CN1088485A - Be used to remove the part on the solid carrier of being stated from that contains the aminoalkyl phosphonic acids of metal ion - Google Patents
Be used to remove the part on the solid carrier of being stated from that contains the aminoalkyl phosphonic acids of metal ion Download PDFInfo
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- CN1088485A CN1088485A CN92114641A CN92114641A CN1088485A CN 1088485 A CN1088485 A CN 1088485A CN 92114641 A CN92114641 A CN 92114641A CN 92114641 A CN92114641 A CN 92114641A CN 1088485 A CN1088485 A CN 1088485A
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- 239000007787 solid Substances 0.000 title claims abstract description 29
- -1 aminoalkyl phosphonic acids Chemical class 0.000 title abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 title description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 119
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 238000010668 complexation reaction Methods 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 125000006850 spacer group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- 239000007788 liquid Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- AGINPOJWTDKORT-UHFFFAOYSA-N [H]OP(=O)OC([H])([H])N Chemical group [H]OP(=O)OC([H])([H])N AGINPOJWTDKORT-UHFFFAOYSA-N 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052745 lead Inorganic materials 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 3
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical class CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010891 toxic waste Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical group NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen 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
- 238000012545 processing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 210000003462 vein Anatomy 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
A kind ofly remove and carry dense desired ion such as Sb from multi-ion source solution
3+, Zr
4+, Zn
2+, Pu
4+, Hf
4+, Cu
2+, Ni
2+, Fe
3+, Cd
2+, Ag
+And Hg
2+Method, source solution can contain the H that comprises of higher concentration
+At other interior undesirable ions.This method comprises that source solution links the compound of the part on the solid inorganic carrier and contact with the silica-based covalent bond of organic spacer that passes through that contains the aminoalkyl phosphonic acids.The ligand moiety that contains the aminoalkyl phosphonic acids of this compound has the affinity that desired ion is generated complex compound, removes desired ion from source solution whereby.Then by with this compound of want ion ratio is contained aminoalkyl phosphonic acids ligand moiety the having the reception solution of bigger affinity to contact of described compound and small size more, thereby from this compound, remove the ion of wanting.
Description
The present invention relates to covalent bond and link the part that contains the aminoalkyl phosphonic acids on the inorganic solid support, and relate to and use such part that contains the aminoalkyl phosphonic acids from solution, to remove, separate and put forward the method for dense some desired ion that obtains as support materials, such ion can mix with much higher other ions of concentration in this solution.More particularly, the present invention relates to as follows from solution remove such ion in the mixture of other ions method: this flow of solution is crossed the solid supported material splitter that contains aminoalkyl phosphonic acids part is housed, and the compound that aminoalkyl phosphonic acids part forms that contains that desired ion that obtains and key are linked on the inorganic matrix generates complex compound; Allow the much smaller reception liquid of this liquor capacity of volume ratio flow through splitter then, make the desired ion that obtains in the solution remove and carry dense to receiving in the liquid, decompose this complex compound by this method, the desired ion that obtains is told from the compound that connects these ions.The available then various familiar methods of dense ion of carrying that remove like this reclaim.
From with solution that chelating agent and/or other ions that may exist mix reclaim and/or separate specific transition-metal cation and the cationic effective ways of transition metal heel are needs of a kind of reality in modern technologies.As some concrete examples, (1) separates ppm level Sb cost-effectively from the higher Cu of concentration, Ni, Zn, Ag or other metal cations under acid condition; (2) separation Zr(IV from the salpeter solution that contains a large amount of other metal cations), Pu(IV) with the Hf(IV) flow out Cu, Ni, Fe, Zn, Cd, Ag, Pb and the Hg that separates the liquid as toxic waste with (3) from drinking water or industry, all these is the separation needs of reality, at present or realize that these separate reduction and do not have satisfied technology, perhaps also need more economic technology.These ions usually exist in other ion solution that contain higher concentration with low concentration.Therefore, exist selectivity to carry the reality needs of the method for dense and these ions of recovery.
Knew already that the molecule that contains amine and phosphonyl group had stronger also slightly selectively interact with lanthanide series metal, Ga, Sb, Bi, Mn, Fe, Co, Ni, Cu, Fe, Zn, Al, Hg, Pb and Ag in faintly acid or neutrality under the condition of alkaline pH.These molecules under acid condition to the Sb(III), the Zr(IV) and other positive 4 valency metal cations also have highly single-minded selectivity.
Method of the present invention is particularly suitable for from containing high concentration plated metal cation (as the Cu(II)) H
2SO
4Remove the Sb(III in the stream) and from HNO
3Remove the Zr(IV in the stream) and the Pu(IV).
In fact product and method that the present invention describes have overcome above-mentioned all difficulties, and provide an effective method for the practicality of the desired ion that obtains separates.
The peculiar property that is connected to the part that contains the aminoalkyl phosphonic acids on the suitable inorganic solid support constitutes basis of the present invention.This compound, synthetic method and character are described below.The present invention also comprises the method for separating the desired ion that obtains with these compounds.
Compound of the present invention comprises the suitable part that contains the aminoalkyl phosphonic acids, and this part is linked on the silicon atom by the basic covalent bond in interval, and further covalent bond is linked on the solid carrier.This compound is represented with following formula:
In formula 1, A and B independently are selected from O, NR and N(R) CH
2, R wherein
And R ' independently is selected from (CH
2)
f-
(OH
2), CH
2 )
eN
((CH
2)
f-
(OH)
2)
2, CH
2CH
2R
1, H, low alkyl group, aralkyl, aryl and substitutive derivative thereof; R
1Independently be selected from H, SH, OH, low-carbon alkyl, aryl and aralkyl; C and d respectively are from 0 to about 10 integer; E and f respectively are from 1 to 10 integer; X is the interval base that following formula is arranged:
R wherein
2Be one in H, SH, OH, low-carbon alkyl and the aryl; A is from 3 to about 10 integer; B is 0 or 1 integer.Y and Z respectively are selected from Cl, Br, I, alkyl, alkoxyl, substituted alkyl or substituted alkoxy and 0-matrix; Matrix is selected from sand, silica gel, glass, glass fibre, aluminium oxide, zirconia, titanium oxide, nickel oxide or other hydrophilic inorganic carriers and composition thereof.When Y and Z part and O-matrix not simultaneously, they are categorized as leaving group on function, promptly be connected to the group on the silicon atom, when they react with O-solid hydrophilic host material, might leave away or are replaced by O-matrix.If after siliceous interval base or interval base/ligand groups and the reaction of solid hydrophilic medium carrier, any such function leaving group is left, these groups at the desired ion that obtains and be connected to interact containing between the aminoalkyl phosphonyl group part on the solid carrier in not directly effect.
Unless add explanation in addition, alkyl, alkoxyl, low-carbon alkyl and lower alkoxy refer to the group of 1～6 carbon, and they can be substituted or not replace, they may be straight chain or side chain.Equally, unless add explanation in addition, aryl is selected from phenyl, naphthyl and pyridine radicals, and aralkyl is that the alkyl of 1～3 carbon atom (preferably 1 carbon atom) is connected on the aryl.Aryl and aralkyl also can be substituted.The so-called replacement, refer to by such as Cl, Br, I, NO
2Deng replacement, they not interfering compound remove and function of separating desirable ion and effect.X is the interval base with functional character, and it is enough hydrophilic in aqueous environment, and will separate part from the solid matrix carrier surface, makes part and the desired interaction that separates between the ion that obtains reach maximum.
The representative of X is glycidol oxyalkyl, alkoxyalkyl, alkyl etc.
The excellent R that gets
1Be H.The integer of e and f representative preferably 1, c and d preferably 0 or 1.
In said structure, suitable subbase group comprises that X is (CH
2)
a(OCH
2CHR
2CH
2)
b, wherein a is 3, b is 0 or 1, R
2Be preferably OH.
It is that c and d are 0 that a kind of subbase is rolled into a ball.This just obtains at least one aminoalkyl phosphonate group
Part.But R
1Preferably be selected from (CH
2)
f-
(OH)
2With
CH
2CH)
eN(CH
2)
f-
(OH)
2, so that two or more aminoalkyl phosphonate groups are always arranged in part.Terminal N atom preferably contains two alkylphosphines acidic groups.
Another kind of subbase is rolled into a ball and is, c is 1, and d is 0, and A is NR, and wherein R is
The subbase group that another are different, c and d all are 1, and A is NR, and wherein R is the alkyl phosphonic acid part of as above stipulating.B also is NR, and wherein R is an alkyl aminoalkyl phosphonic acids part, example
As
This just obtains the side chain part of the complexity of terminal aminoalkyl phosphonate group, a branched alkyl aminoalkyl phosphonate group and another side chain aminoalkyl phosphonate group.As mentioned above, R
1Preferably be selected from
, so that five aminoalkyl phosphonate groups are arranged, wherein two preferably are connected on the terminal N atom.
The example of compound is in above-mentioned each group, and wherein (1) a is 3, and b is 0, and c and d are 0, and f is 1 and R
1Be the methylphosphine acidic group, promptly nitrogen contains the compound of two aminomethyl phosphonate groups endways, and wherein part is connected on the silicon by propyl group; (2) a is 3, and b is 1, R
2Be OH, c is 1, and d is 0, R
1Be H, f be 1 and A be NR, wherein R and R
1For
, promptly contain two terminal aminomethyl phosphonate groups and a compound that is connected to the middle side chain aminomethyl phosphonate group on the silicon by glycidyl oxygen propyl group interval base; (3) a is 3, and b is 0, and c and d respectively are 1, and A is NR, described R and R
1All as describing in (2), wherein B is NR, and described R is the alkyl aminoalkyl phosphonic acids part of side chain, for example
, wherein in all cases, e is 1, f is 1, R
1Be H, promptly contain the compound of the aminomethyl phosphonate group of two terminal aminomethyl phosphonate groups, middle side chain ethylamino two (methylphosphonic acids) base and another side chain.
As shown in Equation 1, the characteristics that covalent bond is linked the aminoalkyl phosphonic acids part on the solid carrier be faintly acid or neutral under the alkaline pH condition highly selective remove desirable ion or ion set, as lanthanide metal ion, Ga, Sb, Bi, Mn, Fe, Co, Ni, Cu, Zn, Al, Hg, Pb, Zr, Hf, Pu and Ag ion.These ions generally exist with low concentration in the solution mutually in the source of the mixture that contains the ion (promptly being called " undesirable ion ") that they remove with not wishing of existing with much higher concentration.Even at other complexing agents or its matter constituent, particularly acid exists down, in separation equipment (as knockout tower), makes flow of solution cross separation equipment and separates.Selectively removing and the method for carrying the dense desired ion that obtains be characterized in, can be quantitatively when the desired ion that obtains exists with low concentration from the solution of larger volume complexing go out the desired ion that obtains.Flow through knockout tower mutually by the reception that contains solubilizer on a small quantity, from knockout tower, reclaim the desired ion that obtains.Solubilizer does not need selectivity, but it wants quantitatively to take out the desired ion that obtains from part.Reclaiming the desired ion that obtains from receive mutually is easy to finish with various familiar methods.
And, covalent bond is as shown in Equation 1 linked terminal aminoalkyl phosphonic acids part on the solid carrier and other covalent bonds and is linked aminoalkyl phosphonic acids part (if existence) on the solid carrier, a kind of above-mentioned isolation technics and equipment of utilizing is provided, under acid condition, from the higher Cu of concentration, Ni, Zn, Ag or other metal cations, separate the method for ppm level Sb.The present invention loads on aminoalkyl phosphonic acids part on the solid and also is used for separating the Zr(IV from the salpeter solution that contains a large amount of other metal cations), the Pu(IV) and the Hf(IV).
The above-mentioned part that loads on the solid is effective at separation of C u, Ni, Fe, Zn, Cd, Ag, Pb and Hg from drinking water or industry outflow liquid as toxic waste.
As top general introduction, the present invention has described new containing and has linked silicon by basic covalent bond at interval and partly go up the part that contains the aminoalkyl phosphonic acids that also further is connected on solid matrix or the carrier, forms the compound of formula 1.The present invention has also described in faintly acid or neutral carried under the alkaline pH value condition dense from other ions and remove the method for some desired ion that obtains, as group of the lanthanides, Ga, Sb, Bi, Mn, Fe, Co, Ni, Cu, Zn, Al, Hg, Pb, Zr, Pu, Hf and Ag ion.For example, the effective ways of recovery and/or separating metal ion from other metal ions reclaim from the higher Cu of concentration, Ni, Zn, Ag or other metal cations under acid condition and/or separation ppm level Sb as (1); (2) from the salpeter solution that contains a large amount of other metal cations, separate the Zr(IV), the Pu(IV) and the Hf(IV); (3) flow out Cu, Ni, Fe, Zn, Cd, Ag, Pb and the Hg that separates the liquid as toxic waste from drinking water or industry.Because these separation do not have feasible set method or need more economic method.Such solution (these ions will be carried dense and/or recovery from this solution) is called " source solution " here.The concentration of other ions that the concentration ratio of desirable ion need separate with them in the solution of source or undesirable ion is much lower in many cases.
Realize that with following steps carrying of the desired ion that obtains is dense: the source flow of solution that contains the desired ion that obtains is crossed the tower of the formula of being equipped with 1 compound, allow the compound shown in desired ion that obtains and the formula 1 generate complex compound, make the desired ion that obtains adhere to the ligand moiety of linking these compounds with key; Allow the reception liquid more much smaller than source liquor capacity flow through this post then, it is dense in receiving solution to make the desired ion that obtains remove and carry.Receive in the liquid or reclaim solution and the desired ion that obtains generates the stronger complex compound of ligand moiety than formula 1 compound, therefore the desired ion that obtains quantitatively is fetched into from part and receives the solution to put forward dense form.Reclaiming the desired ion that obtains from receive liquid can finish with various familiar methods.
Contain the available prepared in various methods of ligand complex (as shown in Equation 1) of aminoalkyl phosphonic acids, these methods illustrate in the following example.
Embodiment 1
In this embodiment, there is the ligand compound of a terminal amino group two (methylphosphonic acid) base to be fixed on the silica gel with following steps.At first 20 gram aminopropyl-triethoxysilanes and 2 equivalent phosphoric acid are dissolved in 400 milliliter of 50% hydrochloric acid.This mixture adds hot reflux, and slowly adds the formalin of 31 grams 37%.Add step and in 2 hours, finish, mixture is chilled to below the reflux temperature, add 180 gram silica gel.This mixture of mechanical agitation was kept 3～18 hours at 70～95 ℃ again.Filtration, washing and air dry silica gel.This step is secured to the lip-deep terminal amino group two of silica gel (methylphosphonic acid) base.This compound is corresponding to formula 1, and wherein part constitutes like this: c and d are 0, and f is 1.Basic X is (CH at interval
2)
a(OCH
2CHR
1CH
2)
b, a is 3, b is 0.Y and Z are O-matrix or ethyoxyl.This compound has following formula:
Y and Z are O-matrix or methoxyl group in the formula.
Embodiment 2
In this embodiment, carry out the step of embodiment 1, the different 1 equivalent phosphoric acid that are to use.Obtain monoamine methylphosphine acidic group like this, wherein c and d are 0, f be 1 and at interval basic X be propyl group.This compound has following formula:
Wherein, Y and Z are O-matrix or methoxyl group
Embodiment 3
In this embodiment, prepared the different ligands that is connected on the solid carrier, it contains three aminomethyl phosphonate groups, has two endways on the nitrogen-atoms.At room temperature, 2.5 gram ethylenediamines at first reacted 18 hours with 3-glycidol oxygen propyl group-trimethoxy silane in methyl alcohol.Add 200 milliliter of 50% hydrochloric acid solution and 3 equivalent phosphoric acid then, this mixture adds hot reflux.Slowly add 100% excessive formaldehyde again.The cooling back adds silica gel, uses the isolated by filtration product again.This method obtains the compound of three aminomethyl phosphonate groups.Prepared the compound corresponding to formula 1, wherein c is 1, and d is 0, and A is NR, wherein R and R
1All be
(CH
2)
f-
(OH)
2, f is 1, R
1Be H.Basic X is (CH at interval
2)
a(OCH
2CHR
1CH
2)
b, a is 3, b is 1 and R
1Be OH.Y and Z are O-matrix or methoxyl group.This compound has following formula:
Y and Z are O-matrix or methoxyl group in the formula.
Embodiment 4
With the step of similar embodiment 1 and 2, preparation contains the complex compound part of 5 aminomethyl phosphonate groups, and c and d are 1, and A is NR, and B is NR, and each R is respectively following group:
R wherein
1Be H, e is 1, and f is 1 and R
1Be the methylphosphine acidic group.X is such interval base, a be 3 and b be 0.This compound has following formula:
Selectivity is quantitatively carried dense and is removed the desired ion that obtains that exists with low concentration or the method for ion set in multiple other undesirable ions from the source solution of different kinds of ions, in this source solution, undesirable ion, acid and other chelating agents may exist with much higher concentration together, this method comprises allows the source solution that contains different kinds of ions contact with as shown in Equation 1 the aminoalkyl phosphonic acids ligand complex that loads on the solid, and what make desired ion that obtains and compound contains the complexing of aminoalkyl phosphonic acids ligand moiety; From complex compound, decomposes or extracts the desired ion that obtains with receiving solution subsequently, receive solution and the desired ion ratio that obtains contain the stronger complex compound of the part generation of aminoalkyl phosphonic acids or with the stronger complex compound of part generation that contains the aminoalkyl phosphonic acids.The solution that receives or reclaim only contains the ion that the higher hope of concentration obtains.
The part solid matrix carrier that contains the aminoalkyl phosphonic acids plays a part according to the formula 2 absorption desired ions that obtain (DI):
(matrix-O)
1-3-Si-X-L+DI-→ (matrix-O)
1-3-Si-X-LiDI (formula 2)
Except that DI, formula 2 is the shorthand of formula 1, and wherein the L representative contains the part of aminoalkyl phosphonic acids.The ion that the hope that the DI representative removes obtains.When matrix-O less than 3 the time, other positions are by Y and Z group occupy as described above.
In case the desired ionic bond that obtains is linked on the part that contains the aminoalkyl phosphonic acids, they are then just separated with receiving liquid more on a small quantity by formula 3:
(matrix-O)
1-3-Si-X-L: DI+RL-→ (matrix-O)
1-3-Si-X-L+RL: DI(formula 3) wherein the RL representative receives liquid.
Disclosed here optimum implementation comprises with following steps and realizes this method: allow a large amount of multi-ion source solution (it may contain ammonium ion and/or also may contain chelating agent) contact in knockout tower with the part that the contains the aminoalkyl phosphonic acids-solid carrier compound of formula 1, this mixture flows through this knockout tower earlier, make desired ion that obtains (DI) and the part that the contains the aminoalkyl phosphonic acids-solid carrier compound complexing shown in following formula 2, receive liquid (RL) on a small quantity (as sulphur arteries and veins, NH with relief
4OH, Na
2S
2O
3, H
2SO
4, HCl, HI, HBr, NaI, ethylenediamine, Na
4The aqueous solution of EDTA, glycine etc.) flow through this knockout tower, it and the desired ion that obtains are generated than key link the stronger complex compound of the part that contains the aminoalkyl phosphonic acids on the solid carrier or generate than the stronger complex compound of the desired ion that obtains with the part that contains the aminoalkyl phosphonic acids that key is linked on the solid carrier.Use this method, as shown in Equation 3, the desired ion that obtains is taken knockout tower out of to put forward dense form in receiving solution.Carry dense degree and quantity obviously with source solution in the desired ion that obtains concentration and need the quantity of source solution of processing relevant.Used concrete reception liquid also is a factor.Unless other requirement is arranged, for removing the desired ion that obtains, it is specific that reception liquid there is no need, because other ions can not be complexed on the part.In general, concentration ratio the concentration in source solution of the desired ion that obtains in receiving liquid is high 20～1000000 times.Other equivalent equipment can be used to replace knockout tower, and for example slurries are filtered, and with receiving the liquid washing complex compound are decomposed then, reclaim the desired ion that obtains.Carry ion that the hope after dense obtains then with the recovery from receive mutually of various familiar methods.
The key that contains the aminoalkyl phosphonic acids is linked part on the solid carrier, and the example of the desired ion that obtains of strong affinity is arranged is lanthanide metal ion, Sb
3+, Zr
4+, Zn
2+, Pu
4+, Hf
4+, Cu
2+, Ni
2+, Fe
3+, Cd
2+, Ag
+And Hg
2+Here listed preferred ion is incomplete, and it only attempts to illustrate the type that can link the preferred ion that is connected the part that contains the aminoalkyl phosphonic acids on the solid carrier by above-mentioned mode key.Part has substantial connection to the compatibility of ion structure obvious and ion and part.Therefore, even in the listed in the above ion, to remove from listed other ions that specific ligand had a more weak affinity be possible on those ion selectivity ground that part is had strong affinity.Therefore, the composition by suitable selection coordination and source solution also might separate and carry the ion that dense a kind of hope obtains from another kind of ion.So term " ion that hope obtains " is relative with " undesirable ion ", it generally is " ion that hope obtains " that part is had the ion of strong compatibility.
Method of the present invention is particularly suitable under acid condition from also containing the Cu(II), the Ni(II), the Zn(II) and/or the Ag(I) source solution remove the Sb(III) ion.In these cases, be used to remove preferably 6M hydrochloric acid of reception liquid that key links the ion on the part.
Remove the desired ion that obtains with part-base complex
Following embodiment illustrates that key links part formula 1 compound that contains the aminoalkyl phosphonic acids of solid carrier and how to be used to carry dense and to remove the desired ion that obtains.The part solid carrier compound that contains the aminoalkyl phosphonic acids knockout tower of packing into.Contain the desired ion gun flow of solution that obtains and cross this knockout tower.Source solution is and the mixture of other undesirable ions and/or chelating agent that they have much higher concentration.By with pump on the top of knockout tower or bottom pressurization or can improve the flow velocity of solution in the method that receiving vessel vacuumizes.Source solution is by after the knockout tower, and the recovery solution of consumption much less (being the aqueous solution) flows through knockout tower, and reclaiming solution has stronger compatibility for the desired ion ratio part that obtains.This reception solution only contains the quilt that is useful on back one step recovery and carries the ion that dense hope obtains.The reception solution that is fit to can be selected from HCl, HBr, thiocarbamide, NaI, HI, NH
4OH, ethylenediamine, Na
4EDTA, H
2SO
4Na
2S
2O
3, glycine and composition thereof.The listed reception solution in front is some examples, also can use other to receive solution, and unique restriction is they remove the desired ion that obtains from the part that contains the aminoalkyl phosphonic acids a ability.Provide by the following examples that the part that contains the aminoalkyl phosphonic acids that the inorganic carrier key of 1～4 method preparation of describing connects separates and some examples of reclaiming ion as an illustration.These embodiment only are illustrative, do not comprise the separation of many ions that may carry out with the material of formula 1.But the separation of other desired ions that obtain can be undertaken by following embodiment, can be easy to determine the correct method or the step that will adopt for those skilled in the art that.
Embodiment 5
In this embodiment, the aminomethyl phosphonic acids parts knockout tower of packing into of 10 gram embodiment 1.70 ℃ following 100 milliliters in 2M sulfuric acid, contain the 290ppmSb(III), 60ppm Bi(III) and 30 grams per liter Cu(II) the source flow of solution cross this knockout tower.The aqueous solution at 70 ℃ of following 25 milliliters of 0.1M sulfuric acid flows through this knockout tower then, residual filling solution in the flush away tower.Use 20 milliliters 70 ℃ 6M hydrochloric acid flush away Sb then.Above-mentioned solution is composed (ICP) with inductive couple plasma and be the analysis showed that, originally the Sb(III more than 98% in above-mentioned 100 ml solns) receive in the solution at 20 milliliters.And the content that receives copper in the liquid is less than 1ppm, the Bi(III) content 3ppm only.
Embodiment 6
Use the diaminourea trimethyl phosphonic acids part of 10 gram embodiment 3, repeat the experiment of embodiment 4.Obtain identical result in fact.
Embodiment 7
In this embodiment, the diaminourea trimethyl phosphonic acids parts knockout tower of packing into of 2 gram embodiment 3.100 milliliters contain the 10ppmCu(II) and the source solution (pH value ≈ 6) of 0.1M NaCl flow through this knockout tower.5 milliliters of 1M aqueous hydrochloric acid solutions are as the Cu(II then) reception liquid flow through this knockout tower.Above-mentioned solution shows that with icp analysis originally the Cu more than 99% in above-mentioned 100 ml solns is in receiving solution.
Embodiment 8
This embodiment is identical with the foregoing description 7, and difference is to use the material of 2 gram embodiment 2.In fact obtain identical result.
Embodiment 9
In this embodiment, the parts knockout tower of packing into of 10 gram embodiment 1.100 milliliters contain 200ppm Zr(IV in 5M nitric acid) the source flow of solution cross this knockout tower.25 milliliters of 0.1M aqueous solution of nitric acid flow through this tower as washing then.25 milliliters of 0.3M Na then
4The EDTA aqueous solution flows through this tower and is used for collecting Zr.Above-mentioned solution shows that with icp analysis originally the Zr more than 99% in above-mentioned 100 ml solns is in receiving solution.
Can recognize that from these embodiment the formula that contains the aminoalkyl phosphonic acids 1 part that key is linked on the solid carrier (as silica gel) provides the material that is used for separating and carrying from these ions and the mixture of other metal ions dense this ion, as confirming above.This recovery even can in the presence of acid and/or complexing agent, finish.Interested ion can be used on the known standard technique of these material science then and reclaims from carry dense recovery solution.
Though the present invention is described and illustrates part that contains the aminoalkyl phosphonic acids and their using method that some the specific silica gel keys that belongs to formula 1 scope connects as a reference, those also belong to formula 1 scope the part that contains the aminoalkyl phosphonic acids, adopt identical separation and reclaim desired ion method other analogs also within the scope of the invention.So the present invention only is limited in the scope of following claim and function equivalent defined thereof.
Claims (34)
1, a kind of from multi-ion source solution carry dense, remove and the method for separating the desired ion that obtains, this source solution also can contain hydrogen ion and/or chelating agent, this method comprises,
(a) described have the multi-ion source solution of first volume to contact with the part that the contains the aminoalkyl phosphonic acids-solid carrier compound of following formula:
Wherein A and B are independently selected from O, NR and N (R) CH
2, wherein R and R ' are only
The derivative of aralkyl and aryl and replacement; R
1Be independently selected from H, SH, OH, low-carbon alkyl, aryl and aralkyl; C and d respectively are from 0 to about 10 integer; E and f respectively are from 1 to 10 integer; X is the interval base that following formula is arranged;
R wherein
2Be selected from H, SH, OH, low-carbon alkanes, aryl, aralkyl and substitutive derivative thereof; A is an integer of from 3 to about 10; B is 0 or 1; Y and Z independently are selected from C1, Br, I, alkyl, alkoxyl, substituted alkyl or substituted alkoxy and O-matrix; Matrix is selected from sand, silica gel, glass, glass fibre, aluminium oxide, zirconia, titanium oxide, nickel oxide or other hydrophilic inorganic carriers and composition thereof;
(b) source solution and described compound disengage, and the ion complexation that described hope obtains is to this compound;
(c) in the described complexing wish the ion obtain compound contact with the reception solution littler than described first volume, receive solution or the ion that described hope obtains is had the affinity higher than described compound, or the ion that described compound obtains than described hope there is higher affinity, described complex compound between the ion that described compound and described hope obtain is decomposed, and be recovered in the described reception solution of described smaller size smaller to carry the ion that dense form obtains hope.
2, according to the process of claim 1 wherein that the ion that the hope that will separate obtains is selected from Sb
3+, Zr
4+, Zn
2+, Pu
4+, Hf
4+, Cu
2+, Ni
2+, Fe
3+, Cd
2+, Ag
+, Bi
3+, Al
3+, Ga
3+, Hg
2+And group of the lanthanides.
3, according to the method for claim 2, R wherein
1For
4, according to the method for claim 3, wherein c and d are 0.
5, according to the method for claim 4, wherein f is 1, a is 3, and b is 0.
6, according to the method for claim 4, wherein f is 1, a is 3, and b is 1, R
2Be OH.
7, according to the method for claim 3, wherein C is 1, d is 0.
8, according to the method for claim 7, wherein A is NR.
9, according to the method for claim 8, R wherein
1Be H, R is
10, according to the method for claim 9, wherein f is 1, a is 3, b is 0.
11, according to the method for claim 9, wherein f is 1, a is 3, b is 1, R
2Be OH.
12, according to the method for claim 3, wherein c and d all be 1, R
1For H, A are that the described R of NR(is
B is that the described R of NR(is CH
2CH)
eN ((CH
2)
f-P(OH)
2)
2)
13, according to the method for claim 12, wherein e is 1, f is 1, a is 3, b is 0.
14, according to the method for claim 12, wherein e is 1, f is 1, a is 3, b is 1, R
2Be OH.
15, according to the method for claim 1, wherein said compound is contained in the packed tower, described multi-ion source solution at first flows through described packed tower, between ion that described hope obtains and described compound, generate complex compound, from described compound, decomposite the ion that described hope obtains subsequently, and cross described packed tower by described reception flow of solution and from described packed tower, remove the ion that described hope obtains, the ion that described hope obtains is recovered in the described reception solution to put forward dense form.
16, according to the method for claim 15, wherein said reception solution is any solution that can decompose the character of wishing the ion obtain from described compound that has.
17, according to the method for claim 3, Sb wherein
3+From also contain the multi-ion source solution that is selected from Cu, Ni, Zn and the undesirable ion of Ag, separate.
18, according to the method for claim 3, wherein a kind of Zr that is selected from
4+, Pn
3+And Hf
4+The ion that obtains of hope from also contain a large amount of alkali-metal multi-ion source solution, separate.
19, according to the method for claim 2, R wherein
1For H, c and d are 0, f is 1.
20, a kind of part that contains the aminoalkyl phosphonic acids-solid carrier compound of following formula:
Wherein A and B independently are selected from O, NR and N(R) CH
2, wherein R and R
1Independently be selected from
(CH
2) f-P(OH)
2, CH
2CH
2R
1, H, low-carbon alkyl, aralkyl, aryl and substitutive derivative thereof; R
1Independently be selected from H, SH, OH, low-carbon alkyl, aryl and aralkyl; C and d respectively are from 0 to about 10 integer; E and f respectively are from 1 to 10 integer; X is the interval base that following formula is arranged:
R wherein
2Be selected from H, SH, OH, low-carbon alkyl, aryl, aralkyl and substitutive derivative thereof; A is an integer of from 3 to about 10; B is 0 or 1; Y and Z independently are selected from Cl, Br, I, alkyl, alkoxyl, substituted alkyl or substituted alkoxy and O-matrix; Matrix is selected from sand, silica gel, glass, glass fibre, aluminium oxide, zirconia, titanium oxide, nickel oxide or other hydrophilic inorganic carriers and composition thereof.
21, according to the compound of claim 20, R wherein
1For
22, according to the compound of claim 21, wherein c and d are 0.
23, according to the compound of claim 22, wherein f is 1, and a is 3, b is 0.
24, according to the compound of claim 22, wherein f is 1, a is 3, b is 1, R
2Be OH.
25, according to the compound of claim 22, wherein c is 1, and d is 0.
26, according to the compound of claim 25, wherein A is NR.
27, according to the compound of claim 26, R wherein
1Be H, R is
28, according to the compound of claim 27, wherein f is 1, a is 3, b is 0.
29, according to the compound of claim 27, wherein f is 1, a is 3, b is 1, R
2Be OH.
30, according to the compound of claim 21, wherein c and d all be 1, R
1For H, A are the described R of NR(
The described R of NR(is CH
2CH)
eN ((CH
2)
f-P(OH)
2)
2)
31, according to the compound of claim 30, wherein e is 1, f is 1, a is 3, b is 0.
32, according to the compound of claim 30, wherein e is 1, f is 1, a is 3, b is 1, R
2Be OH.
33, according to the compound of claim 20, R wherein
1Be H.
34, according to the compound of claim 33, wherein c and d are 0, f is 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114641A CN1041694C (en) | 1992-12-19 | 1992-12-19 | Aminolkylphosphonic acid containing ligands attached to solid supports for removal of metalions. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114641A CN1041694C (en) | 1992-12-19 | 1992-12-19 | Aminolkylphosphonic acid containing ligands attached to solid supports for removal of metalions. |
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| CN1041694C CN1041694C (en) | 1999-01-20 |
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ID=4947032
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049695C (en) * | 1994-07-28 | 2000-02-23 | 北京大学 | Method for purifying noble metal with double function extracting agent containing nitrogen and phosphorus |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN108866359A (en) * | 2018-07-24 | 2018-11-23 | 中国工程物理研究院核物理与化学研究所 | A kind of extracting method of actinides |
| CN109621883A (en) * | 2018-12-24 | 2019-04-16 | 中国环境科学研究院 | Zirconium dioxide loaded and ferroso-ferric oxide tubulose nano titania composite S b adsorbent and its preparation method and application |
| CN111278999A (en) * | 2017-06-08 | 2020-06-12 | 城市采矿有限公司 | Method for recovering lithium |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650784A (en) * | 1986-02-20 | 1987-03-17 | J. T. Baker Chemical Company | Bonded phase of silica for solid phase extraction |
| US4786628A (en) * | 1987-03-09 | 1988-11-22 | Aluminum Company Of America | Chromatographic packings comprising metal oxide/hydroxide reacted with phosphonic acid |
| US4957890A (en) * | 1986-12-29 | 1990-09-18 | Aluminum Company Of America | Surface treated permeable inorganic membranes and method of making same |
| US4767670A (en) * | 1987-01-21 | 1988-08-30 | E. I. Du Pont De Nemours And Company | Chromatographic supports for separation of oligonucleotides |
| US4876232A (en) * | 1987-09-28 | 1989-10-24 | Pedro B. Macedo | Supported heteropolycyclic compounds in the separation and removal of late transition metals |
-
1992
- 1992-12-19 CN CN92114641A patent/CN1041694C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049695C (en) * | 1994-07-28 | 2000-02-23 | 北京大学 | Method for purifying noble metal with double function extracting agent containing nitrogen and phosphorus |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN106964318B (en) * | 2017-03-17 | 2019-08-02 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN111278999A (en) * | 2017-06-08 | 2020-06-12 | 城市采矿有限公司 | Method for recovering lithium |
| CN108866359A (en) * | 2018-07-24 | 2018-11-23 | 中国工程物理研究院核物理与化学研究所 | A kind of extracting method of actinides |
| CN108866359B (en) * | 2018-07-24 | 2020-11-03 | 中国工程物理研究院核物理与化学研究所 | Method for extracting actinide elements |
| CN109621883A (en) * | 2018-12-24 | 2019-04-16 | 中国环境科学研究院 | Zirconium dioxide loaded and ferroso-ferric oxide tubulose nano titania composite S b adsorbent and its preparation method and application |
| CN109621883B (en) * | 2018-12-24 | 2019-09-27 | 中国环境科学研究院 | Zirconium dioxide loaded and ferroso-ferric oxide tubulose nano titania composite S b adsorbent and its preparation method and application |
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