CN87103759A - Synthesis and application of cross-linked 2-ethylpyridyl polystyrene resin - Google Patents
Synthesis and application of cross-linked 2-ethylpyridyl polystyrene resin Download PDFInfo
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- CN87103759A CN87103759A CN87103759.9A CN87103759A CN87103759A CN 87103759 A CN87103759 A CN 87103759A CN 87103759 A CN87103759 A CN 87103759A CN 87103759 A CN87103759 A CN 87103759A
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- resin
- bpr
- gold
- hydrochloric acid
- precious metal
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- 229920005990 polystyrene resin Polymers 0.000 title claims description 14
- -1 2-ethylpyridyl Chemical group 0.000 title claims description 4
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 86
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000010970 precious metal Substances 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- 239000000047 product Substances 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 206010042674 Swelling Diseases 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 67
- 229910052737 gold Inorganic materials 0.000 abstract description 64
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 60
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052802 copper Inorganic materials 0.000 abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052763 palladium Inorganic materials 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to synthesis of resin with special performance and application thereof in separating and enriching precious metals mainly comprising gold. The BPR resin has the following structure:
the method for separating and enriching the noble metal mainly comprising gold by using the BPR resin comprises the following steps: dissolving gold-containing material with aqua regia, passing through exchange column filled with BPR resin to adsorb noble metal mainly containing gold on the resin, and eluting with mixed solution of hydrochloric acid and thiourea. The adsorption amount of BPR resin to gold was 520mg/g (dry resin). Meanwhile, the adsorbent has certain adsorption capacity on palladium and platinum. Au can be quantitatively separated from an acid solution containing a large amount of metal ions such as copper, iron, cobalt, nickel, zinc and the like. The method is suitable for separating and enriching gold and noble metals in gold-containing samples of gold concentrates, electrolytic copper factories and electronic components.
Description
The invention belongs to the synthetic of a kind of resin with property and at separation and concentration with the application in the precious metal of Jin Weizhu.
For the research of the golden method of the synthetic and sorption of the resin that is exclusively used in ADSORPTION OF GOLD, many reports were arranged, for example Vernon on the document
(1) (2)Synthesized the hydroxyl oxime resin Deng the people, in order to the gold of absorption in the acidic medium, its result is because relatively poor and be not applied to the selectivity of gold.Myasoedova
(3)Once synthesized the resin ， And that contains the pyrazoles functional group and be used for SEPARATION ENRICHMENT OF GOLD WITH Deng the people, but found as lot of F e (III), Cu (II) that the suction gold amount of this resin descended significantly during with Au (III) coexistence.Above-mentioned two kinds of resins are not the desirable resins of SEPARATION ENRICHMENT OF GOLD WITH.
Purpose of the present invention, be synthetic a kind of strong to golden selectivity, adsorptive capacity big, the easy resin of wash-out.And studies with the method for its Quantitative Separation enrichment with the precious metal of Jin Weizhu.
In order to achieve the above object, we adopt organometallic compound and the effect of chloromethylated polystyrene resin, carry out carbon---the linked reaction of carbon bond, effective functional group---the ethylpyridine in effective extraction agent of gold, import on the polystyrene resin skeleton, synthesized crosslinked α---the ethyl pyridinyl polystyrene resin that gold is had special sorption property, be called for short the BPR resin, structure is:
Its synthetic route has two:
(1) by Grignard reagent synthetic (I method):
At first use chloromethyl ether under Zinc Chloride Anhydrous catalysis, chloromethyl is introduced on the polystyrene resin skeleton.In addition, with monobromethane and magnesium chips reaction, make ethylmagnesium bromide.With the α-Jia Jibiding effect, convert the α-Jia Jibiding magnesium bromide to again.With α-Jia Jibiding magnesium bromide and chloromethyl polystyrene resin reaction, just obtain the BPR resin.
(2) by organo-metallic sodium reagent synthetic (II method);
At first, obtain α-Jia Jibiding sodium with sodium Metal 99.5 and α-Jia Jibiding reaction.With the chloromethyl polystyrene resin reaction, just make the BPR resin again.
As follows with the enrichment of BPR resin isolation with the method for the precious metal of Jin Weizhu: auriferous material with aqua regia dissolution after, remove by filter undissolved residue.With the BPR resin-column of filtrate by washing with 1-2NHCl in advance.Then the precious metal with Jin Weizhu all is attracted on the resin, and base metal is not because of being flowed out resin column by resin absorption with filtrate.Use HCl and HNO then
3Mixed solution drip washing resin column, the mixed solution with hydrochloric acid and thiocarbamide elutes gold at last.
With synthetic resin of the present invention, in the various mineral acid systems and the acidity scope from weak acid to strong acid of gold, gold all there is the good adsorption effect, adsorptive capacity 520mg/g (dried resin).Simultaneously, platinum, palladium also there is certain adsorptive power.Selectivity is strong, can Quantitative Separation go out Au (III) from the acidic solution that contains metal ions such as a large amount of copper, iron, cobalt, nickel, zinc.Temperature influence is little, inhales golden efficient all more than 98% in 20 °～80 ℃.The easy wash-out of resin.It is the comparatively ideal resin that reclaims gold in gold concentrate, electrolysis copper work, military project, the civil electronic element gold contained matter sample.
Example 1 usefulness I method is synthesized the BPR resin
14.4 gram chloromethyl polystyrene resins are put into 40 milliliters of benzene, place a few hours: until pearl body swelling.
Electronic stirring, thermometer, constant pressure funnel, widely different stream prolong are installed on 500 milliliters of four-hole bottles.Connect a bubbler and a calcium chloride drying tower again successively on the prolong top.In reaction flask, add 4.6 gram magnesium chips and micro iodine earlier, add 15 milliliters of mixed solutions again, start stirring by 20.8 gram monobromethanes and 120 milliliters of n-butyl ethers.It is initial to be swift in response, keeping reactant seethes with excitement slightly, drip remaining monobromethane and n-butyl ether mixed solution, dropwised in 30 minutes, widely different stream 1 hour reacts completely magnesium chips as far as possible, be warming up to 120 °-130 ℃ then, keep this temperature, drip mixed solution, in 30 minutes, dropwise by 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers.Be cooled to 70 °-80 ℃, add use the benzene swelling in advance chloromethyl polystyrene resin, kept this thermotonus 8 hours.Be cooled to room temperature.With ammonium chloride and mixture of ice and water hydrolysis, soak a few hours with 10% hydrochloric acid soln again, take out disacidify liquid, water is given a baby a bath on the third day after its birth time again, takes out with the suction filtration rod and anhydrates, must red pearl body.This red pearl body is placed the Sha Shi extractor, use extraction using alcohol 5 hours, extremely effusive extract is till the water white transparency, obtains orange red pearl body, airing, and sieve goes to broken end, gets the dried BPR resin of 4.1 grams.
Example 2
Experimental installation and monomer consumption are same as example 1.Widely different stream was warming up to 110 °-120 ℃ after 1 hour, kept this temperature, dropping is by the mixed solution of 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers, dropwised in 30 minutes, be cooled to 60 °-70 ℃, all the other are operated with example 1.Obtain 2.6 grams and do the BPR resin.
Example 3
Experimental installation and monomer consumption are same as example 1.Widely different stream 1 hour is warming up to 130 °～140 ℃, keeps this temperature, dropping is by the mixed solution of 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers, dropwised in 30 minutes, be cooled to 80 °-90 ℃, all the other are operated with example 1.Obtain 3.7 grams and do the BPR resin.
Example 4 usefulness II methods are synthesized the BPR resin
On 10 liters four-hole bottle, electric mixer is installed, thermometer, nitrogen protection device, spherical widely different stream prolong ， And connects a bubbler and a calcium chloride drying tower successively on the prolong top.
The sodium Metal 99.5 of 3500 milliliters of α-Jia Jibidings and the new chopping of 190 grams is added in the reaction flask, feed nitrogen, start stirring, be warming up to 100 ℃, keep this temperature until the sodium Metal 99.5 complete reaction.Be cooled to 55 °～60 ℃ then, open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly.Refilled instrument, still under nitrogen protection, 45 ℃ of holding temperatures slowly stirred 8-9 hour.
With the careful hydrolysis of 1200 gram frozen water, temperature is no more than 50 ℃, takes out the mixed solution that anhydrates after separating with the suction filtration rod, washes resin with water to PH
8, with 800 milliliters of 1: 1 salt acid soak a few hours, take out disacidify liquid, wash with water to PH
4, from reaction flask, take out resin, with ethanol continuous extraction 8 hours, airing, obtain the orange red pearl body of 1438 grams.
Example 5
Experimental installation and monomer consumption are same as example 4.Feed nitrogen, start stirring and be warming up to 90 ℃, keep this temperature until the sodium Metal 99.5 complete reaction.Be cooled to 60 ℃ then.Open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly, refilled instrument, still under nitrogen protection, 50 ℃ of holding temperatures.All the other operations are same as example 4.Get 1240 gram pearl bodies.
Example 6
Experimental installation and monomer consumption are same as example 4.Feed nitrogen, start stirring and be warming up to 120 ℃.Keep this temperature, until the sodium Metal 99.5 complete reaction.Be cooled to 60 ℃ then, open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly, refilled instrument, still protect under the expansion 55 ℃ of holding temperatures at nitrogen.All the other operations are same as example 4.Get 1406 gram pearl bodies.
The recovery of example 7 α-Jia Jibidings and isopropyl ether
Liquid after the hydrolysis is partly told, told organic layer wherein again, use the solid sodium hydroxide drying,, collect 67 °-69 ℃ fraction, obtain isopropyl ether, the rate of recovery 30% with the rectifying of rice Ge Shi fractional column.Collect 126 °-131 ℃ fraction, obtain α-Jia Jibiding, the rate of recovery 53.3%.Through gas chromatographic analysis, the water content that reclaims α-Jia Jibiding is 0.697%, meets the use standard.
Example 8
Take by weighing 20 milligrams with I method synthetic BPR resin, join in the beaker that fills 10 milliliter of 1.995 mg/ml potassium chloraurate solution, stirred 2 hours, leach resin, use distilled water wash.Aqua regia dissolution is used in roasting 40 minutes in 400 ℃ muffle furnace then, 1000 times of redilution, sampling, saturated the suctions gold amount that records this resin be 495 milligrams/restrain (dried resin).
Example 9
Take by weighing 20 milligrams with II method synthetic BPR resin, repeat the experiment of example 8, recording its saturated suction gold amount is 520 milligrams/gram (dried resin),
Example 10
In 50 milliliters Erlenmeyer flask, add the gold solution of 2.1 milliliter of 6.39 mg/ml and the hydrochloric acid of 4.9 milliliter of 1 mol, after mixing, add 0.1 gram BPR resin again, vibration at room temperature, get the solution of certain volume at regular intervals, and be diluted to suitable volume, measure the gold content in the solution.The results are shown in Figure 1.(Fig. 1 resin is inhaled gold amount and time relation)
As seen from Figure 1, in the time of 60 minutes, resin is inhaled the gold amount and is reached balance.
Example 11
In 50 milliliters Erlenmeyer flask, add the chlorauric acid solution of 0.1 milliliter of 500 mcg/ml and the hydrochloric acid of 4.9 milliliters of various concentration, add 0.1 gram BPR resin again, 25 ℃ of holding temperatures were vibrated 2 hours.Content with residue gold in the atomic absorption flame sectional light absorbance technique determining solution compares with blank gold solution, the results are shown in Figure 2.(the different acid concentrations of Fig. 2 are to the influence of BPR resin absorption gold)
Use sodium cyanoaurite (NaAu (CN) instead
4) as the solution of standard gold.Sodium chloride aqueous solution with 0.01 mol is a medium in addition, adds dilute hydrochloric acid and diluted sodium hydroxide solution and regulates different PH, and it the results are shown in Figure 3.(Fig. 3 is a medium with NaCl solution, regulates different PH, resin is inhaled the influence of gold).
Find out that by Fig. 2 in hydrochloric acid system, acid concentration does not have influence to the suction gold amount of resin; In nitric acid system, acid concentration is inhaled the gold amount to resin and is not had influence when 6N is following.Find out that by Fig. 3 under alkaline condition, resin also has the good adsorption effect to gold.
Example 12
In 50 milliliters of Erlenmeyer flasks, the hydrochloric acid soln of the gold solution of 0.5 milliliter of 500 μ g/ml of adding and 4.5 milliliters 1 mol adds 0.1 gram BPR resin again, and vibration is 20 minutes under differing temps.Content with residue gold in the atomic absorption spectrophotometric determination solution.It the results are shown in Figure 4.(Fig. 4 temperature is to the influence of resin absorption gold)
Find out that by Fig. 4 temperature is little to the influence of BPR resin absorption gold.
Example 13
Get 0.3 gram resin and pack in the pillar of 0.5 * 3 centimetre of φ,, make pillar reach balance with 2 equivalents/rise hydrochloric acid drip washing.The solution that will contain 100 microgram gold is crossed post from top to bottom.Use 2N hydrochloric acid again---the mixed solution drip washing of 0.777N nitric acid, use 0.1M hydrochloric acid-0.1M thiocarbamide desorb under differing temps then, use the atomic absorption measuring absorbancy.It the results are shown in Figure 5. (inhaling the desorption curve of golden resin under Fig. 5 differing temps)
As seen from the figure, in the time of 45 ℃, just can more fully gold be resolved with 25ml hydrochloric acid one thiocarbamide.
Example 14
In 50 milliliters of Erlenmeyer flasks, add the palladium solution of 0.1 milliliter of 500 mcg/ml and the mineral acid of different concns.Add 0.1 gram BPR resin again, be diluted with water to 10 milliliters.Vibrated 2 hours down at 25 ℃, record the content that remains palladium in the solution, contrast with blank palladium solution again with atomic absorption method.The results are shown in Figure 6, table 1.(Fig. 6 acidity is to the influence of resin absorption palladium; Table 1 in sulfuric acid system acidity to the influence of BPR resin absorption palladium)
By Fig. 6 and table 1 as seen, the BPR resin can adsorb palladium fully below acid concentration 2N.
Example 15
In 50 milliliters of Erlenmeyer flasks, add the platinum reference liquid of 1 milliliter of 100 mcg/ml and the mineral acid of different concns, add 0.1 gram BPR resin again, be diluted with water to 10 milliliters.Vibrated 2 hours down at 25 ℃.Get 1 milliliter of vibration liquid, place 25 milliliters of colorimetric cylinders, be diluted to 15 milliliters with 8N acid.Add 5 milliliters of chloroforms---sherwood oil (60 ° of-90 ℃ of fractions) solvent, 1 milliliter of 0.2%DDO acetone soln and 0.5 milliliter of 45% stannous chloride solution.Extracted standing demix 1 minute.The sucking-off organic phase, with 1 centimetre of cuvette in 510 millimicrons of places, with 721 spectrophotometer measurement absorbancys.The results are shown in Figure 7 (Fig. 7 acidity is to the influences of resin absorption platinum)
As shown in Figure 7, in the hydrochloric acid system of platinum, when acid concentration during less than 2N, the BPR resin can adsorb platinum fully.
Example 16 Au, Fe, Cu, Ni are to the breakthrough experiment of BPR resin
Take by weighing the 0.3 gram BPR resin exchange column of packing into, behind 2N HCl solution equilibria post, gold solution with 2 μ g/ml is crossed post, the control flow velocity is 0.5ml/min, collected a in per four minutes, survey atomic absorption, it the results are shown in Table 3 (table 3 gold solution penetrates the absorbancy situation of BPR resin column).The working curve of gold is seen Fig. 8 (working curve of Fig. 8 gold).The break-through curve of gold is seen Fig. 9 (Fig. 9 Au, Fe, Cu, Ni penetrate the curve of BPR resin column).
The last column liquid concentration of copper is 10 μ g/ml, absorbancy is 0.575, and the flow velocity of copper liquid is 0.55ml/min, collects a in per four minutes, survey atomic absorption, it the results are shown in Figure 9 (Fig. 9 Au, Fe, Cu, Ni penetrate the curve of BPR resin column).
The last column liquid concentration of nickel is 10 μ g/ml, absorbancy is 0.144, and the flow velocity of nickel solution is 0.5ml/min, collects a in per four minutes, survey atomic absorption, it the results are shown in Figure 9 (Fig. 9 Au, Fe, Cu, Ni penetrate the curve of BPR resin column).
The last column liquid concentration of iron is 10 μ g/ml, and absorbancy is 0.355, and the flow velocity of ferrous solution is 0.5ml/min, collects portion in per four minutes, surveys atomic absorption, and it the results are shown in Figure 9.(Fig. 9 Au, Fe, Cu, Ni penetrate the curve of BPR resin column)
The separation of gold in example 17 anode sludge (electrolysis copper work, Tianjin)
The anode sludge is handled through chloroazotic acid, removes residue, and by the BPR resin column, with 0.1 MHCl-0.1M thiocarbamide wash-out gold, recording gold content is the 4.25g/ ton under 45 ℃.
The separation of gold in example 18 anode sludge (electrolysis copper work, the Tianjin) chloridizing leach solution
The results are shown in Table 2.(table 2BPR resin column separates front and back sample content relatively)
The separation of gold in example 19 gold concentrates (Lingbao City, Henan)
Take by weighing the baked gold concentrate of 25 grams, add 40 milliliters of chloroazotic acid, littlely boiled suction filtration 2 hours.Filtrate is diluted to 250 milliliters with the hydrochloric acid of 1N, with filtrate by BPR resin column (φ 1cm * 25cm).Post is used the HCl solution equilibria of 1N in advance.After treating that filtrate is all passed through, wash post with the mixed solution of 2N hydrochloric acid and 0.7N nitric acid, resolve with the mixed solution of thiocarbamide-hydrochloric acid down at 45 ℃ then, recording gold content is 3.64mg/g (gold concentrate).
The separation (chrysanthemum mountain, Ji County, Tianjin) of gold in the example 20 zinc silks
Take by weighing 5 grams and be used for cyanating solution reductive zinc silk, after the washing, use aqua regia dissolution, get yellow solution, directly upper prop is used the thiocarbamide wash-out then, and recording gold content is 241.1 gram/tons, the rate of recovery 99.13%.
Reference (1) Vernon F.Anal.Chim.Acta 123 (1981) 309-313 (2) Vernon F.Shah T.Reactive Polymers 1 (1983) 30l-308 (3) Myasoedova G.V.Talanta 23 (1976) 866-868
Table 1 in sulfuric acid system acidity to the impact of BPR resin adsorption palladium
Sample content relatively before and after table 2 BPR resin column separated* 
*Get the 20ml chlorination and do not have the fluid upper prop. Table 3 gold solution penetrates the absorbance situation of BPR resin column
Annotate: in the absorbance hurdle * 10 or 50 or 100 refer to the multiple that dilutes. Continued 3
| Add palladium amount (μ g) | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Acid concentration (N) | 0.05 | 0.1 | 1 | 2 | 4 | 6 | 8 |
| Ball heavy (g) | 0.1016 | 0.0998 | 0.0991 | 0.1002 | 0.1001 | 0.0998 | 0.1000 |
| The balance absorbance | 0.002 | 0.000 | 0.002 | 0.01 | 0.016 | 0.024 | 0.029 |
| Blank absorbency | 0.206 | 0.202 | 0.205 | 0.197 | 0.195 | 0.182 | 0.174 |
Claims (8)
1. synthetic method with crosslinked α-ethyl pyridinyl polystyrene resin (BPR resin) of structure (IV) is characterized in that it makes by Grignard reagent or organo-metallic sodium and chloromethyl polystyrene resin effect:
＜1〉by Grignard reagent synthetic (I method)
＜2〉by organo-metallic sodium reagent synthetic (II method):
2. according to the synthetic method of the described BPR resin of claim 1, it is characterized in that when synthesizing by Grignard reagent, at first will be with the 1. 0.07 mole of step reaction products therefrom (V), with 40 milliliters of benzene swellings, the 2. the step reaction need add 120 milliliters of n-butyl ethers, 0.2 mole of monobromethane, 0.2 mole of magnesium chips, dropwising needs 30 minutes, temperature is advisable to keep little boiling, consumption that 3. goes on foot the reaction solvent n-butyl ether is 40 milliliters, 0.2 mole of α-Jia Jibiding, 110 °-140 ℃ of temperature of reaction, 4. the go on foot 60 °-90 ℃ of temperature of reaction, and reaction times 8-9 hour, product was with ammonium chloride and mixture of ice and water hydrolysis, extraction using alcohol is used at last with 10% salt acid soak in the back.
3. according to the synthetic method of the described BPR resin of claim 1; it is characterized in that when synthesizing by organo-metallic sodium; the 2. in the step reaction consumption of α-Jia Jibiding be 40 moles; 8.3 moles of sodium Metal 99.5s; 90 °-110 ℃ of temperature of reaction; the 3. in the step reaction; in 3.4 moles of (V) consumptions; 50 °-60 ℃ of temperature of reaction; stirred 8-9 hour; product restrains the frozen water hydrolysis with 1200; 30 °-50 ℃ of hydrolysis temperatures; use 800 milliliters of 1: 1 salt acid soak then, use extraction using alcohol at last, 2.; 3. the step reaction all needs to carry out under nitrogen protection.
4. according to the synthetic method of the described BPR resin of claim 1 to 3, it is characterized in that monomer α-Jia Jibiding and isopropyl ether can recovery set use, use the dried organic layer of rice Ge Shi fractional column rectifying during recovery, 67 °-69 ℃ fraction is an isopropyl ether, and 126 °-131 ℃ fraction is a α-Jia Jibiding.
5. method of using BPR resin isolation, enrichment with the precious metal of Jin Weizhu, it is characterized in that when containing with the precious metal solution of Jin Weizhu when the adsorption column of BPR resin is housed, precious metal with Jin Weizhu just is attracted on the resin, use the elutriant wash-out then, to reach the purpose of separation and concentration with the precious metal of Jin Weizhu.
6. according to the method for the described BPR resin isolation of claim 5 enrichment, it is characterized in that what application operating was performed such with the precious metal of Jin Weizhu; Earlier with hydrochloric acid soln drip washing resin column, then slowly passing through resin column from top to bottom with the precious metal solution behind the aqua regia dissolution with Jin Weizhu, wash post with the mixed solution of hydrochloric acid and nitric acid then, use the precious metal of the mixed solution wash-out of hydrochloric acid and thiocarbamide at last with Jin Weizhu.
7. according to the method for the described BPR resin isolation of claim 6 enrichment with the precious metal of Jin Weizhu, when it is characterized in that application operating, the concentration of hydrochloric acid that is used for the drip washing resin column is 1-2N, the concentration of hydrochloric acid is 2N in the mixed solution of hydrochloric acid and nitric acid, the concentration of nitric acid is 0.777N, the concentration of hydrochloric acid is 0.1-0.2M in the elutriant, and the concentration of thiocarbamide is 0.1-0.2M.
8. according to the method for the described BPR resin isolation of claim 5 to 7 enrichment, it is characterized in that the BPR resin after being the regeneration of hydrochloric acid of 1-2N with concentration with the precious metal of Jin Weizhu, reusable.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103759 CN1023406C (en) | 1987-05-22 | 1987-05-22 | Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103759 CN1023406C (en) | 1987-05-22 | 1987-05-22 | Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application |
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| CN1023406C CN1023406C (en) | 1994-01-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279292B (en) * | 2008-05-06 | 2010-04-14 | 杭州师范大学 | Catalyst for hydrosilylation of olefins containing fluorine and preparation |
| CN102399342A (en) * | 2011-10-09 | 2012-04-04 | 山东省科学院能源研究所 | Surface functionalization method of poly (styrene-divinylbenzene) microspheres |
| CN108704668A (en) * | 2018-06-13 | 2018-10-26 | 福州华博立乐新材料科技有限公司 | A kind of catalyst for synthesizing 7- chloro-2-oxoheptanoates |
| CN115845807A (en) * | 2022-11-29 | 2023-03-28 | 西安交通大学 | Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof |
-
1987
- 1987-05-22 CN CN 87103759 patent/CN1023406C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279292B (en) * | 2008-05-06 | 2010-04-14 | 杭州师范大学 | Catalyst for hydrosilylation of olefins containing fluorine and preparation |
| CN102399342A (en) * | 2011-10-09 | 2012-04-04 | 山东省科学院能源研究所 | Surface functionalization method of poly (styrene-divinylbenzene) microspheres |
| CN108704668A (en) * | 2018-06-13 | 2018-10-26 | 福州华博立乐新材料科技有限公司 | A kind of catalyst for synthesizing 7- chloro-2-oxoheptanoates |
| CN115845807A (en) * | 2022-11-29 | 2023-03-28 | 西安交通大学 | Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof |
| CN115845807B (en) * | 2022-11-29 | 2024-05-07 | 西安交通大学 | Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1023406C (en) | 1994-01-05 |
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