CN101531675A - Chelating agent and preparation method and application thereof - Google Patents
Chelating agent and preparation method and application thereof Download PDFInfo
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- CN101531675A CN101531675A CN200910097402A CN200910097402A CN101531675A CN 101531675 A CN101531675 A CN 101531675A CN 200910097402 A CN200910097402 A CN 200910097402A CN 200910097402 A CN200910097402 A CN 200910097402A CN 101531675 A CN101531675 A CN 101531675A
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- preparation
- phosphoryl
- metal ion
- sequestrant
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002738 chelating agent Substances 0.000 title abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 51
- 239000003352 sequestering agent Substances 0.000 claims description 34
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 26
- -1 amine salts Chemical class 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 150000002466 imines Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000013522 chelant Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 238000003408 phase transfer catalysis Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910003849 O-Si Inorganic materials 0.000 claims description 4
- 229910003872 O—Si Inorganic materials 0.000 claims description 4
- 150000003983 crown ethers Chemical class 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 claims description 2
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical compound Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 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 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 125000000188 beta-D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 abstract 1
- 230000009919 sequestration Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010793 electronic waste Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- DHIVLKMGKIZOHF-UHFFFAOYSA-N 1-fluorooctane Chemical class CCCCCCCCF DHIVLKMGKIZOHF-UHFFFAOYSA-N 0.000 description 1
- QXDDDCNYAAJLBT-UHFFFAOYSA-N 3-chloropropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCCl QXDDDCNYAAJLBT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- YOCZZJWFWDUAAR-UHFFFAOYSA-N sulfanyl-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(S)(=S)CC(C)CC(C)(C)C YOCZZJWFWDUAAR-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a chelating agent, its preparation method and application in the supercritical CO2 chelating extraction of the metal ion. The chelating agent is prepared by reacting disphosphoryl imides as reaction substrate with halogenated hydrocarbons containing hetero atom functional group such as aliphatic hydrocarbon groups with C-O-C ether link or alkyl with C-O-C ether link and fluorine atom, aliphatic hydrocarbon groups with single silicon atom or C-O-C ether link, alkyl with fully-acetylated beta-glucosyl or the like under the mild condition in the presence of phase transfer catalyst. The chelating agent has strong sequestration for the metal ion, and is suitable for the harmless cleaning treatment for the waste water containing metal ion, electronic garbage, nuclear waste and the like, the washing of the high-precision integrated circuit or wafer, in particular for the the supercritical CO2 chelating extraction of the metal ion.
Description
Technical field
The invention belongs to the Green Chemical Technology field, be specifically related to a kind of sequestrant and its production and application.
Background technology
Heavy metal destroys quite serious to the pollution of physical environment, the a large amount of waste liquids that produce in the industry, waste residue etc. include more heavy metal ion, if deal with improperly, not only do not eliminate the pollution of heavy metal ion to environment, can bring secondary pollution to environment on the contrary.Contained the liquid and waste slag produced of radioactive metal ion for nuclear industry produces, scientists is being explored a kind of effective green purification treatment technology always.
Except industrial effluent, residue contamination, current another kind of source of heavy metal pollution---a large amount of electronic waste, the heavy metal environmental pollution that other main electronic product country of consumption causes in China and the world is also serious further.The electronic waste that contains heavy metal at present, or handle through simply burying method, or handle through common chemical precipitation method, though can temporarily eliminate the ground pollution source, be long-range to underground water source or subterranean microorganisms environment damage.The electronic waste of now contains precious metals such as gold and silver more, if can find effective purifying treatment method, not only can solve environmental pollution problems, but also can reclaim a large amount of precious metals.For fear of the harm of heavy metal ion to environment, strict standard and standard have all been formulated in countries in the world, and having dropped into huge human and material resources and financial resources aspect the purification techniques research and development, in the hope of turning bane into boon, turn waste into wealth.
Supercritical CO
2Abstraction technique has developed nearly 30 years, as a kind of outstanding Green Chemical Technology, is applied to fields such as industry, agricultural, environmental protection widely.Supercritical CO
2, have the dual nature of gas and liquid concurrently, have low viscosity, plurality of advantages such as mass transfer is fast, and operational condition is simply gentle, and subsequent disposal is simple, and is environmentally friendly.Because metal ion itself is insoluble to supercritical CO
2, at supercritical CO
2The suitable sequestrant of middle adding, metal ion often can be extracted effectively, and these sequestrants must can be dissolved in supercritical CO
2In, and the ability of charge neutralization can be provided, thus make the metal complex of generation can be dissolved in supercritical CO
2Therefore, by supercritical CO
2And in conjunction with the supercritical CO of sequestrant
2The chelate extraction technology becomes a kind of excellent selection of heavy metal pollution problem in the processing environment.This technology can be applied to that the efficient recovery of the removing of heavy metal ion in purification, food and the medicine of environment heavy metal contamination, nuke rubbish radioactive metal is handled, the numerous areas such as harmless cleaning of effective recycling, highly sophisticated device or the microsize integrated circuit (IC) wafer of precious metal (as gold, platinum, silver etc.) and base metal (as copper, nickel, zinc, iron etc.) in the electronic waste.
Traditional sequestrant such as organic monophosphorous ligand class: tributyl phosphate (TBP), Cyanex272, Cyanex301, Cyanex302 etc., dithiocarbamate(s) (DDC class), the beta-diketon class, crown ether-like etc. are at supercritical CO
2Though certain solubleness is all arranged in the fluid, but extraction efficiency is lower.Can improve supercritical CO to a certain extent though add properties-correcting agent (common) as methyl alcohol, ethanol etc.
2The efficient of chelate extraction metal ion, but properties-correcting agent can bring secondary pollution to environment.So, need the sequestrant of development of new and rational synthesis technique thereof, to strengthen supercritical CO
2Huge legendary turtle is closed " efficient, green " characteristic that the extracting metals ion is had.
Two-(O, O-dialkyl phosphoryl) imines is a kind of ionic of extracting metals efficiently sequestrant, and alkyl wherein is (Solvent Extraction and Ion Exchange.1992,10,729-748 such as methyl, ethyl, propyl group, phenyl; Solvent Extraction and Ion Exchange, 1992,10,749-767).When this sequestrant was used for common liquid-liquid extraction metal ion, its extraction efficiency was all very high, but its traditional synthetic route step is many and the condition harshness (J.Chem.Soc. (A), 1971,2863 that require; Z.Anorg.Allg.Chem., 1974,404,219-226; Z.Anorg.Chem., 1977,430,227-233), byproduct of reaction is more, separates purification difficult, cause the ultimate aim product two-yield of (O, O-dialkyl phosphoryl) imines is very low.
Summary of the invention
The invention provides a kind of two-(O, the disubstituted phosphoryl of O-) imines sequestrant and preparation method thereof, with overcome present common metal ion chelating agent extraction efficiency low, easily cause secondary pollution, preparation method's complexity, the shortcoming that yield is low.
A kind of sequestrant has the structure of general formula (I):
Wherein, R is for having general formula-(A)
nThe substituting group of-Z, A are methylene radical;
When Z is-(CX
2-CX
2-O)
k-CX
2-CX
3The time, wherein X is hydrogen atom or fluorine atom, k is 1,2 or 3, n=1 or 2;
When Z is-Si ((CH
2)
xCH
3)
3The time, wherein x is 0,1,2 or 3, n=3;
When Z is-Si (CH
3)
α[-(O-Si (CH
3)
2)
β-O-Si ((CH
2)
γCH
3)
3]
δThe time, wherein β is 0,1,2 or 3, and γ is 0,1,2 or 3, and α is 1 or 2, and δ is 1 or 2, and α+δ=3, n=3;
When Z is suc as formula shown in (II) time, wherein-Ac is an ethanoyl, m is 0,1,2 or 3, n=3;
The present invention also provides a kind of preparation method of above-mentioned sequestrant, may further comprise the steps:
The compound that with general formula is RX ' is dissolved in the polar aprotic solvent with two phosphoryl inferior amine salts, adds phase-transfer catalyst, stirs and carries out the phase-transfer catalysis esterification, promptly makes finished product after the separation and purification, and wherein X ' is a halogen.
The characteristic reaction equation of solid-liquid phase transfer catalysis esterification is as follows among the preparation method of the present invention:
Described pair of phosphoryl inferior amine salt is preferably two phosphoryl imines sodium or two phosphoryl imines potassium.
Described phase-transfer catalyst is preferably one or more in quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether, the open chain polyethers phase-transfer catalyst, preferably selects in Tetrabutyl amonium bromide, tri-n-octyl methyl ammonium chloride, trimethyl benzyl ammonia chloride, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride, 15-hat-5, the 18-hat-6 one or more for use.
I) when phase-transfer catalyst be QBr (Q
+Be quaternary ammonium cation) time, its reaction mechanism in this reaction, adds less water and helps the solid-liquid phase transfer catalysis esterification as shown in Figure 1.
Ii) when phase-transfer catalyst is crown ether, be example with 15-hat-5, its mechanism as shown in Figure 2, among Fig. 2 in Nu
-Be two phosphoryl imines negative ions; Crown ether forms title complex " crown ether-Na with two phosphoryl imines sodium salts
+-Nu
-", this moment Nu
-Just form naked anion, be exposed and transfer to organic phase, increased reactive activity.
Described polar aprotic solvent is preferably a kind of in dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, acetone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, the hexamethylphosphoramide.
Described phase-transfer catalyst is preferably 0.01～0.10 with the mol ratio of two phosphoryl inferior amine salts.
The temperature of described phase-transfer catalysis esterification is preferably room temperature or back flow reaction temperature (reaction solvent ebullient temperature), and the reaction times is preferably 3～24 hours.
Described separation and purification process is preferably: will react after product vacuum distilling, distillation back gained resistates is dissolved in methylene dichloride, collected organic layer is also used anhydrous sodium sulfate drying behind the deionized water wash, remove by filter sodium sulfate, collect organic solution, vacuum distilling, the quick silica gel chromatography of remaining mixture utilization is further purified.
The present invention also provides above-mentioned sequestrant at supercritical CO
2Application in the chelate extraction metal ion.
Sequestrant of the present invention can be used for the chelate extraction metal ion, is particularly useful for and supercritical CO
2Fluid combines, chelate extraction metal ion from the matrix that contains metal ion.
In conjunction with supercritical CO
2Condition optimization pressure during fluid chelate extraction metal ion is 8～30Mpa, and temperature is 40～60 ℃.
Described matrix is to adding the supercritical CO of sequestrant
2The chelate extraction effect do not have any influence and get final product, can be that solid state substrate also can be a liquid matrix.
Described metal ion comprises metal ions such as lanthanide metal ion, actinide metals ion, iron ion, cobalt ion, nickel ion, cupric ion, zine ion, lead ion, chromium ion, mercury ion, silver ions, gold ion.
Sequestrant of the present invention is the sequestrant that a class has two toothings, has two kinds of resonance structures (suc as formula I, formula II), and wherein pure formula structure (formula II) is the preferred conformation with metallic ion coordination:
Usually utilize two symmetric Sauerstoffatoms and metallic cation to form coordinate bond, to form stable six-membered ring structure, its structural representation is as follows:
This character and beta-diketon class sequestrant have similarity, owing to be positioned at the C atom sp at beta-diketon symmetrical configuration center
2Hybridism, what beta-diketon class sequestrant and metal ion formed is the planar six-ring.But in two-(O, the disubstituted phosphoryl of O-) imine structure, N atom and two P atoms all are sp
3Hydridization, causing the O-P-N-P-O skeleton is nonplanar structure, the changeable nonplanar structure of this distortion provides multiple effective way for sequestrant combines with the coordination of metal ion, make sequestrant easier with metal ion be combined into stable six-membered ring structure; In addition, phosphoryl (P=O) is stronger than acyl group (C=O) alkalescence, is easier to combine with metal ion.So this sequestrant has strong sequestering action to metal ion, be applicable to the harmless cleaningization processing of the waste water that contains metal ion, electronic waste, nuke rubbish etc., and the cleaning of high-accuracy unicircuit or wafer.
Sequestrant of the present invention is a skeleton with two phosphoryl imines; four side-chain radicals of symmetric connection, these side-chain radicals can be aliphatic group, the contain fluorine atoms alkyl, the aliphatic group that contains single Siliciumatom or Si-O-Si key that contain C-O-C ehter bond or carbonyl, contain the alkyl of full acetylated β-glucosyl group etc.This class heteroatom functional group can strengthen sequestrant at supercritical CO
2In solubleness, be to have " CO
2-philic " functional group of function (is close supercritical CO
2Functional group).Except the aliphatic group of contain fluorine atoms, these have " CO
2-philic " when the functional group of function is connected with P-O and at least two methylene radical of P atomic separation, promptly form following structure:
P-O-C
x-G
CO2-philic
Wherein x is 〉=2 integer, G
CO2-philicBe to play close supercritical CO
2The main functional group of effect;
For sterically hindered bigger " CO
2-philic " functional group, the x value need be chosen the integer more than 3, to guarantee the stability of whole chelator molecule; " CO
2-philic " functional group makes the supercritical CO of sequestrant in gentleness
2Just can reach higher solubleness under the operational condition, not only improve supercritical CO
2The efficient of chelate extraction metal ion, and saved the running cost of extraction;
Under the same conditions, of the present invention two-the more traditional metal chelator extraction efficiency of (O, the disubstituted phosphoryl of O-) imines sequestrant is higher, its extraction efficiency is 2～3 times of beta-diketon class sequestrant at least.
The preparation method of sequestrant of the present invention adopts the phase-transfer catalysis esterification, this reaction conditions gentleness, room temperature with fully stir under promptly obtain target product with high purity through simply separating purification, simple to operate, raw materials used being easy to get, byproduct of reaction is few, the yield height is suitable for large-scale commercial production.
Description of drawings
Reaction mechanism synoptic diagram when Fig. 1 uses the QBr phase-transfer catalyst for the inventive method;
Reaction mechanism synoptic diagram when Fig. 2 uses 15-hat-5 phase-transfer catalysts for the inventive method.
Embodiment
Embodiment 1
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, dropping 10mL contains the acetonitrile solution of 0.20mmol iodo octane-iso and 0.005mmol Tetrabutyl amonium bromide, continues to stir stopped reaction behind the reaction 10h; Reactant is removed acetonitrile with vacuum distilling, and the distillation residuum is dissolved in the 30mL methylene dichloride, and with deionized water wash three times (about at every turn 30mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying; remove by filter sodium sulfate; collect organic solution; vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (elutriant is that ethyl acetate and sherwood oil volume ratio are 1: 7 mixing solutions) is purified, and promptly makes 28mg pair-(O, O-diisooctyl phosphoryl) imines; be sundown oily liquids, MS-ESI:[M+H]
+=626.5, [M+Na]
+=648.3.(mass spectrum, Esquire3000plus, ion source ESI)
Embodiment 2
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, Dropwise 5 mL contains the acetonitrile solution of 0.20mmol (3-chloropropyl) trimethyl silane and 0.0003mmol 15-hat-5, continues to stir stopped reaction behind the reaction 8h; Reactant is removed acetonitrile with vacuum distilling, and the distillation residuum is dissolved in the 20mL methylene dichloride, and with deionized water wash three times (about at every turn 20mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying; remove by filter sodium sulfate; collect organic solution; vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (elutriant is that ethyl acetate and sherwood oil volume ratio are 1: 9 mixing solutions) is purified, promptly make 26.6mg two-[O, O-two (3-trimethyl silicon based-propyl group) phosphoryl] imines; be pale brown look oily liquids, MS-ESI:[M+H]
+=634.6, [M+Na]
+=656.5.(mass spectrum, Esquire3000plus, ion source ESI)
Embodiment 3
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, Dropwise 5 mL contains 0.20mmol (2R, 3R, 4S, 5R, 6R)-and 2-(acetoxy-methyl)-6-(3-bromopropyl) tetrahydrochysene-2H-pyrans-3,4, the acetonitrile solution of 5-triacetate and 0.0003mmol 15-hat-5, continue to stir stopped reaction behind the reaction 10h; Reactant is removed acetonitrile with vacuum distilling, and the distillation residuum is dissolved in the 20mL methylene dichloride, and with deionized water wash three times (about at every turn 20mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying; remove by filter sodium sulfate; collect organic solution; vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (elutriant is that ethyl acetate and normal hexane volume ratio are 1: 9 mixing solutions) is purified, and promptly gets two-[O, O-two (3-propyl group-full acetylated glucosyl group) phosphoryl] imines; be pale brown look oily liquids, productive rate 80%.
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, and Dropwise 5 mL contains 0.20mmol1-chloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8, the acetonitrile solution of the Tetrabutyl amonium bromide of 8-15 fluoro-octanes and 0.0009mmol 15-hat-5 and 0.0006mol continues to stir, stopped reaction behind the reaction 20h; Reactant is removed acetonitrile with vacuum distilling, and the distillation residuum is dissolved in the 20mL methylene dichloride, and with deionized water wash three times (about at every turn 20mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying, removes by filter sodium sulfate, collects organic solution, vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (acetone and methylene dichloride are as developping agent) is purified, promptly get pair-[O, O-two (2,2; 3,3,4,4; 5,5,6,6; 7,7,8,8; 80 five fluorine octyl groups) phosphoryl] imines, be yellow oily liquid, productive rate 80%.
Embodiment 5
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, Dropwise 5 mL contains the dimethyl formamide solution of 0.20mmol 1-(3-bromine oxethyl) butane and 0.00006mmol 15-hat-5, continue to stir stopped reaction behind the reaction 15h; Reactant is removed dimethyl formamide with vacuum distilling, and the distillation residuum is dissolved in the 20mL methylene dichloride, and with deionized water wash three times (about at every turn 20mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying; remove by filter sodium sulfate; collect organic solution; vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (ethyl acetate and methylene dichloride are as developping agent) is purified, and promptly gets two-[O, O-two (3-butoxyethyl group) phosphoryl] imines; be yellow oily liquid, productive rate 85%.
Embodiment 6
At room temperature, the acetonitrile solution that 5mL is contained the two phosphoryl imines sodium salts of 0.05mmol joins in the 50mL round-bottomed flask, Dropwise 5 mL contains 0.20mmol3-(1,1,1,3,3-pentamethyl-two siloxies)-tetrahydrofuran solution of 1-N-PROPYLE BROMIDE and 0.00006mmol 15-hat-5, continue to stir stopped reaction behind the reaction 15h; Reactant is removed acetonitrile with vacuum distilling, and the distillation residuum is dissolved in the 20mL methylene dichloride, and with deionized water wash three times (about at every turn 20mL deionized water).Collected organic layer is also used anhydrous sodium sulfate drying, removes by filter sodium sulfate, collects organic solution; vacuum distilling; the quick silica gel chromatography of remaining mixture utilization (ethyl acetate and methylene dichloride are as developping agent) is purified, promptly get pair-[O, (3-(1 for O-two; 1; 1,3,3-pentamethyl-two siloxies) propyl group) phosphoryl] imines; be yellow oily liquid, productive rate 85%.
Application examples 1
Under 308.15K～333.15K and 8MPa～15MPa condition, measured two-(O, O-diisooctyl phosphoryl) imines of embodiment 1 preparation at supercritical CO with stationary method
2In solubleness, the result shows that at 60 ℃ under the 15Mpa condition, its solubleness is up to 1.09 * 10
-2(mole fraction).
4mL is contained La
3+, Eu
3+, Lu
3+Ionic aqueous nitric acid (wherein, the concentration of aqueous nitric acid is 0.5mol/L, and the concentration of each metal ion is 5 μ g/mL), then with the 150mg sequestrant two-(O, O-diisooctyl phosphoryl) imines joins in the extraction kettle.Extraction kettle is heated to 60 ℃, feeds CO
2Make the pressure of extraction kettle reach 20Mpa, static extracting 15min, dynamic extraction 15min (uses CO under the permanence condition that promptly keep-ups pressure then
2The flushing extraction kettle), is decompressed to normal atmosphere at last, extract ICP check and analysis (PQ3 type icp ms, U.S. power ﹠ light company).The result shows that three metal ion species percentage extractions are all near 100%.
Application examples 2
Measure two-[O, O-two (3-trimethyl silicon based-propyl group) phosphoryl] imines of embodiment 2 preparations at supercritical CO with stationary method
2In solubleness, the result shows that at 60 ℃ under 10Mpa～20Mpa condition, its solubleness is the highest near 5 * 10
-2(mole fraction).
At first prepare solid sample: will contain La
3+, Eu
3+, Lu
3+Ion solution (wherein, the quality of each metal ion is 10 μ g) is coated on the filter paper that cleaned in advance, and room temperature (25 ℃) is spent the night evaporate to dryness.
The extraction kettle top is filled with glass wool, above-mentioned air dried filter paper is filled in the extraction kettle, splash into a little deionized water, sealing.Extraction kettle is warming up to 60 ℃ then, feeds supercritical CO
2Be forced into 20Mpa, static extracting 30min, then dynamic extraction 30min slowly is decompressed to normal atmosphere.Extract is collected with chloroform, treats that the chloroform volatilization is dried, dissolves residuum with concentrated nitric acid, uses the ICP check and analysis.Detected result shows that three metal ion species percentage extractions are higher than 98%.
Application examples 3
The phosphoryl imines that contains glucosyl group that adopts embodiment 3 preparations is as sequestrant, and all the other operational conditions are identical with application examples 1, and the result shows that the percentage extraction of three metal ion species is higher than 95%.
Application examples 4
Adopt embodiment 5 preparations two-[O, O-two (3-butoxyethyl group) phosphoryl] imines is as sequestrant, all the other operational conditions are identical with application examples 1, the result shows that the percentage extraction of three metal ion species is higher than 97%.
Claims (10)
1, a kind of sequestrant has the structure of general formula (I):
Wherein, R is for having the substituting group of n-Z of general formula-(A), and A is a methylene radical;
When Z is-(CX
2-CX
2-O)
k-CX
2-CX
3The time, wherein X is hydrogen atom or fluorine atom, k is 1,2 or 3, n=1 or 2;
When Z is-Si ((CH
2)
xCH
3)
3The time, wherein x is 0,1,2 or 3, n=3;
When Z is-Si (CH
3)
α[-(O-Si (CH
3)
2)
β-O-Si ((CH
2)
γCH
3)
3]
δThe time, wherein β is 0,1,2 or 3, and γ is 0,1,2 or 3, and α is 1 or 2, and δ is 1 or 2, and α+δ=3, n=3;
When Z is during suc as formula group shown in (II), wherein-Ac is an ethanoyl, m is 0,1,2 or 3, n=3;
2, the preparation method of the described sequestrant of a kind of claim 1 may further comprise the steps:
The compound that with general formula is RX ' is dissolved in the polar aprotic solvent with two phosphoryl inferior amine salts, adds phase-transfer catalyst, stirs and carries out the phase-transfer catalysis esterification, promptly makes finished product after the separation and purification, and X ' is a halogen.
3, preparation method as claimed in claim 2 is characterized in that: described pair of phosphoryl inferior amine salt is two phosphoryl imines sodium or two phosphoryl imines potassium.
4, preparation method as claimed in claim 2 is characterized in that: described phase-transfer catalyst is one or more in quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether, the open chain polyethers phase-transfer catalyst.
5, preparation method as claimed in claim 4 is characterized in that: described phase-transfer catalyst is one or more in Tetrabutyl amonium bromide, tri-n-octyl methyl ammonium chloride, trimethyl benzyl ammonia chloride, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride, 15-hat-5, the 18-hat-6.
6, preparation method as claimed in claim 2 is characterized in that: described polar aprotic solvent is a kind of in dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, acetone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, the hexamethylphosphoramide.
7, preparation method as claimed in claim 2 is characterized in that: described phase-transfer catalyst is 0.01～0.10 with the mol ratio of two phosphoryl inferior amine salts.
8, preparation method as claimed in claim 2 is characterized in that: the temperature of described phase-transfer catalysis esterification is room temperature or back flow reaction temperature, and the reaction times is 3～24 hours.
9, preparation method as claimed in claim 2, it is characterized in that: described separation and purification process is: will react after product vacuum distilling, distillation back gained resistates is dissolved in methylene dichloride, collected organic layer is also used anhydrous sodium sulfate drying behind the deionized water wash, remove by filter sodium sulfate, collect organic solution, vacuum distilling, the quick silica gel chromatography of remaining mixture utilization is further purified.
10, sequestrant as claimed in claim 1 is at supercritical CO
2Application in the chelate extraction metal ion.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735264B (en) * | 2009-12-18 | 2012-07-18 | 浙江大学 | Chelating agent and application thereof |
| CN106892940A (en) * | 2015-12-17 | 2017-06-27 | 上海东升新材料有限公司 | A kind of open chain crown ether chelating agent and preparation method thereof |
| CN114134338A (en) * | 2021-12-15 | 2022-03-04 | 南开大学 | Application of emulsion liquid membrane with double extraction carriers in recovery of gold and silver bimetallic elements in waste circuit boards |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735264B (en) * | 2009-12-18 | 2012-07-18 | 浙江大学 | Chelating agent and application thereof |
| CN106892940A (en) * | 2015-12-17 | 2017-06-27 | 上海东升新材料有限公司 | A kind of open chain crown ether chelating agent and preparation method thereof |
| CN114134338A (en) * | 2021-12-15 | 2022-03-04 | 南开大学 | Application of emulsion liquid membrane with double extraction carriers in recovery of gold and silver bimetallic elements in waste circuit boards |
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