CN1226313C - Method for removing residue catalyst after polymer hydrogenation using electrostatic separation technology - Google Patents
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- CN1226313C CN1226313C CN 02156704 CN02156704A CN1226313C CN 1226313 C CN1226313 C CN 1226313C CN 02156704 CN02156704 CN 02156704 CN 02156704 A CN02156704 A CN 02156704A CN 1226313 C CN1226313 C CN 1226313C
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Abstract
The present invention relates to a method for removing a residue catalyst generated after polymer hydrogenation by electrostatic separation technology. The method of the present invention comprises the steps that an oxidizing agent and a complexing agent are added into a hydrogenated polymer glue solution; the complexing agent and a metallic catalyst form a compound granule with polarity; then, the polymer containing the polarity granule removes the residue catalyst by electrostatic separation through an electrostatic field. The method of the present invention is characterized in that the residue catalyst in the polymer glue solution is separated in a polarity granule mode by the electrostatic separation technology, and the hydrogenation catalyst is effectively separated.
Description
Technical field
The present invention relates to a kind of method that removes the unsaturated polymer catalyst residure after hydrogenation treatment, more particularly, relate to a kind of novel method of using electrostatic separation technique from the unsaturated polymer glue, to remove catalyst residure after hydrogenation treatment.
Background technology
The heat of unsaturated polymer, oxidative stability and ageing resistance are relatively poor, and the method for therefore normal employing hydrogenation makes the unsaturated link(age) of polymkeric substance saturated, thereby increases its environmental stability greatly, and makes it have good thermostability.Hydrogenation of polymer carries out in the presence of heavy metal catalyst usually, catalyst system therefor is Fe, Co, Ni organometallic compound, therefore organoaluminum or organolithium compound must remove wherein remaining little amount of catalyst behind hydrogenation of polymer, make the anti-marquis of polymkeric substance, heat-resisting oxidation, ageing-resistant.
As United States Patent (USP) 3,780,138 disclose a kind of method that removes the residual metal catalyzer in the prior art, use oxygenant and rare aqueous citric acid solution and the metal ion in the lower aliphatic alcohols extraction polymkeric substance, this method needs a large amount of extraction agents, and the extraction time is long, and difficulty is separated.The treatment process complexity, long flow path easily causes environmental pollution, and has lower aliphatic alcohols in the recovered solvent, and the latter will become the stopping of chain agent in polyreaction, unfavorable to polyreaction.
United States Patent (USP) 4,595,749 disclose another kind of method of removing the residual metal catalyzer from the unsaturated polymer glue, adopt oxygenant and dicarboxylic acid.Lower aliphatic alcohols (carbonatoms is less than 4) or toluene are as the solvent of dicarboxylic acid.When this method adopts lower aliphatic alcohols to make the dicarboxylic acid solvent, because it is approaching with the polymer solvent boiling point, make difficult solvent recovery, when making the dicarboxylic acid solvent with toluene, because dicarboxylic acid solvability in toluene is very poor, the toluene aequum is bigger, and the recovery energy consumption is higher.
Chinese patent CN1027172C discloses the method that removes remainder catalyst from the glue behind the unsaturated polymer hydrogenation, adopts oxygenant and diprotic acid acting in conjunction to remove hydrogenation catalyst, and the precipitation agent solvent for use is the mixture of many alkyl diols ether and/or water.Though adopt this method to remainder catalyst decreasing ratio height in the polymkeric substance, and can the diprotic acid solvent can be separated with polymer solvent by distillation.To use centrifugal or filtration and separation techniques when adopting this method to separate hydrogenation catalyst in addition, centrifugal separation will be used the very high whizzer of separation factor, power consumption is higher and inputs fixed capital are bigger like this, and filtration method complicated operation, separation efficiency are low, filter cloth stops up easily, so operating process all has certain limitation.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the field that removes of unsaturated polymer glue catalyst residure after hydrogenation treatment, found that by on the basis of Chinese patent CN1027172C, using electrostatic separation technique to replace centrifugal or filtration and separation techniques, can simply, effectively separate remainder catalyst and separating energy consumption is low.The present invention just is being based on this discovery and is being accomplished.
Therefore, the purpose of this invention is to provide a kind of method that removes the remainder catalyst behind the unsaturated polymer glue hydrogenation, this method has been used electrostatic separation technique, it is simple that thereby the separation that makes remainder catalyst becomes, the separation efficiency height, even the polymer latex fluid viscosity also can effectively separate when big, and energy consumption is low during solid-liquid separation.
Therefore the present invention provides a kind of method of using electrostatic separation technique to separate catalyst residure after hydrogenation treatment from the unsaturated polymer glue, comprise and add oxygenant and complexing agent in the polymkeric substance glue behind hydrogenation, form a kind of band polar compound particle with the hydrogenation catalyst in the polymkeric substance glue, to contain polarity particulate polymkeric substance glue then by an electrostatic field, remove remainder catalyst by electrostatic separation.
Of the present invention this will become more cheer and bright with other purposes, feature and advantage after reading whole specification sheets in conjunction with the accompanying drawings.
The accompanying drawing summary
Fig. 1 is the synoptic diagram of used electrostatic separating device in the inventive method.
Detailed Description Of The Invention
Can be the random or block copolymer of homopolymers, conjugated diene and the vinyl aromatic compounds of conjugated diene by the unsaturated polymer of hydrogenation in the inventive method. Preparing the used polymerization of these polymer can be referring to United States Patent (USP) 3,792, and 005 and 3,431,323, the whole disclosure of these two is hereby incorporated by reference. Preferred unsaturated polymer is styrene butadiene random copolymer, the homopolymers of conjugated diene such as butadiene, isoprene etc., styrene-butadiene block copolymer, styrene-isoprene block copolymer etc.
Described unsaturated polymer can partial hydrogenation, select hydrogenation or whole hydrogenation, and concrete hydrogenation technique is referring to corresponding United States Patent (USP) 3,595,942 and 3,973,759, and the whole disclosure of these two is hereby incorporated by reference. The example of hydrogenation catalyst has the organo-metallic compound of Fe, Co, Ni etc. and organo-aluminum compound organo-lithium compound etc.
Behind the hydrogenation of polymer, the metallic catalyst that remains in the polymer glue be separated. In the methods of the invention, can at first in the polymer glue, add oxidant, after its abundant oxidation, add again complexing agent and form a polar compound, then be removed by electrostatic separation technique. Certainly, also oxidant can be added with complexing agent in the inventive method.
About the oxidant that uses in the inventive method and the details of complexing agent, can be with reference to Chinese patent CN1027172C, its whole disclosure is hereby incorporated by reference.
The specific examples of oxygenant can be oxygen, air, hydrogen peroxide or alkyl peroxide, as ethyl hydroperoxide, normal-butyl hydrogen peroxide, tertbutyl peroxide, hyperis, and preferred hydrogen peroxide or tertbutyl peroxide.It is 0.1～100 that the consumption of oxygenant should make the mol ratio of the metal ion in itself and the polymkeric substance glue, preferred 1～20.
The example of complexing agent can be that carbonatoms is 2～15 di-carboxylic acid or phosphoric acid salt, is specially hexanodioic acid, nonane diacid, sebacic acid, ammonium phosphate, sodium phosphate etc.It is 0.1～50 that the consumption of complexing agent should make the mol ratio of metal ion in itself and the polymkeric substance glue, preferred 1～20, more preferably 1～10.
In the methods of the invention, complexing agent is made into the solution form use in solvent usually.Can use all used in prior art solvents, for example water, ethanol, many alkyl diols ether, hexane, hexanaphthene etc. and composition thereof.Many alkyl diols ether that can be used for the inventive method can be by general formula R
1-O-[-R
2-O-]
n-R
3Expression, wherein n is 1,2,3 or 4, R
1For H or have the alkyl of 1-8 carbon atom, R
2For having the alkylidene group of 2-5 carbon atom, R
3For having the alkyl of 1-8 carbon atom.
The principle of electrostatic separation is exactly to make in electric field uniformly and has the motion in a certain direction under the effect of electric field outside of polar particle, thereby reaches the purpose of separating polar particle.The slurry oil static separator is developed, designed and made to electrostatic separation technique by United States Gulf science and technology company the earliest, in order to improve the quality of cracking clarification slurry oil.The rich lattice refinery of U.S. Philips Petroleum Co. adopts electrostatic separating device to handle the slurry oil of gas oil and heavy oil catalytically cracking equipment subsequently, can improve cracking yield.
Static separator is made of some static posts in parallel, and glass pellet is housed in the post.When the oil plant that contains solid catalyst particle entered the static post, granules of catalyst was polarized and inhaled between glass pellet, thereby reached the purpose that purifies slurry oil.
The used electrostatic separating device of the present invention has as shown in Figure 1 design (but be not limited to this, for example can increase the number of static post as required and can regulate each parameter according to pending amount).Each reference number implication is as follows in the accompanying drawing:
1-polymkeric substance glue
The 2-granulated glass sphere
The 3-high voltage electrode
4-communicating pipe
The 5-back up pad
Polymkeric substance glue after the 6-electrostatic separation
The 7-high-voltage power supply
In the methods of the invention, by high-voltage power supply high voltage electrode is applied voltage, output voltage can be regulated between 0.5～50KV continuously, and concrete voltage value can be determined according to handling required electrostatic field intensity.Filler is ganoid globular glass pearl in the static post.
The electrostatic separation process comprises these two steps of regeneration of electrostatic adhesion and granulated glass sphere.
1, electrostatic adhesion
(1),, connects high-voltage power supply with a certain amount of granulated glass sphere static post of packing into according to operational requirement.
(2) charge into the static post with polymer solvent (as hexanaphthene, hexane etc.), fully soak into granulated glass sphere, making alive also guarantees that the installation of static post is good.
(3) with the solvent emptying in the static post, add a certain amount of polymkeric substance glue, connect power supply and make it to reach operating voltage.
(4) the static column bottom valve of outwarding winding is regulated flow, makes the polymkeric substance glue flow through the static post.
2, the regeneration of granulated glass sphere
Granulated glass sphere as filled media can be reused.Static post through electrostatic adhesion is crossed has adsorbed a large amount of solid particulates between its filled media granulated glass sphere, and when this particle reached a certain amount of, the static post had promptly lost adsorptive power, thereby granulated glass sphere need be regenerated., granulated glass sphere is taken out from the static post, the polymer solvent thorough washing with clean just obtains the regenerated granulated glass sphere for this reason, with this granulated glass sphere static post of packing into, can carry out the electrostatic adhesion of next cycle.
The factor that influences the electrostatic separation effect comprises: the polymer latex fluid viscosity, with complexing agent kind, separation temperature, granulated glass sphere diameter, glue flow and the electrostatic field intensity etc. of metal catalyst reaction.Usually, the polymer latex fluid viscosity is more little, and the electrostatic separation effect is good more, and general polymerization composition glue liquid viscosity is 1～10, and 000cps is preferred 30～1,000cps.As previously mentioned, be used for forming polarity particulate complexing agent and comprise di-carboxylic acid (as hexanodioic acid, nonane diacid, sebacic acid etc.) and phosphoric acid salt (as ammonium phosphate, sodium phosphate etc.) etc. with metal catalyst.The electrostatic separation temperature is generally 25 ℃～100 ℃, and preferred 50～80 ℃, pressure condition is generally 0.1-5kg/cm
2, preferred 0.5-3kg/cm
2The diameter of granulated glass sphere is 0.1～40mm in the static post, preferred 0.5～10mm.Theoretically, the more little separating effect of granulated glass sphere diameter is good more, but because the granulated glass sphere diameter hour, be not easy the fluidisation backwash after it has adsorbed microparticle, and the granulated glass sphere bed pressure drop is bigger, better when being generally 1～5mm.The electrostatic field intensity of this electrostatic equipment is 100～50000v/cm, and electrostatic field intensity is big more generally speaking, and separating effect is good more, but power consumption is high, investment is big, so electrostatic field intensity is preferably 1000～20000v/cm.
Embodiment
Below by the present invention being carried out more detailed narration by embodiment.But these embodiment must not think limitation of the scope of the invention.
Basic glue is butadiene-styrene block copolymer (number-average molecular weight is 60,000) before the hydrogenation, and gelatin concentration is 10wt%, get glue 1000ml behind the hydrogenation, contain Ni 700ppm in this polymkeric substance glue, contain Al 1500ppm, glue temperature is 70 ℃, gelatin viscosity 50.0cps.Use H
2O
2As oxygenant, sebacic acid is a complexing agent, and use ethanol wherein as shown in table 1, many alkyl diols ether and/or hexanaphthene, many alkyl diols ether and water are as the diprotic acid solvent, and making concentration is the sebacic acid solution of 0.2M or 0.1M.At 70 ℃ of temperature and 1kg/cm
2Under the pressure, in the polymkeric substance glue, add 5.0ml30%H
2O
2The aqueous solution reaches the sebacic acid solution of the amount of Table 1 down, when deposit seeds occurring in the polymkeric substance glue, remove deposit seeds under the following conditions: high voltage electrode diameter phi=6mm with the electrostatic separation method, static post internal diameter of outer cover φ=25mm, static column length L=570mm, granulated glass sphere bed height H=550mm in the post, the electrostatic separation power is 100W, and output voltage is regulated between 0.5～50kV continuously.The gained result and the result of centrifugation under similarity condition compare, and the results are shown in Table 1.
The comparison of table 1. electrostatic separation and centrifugal separating effect
| The complexing agent solvent | Ethanol * | Diethylene glycol monobutyl ether * | Diethylene glycol monobutyl ether/water (50/50) ** | Diethylene glycol monobutyl ether/hexanaphthene (50/50) ** | |
| The electrostatic separation effect | Remaining Ni (ppm) | 1.8 | 1.5 | 2.0 | 1.6 |
| Decreasing ratio (%) | 99.7 | 99.8 | 99.7 | 99.8 | |
| Remaining Al (ppm) | 10.0 | 8.0 | 10.5 | 9.0 | |
| Decreasing ratio (%) | 99.3 | 99.5 | 99.3 | 99.4 | |
| Centrifugal separating effect | Remaining Ni (ppm) | 2.8 | 2.0 | 1.5 | 2.6 |
| Decreasing ratio (%) | 99.6 | 99.7 | 99.8 | 99.6 | |
| Remaining Al (ppm) | 15.0 | 12.0 | 11.5 | 13.5 | |
| Decreasing ratio (%) | 99.0 | 99.2 | 99.2 | 99.1 | |
Annotate:
*Expression sebacic acid concentration is 0.2M;
*Expression sebacic acid concentration is 0.1M;
The mol ratio of sebacic acid and metal ion is 2.5;
Strength of electric field is 10000v/cm in the electrostatic separation field;
The diameter of granulated glass sphere is 2mm;
The treatment capacity of glue is 20ml/min in electrostatic field;
Centrifugation was carried out under the rotating speed of 4500rpm 15 minutes.
As can be seen from Table 1: effectively separate with catalyzer after centrifugal separation all can make hydrogenation of polymer with the electrostatic separation method.
Basic glue is butadiene-styrene random copolymers (number-average molecular weight is about 55,000) before the hydrogenation, and gelatin concentration is 10wt%, diethylene glycol monobutyl ether is used as the sebacic acid solvent, glue temperature and separation temperature are 60 ℃, and gelatin viscosity is 70cps, and pressure is 2kg/cm
2, treatment capacity is 25ml/min, and other condition adopts the electrostatic separation method to separate when deposit seeds occurring in the polymkeric substance glue with embodiment 1, and residual Ni content is 2.5ppm in the polymkeric substance that obtains, decreasing ratio 99.6%, Al content 13ppm, decreasing ratio 99.1%.
Basic glue is butadiene-styrene block copolymer (with embodiment 1) before the hydrogenation, and gelatin concentration is 10wt%, gets glue 1000ml behind the hydrogenation, contains Ni 700ppm in the polymkeric substance, contains Al 1500ppm, 70 ℃ of glue temperatures, and separation temperature is 55 ℃, pressure 1kg/cm
2, treatment capacity is 10ml/min, gelatin viscosity 75.0cps.Use H
2O
2Make oxygenant, use ammonium phosphate solution to be complexing agent, at 70 ℃ of temperature and 1kg/cm
2Under the pressure, in the polymkeric substance glue, add 5.0ml30%H
2O
2The aqueous solution and 47.8ml0.2M ammonium phosphate solution are handled with electrostatic separation method and centrifugal separation when deposit seeds occurring in the polymkeric substance glue, the results are shown in Table 2.
Electrostatic separation method and centrifugal separation result were relatively when table 2. ammonium phosphate was made complexing agent
| Separation method | Remaining Ni (ppm) | Ni decreasing ratio (%) | Remaining Al (ppm) | Al decreasing ratio (%) |
| The electrostatic separation method | 25.0 | 96.4 | 55.0 | 96.3 |
| Centrifugal separation | 35.0 | 95.0 | 68.0 | 95.5 |
Electrostatic separation is identical with centrifugation condition and table 1.
From the result of table 2 as can be seen: the catalyzer behind the hydrogenation of polymer is effectively separated with the electrostatic separation method.
Basic glue is butadiene-styrene block copolymer (with embodiment 1) before the hydrogenation, and diethylene glycol monobutyl ether is as the sebacic acid solvent, and other condition is investigated the influence of different glue treatment capacities to the electrostatic separation effect with embodiment 1, the results are shown in Table 3.
The different glue treatment capacities of table 3. are to the influence of electrostatic separation effect
| Glue treatment capacity (ml/min) | 10 | 20 | 30 | 40 | 100 | ||
| Remaining Ni (ppm) | 1.4 | 1.0 * | 1.5 | 5.0 ** | 4.0 | 8.2 | 100.5 |
| Ni decreasing ratio (%) | 99.8 | 99.9 * | 99.8 | 99.3 ** | 99.4 | 98.8 | 85.6 |
| Remaining Al (ppm) | 7.0 | 5.0 * | 8.0 | 25.0 ** | 20.0 | 31.5 | 260.5 |
| Al decreasing ratio (%) | 99.5 | 99.7 * | 99.5 | 98.3 ** | 98.7 | 97.9 | 82.6 |
*: separation temperature is 80 ℃
*: separation temperature is 50 ℃
When glue treatment capacity during, all can make residual metal catalyzer effective elimination as can be seen from Table 3, can find out simultaneously when separation temperature under 50～80 ℃, all can make the remainder catalyst effective elimination less than 40ml/min.
Basic glue is butadiene-styrene block copolymer (with embodiment 1) before the hydrogenation, and gelatin concentration is 10wt%, and diethylene glycol monobutyl ether is as the sebacic acid solvent, and other condition is investigated the influence of different electrostatic field intensities to separating effect with embodiment 1, the results are shown in Table 4.
Table 4. electrostatic field intensity is to the influence of separating effect
| Electrostatic field intensity (v/cm) | 1000 | 5000 | 10000 | 13000 | 20000 |
| Remaining Ni (ppm) | 80.0 | 10.0 | 1.5 | 1.4 | 1.4 |
| Ni decreasing ratio (%) | 88.6 | 98.6 | 99.8 | 99.8 | 99.8 |
| Remaining Al (ppm) | 150.5 | 22.6 | 8.0 | 7.0 | 6.5 |
| Al decreasing ratio (%) | 90.0 | 98.5 | 99.5 | 99.5 | 99.6 |
By table 4 result as can be known: along with the increase of electrostatic field intensity, separating effect is become better and better, electrostatic field intensity greater than 5000v/cm after, hydrogenation catalyst is effectively separated.
Basic glue is butadiene-styrene block copolymer (with embodiment 1) before the hydrogenation, gelatin concentration is 10wt%, and diethylene glycol monobutyl ether is as the sebacic acid solvent, and other condition is with embodiment 1, investigated that different glass pearl diameter the results are shown in Table 5 to the influence of separating effect in the electrostatic field.
Table 5. granulated glass sphere diameter is to the influence of separating effect
| Granulated glass sphere diameter (mm) | 1.0 | 2.0 | 5.0 | 7.0 | 10.0 |
| Remaining Ni (ppm) | 1.4 | 1.5 | 8.0 | 15.0 | 55.0 |
| Ni decreasing ratio (%) | 99.8 | 99.8 | 98.8 | 97.8 | 92.1 |
| Remaining Al (ppm) | 7.5 | 8.0 | 31.5 | 40.4 | 102.5 |
| Al decreasing ratio (%) | 99.5 | 99.5 | 97.9 | 97.3 | 93.2 |
As can be seen from Table 5: at the granulated glass sphere diameter range that is adopted, can be to the hydrogenation catalyst effective elimination, diameter effect in 1.0～5.0mm scope is better.
Basic glue is that (number-average molecular weight is 55 to isoprene-styrene block copolymer before the hydrogenation, 000), gelatin concentration is 8.0wt%, 10.0wt%, 15.0wt%, 20.0wt%, diethylene glycol monobutyl ether is as the sebacic acid solvent, other condition is with embodiment 1, investigated the influence of different polymer concentrations (or viscosity), the results are shown in Table 6 separating effect.
Table 6. polymer concentration (or viscosity) is to the influence of separating effect
| Polymkeric substance glue concentration (%) | 8.0 | 10.0 | 15.0 | 20.0 |
| Polymer latex fluid viscosity (cps) | 30.0 | 50.0 | 550.0 | 1350.0 |
| Remaining Ni (ppm) | 1.0 | 1.5 | 16.0 | 50.0 |
| Ni decreasing ratio (%) | 99.8 | 99.8 | 97.7 | 92.8 |
| Remaining Al (ppm) | 5.0 | 8.0 | 35.0 | 110.0 |
| Al decreasing ratio (%) | 99.7 | 99.5 | 97.7 | 92.0 |
By table 6 result as can be seen: the inventive method is suitable for the polymkeric substance glue of different viscosity, viscosity during less than 550.0cp effect better.
Claims (22)
1. one kind by using electrostatic separation to remove the method for unsaturated polymer catalyst residure after hydrogenation treatment, comprise and add oxygenant and complexing agent in the polymkeric substance glue behind hydrogenation, form a kind of compound particle with the hydrogenation catalyst in the polymkeric substance glue with polarity charge, to contain polarity particulate polymkeric substance glue then by an electrostatic field, remove remainder catalyst by electrostatic separation, to be the homopolymer of conjugated diene or conjugated diene with vinyl aromatic compounds random become segmented copolymer to wherein said unsaturated polymer.
2. according to the process of claim 1 wherein that described oxygenant is hydrogen peroxide or alkyl peroxide.
3. according to the method for claim 2, wherein said oxygenant is a hydrogen peroxide.
4. according to the method for claim 2, wherein said oxygenant is ethyl hydroperoxide, normal-butyl hydrogen peroxide, tertbutyl peroxide or hyperis.
5. according to the method for claim 4, wherein said oxygenant is a tertbutyl peroxide.
6. according to the process of claim 1 wherein that described unsaturated polymer is a kind of in homopolymer, styrene-butadiene block copolymer and the styrene-isoprene block copolymer of the random copolymers that is selected from styrene butadiene, conjugated diolefine.
7. according to the process of claim 1 wherein that described complexing agent is a di-carboxylic acid.
8. according to the method for claim 7, wherein said complexing agent is hexanodioic acid, nonane diacid or sebacic acid.
9. according to the process of claim 1 wherein that described complexing agent is a phosphoric acid salt.
10. according to the method for claim 9, wherein said complexing agent is ammonium phosphate or sodium phosphate.
11. according to the process of claim 1 wherein that the mol ratio of metal ion is 0.1～100 in described oxygenant and the polymkeric substance glue.
12. according to the method for claim 11, the mol ratio of metal ion is 1～20 in wherein said oxygenant and the polymkeric substance glue.
13. according to the process of claim 1 wherein that the mol ratio of metal ion is 0.1～50 in described complexing agent and the polymkeric substance glue.
14. according to the method for claim 13, the mol ratio of metal ion is 1～10 in wherein said complexing agent and the polymkeric substance glue.
15. according to the process of claim 1 wherein that described oxygenant added before adding described complexing agent.
16. according to the process of claim 1 wherein that described oxygenant and described complexing agent add simultaneously.
17. according to the process of claim 1 wherein that the intensity of described electrostatic field is 100～50000v/cm.
18. according to the method for claim 17, the intensity of wherein said electrostatic field is 1000～20000v/cm.
19. according to the process of claim 1 wherein that using diameter in described electrostatic field is the granulated glass sphere of 0.1～40mm.
20. according to the method for claim 19, wherein using diameter in described electrostatic field is the granulated glass sphere of 0.5～10mm.
21. according to the process of claim 1 wherein that the electrostatic separation temperature is 25 ℃～100 ℃.
22. according to the method for claim 21, wherein the electrostatic separation temperature is 50～80 ℃.
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|---|---|---|---|
| CN 02156704 CN1226313C (en) | 2002-12-17 | 2002-12-17 | Method for removing residue catalyst after polymer hydrogenation using electrostatic separation technology |
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|---|---|---|---|
| CN 02156704 CN1226313C (en) | 2002-12-17 | 2002-12-17 | Method for removing residue catalyst after polymer hydrogenation using electrostatic separation technology |
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| CN108341898B (en) * | 2017-01-24 | 2020-09-15 | 中国石油化工股份有限公司 | Method for removing residual hydrogenation catalyst after unsaturated polymer hydrogenation |
| CN110358576B (en) * | 2019-07-04 | 2021-03-26 | 中国石油大学(华东) | Catalytic cracking slurry oil purification system and purification method thereof |
| CN113912796B (en) * | 2020-07-08 | 2023-08-29 | 沈阳化工研究院有限公司 | Method for removing residual catalyst in unsaturated polymer hydrogenation reaction |
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