Alternative ligand formulations for cellulose products
This disclosure provides compositions suitable as drilling fluids, completion fluids, work-over fluids, or stimulation/fracking fluids, which exhibit shale inhibiting, thermostabilizing, viscosifying, and fluid loss reducing effects when used for these purposes. In some embodiments, this disclosure provides compositions that include a cellulose product comprising the contact product of: at least one cellulosic ether; at least one salt of a polyvalent metal ion; and at least one ligand or a salt of the ligand. The resulting cellulose products are useful in drilling of oil, gas, and other wells.
1. A cellulose product comprising:
a) at least one cellulosic ether selected from carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose (CMHEC), methyl cellulose (MC), hydroxyethyl methyl cellulose (HEMC), ethyl hydroxyl ethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), or combinations thereof;
b) at least one salt that is a water soluble salt of beryllium(II), magnesium(II), calcium(II), strontium(II), barium(II), titanium(II), vanadium(II), vanadium(IV), vanadium(V), chromium(III), chromium(IV), manganese(II), manganese(III), iron(II), iron(III), cobalt(II), cobalt(III), nickel(II), zinc(II), aluminum(III), tin(II), tin (IV), or combinations thereof; and
c) at least one ligand selected from at least one poly(carboxylic) acid or a salt thereof that comprises secondary nitrogen atoms, primary nitrogen atoms, or no nitrogen atoms, wherein the cellulose product has less than 10 wt % water.
2. A cellulose product according to claim 1 , wherein the poly(carboxylic) acid or the salt thereof is selected from citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, 2,2′-azanediyldisuccinic acid, tetrasodium iminodisuccinate, dicarboxymethyl glutamic acid, ethylenediamine-N,N′-disuccinic acid, oxalic acid, aspartic acid, glutaric acid, glutamic acid, salts thereof, or combinations thereof.
3. A cellulose product according to claim 1 , wherein the at least one salt is a water soluble salt of calcium(II), iron(II), iron(III), zinc(II), nickel(II), tin(II), tin (IV), or combinations thereof.
4. A cellulose product according to claim 1 , wherein the at least one salt is calcium chloride, and wherein the ligand is citric acid, malic acid, maleic acid, or combinations thereof.
5. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC);
the at least one salt is a water soluble salt of calcium(II), iron(II), iron(III), zinc(II), nickel(II), tin(II), or tin (IV); and
the ligand is a citric acid cycle substrate or product.
6. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC);
the at least one salt is a water soluble salt of calcium(II); and
the ligand is citric acid, malic acid, or maleic acid.
7. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 2 wt % Brookfield viscosity at 25° C. of from 3,000 to 8,000 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 1 ppb test dosage of greater than 92%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 1 ppb test dosage of less than 18 mL/30 minutes.
8. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 1 wt % Brookfield viscosity at 25° C. of from 1,200 to 4,000 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 2 ppb test dosage of greater than 89%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 2 ppb test dosage of less than 14 mL/30 minutes.
9. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 2 wt % Brookfield viscosity at 25° C. of from 200 to 1,000 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 2 ppb test dosage of greater than 91%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 2 ppb test dosage of less than 18.5 mL/30 minutes.
10. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 2 wt % Brookfield viscosity at 25° C. of from 500 to 3,500 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 1 ppb test dosage of greater than 92%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 1 ppb test dosage of less than 19 mL/30 minutes.
11. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 4 wt % Brookfield viscosity at 25° C. of from 20 to 200 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 4 ppb test dosage of greater than 89.5%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 4 ppb test dosage of less than 19 mL/30 minutes.
12. A cellulose product according to claim 1 , wherein:
the cellulosic ether is carboxymethyl cellulose (CMC), the at least one salt is a water soluble salt of calcium(II); and the ligand is citric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, aconitic acid, iso-citric acid, α-ketoglutaric acid, β-ketoglutaric acid, succinic acid, ascorbic acid, or combinations thereof;
the cellulose product is characterized by 4 wt % Brookfield viscosity at 25° C. of from 20 to 200 mPa·s;
the cellulose product is characterized by a weight percent recovery of shale chips on a 1.18 mm sieve after hot rolling for 16 hours at 100° C. at a 2 ppb test dosage of greater than 90%; and
the cellulose product is characterized by an API Fluid Loss according to ISO 14014-1 at a 2 ppb test dosage of less than 18 mL/30 minutes.
13. A method of using a cellulose product comprising:
a) providing a cellulose product according to claim 1 ;
b) combining the cellulose product with an aqueous carrier to form a water-based modified cellulose composition; and
c) using the water-based modified cellulose composition as a drilling fluid, a completion fluid, a work-over fluid, or a stimulation/fracking fluid.
14. A method of using a cellulose product according to claim 13 , further comprising combining the water-based modified cellulose composition with a cross-linking agent, an inhibition agent, a viscosifying agent, a filtrate reducing agent, a thermal stabilizing agent, a shear strength stabilizing agent, a bentonite clay, an illite clay, a smectite clay, a montmorillonite clay, a kaolite clay, barium sulfate, calcium carbonate, hematite, a starch, a deflocculant, an anionic polyelectrolyte, an acrylate, a polyphosphate, a lignosulfonate, tannic acid, a derivatized tannic acid, an unmodified cellulosic material, a lubricant, a weighting agent, a fluid loss additive, a brine, a formate salt, or combinations thereof.
15. A cellulose product according to claim 1 , wherein the salt of a polyvalent metal ion is aluminum sulfate or a combination of aluminum sulfate and calcium chloride, and wherein the ligand is citric acid, malic acid, maleic acid, or combinations thereof.
16. A cellulose product comprising:
a) carboxymethyl cellulose (CMC);
b) aluminum sulfate or calcium chloride; and
c) at least one ligand selected from citric acid, malic acid, or maleic acid;
wherein the cellulose product has less than 10 wt % water.