Metal free crosslinking of galactomannan
Methods of treating a subterranean formation are disclosed, using a fluid including an essentially metal-free organic crosslinker selected from amines, diamines, poly amines, polyamino polymers, alcohols, polyols, polyhydroxy polymers, hydroxyl amines, peptides and proteins, combined with a polysaccharide or cellulosic material having oxidized functional groups. The fluid is then introduced into a wellbore penetrating the formation to contact the formation. The polysaccharide or cellulosic material may have aldehyde groups as one example of an oxidized group, or any other suitable oxidized functional group. The polysaccharide or the cellulosic material may be oxidized using at least one of an enzymes, oxidizers, photooxidation, bacteria, catalyst, or other suitable technique. The fluid may also further include an inorganic crosslinker.
1. A method of treating a subterranean formation with a fluid, the method comprising
a) providing a fluid comprising:
i. a crosslinker
derived from a reaction product of 1,4-benzenediboronic acid and 2-hydroxy-4-aminobenzoic acid; and
ii. a polysaccharide or cellulosic material comprising oxidized functional groups; and
b) introducing the fluid into a wellbore penetrating the formation and causing the fluid to contact the formation.
2. The method of claim 1 wherein the polysaccharide or cellulosic material comprises aldehyde groups.
3. The method of claim 1 wherein the fluid further comprises an inorganic crosslinker to achieve delay and high temperature stability.
4. The method of claim 1 wherein the fluid is self breaking.
5. The method of claim 1 wherein the fluid has a pH between about 2 to about 9, and wherein the treatment is one of hydraulic fracturing, acid fracturing, gravel packing, frac and pack treatment, wellbore cleanouts, or kill pill application.
6. The method of claim 1 wherein aqueous medium is used to form the fluid, wherein the aqueous medium is contaminated, and whereby fluid viscosity is essentially unaltered by contaminants present in the aqueous medium.
7. The method of claim 1 wherein the polysaccharide or the cellulosic material is at least partially oxidized prior to hydrating or while hydrating in an aqueous medium.
8. The method of claim 1 wherein the polysaccharide or the cellulosic material is oxidized using at least one of an enzymes, oxidizers, photooxidation, bacteria or catalyst.
9. The method of claim 1 wherein the polysaccharide or cellulosic material has polyaldehyde functionality crosslinkable with an organometallic crosslinker.
10. The method of claim 9 , wherein the polysaccharide or cellulosic material is oxidized in situ during an operation to provide a polyaldehyde functionality.
11. A method comprising:
a) providing a fluid comprising a crosslinker
derived from a reaction product of 1,4-benzenediboronic acid and 2-hydroxy-4-aminobenzoic acid; and a polysaccharide or cellulosic material comprising oxidized functional groups; and
b) contacting a target material with the fluid to treat a target zone in a subterranean formation.
12. The method of claim 11 wherein the polysaccharide or cellulosic material comprises aldehyde groups.
13. The method of claim 11 wherein aqueous medium is used to form the fluid, wherein the aqueous medium is contaminated, and whereby fluid viscosity is essentially unaltered by contaminants present in the aqueous medium.
14. The method of claim 11 wherein the polysaccharide or cellulosic material is oxidized in situ during a treatment to provide a polyaldehyde functionality.