Solubilized lignosulfonate derivatives

Abstract

Valuable new and widely used compositions of matter are comprised of products having enhanced solubility and increased dispersant and the like surfactant activity which products are resulfonated units of alkaline oxidized, hydrolyzed, partially desulfonated lignosulfonates.

What is claimed is: .[.1. A composition comprising: 
     
        atoms..]. .[.18.  A composition as claimed in claim 17 wherein said aldehyde is formaldehyde..]. .[.19. A composition as claimed in claim 18 wherein said formaldehyde is present in an amount by weight of said partially desulfonated lignosulfonate of about 1.5 percent to 12 percent..]. .[.20. A composition as claimed in claim 18 wherein said formaldehyde is present with an alkali metal bisulfite in approximately stoichiometric proportions..]. .[.21. A composition as claimed in claim 20 wherein said stiochiometric proportions of formaldehyde to bisulfite may vary by up to 20 percent..]. .[.22. A composition as claimed in claim 1 wherein said lignosulfonate after resulfonation is characterized in being substantially completely soluble in each of aqueous saline solutions and acid media having a pH of at least about 1.5..]. .[.23. A composition as claimed in claim 1 wherein said lignosulfonate prior to resulfonation is characterized by a pH in aqueous solution of 8.5 percent to 9.2 percent; a total sulfur content 2.5 percent to 2.9 percent by weight; the absence of reducing sugars; and a lignosulfonate content of at least 99 percent by weight..]. .[.24. A composition as claimed in claim 1 wherein said lignosulfonate is further characterized by a methoxyl content of from 12.4 to 12.9 weight percent..]. .[.25. A composition as claimed in claim 23 wherein said resulfonated lignosulfonate has a relative molecular size of 4200..]. .[.26. A composition as claimed in claim 23 wherein said resulfonated lignosulfonate has a relative molecular size of about 
     
     
        3500..]. .[.27.  A composition as claimed in claim 22 wherein said aqueous saline solution contains relatively large concentrations of sodium chloride and said acid media comprises an aqueous sulfuric acid solution at a pH within the range of about 1.5 and less than 7..]. .[.28. A composition as claimed in claim 1 wherein said resulfonation is accomplished in an aqueous reaction mass at a temperature between about 50° and about 200° C. using, for the resulfonation agents, an aldehyde of the formula: ##STR3## wherein R is hydrogen or an alkyl group containing from 1 to 3 carbon atoms in approximately stoichiometric admixture with a sulfur of the formula:   XHSO.sub.3     
     
     
       wherein X is an alkali metal..]. .Iadd.29.  A high efficiency, non-gelling retarder composition having a high degree of predictability for use in oil well cementing compositions under highly saline environment, said retarder composition comprising: a lignofulfonate or an alkali metal salt derivative thereof derived from a sulfite waste liquor that has been subjected to alkaline oxidation, hydrolysis and partial desulfonation with subsequent resulfonation;   said lignosulfonate prior to resulfonation being characterized by a relative molecular size of substantially within the range of about 1,000 to about 20,000 and containing combined organic sulfonic sulfur after partial desulfonation of from about 0.5 weight percent to about 5.0 weight percent and from about 4.5 weight percent to about 15 percent by weight of said total combined sulfur upon completion of said resulfonation, and wherein said lignosulfonate after resulfonation is substantially completely soluble in aqueous saline solution containing relatively large concentrations of sodium chloride and in acid media at pH as low as about 1.5. .Iaddend. .Iadd.30. A high efficiency, non-gelling retarder composition having a high degree of predictability for use in oil well cementing compositions under highly saline environment, said retarder composition comprising:   an alkaline oxidized hydrolyzed, partially desulfonated and subsequently resulfonated lignosulfonate;   said resulfonated lignosulfonate having substituted therein, as the resulfonation units, those of the formula:   --(CH 2 ) x  --SO 3  H, wherein x has a numerical integral value from 0 to 3; or alkali metal salt derivatives thereof; and   said resulfonated lignosulfonate containing between about 4.5 weight percent and about 15 weight percent of total sulfur in combined organic sulfonic sulfonate form; said lignosulfonate prior to resulfonation having a relative molecular size of substantially 1,000 to 20,000, and wherein said lignosulfonate after resulfonation is completely soluble in aqueous saline solution containing relatively large concentrations of sodium   
     
     
        chloride and in acid media at pH as low as about 1.5. .Iaddend. .Iadd.31. The combination of claim 30, wherein there is between about 4.5 and about 6.5 weight percent of said total combined sulfur. .Iaddend. .Iadd.32. The composition of claim 30, wherein said resulfomethylation unit is sulfomethyl group of the formula --(CH 2 )SO 3  H. .Iaddend. .Iadd.33. The composition of claim 30 in the form of an alkali metal salt. .Iaddend. .Iadd.34. The composition of claim 30 in the form of sodium salt. .Iaddend. .Iadd.35. The composition of claim 30 further characterized in having a relatively constant molecular size range with molecular size variations in the composition being within no more than about 20 volumetric percent. .Iaddend. .Iadd.36. A composition as in claim 34, wherein said relative molecular size range variation from molecule to molecule in the composition is no more than about 10 volumetric percent. .Iaddend. .Iadd.37. The composition of claim 30 further characterized in having the introduced sulfonate units substituted at least substantially in the resulfonated alkaline oxidized, hydrolyzed, partially desulfonated lignosulfonate material in ortho or para locations, or both, on the aromatic rings of the lignin molecule in the resulfonated, partially desulfonated lignosulfonate material of said composition. .Iaddend. .Iadd.38. A composition as in claim 37, wherein said substituted introduced sulfonate units are located predominantly in the ortho or para locations, or both, of said aromatic ring of the lignin molecule. 
     
     
        .Iaddend. .Iadd.39.  A composition as in claim 29, wherein said combined organic sulfonic sulfur is present, upon completion of sulfonation, in an amount of from about 4.5 to about 6.5 percent by weight. .Iaddend. .Iadd.40. A composition as in claim 29, wherein said resulfonation is carried out in an aqueous medium and in the presence of a reactant composition comprising from about 5 to about 40 percent, by weight of said desulfonated lignosulfonates, of alkali metal sulfite. .Iaddend. .Iadd.41. A composition as in claim 40, wherein said sulfite is an alkali metal bisulfite. .Iaddend. .Iadd.42. A composition as in claim 41, wherein said sulfite is sodium bisulfite. .Iaddend. .Iadd.43. A composition as in claim 40, wherein said reactant composition includes one or more aldehyde of the formula: ##STR4## wherein R is hydrogen or an alkyl group containing from 1 to 3 carbon 
     
     
        atoms. .Iaddend. .Iadd.44.  A composition as in claim 43, wherein said aldehyde is formaldehyde. .Iaddend. .Iadd.45. A composition as in claim 44, wherein said formaldehyde is present in an amount by weight of said partially desulfonated lignosulfonate of about 1.5 to about 12 percent. .Iaddend. .Iadd.46. A composition as in claim 44, wherein said formaldehyde is present with an alkali metal bisulfite in approximately 
     
     
        stoichiometric proportions. .Iaddend. .Iadd.47.  A composition as in claim 46, wherein said stoichiometric proportions of formaldehyde to bisulfite may vary by up to about 20 percent. .Iaddend. .Iadd.48. A composition as in claim 29, wherein said lignosulfonate is further characterized by a methoxy content of from about 12.4 to aout 12.9 weight percent. .Iaddend. .Iadd.49. A composition as in claim 29, wherein said resulfonation is accomplished in an aqueous reaction mass at a temperature between about 50° C. and about 200° C. using, for the resulfonation agent, an aldehyde of the formula: ##STR5## wherein R is hydrogen or an alkyl group containing from 1 to 3 carbon atoms in approximately stoichiometric admixture with a sulfite of the formula XHSO3, wherein X is an alkali metal. .Iaddend.