CA2007311C - Process of removing and concentrating desired ions from solutions thereof - Google Patents
Process of removing and concentrating desired ions from solutions thereof Download PDFInfo
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- CA2007311C CA2007311C CA002007311A CA2007311A CA2007311C CA 2007311 C CA2007311 C CA 2007311C CA 002007311 A CA002007311 A CA 002007311A CA 2007311 A CA2007311 A CA 2007311A CA 2007311 C CA2007311 C CA 2007311C
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- 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
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Abstract
The process of the invention comprises removing and concentrating certain ions, such as the transition metal ions, from solutions thereof admixed with other ions which may be present in much higher concentrations by forming a complex of the desired ion(s) with a compound (see formula I) wherein B and D are each a radical selected from the group consisting of N(R3), N(R3)CH2, O. OCH2, S and SCH2, with the further proviso that if B is selected from the group consisting of O, OCH2, S and SCH2, then D must be selected from the group consisting of N(R3) and N(R3)CH2 ; E is a radical selected From the group consisting of H, NH(R3), SH, OH, lower alkyl, and N(R3)(CH2CH(R1)CH2O] b(CH2)a SiYZ(O-matrix)]; Y and Z are radicals selected from the group of Cl, OCH3, OC2H5, methyl, ethyl and halogenated substituents thereof, and O-matrix; R1 is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl such as phenyl, naphthyl and pyridyl; R2 is a radical selected from the group consisting H and lower alkyl; R3 is a radical selected from the group consisting of H, lower alkyl and aryl such as phenyl, naphthyl and pyridyl; a is 2 to about 10; b is 0 or 1; c is 1 to about 2000; d is 0 to about 2000;
and where matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania. The complex which is formed is then broken by contacting a receiving liquid with the complex to remove and concentrate the desired ion(s) in solution in the receiving liquid. The concentrated ions can then be analyzed or recovered from the receiving liquid using well known procedures.
and where matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania. The complex which is formed is then broken by contacting a receiving liquid with the complex to remove and concentrate the desired ion(s) in solution in the receiving liquid. The concentrated ions can then be analyzed or recovered from the receiving liquid using well known procedures.
Description
PRESS OF RE~10VING AND CONCENTRATING DESIRED IONS FROM
SOLUTIONS THEREOF
INTRODUCTI ON
The process of the present invention comprises removing and concentrating certain ions, such as the transition metal ions, from solutions thereof admixed with other ions which may be present in much higher concentrations. A complex of the desired ion: is formed with a compound comprising an amine-containing hydrocarbon covalently bonded to an inorganic ma tri.x;. The complex can be formed by flowing such solutions through a chromatography column packed with the compound. The complex, is then broken to recover the desired ions. This can be done by flowing a receiving liquid in much smaller volume irhan the: volume of solution passed through the column to remove' and concentrate the desired ions in solution in the receivinc; liquid. The receiving liquid may then be analyzed by knovJn methods, and the desired ions may be recovered from .Lt.
The amine-containing intermediates covalently bonded to an inorganic :mai~rix, e.g., sand, silica gel, glass, glass fibers, alumina" nickel oxide, zirconia, titania and the like, which are used to separate the desired ions are shown by the structural formula (1>.
SOLUTIONS THEREOF
INTRODUCTI ON
The process of the present invention comprises removing and concentrating certain ions, such as the transition metal ions, from solutions thereof admixed with other ions which may be present in much higher concentrations. A complex of the desired ion: is formed with a compound comprising an amine-containing hydrocarbon covalently bonded to an inorganic ma tri.x;. The complex can be formed by flowing such solutions through a chromatography column packed with the compound. The complex, is then broken to recover the desired ions. This can be done by flowing a receiving liquid in much smaller volume irhan the: volume of solution passed through the column to remove' and concentrate the desired ions in solution in the receivinc; liquid. The receiving liquid may then be analyzed by knovJn methods, and the desired ions may be recovered from .Lt.
The amine-containing intermediates covalently bonded to an inorganic :mai~rix, e.g., sand, silica gel, glass, glass fibers, alumina" nickel oxide, zirconia, titania and the like, which are used to separate the desired ions are shown by the structural formula (1>.
i 2 z Matrix-O Si-(CHZ)a(OCHZCHCHZ)b(BCHCH2)~(D HCHZ)dE (1) I
Z
In formula ( 1 ) , B and D are each a radical selected from the group consisting of N (R3) , N (R3) CHz, O and OCH2, with the proviso that at least one of B anal D must be selected from the group consisting of N (R3) .and N (R3) CHZ;
E is a radical selected from the group consisting of H, NH (R3) , SH, OH, lower alkyl, and N (R3) [CH2CH (Rl) CH20] b (CHZ) aSiYZ (O-matrix) ] ;
Y and Z are each a radical selected from the group of C1, OCH3, OCZHS, metY;uyl, ethyl and halogenated substituents thereof, and 0-matrix;
Rl is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl such as phenyl, naphthyl and pyridyl;
RZ is a radical selected from the group consisting of H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl such as phenyl, naphthyl and pyridyl;
a is 2 to about 10;
b is 0 or 1;
c is 1 to about 2000;
Z
In formula ( 1 ) , B and D are each a radical selected from the group consisting of N (R3) , N (R3) CHz, O and OCH2, with the proviso that at least one of B anal D must be selected from the group consisting of N (R3) .and N (R3) CHZ;
E is a radical selected from the group consisting of H, NH (R3) , SH, OH, lower alkyl, and N (R3) [CH2CH (Rl) CH20] b (CHZ) aSiYZ (O-matrix) ] ;
Y and Z are each a radical selected from the group of C1, OCH3, OCZHS, metY;uyl, ethyl and halogenated substituents thereof, and 0-matrix;
Rl is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl such as phenyl, naphthyl and pyridyl;
RZ is a radical selected from the group consisting of H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl such as phenyl, naphthyl and pyridyl;
a is 2 to about 10;
b is 0 or 1;
c is 1 to about 2000;
3 pp~11 d is 0 to about 2000; and Matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania.
Preferred values are: Matrix is silica gel or titanized silica gel; a is 3; b is 1; c is 1 to 5; d is 0; R1 is OH; R2 is H; R3 is H,; B is NH; E is NHCH2CH (OH) CH20 (CH2) 3Si (0-silica gel) 3 or NHCHZCH (OH) CH20 (CHz) 3Si (O-titanized silica gel) 3, provided that when Matrix is silica gel, then E is NHCH2CH (OH) CH20 (CH2) 3Si (0-silica gel) 3 and when Matrix is titanized silica gel., then E is NHCHzCH (OH) CHZO (CHZ) 3Si (O-titanized silica gel.); and Y and Z are each selected from O-silica gel, O-titani.zed silica gel and OCH3, provided that when Matrix is silica gel., then Y and Z are each O-silica gel or OCH3 and when Matrix is titanized silica gel, then Y and Z are each O-titanized silica gel or OCH3.
The compounds of formula (1) can be used in a~novel process of selectively and quantitively removing and concentrating a selE:cted ion or group of ions of the transition metal type, e.g., copper, silver, mercury, lead, zinc, and other transition metals, present at low concentrations from a plurality of other ions in a multiple ion solution in which the other ions may be present at much higher concentrations.
Preferably, those transition metal ions are Cu(II), Pb(II), Ag(I) , Ru(III) , Pd(II) , Ir(III) , Zn(II) , Rh(II) , Cd(II) , Hg (II) , Os (II) , Mn (.CI) , Au (I) , Au (II) , Pt (II) , Pt (IV) , Co (III) , Co(II), Cr(II) and Cr(III). The process comprises bringing the multiple ion solution into contact with a compound of formula (1) to complex the desired ions) with the compound and breaking the comple:~ with a. receiving liquid to render the ions) soluble in the receiving solution in a concentrated from. The receiving liquid may then be analyzed by known A
69912-188 ~ ~ 7-1 1 g 3a methods, or the ions) may be recovered therefrom by known methods. The preferred embadiment disclosed herein involves carrying out the process by bringing a large volume of the multiple ion solution into contact with a compound of formula (1) of the invention in a separation column. The multiple ion solution flows through the column and the desired ion or ions form a complex with the compound of formula (1). A smaller volume of a receiving liquid such as dilute aqueous hydrochloric or nitric acids for example, is then passed through the column to break the complex by chemical or thermal means. The receiving liquid further dissolves the desired ions and carries them out of the column in a concentrated form.
Instead of using a column, the compound of formula (1) may be slurries in a suitable liquid such as water. The multiple ion mixture can be present in the slurrying liquid or subsequently added to the slurry, the A
~,.
Preferred values are: Matrix is silica gel or titanized silica gel; a is 3; b is 1; c is 1 to 5; d is 0; R1 is OH; R2 is H; R3 is H,; B is NH; E is NHCH2CH (OH) CH20 (CH2) 3Si (0-silica gel) 3 or NHCHZCH (OH) CH20 (CHz) 3Si (O-titanized silica gel) 3, provided that when Matrix is silica gel, then E is NHCH2CH (OH) CH20 (CH2) 3Si (0-silica gel) 3 and when Matrix is titanized silica gel., then E is NHCHzCH (OH) CHZO (CHZ) 3Si (O-titanized silica gel.); and Y and Z are each selected from O-silica gel, O-titani.zed silica gel and OCH3, provided that when Matrix is silica gel., then Y and Z are each O-silica gel or OCH3 and when Matrix is titanized silica gel, then Y and Z are each O-titanized silica gel or OCH3.
The compounds of formula (1) can be used in a~novel process of selectively and quantitively removing and concentrating a selE:cted ion or group of ions of the transition metal type, e.g., copper, silver, mercury, lead, zinc, and other transition metals, present at low concentrations from a plurality of other ions in a multiple ion solution in which the other ions may be present at much higher concentrations.
Preferably, those transition metal ions are Cu(II), Pb(II), Ag(I) , Ru(III) , Pd(II) , Ir(III) , Zn(II) , Rh(II) , Cd(II) , Hg (II) , Os (II) , Mn (.CI) , Au (I) , Au (II) , Pt (II) , Pt (IV) , Co (III) , Co(II), Cr(II) and Cr(III). The process comprises bringing the multiple ion solution into contact with a compound of formula (1) to complex the desired ions) with the compound and breaking the comple:~ with a. receiving liquid to render the ions) soluble in the receiving solution in a concentrated from. The receiving liquid may then be analyzed by known A
69912-188 ~ ~ 7-1 1 g 3a methods, or the ions) may be recovered therefrom by known methods. The preferred embadiment disclosed herein involves carrying out the process by bringing a large volume of the multiple ion solution into contact with a compound of formula (1) of the invention in a separation column. The multiple ion solution flows through the column and the desired ion or ions form a complex with the compound of formula (1). A smaller volume of a receiving liquid such as dilute aqueous hydrochloric or nitric acids for example, is then passed through the column to break the complex by chemical or thermal means. The receiving liquid further dissolves the desired ions and carries them out of the column in a concentrated form.
Instead of using a column, the compound of formula (1) may be slurries in a suitable liquid such as water. The multiple ion mixture can be present in the slurrying liquid or subsequently added to the slurry, the A
~,.
desired ions) complex with the compound of formula (1> in the slurry, and t:he slurry is then filtered. The resulting solids are washed with a receiving solution to break the complex and recover the desired ions) in the receiving liquid. The desired ions may then be analyzed by known methods, or recovered from the receiving phase by well known procedures.
In a particularly preferred embodiment of the pracess the bonded matrix-amine compound of formula (1) is placed in a contacting device' such as a tall column. The multiple ion mixture is passed th rough the column with the desired ions from the multiple ion mixture forming a complex with the bonded matrix to separate the desired ions from the rest of the mixture which flows out of the column . A small volume of the receiving liquid is thereafter passed through the column to break the complex as well as to dissolve and carry out of the column the dEaired i.on(s) . The desired ions may then be analyzed by known methods such as atomic absorption spectroscopy. In addition, the ions) can be recovered from the receiving liquid by well known procedures.
BACKGROIJ~ND OF THE IN(iENTION
The fact is known that amine-containing hydrocarbon ligands present as solutes in a solvent such as water are characterized by their ability to selectivity form strong bonds with the transition metal ions or groups of these ions present as solutes in the same solvent as described in a book by R.M. Smith and A.E. Martell, CRITICAL STABILITY CONSTANTS
VOL. 2: AMINES, Plenum Press, New York, 1975, pp. 1-401.
However, researchers have not previously been able to effectively incorporate amine-containing hydrocarbon ligands into separation ~;ystems where the behavior of the amine-containing ligands in the separation systems in comparison to that of the amine-containing ligand as a solute is unchanged and/or the amine-containing ligand will remain in the separation system for repeated separations of cations.
Articles such as those entitled SILANE COMPOUNDS FOR
SILYLATING SURFACES by E.P. Plueddemann, in "Silanes, Surfaces and Interfaces Symposium, Snowmass, 1985,'° Ed. by D.E. Leyden, Gor~ion and Breach, Publishers, 1986, pp. 1-25 and SILANE COUPL~CNG AGENTS by E. P. Plueddemann, Plenum Press, 1982, pp. 1-235 :gist many different types of organic materials which raave been attached to silane compounds and discusses some oi: their properties. The preparation and uses of amine-containLng hydrocarbons attached to silane or silica through a hydrocarbon linkage is discussed. The structures reported in those publications contained only aminopropyl and ethylene diamino~?ropyl groups [ formula ( 1 > where a is 3 , b is 0, c is 0 or l, d is 0, B is NH, D is not present, E is H or NH2 and R2 is H]. These: latter compounds were used to complex copper ions.
E.P. Plueddemann in METAL EXTRACTION FROM SOLUTION AND
IMMOBILIZED CHELATING At~ENTS USED THEREFORE, Canadian Patent number 1,196,618 of November 12, 1985 reported th a preparation of a variety of amine-containing silica gel materials. These materials were made by ffirst reacting chloropropyltrime:thoxysilane with the amine forming a trimethoxysilane containing the amine function which was coated onto silica gel and heated to effect a covalent attachment of the amine to the silica gel. The resulting compound had the amine function three carbon atoms removed f rom sil ica . These materials do complex and thus remove heavy metals. Hc~aever, these types of aminopropyl functions are not completely stable as discussed in the next paragraph.
The Plueddeman:n Canadian patent lists other references concerning the same type of silica gel-bound amine complexing materials.
It is a known fact that amine functional groups attached to silica gel, where the amine function is three carbon atoms removed from th a sil ica gel , are not completely stable . E. P.
Plueddemann, in t:he above mentioned article in the book edited by D.E. Leyden, reported that his amine materials (amine group three atoms removed from silane) slowly lost their ability to complex. copper II. D.~i. Wonnacott and E.V.
Patton in HYDROL'tTIC ST1~,BILITY OF AMINOPROPYL STATIONARY
PHASES USED IN TFiE SIZ E-EXCLUSI ON CHR~lATOGRAPHY OF CATIONIC
POLYi~tERS, Journal of Chromatography, vol. 389, pp. 103-113 (1987) and T.G. Z~addell, D.E. Leyden and M.T. DeBello in THE
NATURE OF ORGANOSILANE TO SILICA-SURFACE BONDING, Journal of Americal Chemica:L Society, vol. 103, pp. 5303-5307 (1981) discuss the stability of the aminopropyl-silica gel types of materials . In the conclusion to the ~lonnacott and Patton article it is stated that "aminoalkyl silanes which have been used extensively in the .synthesis of silica-based, weak ion exchangers do not lend tizemselves to this type of chromatography du'e to their hydrolytic instability."
Bonded silica gel phase supports containing amine functions have been prepared by reacting the amine with 3-glycidoxypropylsilane :bonded to silica gel. S.H. Chang, K.M. Gooding and F.E. Regnier in USE OF OXIRANES IN THE
PREPARA'I°ION OF Bt>NDED PHASE SUPPORTS, Journal of Chromatography, v~ol. 120, pp. 321-333 (i976) and M-A Bagnoud, J-L Veuthey and Ht. Haerdi in INTERACTIONS SILICE METALLIQUE-SOLUTE: POSSIBII'ITE d'APPLICATIONS en PRECONCENTRATION et en CiHROMAOGRAPHIE d'ECHANGE de LIGANDS (LEC)r ChimiCa, VOl. 40, pp. 432-434 (190E~) have reacted amines with 3-glycidoxypropyl-bonded silica gel. Chang, Gooding and Regnier reported on four such compounds prepared from diethylamine [farmula (1>, where a is 3, b is l, c and d is 0, R1 is OH, and E is N (ethyl)2], dimethylaminoethanol [formula (1), where a is 3, b is 1, c is 1, d is 0, B is O, R1 is OH, R2 is H, E is N (methyl)2], diethylaminoethanol [same as the previous structure except N(ethyl)2 at the end], and polyethyleneamine [formula (1>, same as previous formula except c is a lai.-ge number and E is NH2]. These materials were used to separate proteins but not metal cations.
Bagnoud, Veuthey and Haerdi prepared a compound from a cyclic tetraamine (cyclam) which does not have a structure similar to the si:ructurea of f figure ( 1 ) . Thi s material was used to bind metal ions and the bound metallic material was used in liquid exchange chromatography to separate certain organic compound:. In neither of these studies were metal ions separated and recovered. 'There is a particular need in modern society to (1) measure the concentrations of heavy metal rations in the low part per billion (PPB) concentration, (;2> remove low levels of toxic heavy metal ions from solut ions such as potable water, and (3) recover valuable metal ions pre~~ent in solution at low levels. For example the allowable amounts of lead, mercury, cadmium and silver ions in d:rin~ing water are in th a low PPB levels.
Present methods for ana7_ysis of these rations are not accurate at those levels without time consuming methods to concentrate the ~~ations up to the low part per million level.
Furthermore, removal of the metals is not selective, but is expensive and equipment intensive using present methods.
Thus, the comple:xing properties of hydrolytically stable amine-containing hydrocarbon ligands attached to an inorganic support such as silica c;el or titanized silica gel are of the utmost importance for the repeated separation and concentration of certain heavy metal rations for analysis and/or recovery purposes . The process of the present invention using the amine-containing materials of formula (1) accomplish this fea t.
In a particularly preferred embodiment of the pracess the bonded matrix-amine compound of formula (1) is placed in a contacting device' such as a tall column. The multiple ion mixture is passed th rough the column with the desired ions from the multiple ion mixture forming a complex with the bonded matrix to separate the desired ions from the rest of the mixture which flows out of the column . A small volume of the receiving liquid is thereafter passed through the column to break the complex as well as to dissolve and carry out of the column the dEaired i.on(s) . The desired ions may then be analyzed by known methods such as atomic absorption spectroscopy. In addition, the ions) can be recovered from the receiving liquid by well known procedures.
BACKGROIJ~ND OF THE IN(iENTION
The fact is known that amine-containing hydrocarbon ligands present as solutes in a solvent such as water are characterized by their ability to selectivity form strong bonds with the transition metal ions or groups of these ions present as solutes in the same solvent as described in a book by R.M. Smith and A.E. Martell, CRITICAL STABILITY CONSTANTS
VOL. 2: AMINES, Plenum Press, New York, 1975, pp. 1-401.
However, researchers have not previously been able to effectively incorporate amine-containing hydrocarbon ligands into separation ~;ystems where the behavior of the amine-containing ligands in the separation systems in comparison to that of the amine-containing ligand as a solute is unchanged and/or the amine-containing ligand will remain in the separation system for repeated separations of cations.
Articles such as those entitled SILANE COMPOUNDS FOR
SILYLATING SURFACES by E.P. Plueddemann, in "Silanes, Surfaces and Interfaces Symposium, Snowmass, 1985,'° Ed. by D.E. Leyden, Gor~ion and Breach, Publishers, 1986, pp. 1-25 and SILANE COUPL~CNG AGENTS by E. P. Plueddemann, Plenum Press, 1982, pp. 1-235 :gist many different types of organic materials which raave been attached to silane compounds and discusses some oi: their properties. The preparation and uses of amine-containLng hydrocarbons attached to silane or silica through a hydrocarbon linkage is discussed. The structures reported in those publications contained only aminopropyl and ethylene diamino~?ropyl groups [ formula ( 1 > where a is 3 , b is 0, c is 0 or l, d is 0, B is NH, D is not present, E is H or NH2 and R2 is H]. These: latter compounds were used to complex copper ions.
E.P. Plueddemann in METAL EXTRACTION FROM SOLUTION AND
IMMOBILIZED CHELATING At~ENTS USED THEREFORE, Canadian Patent number 1,196,618 of November 12, 1985 reported th a preparation of a variety of amine-containing silica gel materials. These materials were made by ffirst reacting chloropropyltrime:thoxysilane with the amine forming a trimethoxysilane containing the amine function which was coated onto silica gel and heated to effect a covalent attachment of the amine to the silica gel. The resulting compound had the amine function three carbon atoms removed f rom sil ica . These materials do complex and thus remove heavy metals. Hc~aever, these types of aminopropyl functions are not completely stable as discussed in the next paragraph.
The Plueddeman:n Canadian patent lists other references concerning the same type of silica gel-bound amine complexing materials.
It is a known fact that amine functional groups attached to silica gel, where the amine function is three carbon atoms removed from th a sil ica gel , are not completely stable . E. P.
Plueddemann, in t:he above mentioned article in the book edited by D.E. Leyden, reported that his amine materials (amine group three atoms removed from silane) slowly lost their ability to complex. copper II. D.~i. Wonnacott and E.V.
Patton in HYDROL'tTIC ST1~,BILITY OF AMINOPROPYL STATIONARY
PHASES USED IN TFiE SIZ E-EXCLUSI ON CHR~lATOGRAPHY OF CATIONIC
POLYi~tERS, Journal of Chromatography, vol. 389, pp. 103-113 (1987) and T.G. Z~addell, D.E. Leyden and M.T. DeBello in THE
NATURE OF ORGANOSILANE TO SILICA-SURFACE BONDING, Journal of Americal Chemica:L Society, vol. 103, pp. 5303-5307 (1981) discuss the stability of the aminopropyl-silica gel types of materials . In the conclusion to the ~lonnacott and Patton article it is stated that "aminoalkyl silanes which have been used extensively in the .synthesis of silica-based, weak ion exchangers do not lend tizemselves to this type of chromatography du'e to their hydrolytic instability."
Bonded silica gel phase supports containing amine functions have been prepared by reacting the amine with 3-glycidoxypropylsilane :bonded to silica gel. S.H. Chang, K.M. Gooding and F.E. Regnier in USE OF OXIRANES IN THE
PREPARA'I°ION OF Bt>NDED PHASE SUPPORTS, Journal of Chromatography, v~ol. 120, pp. 321-333 (i976) and M-A Bagnoud, J-L Veuthey and Ht. Haerdi in INTERACTIONS SILICE METALLIQUE-SOLUTE: POSSIBII'ITE d'APPLICATIONS en PRECONCENTRATION et en CiHROMAOGRAPHIE d'ECHANGE de LIGANDS (LEC)r ChimiCa, VOl. 40, pp. 432-434 (190E~) have reacted amines with 3-glycidoxypropyl-bonded silica gel. Chang, Gooding and Regnier reported on four such compounds prepared from diethylamine [farmula (1>, where a is 3, b is l, c and d is 0, R1 is OH, and E is N (ethyl)2], dimethylaminoethanol [formula (1), where a is 3, b is 1, c is 1, d is 0, B is O, R1 is OH, R2 is H, E is N (methyl)2], diethylaminoethanol [same as the previous structure except N(ethyl)2 at the end], and polyethyleneamine [formula (1>, same as previous formula except c is a lai.-ge number and E is NH2]. These materials were used to separate proteins but not metal cations.
Bagnoud, Veuthey and Haerdi prepared a compound from a cyclic tetraamine (cyclam) which does not have a structure similar to the si:ructurea of f figure ( 1 ) . Thi s material was used to bind metal ions and the bound metallic material was used in liquid exchange chromatography to separate certain organic compound:. In neither of these studies were metal ions separated and recovered. 'There is a particular need in modern society to (1) measure the concentrations of heavy metal rations in the low part per billion (PPB) concentration, (;2> remove low levels of toxic heavy metal ions from solut ions such as potable water, and (3) recover valuable metal ions pre~~ent in solution at low levels. For example the allowable amounts of lead, mercury, cadmium and silver ions in d:rin~ing water are in th a low PPB levels.
Present methods for ana7_ysis of these rations are not accurate at those levels without time consuming methods to concentrate the ~~ations up to the low part per million level.
Furthermore, removal of the metals is not selective, but is expensive and equipment intensive using present methods.
Thus, the comple:xing properties of hydrolytically stable amine-containing hydrocarbon ligands attached to an inorganic support such as silica c;el or titanized silica gel are of the utmost importance for the repeated separation and concentration of certain heavy metal rations for analysis and/or recovery purposes . The process of the present invention using the amine-containing materials of formula (1) accomplish this fea t.
SUMMARY' OF TfiE IIIe11~7ENTION
The process of the present invention uses compounds of formula (1) having the amine-containing hydrocarbon ligand covalently bonded to an inorganic support, e.g. sand, or silica gel, glasa, glass fibers, alumina, nickel oxide, zirconia or titanic. The compounds of formula (1), are characterized by high selectivity for and removal of desired metal ions or groups of metal ions such as the transition metal ions present at low concentrations from the source phase containing a mixture of these metal ions with other ions. The ions which are not desired to be removed may be present in much greater concentrations in the solution than the metal ions which area to be removed. The process of the present invention comprises selectively removing and concentrating ths~ desired ions) and is characterized by the abil ity to quantitatively complex from a large volume of solution the desired ions) when they are present at low concentrations. The desired ions are complexed with a compound of formvala (1) when brought into contact with such compound. For dais purpose, the solution from which the desired ions are to be i:emoved is passed th rough a column containing the compound of formula (1) . The desired ions are then recovered from the separation column by flowing through it a small volume of a receiving phase which contains a solubilized reagent which need not be selective, but which will strip the ions from the ligand quantitatively. The analysis of the desired metal ions in the concentrated IO
solution is accomplished by known methods such as atomic absorption spectroscopy. The recovery of the desired metal ions from the re<:eiving phase is easily accomplished by well known procedures" The process for producing the compounds of formula (1) will be mentioned but is not a part of the present invention.
BR:CEF DESC',RIPTION OF THE DRAWINGS
The invention will be described and illustrated by reference to a drawing in which Fig. 1 represents schematically a suitable column for holding the matrix bonded amine-containing hydrocarbon ligand material through which a solution of metal ions can be flowed to complex selectively with a desired ion or group of ions in accordance with 'the invention.
DESCRIPTION OE' THE PREFERRED EMBODIMENT OF THE INVENTION
The preferred embodinnent of the ion-recovery process of the invention utilizes t_he compounds represented by f~rmula (1). The process of producing these new compounds is not an aspect of the present invention but will be mentioned briefly here.
Amine-containing hydrocarbon ligands are covalently bonded to the inorganic support. For example, the inorganic support such as silica gel is first heated with 3-glycidoxy-propyltrimethoxysilane to produce a 3-glycidoxypropyl-bound silica gel. 'his gel i s then heated with the appropriate amine to effect a covalent bond as shown in equation (2).
The nature of thE~ amine will determine what B, D, E and R2 are in formula (1).
O
\ Sil ica Gel (CH30) 3Si (CHZ) 30CH2---CH--CH2 heat O R1~H or R ~1H
/ \ 2 2 (2) (Silica Gel-O) 3S:i (CI~2 ) 3C~H~-CH~--CH2 heat (Silica Gel-O)3S:i(CH2>3C~H~CH(OH>CHZ-L~HR or NRZ
The following examples are given to illustrate two representative c~~mpound~~ which have been made in accordance with formula (1) of the present invention. Other amine-containing hydrocarbons bonded to an inorganic support were and can be made in the Name manner.
3a Example 1 In this example, an amine-containing hydrocarbon bonded to a silica gel Haas made corresponding to a compound of formula (1) wherein a is 3, b is 1, c is 5, d is 0, R1 is hydroxy, R2 is hydrogen,, B is 1VH, D is not present since d i~
J, E is NHCH2CH(OH)CH20(CH2)3Si(O-silica gel)3, and Y and Z
are ~-silica gel groups.
Silica gel ( 60-200 mesh ) ( 1. 6 kilograms ) was suspended in 7 liters of toluene which contained 304 grams of 3-glycidoxy-propyltrimethoxy~~ilane. The gel was stirred slowly to insure that the c~el was not physically damaged, and the mixture was heatE:d at 100oC for 8 to 18 hours. Then, 175 to 225 grams of pent.aetnylenehexaamine was slowly added and the mixture was slowly stirred for 5-10 hours while maintaining a temperature of lCiO°C. The solvent was filtered and the solid amine-bound silk°a gel was dried in air in a well ventilated hood.
Example 2 In this example, an amine-containing hydrocarbon bonded to titanized sil~_ca gel was made corresponding to a compound of formula (1) wherein a is 3, b is 1, c is 5, d is 0, R1 is hydroxy, R2 is hydrogen, B is NH, D is not present, E is NHCH2CH(OH)CH20(CH2)3Si(O-Titanized Silica gel)3, and Y and Z
are O-Titani zed Sil ica gel groups .
The titanized silica gel was first prepared by suspending 60-200 Mesh sili<:a gel (50g) in 200 ml of dry toluene.
TetraisopropoxytLtanium ( 20 ml ) was slowly added to the stirred reaction mixture. Heat wa s evolved. The resulting mixture was allovued to ~>tand for 16 hours and f filtered . The residue was washed successively with 100 ml of toluene, 100 ml of methanol and 100 ml. of water and allowed to air dry at room temperature. The overall weight of the silica gel ~~~c~~~
increased to 52.5 g resulting in 1.25 mmoles of Ti02 per gram of material.
Pentaethylenekiexaamin.e was attached to the titanized silica gel in they same manner as in Example 1 using 20 g of titanized silica gel and 4 ml of 3-glycidoxypropyl-trimethoxysilane in 50 ml of toluene to give the 3-glycidoxy-propyl-titanized silica gel material, and then 10 g of this latter titanized silica gel was reacted with 3 ml of pentaethylenehex<~amine i.n 50 ml of refluxing methanol for 1 hour .
I~iETAL ICDN RECOVERY AND CONCENTRATION PROCESS
The metal ion recovery and concentration process of the invention relates to the selective recovery of desired metal ions from mixtures thereof with other metal ions using the compounds of formula (la of the invention as defined above.
Effective method of recovery and/or separation of metal ions, particular:Ly the transition metal ions, from other metal ions in water supplies, waste solutions, deposits and industrial solutions and silver recovery from waste solutions, e.g., from emulsions on photographic and X-ray film, represent a real need in modern technology. These ions are typically present at low concentrations in solutions containing other ions at much greater concentrations.
Likewise there is a need to concentrate these metal ions so that an effective analysis using well known methods such as atomic absorption spectroscopy can be carried out. Hence, ~~~a~~.~
there is a real need for a process to selectively recover and concentrate these metal ions. The present invention accomplishes thi:> separation and concentration effectively and ef f is iently by th a use of compounds selected f rom th a families represented by formula (1>.
The amine-containing inorganic matrix material of formula (1) is placed in a column as shown in Figure 1. An aqueous solution contain~_ng the desired ion or ions, in a mixture of other ions which may be in a much greater concentration, is passed through the column. The flow rate for the solution may be increased by applying pressure (with a pump) on the top of the column or ap~)lying a vacuum in the receiving vessel. After the solution has passed through th a column, a much smaller volume of a. recovery solution, i.e. an aqueous acid solution, which will protonate the amine groups of the ligands thereby _celeasir.~g the metal ions, i.s passed through the column. This receiving solution contains only the desired metal ions in a concentrated form for subsequent ana lys is and/or :recovery .
2(l The following examplEa of separations and recoveries of transition metal ions by the inorganic support-bound amine-containing materials of Examples 1 and 2 and materials prepared in a similar manner are given as illustrations.
These examples are illu:atrative only, and are not comprehensive of th a many separations of transition metal ions that are possible using the materials of formula (1) .
Example 3 In this example, 2 grams of the silica gel-bound arnine-containing hydrocarbon of Example 1 was placed in a column as shown in Figure 1.. A 500 ml solution of about 10 ppm of Cu2+
in 0.1 M aqueous MgCl2 was passed through the column using a vacuum pump at 6~I0 torr to increase the flow rate. A 10 ml aqueous solution of 1 M HC1 was passed through the column.
An analysis of the recovery solution by atomic absorption spectroscopy (AA,'~ snowed that greater than 99~ of the copper II ions original7_y in the 500 ml copper II solution was in the 10 ml recovery solution.
Example 4 The experiment: of Example 3 was repeated with about 1 ppm of Cd2+ in an aqueous solution of 0.1 M MgCl2. Again, greater than 99~ of the Cd2+ ion in the original solution was found in the recovery solution.
Example 5 The experimeni~ of Example 3 was repeated with about 13 ppm of Hg2+ in an aqueous solution of 0.1 M Mg3r2. In this case, 42~ of the Hg2+ ion in the original solution was found in the recovery :~olutior~.
Example 6 In this example, the titanized silica gel-amine material of Example 2 was used to separate 10 ppm Cu2+ in an aqueous ~~~~! a~~.~
solution of 0.1 M MgCl2 as in Example 3. The Cu2+ was removed and concE:ntrated in the same manner and with th a same results as the E~aample 3.
Example 7 'The amine matE~rial of Example 1 has also been used to make separations among the transition metals and the common salt ions in solution. An example of this is the separation and concentration of Cd2+, Pb2+ and Cu2+ from Na+, ~+, Mg2+
and Ca2+ solutions normally found in potable water. The solution (1000 ml) was passed through the column, then a 10 ml of 1 M aqueou:~ HCl recovery solution. The lU ml recovery solution containESd Cd2+, pd2+ and Cu2+ in concentrated form.
The concentrated solution was analyzed by atomic absorption spectroscopy and found t:o contain the expected amounts of the three ca tions.
Example 8 The experiment of Example 7 was repeated with trace concentrations o:E Zn2+, ~,gn2+ and Ni2+ in an aqueous solution containing the common salts found in ocean water at the concentrations found in ocean water. The 10 m1 recovery solution was found to contain only Zn2+, Mn2+ and ~Ti2+ in the expected concentrations,.
Example 9 In this example, 2 grams of th a silica gel-bound amine-containing hydrocarbon was prepared following th a procedure of Example 1, except that ethylene diamine was used rather than pentaethyleneh exaam.ine of Example 1. The amine-containing silica gel used in Example 9 was that shown in formula ( 1 ) where a is 3, b is 1, c is l, d is 0, B is NH, E
is NHCH2CH(Oz~)CH,yO(CH2)3 Si(O-silica gel), Rl is OH and R2 s is H. Solutions (500 ml) of Cu2+ and Pd2+ ions in aqueous 0.1 M Mg(N 03)2 solutions were each separated as in Example 3.
In both cases, o~rer 99~ of the Cu2~ or Pd2+ was recovered in the recovery solutions.
From the foregoing, it will be appreciated that the inorganic matrix--bound amine-containing hydrocarbon ligands of formula (1) oj_ the present invention provide a material useful for the separation and concentration of the transition metal rations from mixtures of those rations with other metal rations. The transition metals can th en be analyzed and/or recovered from the concentrated recovery solution by standard techniques ~.nown in the science of these materials.
Although the .c~rocess of separating and concentrating certain metal ions in this invention has been described and illustrated by reference to certain specific silica gel-bound amine-containing hydrocarbon ligands of formula (1), processes using analogs of these amine-containing hydrocarbon ligands are within the scope of the processes of the invention as defined in th a following claims.
The process of the present invention uses compounds of formula (1) having the amine-containing hydrocarbon ligand covalently bonded to an inorganic support, e.g. sand, or silica gel, glasa, glass fibers, alumina, nickel oxide, zirconia or titanic. The compounds of formula (1), are characterized by high selectivity for and removal of desired metal ions or groups of metal ions such as the transition metal ions present at low concentrations from the source phase containing a mixture of these metal ions with other ions. The ions which are not desired to be removed may be present in much greater concentrations in the solution than the metal ions which area to be removed. The process of the present invention comprises selectively removing and concentrating ths~ desired ions) and is characterized by the abil ity to quantitatively complex from a large volume of solution the desired ions) when they are present at low concentrations. The desired ions are complexed with a compound of formvala (1) when brought into contact with such compound. For dais purpose, the solution from which the desired ions are to be i:emoved is passed th rough a column containing the compound of formula (1) . The desired ions are then recovered from the separation column by flowing through it a small volume of a receiving phase which contains a solubilized reagent which need not be selective, but which will strip the ions from the ligand quantitatively. The analysis of the desired metal ions in the concentrated IO
solution is accomplished by known methods such as atomic absorption spectroscopy. The recovery of the desired metal ions from the re<:eiving phase is easily accomplished by well known procedures" The process for producing the compounds of formula (1) will be mentioned but is not a part of the present invention.
BR:CEF DESC',RIPTION OF THE DRAWINGS
The invention will be described and illustrated by reference to a drawing in which Fig. 1 represents schematically a suitable column for holding the matrix bonded amine-containing hydrocarbon ligand material through which a solution of metal ions can be flowed to complex selectively with a desired ion or group of ions in accordance with 'the invention.
DESCRIPTION OE' THE PREFERRED EMBODIMENT OF THE INVENTION
The preferred embodinnent of the ion-recovery process of the invention utilizes t_he compounds represented by f~rmula (1). The process of producing these new compounds is not an aspect of the present invention but will be mentioned briefly here.
Amine-containing hydrocarbon ligands are covalently bonded to the inorganic support. For example, the inorganic support such as silica gel is first heated with 3-glycidoxy-propyltrimethoxysilane to produce a 3-glycidoxypropyl-bound silica gel. 'his gel i s then heated with the appropriate amine to effect a covalent bond as shown in equation (2).
The nature of thE~ amine will determine what B, D, E and R2 are in formula (1).
O
\ Sil ica Gel (CH30) 3Si (CHZ) 30CH2---CH--CH2 heat O R1~H or R ~1H
/ \ 2 2 (2) (Silica Gel-O) 3S:i (CI~2 ) 3C~H~-CH~--CH2 heat (Silica Gel-O)3S:i(CH2>3C~H~CH(OH>CHZ-L~HR or NRZ
The following examples are given to illustrate two representative c~~mpound~~ which have been made in accordance with formula (1) of the present invention. Other amine-containing hydrocarbons bonded to an inorganic support were and can be made in the Name manner.
3a Example 1 In this example, an amine-containing hydrocarbon bonded to a silica gel Haas made corresponding to a compound of formula (1) wherein a is 3, b is 1, c is 5, d is 0, R1 is hydroxy, R2 is hydrogen,, B is 1VH, D is not present since d i~
J, E is NHCH2CH(OH)CH20(CH2)3Si(O-silica gel)3, and Y and Z
are ~-silica gel groups.
Silica gel ( 60-200 mesh ) ( 1. 6 kilograms ) was suspended in 7 liters of toluene which contained 304 grams of 3-glycidoxy-propyltrimethoxy~~ilane. The gel was stirred slowly to insure that the c~el was not physically damaged, and the mixture was heatE:d at 100oC for 8 to 18 hours. Then, 175 to 225 grams of pent.aetnylenehexaamine was slowly added and the mixture was slowly stirred for 5-10 hours while maintaining a temperature of lCiO°C. The solvent was filtered and the solid amine-bound silk°a gel was dried in air in a well ventilated hood.
Example 2 In this example, an amine-containing hydrocarbon bonded to titanized sil~_ca gel was made corresponding to a compound of formula (1) wherein a is 3, b is 1, c is 5, d is 0, R1 is hydroxy, R2 is hydrogen, B is NH, D is not present, E is NHCH2CH(OH)CH20(CH2)3Si(O-Titanized Silica gel)3, and Y and Z
are O-Titani zed Sil ica gel groups .
The titanized silica gel was first prepared by suspending 60-200 Mesh sili<:a gel (50g) in 200 ml of dry toluene.
TetraisopropoxytLtanium ( 20 ml ) was slowly added to the stirred reaction mixture. Heat wa s evolved. The resulting mixture was allovued to ~>tand for 16 hours and f filtered . The residue was washed successively with 100 ml of toluene, 100 ml of methanol and 100 ml. of water and allowed to air dry at room temperature. The overall weight of the silica gel ~~~c~~~
increased to 52.5 g resulting in 1.25 mmoles of Ti02 per gram of material.
Pentaethylenekiexaamin.e was attached to the titanized silica gel in they same manner as in Example 1 using 20 g of titanized silica gel and 4 ml of 3-glycidoxypropyl-trimethoxysilane in 50 ml of toluene to give the 3-glycidoxy-propyl-titanized silica gel material, and then 10 g of this latter titanized silica gel was reacted with 3 ml of pentaethylenehex<~amine i.n 50 ml of refluxing methanol for 1 hour .
I~iETAL ICDN RECOVERY AND CONCENTRATION PROCESS
The metal ion recovery and concentration process of the invention relates to the selective recovery of desired metal ions from mixtures thereof with other metal ions using the compounds of formula (la of the invention as defined above.
Effective method of recovery and/or separation of metal ions, particular:Ly the transition metal ions, from other metal ions in water supplies, waste solutions, deposits and industrial solutions and silver recovery from waste solutions, e.g., from emulsions on photographic and X-ray film, represent a real need in modern technology. These ions are typically present at low concentrations in solutions containing other ions at much greater concentrations.
Likewise there is a need to concentrate these metal ions so that an effective analysis using well known methods such as atomic absorption spectroscopy can be carried out. Hence, ~~~a~~.~
there is a real need for a process to selectively recover and concentrate these metal ions. The present invention accomplishes thi:> separation and concentration effectively and ef f is iently by th a use of compounds selected f rom th a families represented by formula (1>.
The amine-containing inorganic matrix material of formula (1) is placed in a column as shown in Figure 1. An aqueous solution contain~_ng the desired ion or ions, in a mixture of other ions which may be in a much greater concentration, is passed through the column. The flow rate for the solution may be increased by applying pressure (with a pump) on the top of the column or ap~)lying a vacuum in the receiving vessel. After the solution has passed through th a column, a much smaller volume of a. recovery solution, i.e. an aqueous acid solution, which will protonate the amine groups of the ligands thereby _celeasir.~g the metal ions, i.s passed through the column. This receiving solution contains only the desired metal ions in a concentrated form for subsequent ana lys is and/or :recovery .
2(l The following examplEa of separations and recoveries of transition metal ions by the inorganic support-bound amine-containing materials of Examples 1 and 2 and materials prepared in a similar manner are given as illustrations.
These examples are illu:atrative only, and are not comprehensive of th a many separations of transition metal ions that are possible using the materials of formula (1) .
Example 3 In this example, 2 grams of the silica gel-bound arnine-containing hydrocarbon of Example 1 was placed in a column as shown in Figure 1.. A 500 ml solution of about 10 ppm of Cu2+
in 0.1 M aqueous MgCl2 was passed through the column using a vacuum pump at 6~I0 torr to increase the flow rate. A 10 ml aqueous solution of 1 M HC1 was passed through the column.
An analysis of the recovery solution by atomic absorption spectroscopy (AA,'~ snowed that greater than 99~ of the copper II ions original7_y in the 500 ml copper II solution was in the 10 ml recovery solution.
Example 4 The experiment: of Example 3 was repeated with about 1 ppm of Cd2+ in an aqueous solution of 0.1 M MgCl2. Again, greater than 99~ of the Cd2+ ion in the original solution was found in the recovery solution.
Example 5 The experimeni~ of Example 3 was repeated with about 13 ppm of Hg2+ in an aqueous solution of 0.1 M Mg3r2. In this case, 42~ of the Hg2+ ion in the original solution was found in the recovery :~olutior~.
Example 6 In this example, the titanized silica gel-amine material of Example 2 was used to separate 10 ppm Cu2+ in an aqueous ~~~~! a~~.~
solution of 0.1 M MgCl2 as in Example 3. The Cu2+ was removed and concE:ntrated in the same manner and with th a same results as the E~aample 3.
Example 7 'The amine matE~rial of Example 1 has also been used to make separations among the transition metals and the common salt ions in solution. An example of this is the separation and concentration of Cd2+, Pb2+ and Cu2+ from Na+, ~+, Mg2+
and Ca2+ solutions normally found in potable water. The solution (1000 ml) was passed through the column, then a 10 ml of 1 M aqueou:~ HCl recovery solution. The lU ml recovery solution containESd Cd2+, pd2+ and Cu2+ in concentrated form.
The concentrated solution was analyzed by atomic absorption spectroscopy and found t:o contain the expected amounts of the three ca tions.
Example 8 The experiment of Example 7 was repeated with trace concentrations o:E Zn2+, ~,gn2+ and Ni2+ in an aqueous solution containing the common salts found in ocean water at the concentrations found in ocean water. The 10 m1 recovery solution was found to contain only Zn2+, Mn2+ and ~Ti2+ in the expected concentrations,.
Example 9 In this example, 2 grams of th a silica gel-bound amine-containing hydrocarbon was prepared following th a procedure of Example 1, except that ethylene diamine was used rather than pentaethyleneh exaam.ine of Example 1. The amine-containing silica gel used in Example 9 was that shown in formula ( 1 ) where a is 3, b is 1, c is l, d is 0, B is NH, E
is NHCH2CH(Oz~)CH,yO(CH2)3 Si(O-silica gel), Rl is OH and R2 s is H. Solutions (500 ml) of Cu2+ and Pd2+ ions in aqueous 0.1 M Mg(N 03)2 solutions were each separated as in Example 3.
In both cases, o~rer 99~ of the Cu2~ or Pd2+ was recovered in the recovery solutions.
From the foregoing, it will be appreciated that the inorganic matrix--bound amine-containing hydrocarbon ligands of formula (1) oj_ the present invention provide a material useful for the separation and concentration of the transition metal rations from mixtures of those rations with other metal rations. The transition metals can th en be analyzed and/or recovered from the concentrated recovery solution by standard techniques ~.nown in the science of these materials.
Although the .c~rocess of separating and concentrating certain metal ions in this invention has been described and illustrated by reference to certain specific silica gel-bound amine-containing hydrocarbon ligands of formula (1), processes using analogs of these amine-containing hydrocarbon ligands are within the scope of the processes of the invention as defined in th a following claims.
Claims (19)
1. A process of removing and concentrating a desired ion from a mixture thereof in a solution with at least one other ion, which process comprises:
complexing the desired ion in the solution with a compound having the structural formula:
(wherein:
B and D are each a radical selected from the group consisting of N(R3), N(R3)CH2, O and OCH2, with the proviso that at least one of B and D must be selected from the group consisting of N(R3) and N(R3)CH2;
E is a radical selected from the group consisting of H, NH(R3), SH, OH, lower alkyl, and N(R3)[CH2CH(R1)CH2O]b(CH2)a SiYZ(O-matrix)];
Y and Z are each a radical selected from the group of Cl, OCH3, OC2H5, methyl, ethyl and halogenated substituents thereof, and O-matrix;
R1 is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl;
R2 is a radical selected from the group consisting of H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl;
a is 2 to 10;
b is 0 or 1;
c is 1 to 2000;
d is 0 to 2000; and Matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania), to form a complex of the desired ion with the compound, and breaking the complex to liberate the complexed ion with and dissolving the liberated ion in a receiving liquid in much smaller volume than the volume of the solution from which the desired ion has been removed.
complexing the desired ion in the solution with a compound having the structural formula:
(wherein:
B and D are each a radical selected from the group consisting of N(R3), N(R3)CH2, O and OCH2, with the proviso that at least one of B and D must be selected from the group consisting of N(R3) and N(R3)CH2;
E is a radical selected from the group consisting of H, NH(R3), SH, OH, lower alkyl, and N(R3)[CH2CH(R1)CH2O]b(CH2)a SiYZ(O-matrix)];
Y and Z are each a radical selected from the group of Cl, OCH3, OC2H5, methyl, ethyl and halogenated substituents thereof, and O-matrix;
R1 is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl;
R2 is a radical selected from the group consisting of H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl;
a is 2 to 10;
b is 0 or 1;
c is 1 to 2000;
d is 0 to 2000; and Matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania), to form a complex of the desired ion with the compound, and breaking the complex to liberate the complexed ion with and dissolving the liberated ion in a receiving liquid in much smaller volume than the volume of the solution from which the desired ion has been removed.
2. A process of separating a selected metal ion or ions from a plurality of other ions including Ca(II), Mg(II), Na+ and K+ in a multiple ion solution, which process comprises:
contacting the multiple ion solution with a compound having the structural formula:
(wherein:
B and D are each a radical selected from the group consisting of N(R3), N(R3)CH2, O and OCH2, with the proviso that at least one of B and D must be selected from the group consisting of N(R3) and N(R3)CH2;
E is a radical selected from the group consisting of H, NH (R3), SH, OH, lower alkyl, and N(R3)[CH2CH(R1)CH2O]b(CH2)a SiYZ(O-matrix)];
Y and Z are each a radical selected from the group of Cl, OCH3, OC2H5, methyl, ethyl and halogenated substituents thereof, and O-matrix;
R1 is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl;
R2 is a radical selected from the group consisting H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl;
a is 2 to 10;
b is 0 or 1;
c is 1 to 2000;
d is 0 to 2000; and Matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania), thereby forming a complex between the selected metal ion or ions and the compound and removing the selected metal ion or ions from the multiple ion solution; and breaking the complex to free and recover the selected ion or ions in a receiving liquid.
contacting the multiple ion solution with a compound having the structural formula:
(wherein:
B and D are each a radical selected from the group consisting of N(R3), N(R3)CH2, O and OCH2, with the proviso that at least one of B and D must be selected from the group consisting of N(R3) and N(R3)CH2;
E is a radical selected from the group consisting of H, NH (R3), SH, OH, lower alkyl, and N(R3)[CH2CH(R1)CH2O]b(CH2)a SiYZ(O-matrix)];
Y and Z are each a radical selected from the group of Cl, OCH3, OC2H5, methyl, ethyl and halogenated substituents thereof, and O-matrix;
R1 is a radical selected from the group consisting of H, SH, OH, lower alkyl and aryl;
R2 is a radical selected from the group consisting H and lower alkyl;
R3 is a radical selected from the group consisting of H, lower alkyl and aryl;
a is 2 to 10;
b is 0 or 1;
c is 1 to 2000;
d is 0 to 2000; and Matrix is selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, nickel oxide, zirconia, and titania), thereby forming a complex between the selected metal ion or ions and the compound and removing the selected metal ion or ions from the multiple ion solution; and breaking the complex to free and recover the selected ion or ions in a receiving liquid.
3. The process as set forth in claim 2, in which Matrix is silica gel, a is 3 b is 1, c is 5 d is 0, R1 is OH, R2 is H, R3 is H, B is NH, D is absent since d is 0, E is NHCH2CH(OH)CH2O(CH2)3Si (O-silica gel)3, and Y and Z are selected from the group consisting of O-silica gel and OCH3.
4. The process set forth in claim 2, in which Matrix is silica gel, a is 3, b is 1, c is 1, d is 0, R1 is OH, R2 is H, R3 is H, B is NH, E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3, and Y and Z are selected from the group consisting of O-silica gel and OCH3.
5. The process as set forth in claim 2, in which Matrix is titanized silica gel, a is 3, b is 1, c is 5, d is 0, R1 is OH, R2 is H, R3 is H, B is NH, D is absent since d is 0, E is NHCH2CH(OH)CH2O(CH2)3Si(O-titanized silica gel)3, and Y and Z are selected from the group consisting of O-titanized silica gel and OCH3.
6. The process as set forth in any one of claims 2 to 5, in which the selected metal ion is a member selected from the group consisting of Cu(II), Pb(II), Ag(I), Ru(III), Pd(II), Ir(III), Zn(II), Rh(II), Cd(II), Hg(II), Os(II), Mn(II), Au(I), Au(II), Pt(II), Pt(IV), Co(III), Co(II), Cr(II), Cr(III) and mixtures thereof.
7. The process according to claim 1, wherein:
the desired ion is a cation of a transition metal; and the complexing step is conducted by flowing the solution through a chromatography or separation column packed with the compound of the formula (1) and then the complex breaking step is conducted by flowing the receiving liquid through the column; or the complesxing step is conducted by forming an aqueous slurry of the compound of the formula (1) with the solution and the slurry is filtered to obtain solids and the complex breaking step is conducted by washing the solids with the receiving liquid.
the desired ion is a cation of a transition metal; and the complexing step is conducted by flowing the solution through a chromatography or separation column packed with the compound of the formula (1) and then the complex breaking step is conducted by flowing the receiving liquid through the column; or the complesxing step is conducted by forming an aqueous slurry of the compound of the formula (1) with the solution and the slurry is filtered to obtain solids and the complex breaking step is conducted by washing the solids with the receiving liquid.
8. The process according to claim 7, wherein a tall column is used as the chromatography or separation column.
9. The process according to claim 7 or 8, wherein the receiving liquid is dilute aqueous hydrochloric or nitric acid.
10. The process according to any one of claims 7 to 9, wherein Matrix is silica gel or titanized silica gel; a is 3; b is 1; c is 1 to 5; d is 0; R1 is OH; R2 is H; R3 is H; B is NH;
E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3 or NHCH2CH(OH)CH2O(CH2)3Si(O-titanized silica gel)3; and Y and Z are each selected from O-silica gel, O-titanized silica gel and OCH3, provided that when Matrix is silica gel, then E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3 and Y and Z are each O-silica gel or O-CH3 and when Matrix is titanized silica gel, then E is NHCH2CH(OH)CH2O(CH2)3Si(O-titanized silica gel) and Y
and Z are each O-titanized silica gel or O-CH3.
E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3 or NHCH2CH(OH)CH2O(CH2)3Si(O-titanized silica gel)3; and Y and Z are each selected from O-silica gel, O-titanized silica gel and OCH3, provided that when Matrix is silica gel, then E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3 and Y and Z are each O-silica gel or O-CH3 and when Matrix is titanized silica gel, then E is NHCH2CH(OH)CH2O(CH2)3Si(O-titanized silica gel) and Y
and Z are each O-titanized silica gel or O-CH3.
11. The process according to claim 10, wherein Matrix is silica gel, E is NHCH2CH(OH)CH2O(CH2)3Si(O-silica gel)3 and Y and Z are each O-silica gel; or Matrix is titanized silica gel, E
is NHCH2CH(OH)CH2O(CH2)3(O-titanized silica gel) and Y and Z are each titanized silica gel.
is NHCH2CH(OH)CH2O(CH2)3(O-titanized silica gel) and Y and Z are each titanized silica gel.
12. The process according to any one of claim 7 to 10, wherein the other ion is contained in the solution at a concentration much higher than the desired ion.
13. The process according to claim 12, wherein the desired ion is Cu2+ and the other ion is Mg2+.
14. The process according to claim 12, wherein the desired ion is Cd2+ and the other ion is Mg2+.
15. The process according to claim 12, wherein the desired ion is Hg2+ and the other ion is Mg2+.
16. The process according to claim 12, wherein the desired ion is a mixture of Cd2+, Pb2+ and Cu2+ and the other ion is a mixture of Na+, K+, Mg2+ and Ca2+.
17. The process according to claim 12, wherein the desired ion is a mixture of Zm2+, Mn2+ Ni2+ and the other ion is a mixture of Na+, K+, Mg2+ and Ca2+.
18. The process according to claim 12, wherein the desired ion is a mixture of Cu2+ and Pd2+ and the other ion is Mg2t.
19. The process according to claim 12, wherein:
the desired ion is at least one member selected from the group consisting of Cu(II), Pb(II), Ag(I), Ru(III), Pd(II), Ir(III), Zn(II), Rh(II), Cd(II), Hg(II), Os(II), Mn(II), Au(I), Au(II), Pt(II), Pt(IV), Co(III), Co(II), Cr(II) and Cr(III);
and the other is at least one member selected from the group consisting of Na+, K+, Mg2+ and Ca2+.
the desired ion is at least one member selected from the group consisting of Cu(II), Pb(II), Ag(I), Ru(III), Pd(II), Ir(III), Zn(II), Rh(II), Cd(II), Hg(II), Os(II), Mn(II), Au(I), Au(II), Pt(II), Pt(IV), Co(III), Co(II), Cr(II) and Cr(III);
and the other is at least one member selected from the group consisting of Na+, K+, Mg2+ and Ca2+.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002007311A CA2007311C (en) | 1988-10-07 | 1990-01-08 | Process of removing and concentrating desired ions from solutions thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/255,353 US4952321A (en) | 1988-10-07 | 1988-10-07 | Process of removing and concentrating desired ions from solutions |
| CA002007311A CA2007311C (en) | 1988-10-07 | 1990-01-08 | Process of removing and concentrating desired ions from solutions thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2007311A1 CA2007311A1 (en) | 1991-07-08 |
| CA2007311C true CA2007311C (en) | 2002-03-26 |
Family
ID=25673870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002007311A Expired - Lifetime CA2007311C (en) | 1988-10-07 | 1990-01-08 | Process of removing and concentrating desired ions from solutions thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2007311C (en) |
-
1990
- 1990-01-08 CA CA002007311A patent/CA2007311C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2007311A1 (en) | 1991-07-08 |
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