of reaction also is difficult to steadily control even temperature of reaction can raise significantly, thereby and high temperature can make the hydrogenation catalyst inactivation that hydrogenation reaction cycle stretch-out or the finished product degree of hydrogenation are reduced, used everything all be unfavorable for normally carrying out of hydrogenation reaction.
English Patent GB1,343,447 adopt a kind of special gas-liquid contact reactor to be used for the hydrogenation of high-viscosity polymer, there are two rotation stir shafts to stir polymers soln in the described reactor, a lot of retaining elements wherein are installed on the turning axle, polymers soln remains between the spinner member, between the viscous soln of the internal surface of reactor wall and spinner member, form certain space, again form the solution-air surface by shear-mixed, realize gas-to-liquid contact, and bring in constant renewal in the gas-to-liquid contact face, can continuous feeding and discharging, when hydrogen pressure is 0.2MPa, the rotation agitator shaft speed is 60 rev/mins, when being controlled at 68 ± 30 ℃, react after 50 minutes hydrogenation of polymer Du Keda 82% with the hydrogenation reaction temperature.Though this reactor can be realized continuous feeding and discharging, the structure of reactor complexity, the manufacturing cost height, and the finished product degree of hydrogenation is lower.
United States Patent (USP) USP 4 in the prior art, 501,875, USP 4,673,714 and English Patent GB 2,159,819A all adopts stirring tank to carry out the hydrogenation reaction at intermittence, owing to the hydrogenation of polymer reaction that contains unsaturated link(age) is thermopositive reaction, reacting early stage owing to unsaturated link(age) concentration height in the solution, hydrogenation reaction speed is fast, so thermal discharge is also big, at this moment temperature of reaction is difficult to steadily control, thereby will make the part catalyst deactivation influence hydrogenation reaction efficient like this, when especially used hydrogenation technique is batch technology, material consumption, the energy consumption height, control is complicated, and reaction efficiency is low, is unfavorable for the industry amplification.
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the polymkeric substance glue field of hydrogenation that contains unsaturated link(age), found that by a kind of hydrogenation of polymer method of novel combined hydrogenation reactor that adopts and to address the above problem, thereby improve hydrogenation reaction efficient, the process cost that reduces reaction process and the manufacturing cost of reactor, adopt the inventive method in the long operational cycle, stably to make the hydrogenation of polymer degree reach ideal value simultaneously.
Summary of the invention
The invention provides a kind of hydrogenator, it is the combination of two or more bubbling reactors, first bubbling reactor wherein is set makes its Flow of Goods and Materials state near complete mixing flow, and be provided with second and later bubbling reactor make its Flow of Goods and Materials state near plug flow.
Preferably, according to reactor of the present invention, wherein the aspect ratio of each bubbling reactor was respectively 30: 1 to 1: 2, was preferably 15: 1 to 1: 1; Wherein the first bubbling reactor inside is empty or is furnished with spiral coil cooling tube, this spiral coil cooling tube can be used for the heat exchange of reaction process, with be furnished with water cooler on the first bubbling reactor top, this water cooler is used for preventing that hot hydrogen from taking away the solvent of polymers soln, second and later bubbling reactor inside be empty or filler be housed, but filler preferably is housed, and this filler can be in bulk or regular inert filler, and its material can be stainless steel, pottery or plastics.
Preferably, according to reactor of the present invention, wherein each bubbling reactor outside is furnished with chuck, and this chuck can be used for the heat exchange of reaction process, by hot water or cooling water control temperature of reaction.
Particularly, hydrogenator of the present invention is combined by two or more bubbling reactors, wherein hydrogen flow rate is bigger in first bubbling reactor, unsaturated link(age) concentration is higher relatively in the polymers soln, the flow state of polymers soln is near complete mixing flow, this moment, reaction heat can be withdrawn from by the outer chuck of reactor, and further improve polymer solution concentration if desired, the augmenting response body is long-pending, also can be by the auxiliary heat of removing of the spiral coil cooling tube of inside reactor, can be furnished with water cooler on the first bubbling reactor top in addition, take away the solvent in the polymers soln to prevent hot hydrogen; With second and subsequently bubbling reactor in filler is housed, this moment, the unsaturated link(age) concentration of polymers soln reduced gradually, exothermic heat of reaction also reduces gradually, make the flow state of polymers soln near plug flow by the reduction hydrogen flow rate and the filler of in reactor, packing into, be easy to make unsaturated link(age) hydrogenation in the polymkeric substance to reach capacity like this and reach very high degree of hydrogenation, this moment, exothermic heat of reaction also can be withdrawn from by the outer chuck of reactor.
Therefore, according to the present invention, temperature of reaction can be controlled very reposefully in entire reaction course, and is can Yin Wendu not unstable and make the hydrogenation catalyst inactivation, thereby can improve activity of hydrocatalyst and hydrogenation reaction efficient.
Therefore, according to the present invention, that the advantage of described hydrogenator is is simple in structure, liquid holdup is big, manufacturing and maintenance cost are low, and control is simple, and all these aspects all can reduce the cost of hydrogenation of polymer.
The present invention also provides a kind of method of hydrotreating, wherein uses hydrogenator of the present invention to containing the polymers soln continuous hydrogenation of unsaturated link(age) in the presence of hydrogenation catalyst.
Preferably, according to method of the present invention, the wherein said polymkeric substance that contains unsaturated link(age) is the multipolymer of conjugated diene homopolymers or conjugated diolefine and vinyl-arene, described conjugated diene homopolymers is that the multipolymer of polyhutadiene or polyisoprene and described conjugated diolefine and vinyl-arene is the 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.These strength of solution that contain the polymkeric substance of unsaturated link(age) can be 5-30wt%, are preferably 8-20wt%, and this moment, employed solvent was an inert hydrocarbon solvent, was specially alkane, naphthenic hydrocarbon and aromatic solvent, for example hexane, hexanaphthene, toluene etc.
Particularly, method of hydrotreating of the present invention can be used for containing the hydrogenation of the polymkeric substance of unsaturated link(age), be particularly useful for the hydrogenation of the multipolymer (comprising random or segmented copolymer) of conjugated diene homopolymers or conjugated diolefine and vinyl-arene, for example can be used for the hydrogenation of polyhutadiene, polyisoprene, butadiene-styrene copolymer, isoprene-styrol copolymer, divinyl-α-Jia Jibenyixigongjuwu, isoprene-α-Jia Jibenyixigongjuwu etc.These polymer solution concentrations that contain unsaturated link(age) are 5-30wt%, are preferably 8-20wt%, and this moment, employed inert hydrocarbon solvent can be hexane, hexanaphthene, toluene etc.
Preferably, according to method of the present invention, wherein hydrogenation catalyst and polymers soln mix the back or pass in and out each bubbling reactor respectively separately in a continuous manner in hydrogenation process, wherein polymers soln enters top overflow outflow or enters the bottom from each bubbling reactor top and flows out from each bubbling reactor bottom, entering the top with hydrogen from each bubbling reactor bottom flows out, and in reaction system, circulate by hydrogen recycle equipment, wherein the hydrogen apparent velocity of first bubbling reactor is 0.01-0.3m/s, be preferably 0.05-0.15m/s, second and the hydrogen apparent velocity of later bubbling reactor be 0.001-0.06m/s, be preferably 0.003-0.05m/s.
Preferably, according to method of the present invention, wherein the temperature in each bubbling reactor can be the same or different in hydrogenation process, be respectively 30-120 ℃, be preferably 40-70 ℃, reaction pressure in each bubbling reactor can be the same or different, and is respectively 0.5-10.0MPa, is preferably 0.5-5.0MPa.
Preferably, according to method of the present invention, wherein second and later bubbling reactor in since in the polymers soln unsaturated link(age) concentration lower, exothermic heat of reaction is also less, this moment is by the steady control reaction temperature of chuck; In addition since second and later bubbling reactor in dosed filler, thereby can effectively prevent the back-mixing of polymers soln, and this moment, hydrogen flow rate was less, therefore, the flow state of polymers soln is near plug flow, and this degree of hydrogenation to enhanced products is highly beneficial.
According to method of the present invention, described hydrogenation catalyst can be various available polymer hydrogenating catalysts, the catalyzer formed of periodic table of elements group VIII metal and organoaluminum for example, and the catalyzer of metallocene catalyst and the organolithium mixture composition of choosing wantonly, described group VIII metal comprises iron, cobalt, nickel and palladium etc., for activity and cost consideration, nickel and cobalt are particularly preferred, organoaluminum is an aluminum alkyls, be preferably triisobutyl aluminium or triethyl aluminum, be preferably luxuriant titanium with metallocene, organolithium is a lithium alkylide, is preferably n-Butyl Lithium.
In the methods of the invention, described hydrogenation catalyst can mix with the polymers soln that contains unsaturated link(age) in advance, enters each bubbling reactor then, also can enter each bubbling reactor separately.
Preferably, according to method of the present invention, wherein said hydrogenation catalyst is 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, is preferably 6: 1 to 3: 1, described organic acid nickel is preferably nickel naphthenate, the consumption that aluminum alkyls is preferably triisobutyl aluminium or triethyl aluminum and described hydrogenation catalyst is a 0.01-0.10g Ni/100g polymkeric substance, is preferably 0.03-0.08g Ni/100g polymkeric substance.
Preferably, according to method of the present invention, wherein said hydrogenation catalyst is a metallocene catalyst and the mixture of optional lithium alkylide, wherein said metallocene catalyst is preferably metallocene-titanium catalyst, the mol ratio of lithium and titanium is 0: 1 to 40: 1 in this mixture, be preferably 3: 1 to 20: 1 and the consumption of described metallocene-titanium catalyst is a 0.01-0.5mmol Ti/100g polymkeric substance, be preferably 0.05-0.3mmol Ti/100g polymkeric substance.
Description of drawings
Followingly further describe the present invention with reference to accompanying drawing, wherein:
Fig. 1 has described the process flow diagram and the structure of reactor of the inventive method.
Embodiment
The present invention is described by the following examples in more detail.But these embodiment are not limitation of the scope of the invention.
Embodiment 1
500L strap clamp cover stirred autoclave is with making with extra care nitrogen replacement, the displacement back adds the refining mixed solvent (weight percent of hexanaphthene is 87wt%) and the 3.6L commercial benzene ethene of 250L hexanaphthene and hexane, add n-Butyl Lithium and tetrahydrofuran (THF) 50-60 ℃ of reaction 30 minutes, continue to add the refining divinyl reaction of 24.6L 30 minutes, add 3.6L commercial benzene ethylene reaction then 30 minutes, and added 30mL Virahol termination reaction after reaction is finished.Butadiene-styrene block copolymer concentration is 10wt% based on whole polymerization system, the mol ratio of tetrahydrofuran (THF) and n-Butyl Lithium is 37: 1, the number-average molecular weight of this segmented copolymer is 5.5 ten thousand, the weight ratio of vinylbenzene and butadiene monomer unit is 3: 7, and the contents of ethylene of divinyl section is 38wt% in the polymkeric substance.With nickel naphthenate (synthetic rubber plant, the Yanshan Mountain, Beijing, 3gNi/L, technical grade) and triisobutyl aluminium (synthetic rubber plant, the Yanshan Mountain, Beijing, 4gAl/L, technical grade) is to mix at 4: 1 according to aluminium and nickel mol ratio (by metal),, then it is added in the butadiene-styrene block copolymer solution that obtains above in 50 ℃ of following ageings 30 minutes, and stir, the hydrogenation catalyst consumption is a 0.07g Ni/100g polymkeric substance.
The butadiene-styrene block copolymer solution that will contain hydrogenation catalyst then adds in the hydrogenator (referring to accompanying drawing 1) continuously, and reacting system pressure is about 4.0MPa (gauge pressure).Hydrogenator is made up of a bubble tower and a filler bubble tower.First reactor inside diameter is 205mm, tower height overall 6m (the wherein high 3m of hydrogen cooler), and second reactor inside diameter is 205mm, tower height 6m, the Stainless Steel Helices of interior dress Φ 10 * 10.The polymers soln flow is 50L/h, and the first reactor hydrogen airshed is 400NM
3/ h (standard cubic meter/hour), temperature of reaction is 53-55 ℃, and liquid level is 1.6m, and the second reactor hydrogen airshed is 80NM
3/ h, temperature of reaction is 63-67 ℃, liquid level is 6m.Hydrogenation prepolymer solution enters from first reactor middle part (apart from reactor bottom 3m), and flow out the bottom, and the polymers soln that first reactor comes out enters from second reactor bottom, and second reactor is flowed out in overflow.The liquid level of first reactor is controlled by the aperture of pressure reduction between one, two reactors and outlet regulating valve, and this moment, to control two pressure reduction between the reactor be 0.01-0.1MPa, and by pressure reduction make polymers soln from first reactor stream to second reactor.Survey its degree of hydrogenation from first and second reactor polymer taphole sampling and with iodimetry,iodometry respectively.Reaction has continued 50 hours, per hour gets a sample and surveys degree of hydrogenation, and the degree of hydrogenation of surveying the results are shown in Table 1, and wherein table 1 column data is a mean value.
Embodiment 2
Repeat embodiment 1, just the polymers soln flow is 25L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 3
Repeat embodiment 1, just the polymers soln flow is 35L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 4
Repeat embodiment 1, just the polymers soln flow is 40L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 5
Repeat embodiment 1, just the polymers soln flow is 75L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 6
Repeat embodiment 1, just the polymers soln flow is 100L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 7
Repeat embodiment 1, just the filling material is the ceramic packing of Φ 10 * 10 in second reactor, and hydrogenation reaction the results are shown in Table 1
Embodiment 8
Repeat embodiment 1, just the filling material is the stainless steel structured packing in second reactor, and Φ 200 * 10, and hydrogenation reaction the results are shown in Table 1
Embodiment 9
Repeat embodiment 1, just the first reactor hydrogen airshed is 200NM
3/ h, hydrogenation reaction the results are shown in Table 1.
Embodiment 10
Repeat embodiment 1, just the first reactor hydrogen airshed is 600NM
3/ h, hydrogenation reaction the results are shown in Table 1.
Embodiment 11
Repeat embodiment 1, just the first reactor hydrogen airshed is 800NM
3/ h, hydrogenation reaction the results are shown in Table 1.
Embodiment 12
Repeat embodiment 1, just the second reactor hydrogen airshed is 30NM
3/ h, hydrogenation reaction the results are shown in Table 1.
Embodiment 13
Repeat embodiment 1, just do not load material in second reactor, hydrogenation reaction the results are shown in Table 1.
Embodiment 14
Repeat embodiment 1, just the first reactor hydrogenation reaction pressure is 2.0MPa, and the first reactor hydrogen airshed is 200NM
3/ h, the second reactor hydrogen airshed is 40NM
3/ h, hydrogenation reaction the results are shown in Table 1.
Embodiment 15
Repeat embodiment 1, just the hydrogenation catalyst consumption is a 0.05g Ni/100g polymkeric substance, and hydrogenation reaction the results are shown in Table 1.
Embodiment 16
Repeat embodiment 1, just the hydrogenation catalyst consumption is a 0.03g Ni/100g polymkeric substance, and hydrogenation reaction the results are shown in Table 1.
Embodiment 17
Repeat embodiment 1, just the first reactor height overall is 3.0m (the high 1.5m of its middle and upper part water cooler), and liquid level is 1.0m, and reactor inside diameter is 1m, and hydrogenation reaction the results are shown in Table 1.
Embodiment 18
Repeat embodiment 1, just the height of second reactor is 3.0m, and reactor inside diameter is 0.5m, and hydrogenation reaction the results are shown in Table 1.
Embodiment 19
Repeat embodiment 1, just polymers soln and hydrogenation catalyst agent solution add respectively, and the polymers soln flow that contains unsaturated link(age) is 50L/h, and hydrogenation catalyst strength of solution flow is 2L/h, and hydrogenation reaction the results are shown in Table 1.
Embodiment 20
Repeat embodiment 1, the cyclohexane solution that just adds a certain amount of 0.1M n-Butyl Lithium in the butadiene-styrene block polymer solution that contains active group that polymerization obtains, then stop 15 minutes with hydrogen, add the toluene solution that contains cyclopentadienyl titanium dichloride then, enter first hydrogenator after mixing, catalyst levels is a 0.2mmol Ti/100g polymkeric substance, and catalyst solution concentration is 0.4mmol Ti/L, the mol ratio of lithium and titanium is 10: 1 in the solution, and hydrogenation reaction the results are shown in Table 1.
Embodiment 21
Repeat embodiment 1, just the butadiene-styrene block polymer solution that contains active group that obtains of polymerization directly stops 15 minutes with hydrogen, add the toluene solution that contains two pairs of toluene two luxuriant titaniums then, enter first hydrogenator after mixing, catalyst levels is a 0.2mmol Ti/100g polymkeric substance, catalyst solution concentration is 0.4mmol Ti/L, and hydrogenation reaction the results are shown in Table 1.
Embodiment 22
Repeat embodiment 1, just polymer solution concentration is 15wt%, and hydrogenation reaction the results are shown in Table 1.
Embodiment 23
Repeat embodiment 1, vinylbenzene and divinyl add simultaneously when being polyreaction, the polymkeric substance that obtains is a styrene butadiene random copolymer, contents of ethylene of divinyl section etc. is all identical with embodiment 1 in molecular weight, vinylbenzene and butadiene unit weight ratio, the polymkeric substance, and its hydrogenation reaction the results are shown in Table 1.
Embodiment 24
Repeat embodiment 1, substitute divinyl with isoprene when being polyreaction, the polymkeric substance that obtains is a styrene-isoprene block copolymer, and hydrogenation reaction the results are shown in Table 1.
Embodiment 25
Repeat embodiment 1, just hydrogenator is made up of a bubble tower and two filler bubble towers.First and second reactor is with dress Φ 200 * 10 stainless steel structured packings in embodiment 1, the second reactor, and the 3rd reactor inside diameter is 205mm, tower height 6m, the Stainless Steel Helices of interior dress Φ 10 * 10.The first reactor outlet degree of hydrogenation is that 96.9%, the second reactor outlet degree of hydrogenation is that 98.7%, the three reactor outlet degree of hydrogenation is 99.5%.
Comparative Examples
Repeat embodiment 1, just hydrogenation process is an intermittent process, and reactor used only is first reactor.The polymers soln that contains hydrogenation catalyst is introduced into first reactor before logical hydrogen, polymers soln is heated to 55 ℃, and to the logical hydrogen of system, hydrogen pressure is 4.0MPa then, and hydrogen flowing quantity is 400NM
3/ h does not stop circulation, and temperature of reaction was elevated to about 85 ℃ by 55 ℃ in about 10 minutes, returned to 55 ℃ then gradually, and reacting 1 hour its degree of hydrogenation of sampling analysis is 92.7%, and reacting 2 hours degrees of hydrogenation is 96.5%, and reacting 3 hours degrees of hydrogenation is 97.1%.
Table 1. different condition is to the influence of hydrogenation reaction
| Embodiment | Polymers soln flow (L/h) | Hydrogenation of polymer degree (%) | |
| First reactor outlet | Second reactor outlet | ||
| 1 | 50 | 96.9 | 98.6 |
| 2 | 25 | 98.3 | 99.3 |
| 3 | 35 | 98.0 | 99.0 |
| 4 | 40 | 97.4 | 98.8 |
| 5 | 75 | 95.3 | 98.6 |
| 6 | 100 | 94.5 | 98.2 |
| 7 | 50 | 96.8 | 98.5 |
| 8 | 50 | 96.6 | 98.4 |
| 9 | 50 | 96.7 | 98.4 |
| 10 | 50 | 97.0 | 98.7 |
| 11 | 50 | 97.0 | 98.7 |
| 12 | 50 | 96.9 | 98.6 |
| 13 | 50 | 96.9 | 98.2 |
| 14 | 50 | 96.7 | 98.4 |
| 15 | 50 | 96.5 | 98.5 |
| 16 | 50 | 96.0 | 98.2 |
| 17 | 50 | 96.7 | 98.4 |
| 18 | 50 | 96.7 | 98.5 |
| 19 | 50 | 96.8 | 98.5 |
| 20 | 50 | 96.2 | 98.2 |
| 21 | 50 | 96.5 | 98.6 |
| 22 | 50 | 96.3 | 98.3 |
| 23 | 50 | 96.5 | 98.6 |
| 24 | 50 | 96.1 | 98.0 |
The degree of hydrogenation result is the degree of hydrogenation of diolefine section in the polymkeric substance, surveys the degree of unsaturation (being iodine number) of hydrogenation front and back in the polymkeric substance by iodimetry,iodometry and determines.The benzene ring hydrogenation degree is all less than 2%, by nmr for the determination.As follows.
By above result as can be seen, reaction process can steadily be controlled when adopting successive reaction, especially the temperature in the reaction process can be easy to steadily be controlled, hydrogenation reaction efficient height, the degree of hydrogenation of product can stably reach requirement, and along with the prolongation of reaction time, the hydrogenation of polymer degree further improves; And the employing batch technology, reaction process especially temperature of reaction is difficult to steadily be controlled, and the finished product degree of hydrogenation is lower, and the rhythmic reaction process consumes energy greatly, operates and control all more complicated simultaneously, and labour intensity is also big.
Therefore, in tandem reaction sequence, adopt combined reactor of the present invention can improve hydrogenation reaction efficient greatly, help improving the finished product degree of hydrogenation.The present invention adopts nickel to be in addition and luxuriant titanium hydrogenation catalyst all can be to the effective hydrogenation of various polymkeric substance.
Claims (21)
1. method of hydrotreating, wherein in the presence of hydrogenation catalyst, use hydrogenator to containing the polymers soln continuous hydrogenation of unsaturated link(age), wherein said hydrogenator is the combination of two or more bubbling reactors, first bubbling reactor wherein is set makes its Flow of Goods and Materials state near complete mixing flow, and be provided with second and later bubbling reactor make its Flow of Goods and Materials state near plug flow, wherein the hydrogen apparent velocity is 0.01-0.3m/s in first bubbling reactor, the flow state of polymers soln near complete mixing flow and second and later bubbling reactor in make the flow state of polymers soln near plug flow by reducing the hydrogen apparent velocity to the 0.001-0.06m/s and the filler of in reactor, packing into.
2. the method for claim 1, the wherein said concentration that contains the polymers soln of unsaturated link(age) is 5-30wt%, this moment, the solvent of polymers soln was an inert hydrocarbon solvent, be selected from alkane, naphthenic hydrocarbon and aromatic hydrocarbons and the described polymkeric substance that contains unsaturated link(age) is the multipolymer of conjugated diene homopolymers or conjugated diolefine and vinyl-arene.
3. the method for claim 2, the wherein said concentration that contains the polymers soln of unsaturated link(age) is 8-20wt%.
4. claim 2 or 3 method, wherein said conjugated diene homopolymers is that the multipolymer of polyhutadiene or polyisoprene and described conjugated diolefine and vinyl-arene is the 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.
5. each method of claim 1-3, wherein hydrogenation catalyst and polymers soln mix the back or pass in and out each bubbling reactor respectively separately in a continuous manner in hydrogenation process, wherein polymers soln enters top overflow outflow or enters the bottom from each bubbling reactor top and flows out from each bubbling reactor bottom, enter the top with hydrogen from each bubbling reactor bottom and flow out, and in reaction system, circulate by hydrogen recycle equipment.
6. each method of claim 1-3, wherein the hydrogen apparent velocity of first bubbling reactor is 0.05-0.15m/s, second and the hydrogen apparent velocity of later bubbling reactor be 0.003-0.05m/s.
7. each method of claim 1-3, wherein the temperature in each bubbling reactor is identical or different in hydrogenation process, is respectively 30-120 ℃.
8. the method for claim 7, wherein the temperature in each bubbling reactor is identical or different in hydrogenation process, is respectively 40-70 ℃.
9. each method of claim 1-3, wherein the reaction pressure in each bubbling reactor is identical or different in hydrogenation process, is respectively 0.5-10.0MPa.
10. the method for claim 9, wherein the reaction pressure in each bubbling reactor is identical or different in hydrogenation process, is respectively 0.5-5.0MPa.
11. each method of claim 1-3, wherein said hydrogenation catalyst is the mixture of organic acid nickel and aluminum alkyls, and the mol ratio of aluminium and nickel is that the consumption of 8: 1 to 1: 1 and described hydrogenation catalyst is the 0.01-0.10gNi/100g polymkeric substance in this mixture.
12. the method for claim 11, wherein said hydrogenation catalyst are the mixture of organic acid nickel and aluminum alkyls, the mol ratio of aluminium and nickel is that the consumption of 6: 1 to 3: 1 and described hydrogenation catalyst is the 0.03-0.08gNi/100g polymkeric substance in this mixture.
13. the method for claim 11, wherein said organic acid nickel are nickel naphthenate and aluminum alkyls is triisobutyl aluminium or triethyl aluminum.
14. each method of claim 1-3, wherein said hydrogenation catalyst is a metallocene catalyst and the mixture of optional lithium alkylide, the mol ratio of lithium and titanium is that the consumption of 0: 1 to 40: 1 and described metallocene-titanium catalyst is the 0.01-0.5mmolTi/100g polymkeric substance in this mixture.
15. the method for claim 14, wherein said hydrogenation catalyst is a metallocene catalyst and the mixture of optional lithium alkylide, the mol ratio of lithium and titanium is that the consumption of 3: 1 to 20: 1 and described metallocene-titanium catalyst is the 0.05-0.3mmolTi/100g polymkeric substance in this mixture.
16. the method for claim 14, wherein said metallocene catalyst are metallocene-titanium catalyst, lithium alkylide is a n-Butyl Lithium.
17. each method of claim 1-3, wherein the aspect ratio of each bubbling reactor was respectively 30: 1 to 1: 2.
18. the method for claim 17, wherein the aspect ratio of each bubbling reactor was respectively 15: 1 to 1: 1.
19. each method of claim 1-3, wherein each bubbling reactor outside is furnished with chuck with by hot water or cooling water control temperature of reaction.
20. each method of claim 1-3, wherein the first bubbling reactor inside is empty or is furnished with spiral coil cooling tube and is furnished with water cooler on the first bubbling reactor top.
21. each method of claim 1-3, wherein second and later bubbling reactor in the filler that is equipped be in bulk or regular inert filler, its material is stainless steel, pottery or plastics.
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| CN2008100568758A CN101492513B (en) | 2008-01-25 | 2008-01-25 | Hydrogenator and polymer hydrogenation method |
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| CN105732868B (en) * | 2014-12-12 | 2018-05-11 | 中国石油化工股份有限公司 | The continuous solution polymerization method and rare-earth isoprene rubber and vulcanization rubber of rare-earth isoprene rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1184119A (en) * | 1996-12-03 | 1998-06-10 | 北京燕山石油化工公司研究院 | Preparation of polymer hydrogenating catalyst |
| CN1373008A (en) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
| CN1569789A (en) * | 2003-07-11 | 2005-01-26 | 中国石油化工股份有限公司齐鲁分公司 | Process for the preparation of 2-ethylhexanal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184119A (en) * | 1996-12-03 | 1998-06-10 | 北京燕山石油化工公司研究院 | Preparation of polymer hydrogenating catalyst |
| CN1373008A (en) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
| CN1569789A (en) * | 2003-07-11 | 2005-01-26 | 中国石油化工股份有限公司齐鲁分公司 | Process for the preparation of 2-ethylhexanal |
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