CN106749782A - Method for removing aluminum and nickel in residual catalyst after unsaturated polymer hydrogenation - Google Patents
Method for removing aluminum and nickel in residual catalyst after unsaturated polymer hydrogenation Download PDFInfo
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- CN106749782A CN106749782A CN201510818313.2A CN201510818313A CN106749782A CN 106749782 A CN106749782 A CN 106749782A CN 201510818313 A CN201510818313 A CN 201510818313A CN 106749782 A CN106749782 A CN 106749782A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910052759 nickel Inorganic materials 0.000 title abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 160
- 238000006243 chemical reaction Methods 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 150000001991 dicarboxylic acids Chemical group 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 241000040710 Chela Species 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 15
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 16
- 102000002322 Egg Proteins Human genes 0.000 description 16
- 108010000912 Egg Proteins Proteins 0.000 description 16
- 239000002738 chelating agent Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 238000001514 detection method Methods 0.000 description 16
- 235000014103 egg white Nutrition 0.000 description 16
- 210000000969 egg white Anatomy 0.000 description 16
- 239000012467 final product Substances 0.000 description 16
- 238000010998 test method Methods 0.000 description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- -1 acyl peroxide Chemical class 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003408 phase transfer catalysis Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical compound [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for removing aluminum and nickel in a residual catalyst after hydrogenation of an unsaturated polymer. The method comprises the following process steps: oxidizing the polymer solution, chelating the catalyst metal, separating liquid, and drying the precipitate. The invention solves the problem of poor metal removal effect caused by slow and incomplete oxidation when processing the glue solution of high-viscosity polymer (the viscosity is more than 600mPa & s) by adding hydrochloric acid in the oxidation stage of the polymer solution. The method is suitable for polymer solutions with various viscosities, has high oxidation speed, can obtain the target polymer solution only by standing and separating liquid in the following process, does not need centrifugal equipment, and not only saves equipment cost, but also saves time cost.
Description
Technical field
It is residual after particularly a kind of unsaturated polymer hydrogenation the present invention relates to a kind of post-processing technology of polymer
The removal methods of the al and ni in remaining catalyst.
Background technology
In polymer particularly hydrogenated polymers often contain various metal impurities, these impurity by oxidation,
The series reactions such as photochemical and metallization, can make the performance of polymer, such as colourity, stability, electrically
Energy etc. is rapid to be deteriorated, and can also interfere with the successive modified of polymer, therefore hydrogenated polymers must be built
A set of product purification method is found, metallic residue is removed.Nickel aluminum catalytic hydrogenation system due to high selectivity,
It is cheap, be widely used in the hydrogenation reaction of polymer the advantages of hydrogenation efficiency is high, for the system
The removing of middle metallic residue has had many document reports, is broadly divided into wet method and dry method.So-called wet method refers to：
The aqueous solution of certain reagent is added in hydrogenated polymers solution, makes the metal in reagent and polymer solution
Ionic reaction generates the sediment that can be dissolved in water and be insoluble in polymer solution, is then demultiplex out metal ion
Water mutually reach removing metal purpose；So-called dry method refers to：One kind is added toward hydrogenated polymers solution not
Certain reagent containing or containing only a small amount of water, this reagent can react with the metal ion in polymer solution gives birth to
Into a kind of sediment insoluble in polymer solution, then by separation means the precipitation containing metallic residue
Thing is separated.
United States Patent (USP) US3780138 discloses the metallic residue in citric acid method removing hydrogenated polymers solution,
It is specific as follows：First with oxidant such as oxygen, hydrogen peroxide, acyl peroxide etc. to hydrogenated polymers solution
Pre-processed, low-valent metal is oxidized to high-valency metal；Again with the aqueous citric acid solution containing lower alcohol with
Above-mentioned glue is fully contacted, and the high-valency metal in polymer solution is dissolved in aqueous citric acid solution；Then from
The organic phase containing polymer and the citric acid solution water phase containing dissolving metal are isolated in the solution of standing,
So as to realize the removing of metallic residue, Ni removal efficiencies are 98%.The shortcoming of the above method is easily to produce breast
Change liquid, be separated and be deteriorated, so as to influence the removing of metallic residue.
The characteristics of United States Patent (USP) US4992529 discloses a kind of mixed acid process, this method is by unitary
Metal reaction in carboxylic acid and organic phase, generates the carboxylate insoluble in organic phase, the carboxylate and mixed acid
In inorganic acid reaction, the inorganic salts that are soluble in the aqueous phase of generation, carboxylic acid is reduced in coming back to organic phase, then
Carboxylate, so circulation, until the metal in polymer solution are generated with the metal reaction in polymer solution
It is completely transferred in water phase, so as to realize the removing of metallic residue.Herein, carboxylic acid serves as phase transfer catalysis (PTC)
Agent is acted on.The method thinking is relatively new, but removal effect is unsatisfactory, further needs exist for substantial amounts of water.
United States Patent (USP) US4396761 uses the Alpha-hydroxy sulfonic acid aqueous solution and polymer solution of 0.1%-10%
In metal reaction into the sulfonate being soluble in the aqueous phase, the removing of metallic residue is then realized by being separated.This
The characteristics of method of kind is that the Alpha-hydroxy sulfonic acid for remaining in a polymer solution can be by heating or vacuum skill
Art is removed.
Compared with above-mentioned wet method, dry method is not due to using or only with a small amount of water without the biochemistry of waste water
Process problem, thus it is more advantageous.For example with adsorbents such as activated carbon, diatomite or atlapulgites
Absorption method.United States Patent (USP) US5089541 is using a kind of brown coal base active carbon through pickling, consumption
The 0.2%-10% of glue.Detailed process is as follows：The nitrogen 1 that oxygen content is 3% is passed through at 60-90 DEG C small
When, a certain amount of activated carbon is subsequently adding, stir 2-3 days, sedimentation overnight, as a result tenor reaches and wants
Ask.The shortcoming of this method is the long sedimentation time, is had much room for improvement.United States Patent (USP) US5104972 uses diatom
Used as adsorbent, consumption is the 0.7-10% of glue to soil, and adsorbent hydroxyl aluminum is 30 minutes, it is sufficient to from glue
Ni to desired level is removed in liquid.Japanese Kuraray companies (JP 2002-317008) are using activity
Carclazyte is removed to metal ion in hydrogenation diene polymer, and its consumption is 1-500 times of metal quality,
Stirring 30 minutes, transparent glue is obtained through settling filtration under diminished pressure.Although the above method is simple and easy to do,
When Polymer Solution Viscosity is larger, effect becomes very poor, and operation also becomes to be difficult to carry out, especially
The polymer solution filter operation larger to viscosity.
Another dry method is inorganic salts method.In European patent EP 372213, using water-soluble silicate,
The aqueous solution of borate or carbonate, can load on porous carrier inorganic salts, or adopt if desired
With ethoxylated fatty acid ester as dispersant, preferable metal removal effect is can reach.
Many patent reports another dry method, i.e. dicarboxylic acids method.The step of this method, is as follows：First to
A certain amount of oxidant is added in glue, metal is oxidized to high-valence state, be subsequently added dicarboxylic acids and metal
Ionic reaction generation precipitation, metallic residue is removed finally by centrifugation.One of this method it is crucial because
Element is the suitable dicarboxylic acids of selection, and selectable dicarboxylic acids has a many kinds, such as malonic acid, succinic acid,
Fumaric acid, maleic acid, 2,3 dihydroxybutanedioic acid, adipic acid, azelaic acid, decanedioic acid and neighbour
Phthalic acid etc..Another key factor of this method is solubility problem of the dicarboxylic acids in glue, selection
Suitable solubilizer is the emphasis of research and development all the time.United States Patent (USP) US4595749 uses lower aliphatic alcohols such as first
Alcohol, ethanol and isopropanol are dissolved in water as solubilizer, the characteristics of this kind of alcohol, and it is clear to be separated, but by
Very big difficulty is caused in recovery of the lower alcohol to polymer solvent, while the sedimentation time is also long, therefore not
Industrialized.United States Patent (USP) US5073621 discloses another solubilizer, water.This method is first by binary
Then carboxylic acid is then added in glue in water, so can preferably remove the metal in glue,
But this method is easy to cause glue to emulsify, it is unfavorable for the reaction of dicarboxylic acids and metal ion, influences metal
Removal efficiency, technique is difficult to control to.Chinese patent CN1067898 discloses residual after a kind of hydrogenation of polymer
The removal methods of remaining metallic catalyst, dioxygen is added in hydrogenated butadiene-styrene random copolymerization composition glue liquid
Water, as precipitating reagent, decanedioic acid is dissolved in the diethylene glycol monobutyl ether aqueous solution and is made as oxidant, decanedioic acid
Into decanedioic acid solution, the removal effect of metal in glue is substantially increased, particularly when glue viscosity exists
During 50-600mPas, remain to preferably remove metallic residue.The defect of the method is：It is high glutinous in treatment
During degree polymer glue (viscosity is more than 600mPas), it is very slow that oxidation is carried out, and not exclusively,
Cause metal removal poor effect.
The content of the invention
It is an object of the invention to provide the al and ni in a kind of unsaturated polymer catalyst residure after hydrogenation treatment
Removal methods, the method is to metal removal effect in various viscosity polymer especially high viscosity polymer
Significantly, easy to operate, low cost, industrial prospect is wide.
Above-mentioned purpose of the invention is achieved in that the aluminium in unsaturated polymer catalyst residure after hydrogenation treatment
With the removal methods of nickel, comprise the following steps that：
The oxidation of S1, polymer solution：Polymer solution is aoxidized using hydrogen peroxide and hydrochloric acid, dioxygen
The addition of water is 1-20 times of the amount of the material of metal in polymer solution, and the addition of hydrochloric acid is polymerization
0.1-5.0 times of the amount of the material of thing GOLD FROM PLATING SOLUTION category, oxidizing reaction temperature is 30-100 DEG C, oxidation reaction
Time is 30-240 minutes；
The chelating of S2, catalyst metals：It is the chelating liquid of 0.2-5% to prepare mass concentration, the chelating liquid
Solute is dicarboxylic acids, and solvent is the diethylene glycol monobutyl ether aqueous solution, and the mass concentration of the solvent is
35-85%, chelating liquid is added in the polymer solution after step S1 is aoxidized and is reacted, chelating liquid
Addition is 1-5 times of the amount of the material of metal in polymer solution, chelatropic reaction temperature in terms of dicarboxylic acids
It is 30-100 DEG C to spend, and the chelatropic reaction time is 30-180 minutes；
S3, point liquid and precipitation drying：Polymer solution after S2 is chelated is transferred to separatory funnel, quiet
Put 60 minutes, solution is divided into three layers, divide and go lower two layers, upper solution is to be stripped of catalyst metals
Solution；Then by upper solution according to volume ratio 1:1 is injected into absolute ethyl alcohol, and flocculation sediment goes out polymer
Afterwards, precipitation is inserted in 50 DEG C of vacuum drying chambers and is dried to constant weight, obtain final polymer.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step
In rapid S1, the oxidizing reaction temperature is preferably 50-70 DEG C, and the oxidation time is preferably 60-120
Minute.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step
In rapid S2, the dicarboxylic acids is preferably decanedioic acid or adipic acid.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step
In rapid S2, the mass concentration of the diethylene glycol monobutyl ether aqueous solution is preferably 50-70%.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step
In rapid S2, the addition of the chelating liquid is preferably metal in polymer solution in terms of dicarboxylic acids
1.5-2.5 times.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, step
In rapid S2, the chelatropic reaction temperature is preferably 50-70 DEG C, and the chelatropic reaction time is preferably 60-120
Minute.
The removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment of the present invention, its
In, the unsaturated polymer be preferably the homopolymers of conjugated diene, the copolymer of conjugated diene or
The copolymer of conjugated diene and styrene.
Beneficial effects of the present invention are：Hydrochloric acid is added by the oxidation stage in polymer solution so that each
Plant the fast simultaneous oxidation of oxidation rate of polymer glue of viscosity completely, metal removal effect is good, solves
Prior art when high viscosity polymer (viscosity is more than 600mPas) glue is processed, due to oxidation
It is slow and incomplete, the problem of metal removal effect difference.This method is applied to the polymer of various viscositys
Solution, oxidation rate is fast, and later during need to only carry out standing point liquid and can obtain target polymerization
Thing solution, without centrifugation apparatus, has not only saved equipment cost, and saved time cost.
Specific embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to these embodiments.
First, the formula of chelating liquid is as shown in table 1：
Table 1. chelates the formula of liquid
2nd, tenor is tested using ICP in polymer solution, and method standard is GB/T
17476-1998。
Embodiment 1
Take the polymer after hydrogenation (being isoprene/butadiene-styrene block copolymer before hydrogenation) solution
100g is placed in and is equipped with the 500mL there-necked flasks of condenser pipe, and detection Polymer Solution Viscosity is 450
MPas, Ni content are 329ppm, and Al content is 456ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 0.67mL of aqueous solution 2.3mL, 37% concentration, 120 are reacted under 65 DEG C of temperature conditionss
Minute.
Then to 91.0g chelating agent P3 are added in reaction bulb, reacted 120 minutes under 65 DEG C of temperature conditionss.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 2
Take the polymer after hydrogenation (being star isoprene/butadiene-styrene block copolymer before hydrogenation)
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 1030 to solution about 100g
MPas, Ni content are 346ppm, and Al content is 567ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 1.33mL of aqueous solution 5.5mL, 37% concentration, reacts 240 minutes at 30 DEG C.
Then to 272.0g chelating agents P1 is added in reaction bulb, reacted 180 minutes at 30 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 3
(being polyisoprene before hydrogenation) the solution about 100g of the polymer after hydrogenation is taken in outfit condenser pipe
In 500mL there-necked flasks, detection Polymer Solution Viscosity is 50mPas, and Ni contents are 352ppm,
Al content is 621ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2Aqueous solution 1.48mL, 37%
The hydrochloric acid 0.03mL of concentration, reacts 100 minutes at 70 DEG C.
Then to 59.0g chelating agents P6 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 4
Polymer (hydrogenation before for butadiene-isoprene copolymer) the solution about 100g after hydrogenation is taken in matching somebody with somebody
In the 500mL there-necked flasks of standby condenser pipe, detection Polymer Solution Viscosity is 860mPas, Ni contents
It is 587ppm, Al content is 891ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2The aqueous solution
The hydrochloric acid 0.21mL of 0.44mL, 37% concentration, reacts 30 minutes at 100 DEG C.
Then to 174.0g chelating agents P2 is added in reaction bulb, reacted 30 minutes at 100 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 5
The polymer after hydrogenation (being butadienestyrene copolymer before hydrogenation) solution about 100g is taken in outfit
In the 500mL there-necked flasks of condenser pipe, detection Polymer Solution Viscosity is 340mPas, and Ni contents are
470ppm, Al content is 837ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2The aqueous solution
The hydrochloric acid 0.38mL of 0.8mL, 37% concentration, reacts 180 minutes at 50 DEG C.
Then to 79.0g chelating agents P4 is added in reaction bulb, reacted 150 minutes at 50 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 6
Take the polymer after hydrogenation (being star isoprene styrene di-block copolymer before hydrogenation) solution
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 550 to about 100g
MPas, Ni content are 350ppm, and Al content is 840ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 0.73mL of aqueous solution 5.67mL, 37% concentration, reacts 120 minutes at 60 DEG C.
Then to 150.0g chelating agents P5 is added in reaction bulb, reacted 120 minutes at 60 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 7
Take the polymer after hydrogenation (being isoprene-butadiene/styrene di-block copolymer before hydrogenation) molten
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 580 to liquid about 100g
MPas, Ni content are 410ppm, and Al content is 945ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 1.24mL of aqueous solution 4.29mL, 37% concentration, reacts 80 minutes at 80 DEG C.
Then to 170.0g chelating agents P8 is added in reaction bulb, reacted 80 minutes at 80 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 8
(being star polybutadiene before hydrogenation) the solution about 100g of the polymer after hydrogenation is taken in outfit condenser pipe
500mL there-necked flasks in, detection Polymer Solution Viscosity be 640mPas, Ni contents be 358ppm,
Al content is 923ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2Aqueous solution 4.11mL, 37%
The hydrochloric acid 1.60mL of concentration, reacts 60 minutes at 90 DEG C.
Then to 163.0g chelating agents P8 is added in reaction bulb, reacted 60 minutes at 90 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 9
The polymer after hydrogenation (being star polyisoprene before hydrogenation) solution about 100g is taken to be condensed in outfit
In the 500mL there-necked flasks of pipe, detection Polymer Solution Viscosity is 680mPas, and Ni contents are
423ppm, Al content is 910ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2The aqueous solution
The hydrochloric acid 0.2mL of 2.1mL, 37% concentration, reacts 100 minutes at 70 DEG C.
Then to 83.0g chelating agents P9 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 10
Take the polymer after hydrogenation (being isoprene/butadiene-styrene di-block copolymer before hydrogenation) molten
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 420 to liquid about 100g
MPas, Ni content are 323ppm, and Al content is 743ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 0.98mL of aqueous solution 3.37mL, 37% concentration, reacts 100 minutes at 70 DEG C.
Then to 67.0g chelating agents P9 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 11
Take the polymer after hydrogenation (being star isoprene/butadiene-styrene di-block copolymer before hydrogenation)
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 880 to solution about 100g
MPas, Ni content are 335ppm, and Al content is 691ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 0.93mL of aqueous solution 3.83mL, 37% concentration, reacts 120 minutes at 65 DEG C.
Then to 126.0g chelating agents P2 is added in reaction bulb, reacted 120 minutes at 65 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.The removal effect of catalyst is shown in Table 2.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 12
Solution is about to take the polymer after hydrogenation (being butadiene-isoprene styrene random copolymer before hydrogenation)
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 210mPas to 100g,
Ni contents are 352ppm, and Al content is 640ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2
The hydrochloric acid 0.88mL of aqueous solution 2.43mL, 37% concentration, reacts 120 minutes at 65 DEG C.
Then to 48.0g chelating agents P11 is added in reaction bulb, reacted 120 minutes at 65 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.The removal effect of catalyst is shown in Table 2.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 13
Polymer (hydrogenation before for butadiene-isoprene copolymer) the solution about 100g after hydrogenation is taken in matching somebody with somebody
In the 500mL there-necked flasks of standby condenser pipe, detection Polymer Solution Viscosity is 320mPas, Ni contents
It is 411ppm, Al content is 651ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2The aqueous solution
The hydrochloric acid 0.92mL of 3.18mL, 37% concentration, reacts 120 minutes at 65 DEG C.
Then to 126.0g chelating agents P3 is added in reaction bulb, reacted 120 minutes at 65 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 14
Take the polymer after hydrogenation (being star butadiene/isoprene-styrene block copolymer before hydrogenation)
In the 500mL there-necked flasks of condenser pipe are equipped with, detection Polymer Solution Viscosity is 830 to solution about 100g
MPas, Ni content are 235ppm, and Al content is 410ppm.It is dense to sequentially adding 30% in reaction bulb
The H of degree2O2The hydrochloric acid 0.57mL of aqueous solution 1.96mL, 37% concentration, reacts 100 minutes at 70 DEG C.
Then to 388.0g chelating agents P7 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 15
Take polymer (hydrogenation before for butadiene styrene random copolymer) the solution about 100g after hydrogenation in
It is equipped with the 500mL there-necked flasks of condenser pipe, detection Polymer Solution Viscosity is 550mPas, Ni contains
It is 470ppm to measure, and Al content is 866ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2It is water-soluble
The hydrochloric acid 1.2mL of liquid 4.1mL, 37% concentration, reacts 100 minutes at 70 DEG C.
Then to 82.0g chelating agents P4 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Solution is transferred in separatory funnel after reacting after terminating, 60 minutes are stood under normal temperature, solution is divided into three
Layer, upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is that light green is transparent molten
Liquid.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
Embodiment 16
The polymer after hydrogenation (being star polyisoprene before hydrogenation) solution about 100g is taken to be condensed in outfit
In the 500mL there-necked flasks of pipe, detection Polymer Solution Viscosity is 540mPas, and Ni contents are
452ppm, Al content is 953ppm.To the H that 30% concentration is sequentially added in reaction bulb2O2The aqueous solution
The hydrochloric acid 1.27mL of 4.39mL, 37% concentration, reacts 100 minutes at 70 DEG C.
Then to 87.0g chelating agents P10 is added in reaction bulb, reacted 120 minutes at 70 DEG C.
Be transferred to solution in separatory funnel after terminating by reaction, and 60 minutes are stood under normal temperature, and solution is divided into three layers,
Upper strata is egg white shape opaque liquid, and middle level is semi-transparent clear solution, and lower floor is light green clear solution.
Take upper solution by volume 1:1 is injected into absolute ethyl alcohol, and the polymer for that flocculates is transferred to 50 DEG C very
Dried to constant weight in empty drying box, obtain final product product.
Using ICP method of testings, polymer and Removal of catalyst metal to non-Removal of catalyst metal it is poly-
Compound detected, show that comparing result is shown in Table 2.
The catalyst metals removal effect of table 2
From Table 2, it can be seen that viscosity scope from the polymer glue of 50-1030mPas by this hair
The content of al and ni is very low in polymer after bright method treatment, and total content is not higher than 15ppm,
It is satisfied with products application requirement.In addition, the present invention can make treatment by adjusting the concentration of dicarboxylic acids
Glue viscosity scope is expanded to 1000mPas, considerably increases the applicability of the method.
The present invention adds hydrochloric acid by the oxidation stage in polymer solution so that the polymerization of various viscositys
Completely, metal removal effect is good for the fast simultaneous oxidation of oxidation rate of composition glue liquid, solves high glutinous in treatment
During degree polymer (viscosity is more than 600mPas) glue, because oxidation is slow and incomplete, metal
The problem of removal effect difference.
This method is applied to the polymer solution of various viscositys, and oxidation rate is fast, and in mistake below
Need to only carry out standing in journey dividing liquid to can obtain subject polymer solution, without centrifugation apparatus, not only save
About equipment cost, and saved time cost.Method of the present invention process stabilizing, it is simple and easy to do,
Industrial prospect is wide.
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention
Shape, but these corresponding changes and deformation should all belong to protection scope of the present invention.
Claims (7)
1. removal methods of the al and ni in unsaturated polymer catalyst residure after hydrogenation treatment, it is characterised in that
Comprise the following steps that：
The oxidation of S1, polymer solution：Polymer solution is aoxidized using hydrogen peroxide and hydrochloric acid, dioxygen
The addition of water is 1-20 times of the amount of the material of metal in polymer solution, and the addition of hydrochloric acid is polymerization
0.1-5.0 times of the amount of the material of thing GOLD FROM PLATING SOLUTION category, oxidizing reaction temperature is 30-100 DEG C, oxidation reaction
Time is 30-240 minutes；
The chelating of S2, catalyst metals：It is the chelating liquid of 0.2-5% to prepare mass concentration, the chelating liquid
Solute is dicarboxylic acids, and solvent is the diethylene glycol monobutyl ether aqueous solution, and the mass concentration of the solvent is
35-85%, chelating liquid is added in the polymer solution after step S1 is aoxidized and is reacted, chelating liquid
Addition is 1-5 times of the amount of the material of metal in polymer solution, chelatropic reaction temperature in terms of dicarboxylic acids
It is 30-100 DEG C to spend, and the chelatropic reaction time is 30-180 minutes；
S3, point liquid and precipitation drying：Polymer solution after S2 is chelated is transferred to separatory funnel, quiet
Put 60 minutes, solution is divided into three layers, divide and go lower two layers, upper solution is to be stripped of catalyst metals
Solution；Then by upper solution according to volume ratio 1:1 is injected into absolute ethyl alcohol, and flocculation sediment goes out polymer
Afterwards, precipitation is inserted in 50 DEG C of vacuum drying chambers and is dried to constant weight, obtain final polymer.
2. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that in step S1, the oxidizing reaction temperature is 50-70 DEG C, the oxygen
Change the reaction time for 60-120 minutes.
3. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that in step S2, the dicarboxylic acids is decanedioic acid or adipic acid.
4. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that in step S2, the mass concentration of the diethylene glycol monobutyl ether aqueous solution
It is 50-70%.
5. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that in step S2, the addition of the chelating liquid is poly- in terms of dicarboxylic acids
1.5-2.5 times of metal in polymer solution.
6. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that in step S2, the chelatropic reaction temperature is 50-70 DEG C, the chela
The reaction time is closed for 60-120 minutes.
7. al and ni in unsaturated polymer catalyst residure after hydrogenation treatment according to claim 1
Removal methods, it is characterised in that the unsaturated polymer is homopolymers, the conjugated diene of conjugated diene
The copolymer or conjugated diene of hydrocarbon and the copolymer of styrene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734828A (en) * | 2018-12-25 | 2019-05-10 | 山东玉皇化工有限公司 | A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst |
| CN111533831A (en) * | 2020-06-01 | 2020-08-14 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal after hydrogenation of unsaturated polymer |
| CN111607023A (en) * | 2020-06-05 | 2020-09-01 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal catalyst in hydrogenated polymer |
| CN114534694A (en) * | 2022-03-07 | 2022-05-27 | 万华化学集团股份有限公司 | Hydroxyquinoline filler and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | Method for removing residual metal catalyst after polymer hydrogenation |
| CN1640894A (en) * | 2004-01-08 | 2005-07-20 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method for separating residual catalyst of unsaturated polymer after hydrogenation |
-
2015
- 2015-11-23 CN CN201510818313.2A patent/CN106749782B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067898A (en) * | 1992-07-08 | 1993-01-13 | 北京燕山石油化工公司研究院 | Method for removing residual metal catalyst after polymer hydrogenation |
| CN1640894A (en) * | 2004-01-08 | 2005-07-20 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method for separating residual catalyst of unsaturated polymer after hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| 李传清等: "苯乙烯-共轭二烯共聚物镍系加氢催化剂脱除研究进展", 《化工新型材料》 * |
| 贺小进等: "苯乙烯-丁二烯-苯乙烯嵌段共聚物中加氢催化剂脱除研究", 《弹性体》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734828A (en) * | 2018-12-25 | 2019-05-10 | 山东玉皇化工有限公司 | A method of removing unsaturated polymer residure after hydrogenation treatment metallic catalyst |
| CN111533831A (en) * | 2020-06-01 | 2020-08-14 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal after hydrogenation of unsaturated polymer |
| CN111607023A (en) * | 2020-06-05 | 2020-09-01 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal catalyst in hydrogenated polymer |
| CN111607023B (en) * | 2020-06-05 | 2022-11-04 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal catalyst in hydrogenated polymer |
| CN114534694A (en) * | 2022-03-07 | 2022-05-27 | 万华化学集团股份有限公司 | Hydroxyquinoline filler and preparation method and application thereof |
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