Membranes, Methods of Making Membrane, and Methods of Separating Gases Using Membranes

Abstract

Membrane, methods of making membranes, and methods of separating gases using membranes are provided. The membranes can include at least one hydrophilic polymer, at least one cross-linking agent, at least one base, and at least one amino compound. The methods of separating gases using membranes can include contacting a gas stream containing at least one of CO 2 , H 2 S, and HCl with one side of a nonporous and at least one of CO 2 , H 2 S, and HCl selectively permeable membrane such that at least one of CO 2 , H 2 S, and HCl is selectively transported through the membrane.

1 . A composition comprising:
 at least one hydrophilic polymer, at least one cross-linking agent, at least one base, and at least one amino compound, wherein the amino compound comprises at least one of a polyamine and a salt of aminoacid, and wherein the aminoacid salt is selected from salts having the formula:   
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3 , and R 4  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, n is an integer ranging from 0 to 4, A m+  is a cation having a valence of 1 to 3 and an amine cation having the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 5  and R 6  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, R 7  is hydrogen or a hydrocarbon group having from 1 to 4 carbon atoms or an alkyl amine of from 2 to 6 carbon atoms and 1 to 4 nitrogen atoms, y is an integer ranging from 1 to 4, and m is an integer equal to the valence of the cation;
 and wherein said base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine, N,N-dimethylaminopyridine, hexamethyltriethylenetetraamine, potassium carbonate, sodium carbonate, lithium carbonate, and combinations thereof. 
 
     
     
         2 . The composition as claimed in  claim 1  wherein said at least one amino compound comprises a polyamine selected from polyallylamine, polyethylenimine, poly-N-1,2-dimethylpropylallylamine, poly-N-methylallylamine, poly-N,N-dimethylallylamine, poly-2-vinylpiperidine, and poly-4-vinylpiperidine, and blends and copolymers thereof. 
     
     
         3 . The composition as claimed in  claim 1  wherein said at least one amino compound comprises polyallylamine. 
     
     
         4 . The composition as claimed in  claim 1  wherein said at least one amino compound comprises polyethylenimine. 
     
     
         5 . The composition as claimed in  claim 1  wherein said at least one hydrophilic polymer is selected from polyvinylalcohol, polyvinylacetate, polyethylene oxide, polyvinylpyrrolidone, polyacrylamine, and blends, and copolymers thereof. 
     
     
         6 . The composition as claimed in  claim 1  wherein said at least one hydrophilic polymer comprises polyvinylalcohol. 
     
     
         7 . The composition as claimed in  claim 6  wherein said at least one amino compound comprises polyallylamine. 
     
     
         8 . The composition as claimed in  claim 6  wherein said at least one amino compound comprises polyethylenimine. 
     
     
         9 . The composition as claimed in  claim 1  wherein A m+  is a metal cation selected from Groups Ia, IIa, IIIa, and VIII of the Periodic Table of Elements. 
     
     
         10 . The composition as claimed in  claim 9  wherein said at least one amino compound comprises aminoisobutyric acid-K salt. 
     
     
         11 . The composition as claimed in  claim 9  wherein said at least one amino compound comprises dimethylglycine-K salt. 
     
     
         12 . The composition as claimed in  claim 9  wherein said at least one amino compound comprises dimethylglycine-Li salt. 
     
     
         13 . The composition as claimed in  claim 1  wherein said at least one cross-linking agent is selected from formaldehyde, glutaraldehyde, maleic anhydride, glyoxal, divinylsulfone, toluenediisocyanate, trimethylol melamine, terephthalatealdehyde, epichlorohydrin, vinyl acrylate, and combinations thereof. 
     
     
         14 . The composition as claimed in  claim 13  wherein said at least one cross-linking agent comprises formaldehyde. 
     
     
         15 . The composition as claimed in  claim 1  wherein said at least one cross-linking agent comprises from about 1 to about 40 percent by weight of said composition. 
     
     
         16 . The composition as claimed in  claim 1  wherein said at least one base comprises from about 1 to about 40 percent by weight of said composition. 
     
     
         17 . The composition as claimed in  claim 1  wherein said at least one hydrophilic polymer comprises from about 10 to about 90 percent by weight of said composition. 
     
     
         18 . The composition as claimed in  claim 1  wherein said at least one amino compound comprises from about 10 to about 90 percent by weight of said composition. 
     
     
         19 . The composition as claimed in  claim 1  wherein said at least one base comprises potassium hydroxide. 
     
     
         20 . A nonporous membrane formed from the composition of  claim 1 . 
     
     
         21 . A process for separating at least one of CO 2 , H 2 S, and HCl from a gas stream containing at least one of CO 2 , H 2 S, and HCl, comprising:
 contacting a gas stream containing at least one of CO 2 , H 2 S, and HCl with one side of a nonporous and at least one of CO 2 , H 2 S, and HCl selectively permeable membrane comprising:
 at least one hydrophilic polymer, at least one cross-linking agent, at least one base, and at least one amino compound, wherein said amino compound comprises at least one of a polyamine and a salt of aminoacid, and wherein the aminoacid salt is selected from salts having the formula: 
   
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3 , and R 4  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, n is an integer ranging from 0 to 4, A m+  is a cation having a valence of 1 to 3 and an amine cation having the formula: 
       
       
         
           
           
               
               
           
         
         
           wherein R 5  and R 6  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, R 7  is hydrogen or a hydrocarbon group having from 1 to 4 carbon atoms or an alkyl amine of from 2 to 6 carbon atoms and 1 to 4 nitrogen atoms, y is an integer ranging from 1 to 4, and m is an integer equal to the valence of the cation; 
           wherein said base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine, N,N-dimethylaminopyridine, hexamethyltriethylenetetraamine, potassium carbonate, sodium carbonate, lithium carbonate, and combinations thereof; 
         
         wherein at least one of CO 2 , H 2 S, and HCl is selectively transported through the membrane; and 
         withdrawing from the obverse side of said membrane a permeate containing of at least one of CO 2 , H 2 S, and HCl, wherein at least one of CO 2 , H 2 S, and HCl is selectively removed from said gaseous stream. 
       
     
     
         22 . The process as claimed in  claim 21  wherein said at least one amino compound comprises a polyamine selected from polyallylamine, polyethylenimine, poly-N-1,2-dimethylpropylallylamine, poly-N-methylallylamine, poly-N,N-dimethylallylamine, poly-2-vinylpiperidine, and poly-4-vinylpiperidine, and blends and copolymers thereof. 
     
     
         23 . The process as claimed in  claim 22  wherein said at least one amino compound comprises polyallylamine. 
     
     
         24 . The process as claimed in  claim 22  wherein said at least one amino compound comprises polyethylenimine. 
     
     
         25 . The process as claimed in  claim 21  wherein said at least one hydrophilic polymer is selected from polyvinylalcohol, polyvinylacetate, polyethylene oxide, polyvinylpyrrolidone, polyacrylamine, and blends, and copolymers thereof. 
     
     
         26 . The process as claimed in  claim 21  wherein said at least one hydrophilic polymer comprises polyvinylalcohol. 
     
     
         27 . The process as claimed in  claim 21  wherein said at least one amino compound comprises aminoisobutyric acid-K salt. 
     
     
         28 . The process as claimed in  claim 21  wherein at least one amino compound comprises dimethylglycine-K salt. 
     
     
         29 . The process as claimed in  claim 21  wherein said amino compound comprises dimethylglycine-Li salt. 
     
     
         30 . The process as claimed in  claim 21  wherein at least one cross-linking agent is selected from formaldehyde, glutaraldehyde, maleic anhydride, glyoxal, divinylsulfone, toluenediisocyanate, trimethylol melamine, terephthalatealdehyde, epichlorohydrin, vinyl acrylate, and combinations thereof. 
     
     
         31 . The process as claimed in  claim 21  wherein at least one cross-linking agent comprises formaldehyde. 
     
     
         32 . A method for producing a nonporous membrane for separating at least one of CO 2 , H 2 S, and HCl from a gaseous stream containing at least one of CO 2 , H 2 S, and HCl, the method comprising:
 forming a casting solution of a solvent, at least one hydrophilic polymer, at least one cross-linking agent, at least one base, and at least one amino compound, wherein the amino compound comprises at least one of a polyamine and a salt of aminoacid, and wherein the aminoacid salt is selected from salts having the formula:   
       
         
           
           
               
               
           
         
         
           wherein R 1 , R 2 , R 3 , and R 4  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, n is an integer ranging from 0 to 4, A m+  is a cation having a valence of 1 to 3 and an amine cation having the formula: 
         
       
       
         
           
           
               
               
           
         
         
           wherein R 5  and R 6  are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, R 7  is hydrogen or a hydrocarbon group having from 1 to 4 carbon atoms or an alkyl amine of from 2 to 6 carbon atoms and 1 to 4 nitrogen atoms, y is an integer ranging from 1 to 4, and m is an integer equal to the valence of the cation, and wherein said base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine, N,N-dimethylaminopyridine, hexamethyltriethylenetetraamine, potassium carbonate, sodium carbonate, lithium carbonate, and combinations thereof; 
         
         casting the solution on a substrate; and 
         evaporating the solvent such that a nonporous membrane is formed. 
       
     
     
         33 . The method as claimed in  claim 32  wherein said at least one amino compound comprises a polyamine selected from polyallylamine, polyethylenimine, poly-N-1,2-dimethylpropylallylamine, poly-N-methylallylamine, poly-N,N-dimethylallylamine, poly-2-vinylpiperidine, and poly-4-vinylpiperidine, and blends and copolymers thereof. 
     
     
         34 . The method as claimed in  claim 33  wherein said polyamine comprises polyallylamine. 
     
     
         35 . The method as claimed in  claim 33  wherein said polyamine comprises polyethylenimine. 
     
     
         36 . The method as claimed in  claim 32  wherein said at least one hydrophilic polymer is selected from polyvinylalcohol, polyvinylacetate, polyethylene oxide, polyvinylpyrrolidone, polyacrylamine, and blends, and copolymers thereof. 
     
     
         37 . The method as claimed in  claim 32  wherein said at least one hydrophilic polymer comprises polyvinylalcohol. 
     
     
         38 . The method as claimed in  claim 32  wherein said at least one amino compound comprises aminoisobutyric acid-K salt. 
     
     
         39 . The method as claimed in  claim 32  wherein said at least one amino compound comprises dimethylglycine-K salt. 
     
     
         40 . The method as claimed in  claim 32  wherein said at least one amino compound comprises dimethylglycine-Li salt. 
     
     
         41 . The method as claimed in  claim 32  wherein said at least one cross-linking agent is selected from formaldehyde, glutaraldehyde, maleic anhydride, glyoxal, divinylsulfone, toluenediisocyanate, trimethylol melamine, terephthalatealdehyde, epichlorohydrin, vinyl acrylate, and combinations thereof. 
     
     
         42 . The method as claimed in  claim 32  wherein said at least one cross-linking agent comprises formaldehyde. 
     
     
         43 . The method as claimed in  claim 32  further comprising the step of heating the solution prior to the step of casting the solution on a substrate.