Stable immobilized amine sorbents for ree and heavy metal recovery from liquid sources

Abstract

Materials, methods of making, and methods of using a stable and regenerable immobilized amine sorbents for rare earth element and heavy metal recovery from liquid sources. Embodiments of the invention relate to the novel combination of different polyamines, primarily polyethylenimine Mw=800 (PEI 800 ), and an epoxysilane, namely 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS), covalently immobilizing the REE and heavy metal-adsorbing amine sites within low cost, porous silica particles.

We claim: 
     
         1 . A stable and regenerable immobilized amine sorbent, characterized by:
 covalently immobilized polyamine combined with epoxysilane.   
     
     
         2 . The immobilized amine sorbent further including a wherein the polyamine is polyethylenimine having a Mw ranging from about 400 to about 1,000,000. 
     
     
         3 . The immobilized amine sorbent of  claim 1  wherein the polyamine is selected from the group consisting of: polyethylenimine (Mw=400 to 1,000,000), ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, 1,3-cyclohexanebis(methylamine), 4,4′-Methylenebis(cyclohexylamine), 3,3′-Methylenedianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Tris(2-aminoethyl)amine, p-Xylylenediamine, 4-Chloro-o-phenylenediamine, N,N′-Dimethyl-1,3-propanediamine, N,N′-Diphenyl-p-phenylenediamine, N,N′-Diisopropyl-1,3-propanediamine, polyvinyl amine, poly(allylamine). 
     
     
         4 . The immobilized amine sorbent of  claim 1  wherein the epoxysilane is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS). 
     
     
         5 . The immobilized amine sorbent of  claim 1  wherein the immobilized amine combined with epoxysilane is either a pure polymer chunk or particle, or functionalized on silica to in the form of an immobilized amine sorbent. 
     
     
         6 . The immobilized amine sorbent of  claim 1  further including a mono-epoxide or di-epoxide terminated polydimethylsiloxane, such as MCR-E11 PDMS or aminosilane. 
     
     
         7 . The immobilized amine sorbent of  claim 6  wherein the aminosilane is selected from the group consisting of 3-aminopropyltrimethoxysilane (APTMS), N-(3-trimethoxysilyl) propyl)ethylenediamine (TMPED), and N-(3 Trimethoxysilylpropyl)diethylenetriamine (TMPDET). 
     
     
         8 . A stable and regenerable immobilized amine sorbent, characterized by
 a porous, crosslinked polymer network consisting of polyamines combined with a covalent crosslinker species.   
     
     
         9 . The immobilized amine sorbent of  claim 8  wherein the porous, crosslinked polymer network is an amine-epoxy monolith. 
     
     
         10 . The immobilized amine sorbent of  claim 9  wherein the covalent crosslinker species comprises the monolith is selected from the group consisting of: di-epoxide as bisphenyl A diglycidyl ether), tri-epoxide as N—N-diglycidyl-4-glycidyloxyanaline, and tetra-epoxide as 4,4′-methylenebis(N,N-diglycidylaniline). 
     
     
         11 . The immobilized amine sorbent of  claim 9  wherein the monolith is immobilized within silica. 
     
     
         12 . The immobilized amine sorbent of  claim 8  wherein the porous polymer network is an acrylamide-based hydrogel. 
     
     
         13 . The immobilized amine sorbent of  claim 12  wherein the acrylamide-based hydrogel is an organic acrylamide hydrogel containing no silica particles. 
     
     
         14 . The immobilized amine sorbent of  claim 11  wherein the acrylamide-based hydrogel is an organic-inorganic hybrid acrylamide hydrogel, containing silica particles within the polymer network and also serving as a support that contains the hydrogel. 
     
     
         15 . The immobilized amine sorbent of  claim 12  wherein the acrylamide hydrogel is synthesized by thermo-polymerization of acrylamide onto PEI polymer chain with N,N′-methylene bisacrylamide. 
     
     
         16 . The immobilized amine sorbent of  claim 8  wherein the polyamine is selected from the group consisting of: polyethylenimine having a Mw ranging from about 400 to about 1,000,000, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, 1,3-cyclohexanebis(methylamine), 4,4′-Methylenebis(cyclohexylamine), 3,3′-Methylenedianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Tris(2-aminoethyl)amine, p-Xylylenediamine, 4-Chloro-o-phenylenediamine, N,N′-Dimethyl-1,3-propanediamine, N,N′-Diphenyl-p-phenylenediamine, N,N′-Diisopropyl-1,3-propanediamine, polyvinyl amine, poly(allylamine). 
     
     
         17 . A method of making a stable and regenerable immobilized amine sorbent composition, comprising;
 selecting an amount of different polyamines and epoxysilane;   combining the selected amounts of different polyamines with the epoxysilane, forming the sorbent.   
     
     
         18 . The method of  claim 17  wherein the amount of different polyamines and epoxysilanes is selected based on at least an amount of rare earth elements (REEs) to be captured. 
     
     
         19 . The method of  claim 17  wherein the polyamine is selected from the group consisting of: polyethylenimine having a Mw=400 to 1,000,000, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, 1,3-cyclohexanebis(methylamine), 4,4′-Methylenebis(cyclohexylamine), 3,3′-Methylenedianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Tris(2-aminoethyl)amine, p-Xylylenediamine, 4-Chloro-o-phenylenediamine, N,N′-Dimethyl-1,3-propanediamine, N,N′-Diphenyl-p-phenylenediamine, N,N′-Diisopropyl-1,3-propanediamine, polyvinyl amine, poly(allylamine). 
     
     
         20 . The method of  claim 17  wherein the epoxysilane is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. 
     
     
         21 . The method of  claim 17  further including combining silica with the selected amounts of different polyamines with an epoxysysilane. 
     
     
         22 . The method of  17  further including aminosilane. 
     
     
         23 . The method of  claim 22  wherein the aminosilane is selected from the group consisting of 3-aminopropyltrimethoxysilane (APTMS), N-(3-trimethoxysilyl) propyl)ethylenediamine (TMPED), and N-(3-Trimethoxysilylpropyl)diethylenetriamine (TMPDET). 
     
     
         24 . A method of using a stable and regenerable sorbent material to capture a rare earth element (REEs) from a source,
 the sorbent material characterized by:
 covalently immobilized polyamine combined with epoxysilane; 
   the method comprising:
 exposing the sorbent material to the liquid source; and 
 capturing at least one REE in the source. 
   
     
     
         25 . The method of  claim 24  further comprising REEs-adsorbing sites within low cost silica particles. 
     
     
         26 . The method of  claim 24  further comprising releasing the adsorbed metals and regenerating the sorbent material. 
     
     
         27 . The method of  claim 24  wherein the at least one REE is selected from the group consisting of La, Ce, Nd, Eu, Pr, Y, Dy and Yb, plus Sc and the remaining series of the lanthanide metals (REEs; Pm, Sm, Gd, Tb, Ho, Er, Tm, and Lu. 
     
     
         28 . The method of  claim 24  further comprising pre-concentrating the at least one REE to ppm levels. 
     
     
         29 . The method of  claim 24  further comprising selectively releasing critical heavy metals from the source. 
     
     
         30 . The method of  claim 29  wherein the critical heavy metals is selected from the group consisting of Pb, Cu, Zn, Fe, Al, Mn, Ni, Mg. 
     
     
         31 . The method of  claim 24  wherein the source is a liquid source. 
     
     
         32 . The method of  claim 31  wherein the liquid source is water from hydraulic fracturing. 
     
     
         33 . The method of  claim 31  wherein the liquid source is acid mine drainage. 
     
     
         34 . The method of  claim 31  further including capturing at least one heavy metal. 
     
     
         35 . The method of  claim 34  wherein the at last one heavy metal is selected from the group consisting of: Pb, Cu, Zn, Fe, Al, Mn, Ni, Mg, La, Ce, Nd, Eu, Pr, Y, Dy and Yb, plus Sc and the remaining series of the lanthanide metals (REEs; Pm, Sm, Gd, Tb, Ho, Er, Tm, and Lu. 
     
     
         36 . A method of using a stable and regenerable sorbent material to capture an element from a source,
 the sorbent material characterized by:
 covalently immobilized polyamine combined with epoxysilane; 
   the method comprising:
 exposing the sorbent material to the liquid source; and 
 capturing at least one naturally occurring element in the source. 
   
     
     
         37 . The method of  claim 36  wherein the naturally occurring element is barium. 
     
     
         38 . The method of  claim 37  wherein barium is selected from the group consisting of: 
     
     
         39 . The method of  claim 36  wherein the naturally occurring element is strontium. 
     
     
         40 . The method of  claim 36  wherein strontium is selected from the group consisting of: