CN103157446B - Adsorbent for separating palladium from alkali metals and alkaline-earth metals and its preparation method and use - Google Patents
Adsorbent for separating palladium from alkali metals and alkaline-earth metals and its preparation method and use Download PDFInfo
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- CN103157446B CN103157446B CN201310076313.0A CN201310076313A CN103157446B CN 103157446 B CN103157446 B CN 103157446B CN 201310076313 A CN201310076313 A CN 201310076313A CN 103157446 B CN103157446 B CN 103157446B
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- adsorbent
- palladium
- alkali
- alkaline earth
- methyl
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 68
- 239000003463 adsorbent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 title abstract 3
- 150000001340 alkali metals Chemical class 0.000 title abstract 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 title abstract 3
- 150000001342 alkaline earth metals Chemical class 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000005011 phenolic resin Substances 0.000 claims abstract description 19
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims description 21
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 19
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229920001688 coating polymer Polymers 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 150000003983 crown ethers Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 3
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- -1 phthalic acid ester Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorbent for separating palladium from alkali metals and alkaline-earth metals. 4-[3-(3-benzo-15-crown-5)methyl-4-hydroxy-phenyl]methylethyl-phenolic resin is supported by carriers to form the adsorbent. The 4-[3-(3-benzo-15-crown-5)methyl-4-hydroxy-phenyl]methylethyl-phenolic resin has a structural general formula (I), wherein in the structural general formula (I), n is an integer of 7-15. The carriers are porous silica gel or large-hole SiO2 coated by a polymer. The invention also discloses a preparation method and a use of the adsorbent for separating palladium from alkali metals and alkaline-earth metals. The preparation method has simple processes. The adsorbent obtained by the preparation method has good selectivity in palladium separation. The palladium separation process adopting the adsorbent is simple. The adsorbent has high separation efficiency and can be industrially produced easily.
Description
Technical field
The present invention relates to the separation technology field of element palladium, be specifically related to a kind of from alkali and alkaline earth metal ions the adsorbent and its preparation method and application of separating element palladium.
Background technology
Element palladium is argenteous transition metal, and quality is softer, has good ductility and plasticity, energy forging, calendering and wire drawing.
The chemical property torpescence of element palladium, all stable in air and wet environment under normal temperature, be heated to 800 DEG C, palladium surface forms palladium monoxide film.The erosion of element palladium energy hydrofluoric acid resistant, phosphoric acid, perchloric acid, hydrochloric acid and sulfuric acid vapor, but be soluble in chloroazotic acid and the hot concentrated sulfuric acid and red fuming nitric acid (RFNA), the NaOH of melting, sodium carbonate, sodium peroxide all have corrosiveness to element palladium.
Reguline metal palladium can absorb a large amount of hydrogen, under normal temperature, 1 volume palladium sponge can absorb 900 volume hydrogen, 1 volume colloid palladium can absorb 1200 volume hydrogen, and be heated to after 40～50 DEG C, the hydrogen of absorption is that major part is disengaged, and is widely used as gas reaction, particularly hydrogenation or dehydrogenation, also can make resistive conductor, clock and watch alloy etc.
Granted publication number be CN100497676C disclosure of the invention a kind of method of SPE extraction and separate palladium, extract and separate palladium for the concentration of precious metal thing obtaining from platinum group metal concentrate or secondary resource.Adopt a kind of bonding the polymer microsphere polymer of palladium extractant be fixing phase, make mobile phase with the hydrochloric acid solution containing high and low metal, realizing palladium separates with metallic elements such as platinum, rhodium, iridium and copper base metal, iron, nickel, zinc, and make leacheate with watery hydrochloric acid, with a kind of can be eluent with the reagent solution of palladium complexing, and solid-phase extraction column can be regenerated with dilute hydrochloric acid solution.
Patent publication No. be CN102586607A disclosure of the invention a kind of method of extracting platinum, rhodium, palladium from inefficacy platinum alloy net, utilize the mixed solution of hydrochloric acid and nitric acid to dissolve, remove nitro, turn sodium type, suction filtration, obtain platinum rhodium palladium complex solution, adopt chloride precipitation method Separation of Platinum, use natrium nitrosum complexing seperation palladium, rhodium, with six nitroso rhodium acid ammonium method purification rhodiums, with the sub-palladium method of dichloro two amminos purification palladium, through adding hydrazine hydrate reduction to obtain spongy platinum, palladium sponge and rhodium powder, through vacuum drying, roasting, again purify, obtain noble metal platinum rhodium palladium.
Element palladium is the indispensable critical materials of high-tech area and auto manufacturing such as space flight, aviation, navigation, weapons and nuclear energy; Palladium bichloride can be for electroplating; Palladium bichloride and relevant chloride thereof are that circulation refining utilizes thermal decomposition method to manufacture the raw material of pure palladium sponge; Palladium monoxide (PdO) and palladium dydroxide [Pd (OH)
2] can do the source of palladium catalyst.
Because element palladium is in the extensive use of every field, need to provide effective method that element palladium and other element are carried out to separating-purifying, simultaneously, in order to extract element palladium from contain the trade waste of element palladium, carry out the recycling of element palladium, also needing to provide simple method to carry out the separation of element palladium.
The high activity liquid waste (HLLW) that spentnuclear fuel post processing produces, a kind of peracidity, high radioactivity and highly toxic mixed solution, in the separation process of heating element Cs and heating element Sr, gained alkali and alkaline earth metal ions solution generally may contain NaNO
3, KNO
3, RbNO
3, CsNO
3, Sr (NO
3)
2, Ba (NO
3)
2and a certain amount of palladium, in prior art, also do not have a kind of effective method the palladium in this solution effectively can be separated.
Summary of the invention
The invention provides a kind of adsorbent and application thereof of separating element palladium from alkali and alkaline earth metal ions, the preparation method of adsorbent is simple, selectively good when the adsorbent separating element palladium that obtains, simple to operate when using adsorbent separating element palladium, separative efficiency is high, is easy to suitability for industrialized production.
A kind of from alkali and alkaline earth metal ions the adsorbent of separating element palladium, by 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin loads on carrier and makes, described 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin has general structure (I)
N is 7～15 integer.
As preferably, described carrier is the macro-pore SiO of Bio-sil or coating polymer
2.
Described Bio-sil can adopt commercially available prod, for example, can be the Bio-sil that is applied to the various models of packed column, the not strict restriction such as its aperture.The macro-pore SiO of described coating polymer
2be SiO
2-styrene-divinylbenzene polymer (SiO
2-P), be a class novel inorganic/organic carrier, in US Patent No. 6843921, SiO is disclosed
2-styrene-divinylbenzene polymer, SiO
2-P is a kind of organic high polymer complex carrier containing porous silica carrier granular, and its preparation method is:
(1) by the SiO of macropore
2be washed till neutrality by red fuming nitric acid (RFNA) washing, suction filtration, deionized water, repeat more than 10 times, dry.
(2) vacuum having under argon shield condition, with 1,2,3-trichloropropane and m-dimethylbenzene for solvent, to macro-pore SiO
2in add the m/p-formyl styrene of 48.7g, the m/p-divinylbenzene of 8.9g, 72.2g dioctyl faces phthalic acid ester, 54.0g benzoin methyl acid sodium, 0.56g α, α-even bis-isobutyronitrile and 0.57g1,1 '-even dicyclohexyl amine-1-nitrile, is progressively heated to 90 ° of C by room temperature, and keeps 13 hours, afterwards, be progressively cooled to room temperature.
(3) use respectively acetone and methanol wash, the above-mentioned product of suction filtration, repeat more than 10 times, dry.
As preferably, the quality of described carrier is 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] 0.5～40 times of the quality of Methylethyl-phenolic resin.Further preferably, the quality of described carrier is 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] 1～20 times of the quality of Methylethyl-phenolic resin.
As preferably, the integer that in general structure (I), n is 8～12.
The value of n will affect 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] number of crown ether in Methylethyl-phenolic resin, utilize adsorbent of the present invention from alkali and alkaline earth metal ions when separating element palladium, utilize the specific adsorption of crown ether and element palladium to carry out, if the quantity of crown ether is very few, the efficiency of separating element palladium will reduce greatly, if the quantity of crown ether is too much, the corresponding shielding action occurring between crown ether, separative efficiency also can reduce.
The present invention also provides the preparation method of described adsorbent, comprise: in trichloroacetic acid, add 2,2-bis-(4-hydroxyphenyl)propanes and phendioxin 5-hat 5, stirring and dissolving wiring solution-forming, then paraformaldehyde is added and in this solution, react and generate sediment, isolate this sediment, dissolve in after drying in carrene, add again carrier, after stirring, be dried and obtain described adsorbent.
Trichloroacetic acid and 2,2-, bis-(4-hydroxyphenyl)propanes, the mass ratio of phendioxin 5-hat 5 and paraformaldehyde is: 100:7～15:7～15:3～8.
Dried sediment dissolves in after carrene, initial stage carrene content is more, the load of vavuum pump when alleviating later stage vacuum drying, can first about 45 DEG C stirrings under normal pressure, make carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The method of the adsorbent separating element palladium from alkali and alkaline earth metal ions described in the present invention also provides, comprise the steps: the aqueous solution that contains alkali nitrates, alkaline earth nitrate and palladium nitrate to contact with described adsorbent, make element palladium be adsorbed agent absorption and separate.
Described alkali nitrates comprises NaNO
3, KNO
3, RbNO
3, CsNO
3, described alkaline earth nitrate comprises Sr (NO
3)
2, Ba (NO
3)
2, in the aqueous solution, alkali nitrates, alkaline earth nitrate and palladium nitrate can ionize, and therefore, in esse in the aqueous solution is alkali metal ion, alkaline-earth metal ions, palladium ion and nitrate ion.
In the aqueous solution contacting with adsorbent, can have trace impurity, not affect the separating effect of element palladium, the solute in the aqueous solution can only be made up of alkali metal ion, alkaline-earth metal ions, palladium ion and nitrate ion.
Na in the aqueous solution
+, K
+, Rb
+, Cs
+, Sr
+, Ba
2+and Pb
2+concentration range be 1 × 10
-3～5.0 × 10
-3mol/L.
Can, by adding nitric acid, regulate the concentration of nitric acid in the aqueous solution, reach the optimum efficiency of adsorbent adsorbing separation element palladium, preferably, in the described aqueous solution, concentration of nitric acid is 0.4～6mol/L.
Also will affect the separating effect of element palladium the time of contact of adsorbent and the aqueous solution, time of contact is too short, element palladium is not yet adsorbed agent and adsorbs completely, time of contact is long, reduce separative efficiency, preferably, be 100～1000min the time of contact of the aqueous solution and described adsorbent, further preferably, be 350～750min the time of contact of the aqueous solution and described adsorbent.
The inventive method at room temperature operates.
Adsorbent of the present invention does not need to use the diluent with property to dilute or dissolve in adsorption process, do not need to add other organic compounds yet, the complexity of minishing method, be easy in industrial popularization, and environmentally friendly, utilize adsorbent selectively good when separating element palladium from alkali and alkaline earth metal ions, separating rate is fast.
Brief description of the drawings
Fig. 1 is the graph of a relation that utilizes the distribution coefficient of adsorbent separating element palladium from alkali and alkaline earth metal ions prepared by the present invention to change with concentration of nitric acid;
Fig. 2 is the graph of a relation that utilizes the distribution coefficient of adsorbent separating element palladium from alkali and alkaline earth metal ions prepared by the present invention to change with time of contact.
Detailed description of the invention
Embodiment 1
4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] preparation of Methylethyl-phenolic resin
In 30g trichloroacetic acid, add 3.42g(15mmol) 2, 2-bis-(4-hydroxyphenyl)propanes and 3.49g(13mmol) phendioxin 5-hat 5, stirring and dissolving at 90 DEG C, wiring solution-forming, then in 4.5 hours, 1.79g paraformaldehyde (containing 60mmol formaldehyde) is added in this solution, after having added, reaction temperature is risen to 140 DEG C, react after 4 hours and in reaction system, start to occur precipitating, quality to be precipitated no longer increases, reaction system is cooled to room temperature, in the reactant liquor of gained, add 150mL methyl alcohol, make to precipitate atomization, through crushing, filtration obtains solid state powder, continue with this solid state powder of 50mL methanol wash, repeated washing several times to cleaning fluid (being methyl alcohol) without change color, finally obtain brown powder, be 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (being called for short: poly-two 15 hat 5 resins), it is 70% that drying under reduced pressure obtains 4.88g(yield).
N in the present embodiment is 8, can, as required by changing the ratio of each raw material, regulate the value of n.
The 4-[3-that uses in following examples (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin all prepared by the method.
The preparation of embodiment 2 adsorbents
By 100 grams of 4-[3-with structural formula (I) (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (n is 7) is dissolved in 1000mL carrene, mixes; Add 150 grams of Bio-sils, stir and make carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The preparation of embodiment 3 adsorbents
By 100 grams of 4-[3-with structural formula (I) (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (n is 9) is dissolved in 1000mL carrene, mixes; Add 200 grams of Bio-sils, stir and make carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The preparation of embodiment 4 adsorbents
By 100 grams of 4-[3-with structural formula (I) (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (n is 11) is dissolved in 1000mL carrene, mixes; Add 250 grams of Bio-sils, stir and make carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The preparation of embodiment 5 adsorbents
By 100 grams of 4-[3-with structural formula (I) (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (n is 13) is dissolved in 1000mL carrene, mixes; Add the macro-pore SiO of 300 grams of coating polymer
2(SiO
2-P) stirring makes carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The preparation of embodiment 6 adsorbents
By 100 grams of 4-[3-with structural formula (I) (3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin (n is 15) is dissolved in 1000mL carrene, mixes; Add the macro-pore SiO of 350 grams of coating polymer
2(SiO
2-P) stirring makes carrene volatilization most of to material to nearly dry state, and then material vacuum drying 24h at 45 DEG C of dry state nearly.
The separation of element palladium in embodiment 7 alkali and alkaline earth metal ions
By NaNO
3, KNO
3, RbNO
3, CsNO
3, Sr (NO
3)
2, Ba (NO
3)
2and Pd (NO
3)
2the water-soluble aqueous solution that is mixed with, NaNO in this aqueous solution
3, KNO
3, RbNO
3, CsNO
3, Sr (NO
3)
2, Ba (NO
3)
2and Pd (NO
3)
2concentration be respectively 5.0 × 10
-3mol/L.
Add nitric acid to regulate HNO in the aqueous solution
3concentration is 5.0mol/L, and the adsorbent of then aqueous solution obtaining being prepared with embodiment 3 mixing that contacts in container can be aided with concussion for improving adsorption effect, and element palladium is adsorbed on adsorbent.
Adsorption separation process is that solid-liquid separates, and is set up and states solution in 100mL conical flask, and the adsorbent of simultaneously being prepared by the present invention adds in 100mL conical flask, on TAITEC MM-10 type concussion instrument, adsorbs concussion, and concussion speed is 120rpm, ambient operation.Because adsorbent has good selectively to Pd, so can and separate with other metallic elements Pd absorption, there is good separating effect.
Adsorbent of the present invention has good selective to element palladium, can and separate with other metallic elements the absorption of element palladium, has good separating effect.Separating effect spectrogram is shown in Fig. 2, and while being 750min, can realize the separation completely of element palladium time of contact.
Embodiment 8～14
Utilize the method for embodiment 7, only change the concentration of nitric acid in the aqueous solution, when the concentration of nitric acid is respectively 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, gained separating resulting as shown in Figure 1, in the time that concentration of nitric acid is 5mol/L, the effect of separating element palladium is best.
Claims (8)
1. the adsorbent of a separating element palladium from alkali and alkaline earth metal ions, it is characterized in that, by 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin loads on carrier and makes, described 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] Methylethyl-phenolic resin has general structure (I)
N is 7～15 integer.
As claimed in claim 1 from alkali and alkaline earth metal ions the adsorbent of separating element palladium, it is characterized in that, described carrier is the macro-pore SiO of Bio-sil or coating polymer
2.
As claimed in claim 2 from alkali and alkaline earth metal ions the adsorbent of separating element palladium, it is characterized in that, the quality of described carrier is 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] 0.5～40 times of the quality of Methylethyl-phenolic resin.
As claimed in claim 3 from alkali and alkaline earth metal ions the adsorbent of separating element palladium, it is characterized in that, the quality of described carrier is 4-[3-(3-phendioxin 5-hat-5) methyl-4-hydroxyl-phenyl] 1～20 times of the quality of Methylethyl-phenolic resin.
5. the adsorbent of separating element palladium from alkali and alkaline earth metal ions as described in as arbitrary in claim 1～4, is characterized in that the integer that in general structure (I), n is 8～12.
6. the method for adsorbent from the alkali and alkaline earth metal ions separating element palladium of a utilization as described in as arbitrary in claim 1～5, it is characterized in that, comprise the steps: the aqueous solution that contains alkali nitrates, alkaline earth nitrate and palladium nitrate to contact with described adsorbent, make element palladium be adsorbed agent absorption and separate.
7. method as claimed in claim 6, is characterized in that, in the described aqueous solution, concentration of nitric acid is 0.4～6mol/L.
8. method as claimed in claim 6, is characterized in that, be 100～1000min the time of contact of the described aqueous solution and described adsorbent.
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| CN104805286B (en) * | 2015-04-22 | 2016-11-30 | 浙江大学 | A kind of polymer-based supermolecule adsorbent and its preparation method and application |
| CN106179273A (en) * | 2016-08-10 | 2016-12-07 | 清华大学 | A kind of adsorbent for lithium isotope separation and its preparation method and application |
| CN108531732B (en) * | 2018-01-31 | 2019-05-17 | 福州大学 | A kind of activated carbon supported ruthenium catalyst gives up the recovery method of ruthenium in agent |
| CN108998672B (en) * | 2018-08-02 | 2019-09-20 | 浙江大学 | A kind of method of separate palladium |
| CN109179550B (en) * | 2018-08-02 | 2019-10-29 | 浙江大学 | A method of using adsorbent from acidic aqueous solution separate palladium |
| CN109182776B (en) * | 2018-08-02 | 2019-10-25 | 浙江大学 | A method of the separate palladium from acidic aqueous solution |
| CN113481379B (en) * | 2021-06-18 | 2022-08-12 | 金川集团股份有限公司 | Method for removing impurities by using palladium extracting agent |
| CN115178300B (en) * | 2022-07-13 | 2024-04-16 | 安徽东至广信农化有限公司 | Hydrogenation catalyst regeneration wastewater treatment method |
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