Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations

Abstract

Disclosed herein is a novel class of multiple charged cationic or anionic compounds that are derived from an aza-Michael Addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor), methods of making the same, and use thereof. Also disclosed herein are the methods of using multiple charged cationic or anionic compounds disclosed herein in a reverse emulsion breaker composition to break reverse emulsion commonly found in a produced fluid in oil and gas operations. The disclosed REB methods or compositions are found to be more effective than those methods or compositions including commonly used for oil/solid and water separation.

What is claimed is: 
     
         1 . A compound derived from an aza-Michael Addition Reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) having an ionic group according to one of the following formulas; 
       
         
           
           
               
               
           
         
       
       wherein:
 X is NH or O; 
 R 2  is H, CH 3 , or an unsubstituted, linear or branched C 2 -C 10  alkyl, alkenyl, or alkynyl group; 
 R 2′  is H, CH 3 , or an unsubstituted or substituted, linear or branched C 1 -C 10  alkyl, alkenyl, alkynyl group, —COOH, —CH 2 COOH, Y′, or —(CH 2 ) m —Y′ wherein m is an integer of 2 to 4; 
 R 3  is absent or an unsubstituted, linear or branched C 1 -C 30  alkylene group; 
 Y is —NR 4 R 5 R 6   (+) , wherein R 4 , R 5 , and R 6  are independently a C 1 -C 10  alkyl group, and 
 Y′ is —COOH, —SO 3 H, —PO 3 H, —OSO 3 H, —OPO 3 H, or a salt thereof; 
 wherein the compound is a multiple charged cationic compound having 2 or more positive charges or multiple charged anionic compound having 2 or more negative charges. 
 
     
     
         2 . The compound according to  claim 1 , wherein the polyamine is a linear, branched, or dendrimer polyamine with a general formula of NH 2 —[R 10′ ] n —NH 2 , (RNH) n —RNH 2 , H 2 N—(RNH) n —RNH 2 , or H 2 N—(RN(R′)) n —RNH 2 , wherein R 10′  is a linear or branched, unsubstituted or substituted C 2 -C 10  alkylene group, or combination thereof; R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10  alkylene group, or combination thereof; R′ is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10  alkyl group, RNH 2 , RNHRNH 2 , or RN(RNH 2 ) 2 ; and n is from 2 to 1,000,000. 
     
     
         3 . The compound according to  claim 1 , wherein the polyamine is (i) an unmodified polyamine, (ii) a modified polyamine, (iii) an ethoxylated polyamine, propylated polyamine, polyamine with polyquat, polyamine with polyglycerol, or combination thereof, or (iv) a linear, branched, or dendrimer polyethyleneimine. 
     
     
         4 . The compound according to  claim 1 , wherein the polyamine comprises (i) only primary and secondary amine groups; (ii) only primary, secondary, and tertiary amine groups; or (iii) only primary and tertiary amine groups. 
     
     
         5 . The compound according to  claim 1 , wherein the polyamine is a polyamine with a general formula of: (i) NH 2 —[R 10′ ] n —NH 2 , wherein R 10′  is a linear or branched, unsubstituted or substituted C 2 -C 10  alkylene group, or combination thereof; (ii) (RNH) n —RNH 2  or H 2 N—(RNH) n —RNH 2 , wherein R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10  alkylene group, or combination thereof; or (iii) H 2 N—(RN(R′)) n —RNH 2 , wherein R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10  alkylene group, or combination thereof and R′ is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10  alkyl group, RNH 2 , RNHRNH 2 , or RN(RNH 2 ) 2 . 
     
     
         6 . The compound according to  claim 1 , the activated olefin is (i) (3-acrylamidopropyl)trimethylammonium chloride (APTAC) or [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC); (ii) (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methyl sulfate (DMAEMA-MSQ); or (iii) an acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), itaconic acid, maleic acid, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, vinylsulfonic acid, vinylphosphonic acid, or mixture thereof. 
     
     
         7 . The compound according to  claim 1 , wherein the polyamine has an average molecular weight (M w ) of from about 60 to about 2,000,000 Da, or from about 60 to about 5,000 Da. 
     
     
         8 . The compound according to  claim 1 , wherein the compound is (i) a single molecule; (ii) a mixture of at least two multiple charged cationic compounds or at least two multiple charged anionic compounds; (iii) a mixture of at least two multiple charged cationic compounds or at least two multiple charged anionic compounds derived from the same polyamine and the activated olefin; or (iv) a mixture of at least two multiple charged cationic compounds or at least two multiple charged anionic compounds derived from different polyamines and the same activated olefin. 
     
     
         9 . The compound according to  claim 1 , wherein the compound has an average molecular weight of from about 100 to about 2,000,000 Da, or from about 100 to about 5,500 Da. 
     
     
         10 . The compound according to  claim 1 , wherein the compound has (i) at least 10, 15, 20, or 30 positive charges; (ii) at least 4, 5, 6, 7, or 8 positive charges; (iii) at least 10, 15, 20, or 30 negative charges; or (iv) at least 4, 5, 6, 7, or 8 negative charges. 
     
     
         11 . The compound according to  claim 1 , wherein the compound is one or more of 
       
         
           
           
               
               
           
         
       
       wherein n=0-1000. 
     
     
         12 . The compound according to  claim 1 , wherein the compound is one or more of 
       
         
           
           
               
               
           
         
       
     
     
         13 . The compound according to  claim 1 , wherein the compound is derived from a polyethyleneimine and (3-Acrylamidopropyl)trimethylammonium chloride (APTAC), wherein the polyethyleneimine is a linear PEI and has an average molecular weight (M w ) of about 5,000. 
     
     
         14 . The compound according to  claim 1 , wherein the compound is derived from a polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC), wherein the polyethyleneimine is a linear PEI and has an average molecular weight (M w ) of about 750,000. 
     
     
         15 . The compound according to  claim 1 , wherein the compound is derived from a polyethyleneimine and (3-Acrylamidopropyl)trimethylammonium chloride (APTAC), wherein the polyethyleneimine is a branched PEI and has an average molecular weight (M w ) of about 25,000. 
     
     
         16 . The compound according to  claim 1 , wherein the compound is soluble in water. 
     
     
         17 . An article, product, or composition comprising one or more compounds according to  claim 1 . 
     
     
         18 . The article, product, or composition according to  claim 17 , wherein the article, product or composition further comprises a carrier. 
     
     
         19 . The article, product, or composition according to  claim 17 , wherein the article, product or composition is an aqueous article, product, or composition. 
     
     
         20 . The article, product, or composition according to  claim 18 , wherein the carrier is water, an alcohol, an alkylene glycol, an alkyleneglycol alkyl ether, or a combination thereof. 
     
     
         21 . The article, product, or composition according to  claim 17 , further comprising an additional surfactant, wherein the additional surfactant is a nonionic, semi-nonionic, cationic, anionic, amphoteric, zwitterionic, Gemini, surfactant or mixtures thereof.