Obtention of random bipolymers based on acrylics with amphoteric fragments for the removal of aqueous dispersion in crude oils

Abstract

The present disclosure relates to novel demulsifying agents obtained from the functionalization of random bipolymers based on alkyl acrylate and aminoalkyl acrylate with different acrylic derivatives, using the aza-Michael addition reaction. The amphoteric random acrylic bipolymers were evaluated as demulsifying agents for crude oils with API densities between 10 and 40° API, showing superior performance as breakers, coalescers and clarifiers than the non-functionalized acrylic bipolymer and a commercial formulation based on polyethers.

1 . Random acrylic bipolymers based on alkyl acrylic-aminoalkyl acrylic with amphoteric endings, as dehydrating agents to remove emulsified water in crude oil with gravities from 10 to 40° API, comprising structural formulas (3) and (4), with molecular masses from 1,900 to 600,000 g-mol −1  as follows: 
       
         
           
           
               
               
           
         
         where: 
         R 6 =H (hydrogen) or CH 3  (methyl); 
         R 7 =H (hydrogen), CH 3  (methyl), alcoxyalkyl radicals such as: C 2 H 5 O (metoxymethyl), C 3 H 7 O (2-metoxyethyl), C 4 H 9 O (2-etoxyethyl), C 4 H 9 O (3-metoxypropyl), C 5 H 11 O (3-etoxyopropyl), C 5 H 11 O 2  (2-(2-metoxyetoxy)ethylil) or C 8 H 9 O (2-phenoxyethyl); hydroxyalkyl radicals such as: CH 2 OH (hydroxymethyl), C 2 H 4 OH (2-hiydroxyethyl), C 3 H 6 OH (3-hydroxypropyl), C 4 H 8 OH (4-hydroxybutyl), C 5 H 10 OH (5-hydroxypentyl), C 6 H 12 OH (6-hydroxyhexyl), C 7 H 14 OH (7-hydroxyheptyl), C 8 H 16 OH (8-hydroxyoctyl), C 9 H 18 OH (9-hydroxynonyl), C 10 H 20 OH (10-hydroxydecyl), C 11 H 22 OH (11-hydroxyundecyl) or C 12 H 24 OH (12-hydroxydodecyl); carboxyalkyl radicals: C 3 H 5 O 2  (2-carboxyethyl), C 4 H 7 O 2  (carboxypropyl), or C 5 H 9 O 2  (carboxybutyl); aminoalkyl radicals such as: CH 2 NH 2  (methylamino), CH 2 CH 2 NH 2  (2-ethylamino), CH 2 CH 2 CH 2 NH 2  (3-propylamino), CH 2 N(CH 3 ) 2  (dimethylamino methyl), CH 2 CH 2 N(CH 3 ) 2  (2-(dimehtylamino)etihyl), CH 2 CH 2 CH 2 N(CH 3 ) 2  (3-(dimethylamino)propyl), CH 2 CH 2 N(CH 2 CH 3 ) 2  (2-(diethylamino)etthyl); or CH 2 CH 2 CH 2 SO 3 K (potassium 3-sulfunate); 
         x=a number in the range from 2 to 900; 
         y=a number in the range from 2 to 900; and 
         z=a number in the range from 1 to 3. 
       
     
     
         2 . A process of synthesizing amphoteric random acrylic bipolymers for use as dehydrating agents for crude oils according with the  claim 1 , wherein the process comprises carrying out an aza-Michael addition reaction by dissolving the alkyl acrylic-aminoalkyl acrylic in an organic solvent, wherein the organic solvent has a boiling point ranging from about 40° C. to about 130° C., said organic solvent being selected from the group consisting of methanol, ethanol, isopropanol, chloroform, benezene and its derivatives, toluene, and xylene. 
     
     
         3 . The process according to  claim 2 , wherein the acrylic derivatives used for functionalization are selected from the group consisting of: acrylic acid, methacrylic acid, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, di(ethylene glycol) ethyl ether acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl methacrylate, di(ethylene glycol) ethyl ether methacrylate, 2-ethoxyethyl, 2-ethoxyethyl methacrylate, 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, 2-ethoxymethyl acrylate, 2-ethoxymethyl methacrylate, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 7-hydroxyheptyl acrylate, 8-hydroxyoctyl acrylate, 9-hydroxynonyl acrylate, 10-hydroxydecyl acrylate, 11-undecyl acrylate, 12-dodecyl, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 7-hydroxyheptyl methacrylate, 8-hydroxyoctyl methacrylate, 9-hydroxynonyl methacrylate, 10-hydroxydecyl methacrylate, 11-undecyl methacrylate or 12-dodecyl methacrylate, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 2-carboxyethyl methacrylate, 3-carboxypropyl, 4-carboxybutyl methacrylate, 2-ethylamino acrylate, 2-(dimethylamino)ethyl acrylate, 3-propylamino acrylate, 3-(dimethylamino)propyl acrylate, 2-(diethylamino)ethyl acrylate, 2-ethylamino methacrylate, 2-(dimethylamino)ethyl methacrylate, 3-propylamino methacrylate, 3-(dimethylamino)propyl methacrylate, 2-(diethylamino)ethyl methacrylate, and 3-sulfonatopropyl acrylate potassium salt. 
     
     
         4 . The process according to  claim 2 , wherein the functionalization comprises the aza-Michael addition reaction, where a molar ratio of random bipolymer based on alkyl acrylic aminoalkyl acrylic/acrylic derivative is in a range from about 1.0/1.0 to 1.0/8.0 the weight percentage of the aminoalkyl acrylate monomer. 
     
     
         5 . The process according to  claim 2 , wherein the acrylic derivative is added under reagent deficiency conditions at a mass flow ranging from between about 1 and about 50 g L −1  min −1 . 
     
     
         6 . The process according to  claim 2 , wherein the aza-Michael addition reaction is carried out at a reaction temperature ranging from between about 45° C. and about 120° C. for a period ranging from about 2 h to about 12 h. 
     
     
         7 . A method of using the amphoteric random acrylic bipolymers according to  claim 1 , comprising dissolving the dry amphoteric random acrylic bipolymer in a suitable organic solvent, wherein the organic solvent is selected from the group consisting of dichloromethane, methanol, ethanol, isopropanol, chloroform, acetone, dimethyl sulfoxide, tetrahydrofuran, dioxane, 2-butoxyethanol, 2-butoxyethanol acetate, benzene and its derivatives, toluene, xylene, jet fuel, and naphtha, for its final application as a dehydrating agent in crude oils with gravities ranging from about 10 to about 40° API. 
     
     
         8 . The method according to  claim 7 , where concentration of a solution of the amphoteric random acrylic bipolymer ranges from about 1.0 to about 50.0 wt %. 
     
     
         9 . The method according to  claim 8 , where the solution is dosed in the crude oil with a concentration in a range from about 10 to about 2,000 ppm.