Friction reducers, fracturing fluid compositions and uses thereof

Information

  • Patent Grant
  • 11274243
  • Patent Number
    11,274,243
  • Date Filed
    Friday, March 13, 2020
    4 years ago
  • Date Issued
    Tuesday, March 15, 2022
    2 years ago
Abstract
Friction reducers, fracturing fluid compositions and methods for treating subterranean formations, wherein friction reducer is a reacted, grafted or blend of natural gum and polyacrylamide having a molecular weight between 300,000 and 30,000,000.
Description
FIELD OF THE INVENTION

The invention relates to friction reducer fluid compositions and methods for treating subterranean formations.


BACKGROUND OF THE INVENTION

Galactomannan gums have many industrial and nonindustrial uses, such as the use in oil and gas fields as part of fracturing fluid and as a crosslinkable polymer to carry proppants, and in food and beverages as a thickener, stabilizer, suspension and binding agent, and in explosives. Similarly, polyacrylamides also have various uses such as water treatment, flocculants, absorbents, thickening agents, oil and gas fields for secondary oil recovery and as a proppant carrier and friction reducer.


In oil well operations, a fracturing fluid is pumped into the well bore under high pressure to fracture the rock formations surrounding it. The pressure is then relieved, allowing the oil to seep through the fractures into the well bore where it is pumped to the surface. It is desirable to have the thickening agent degrade because degradation should decrease the viscosity to near the levels it would be at without the thickening agent. This is desirable because, when the viscosity of the fracturing fluid is high, oil will not flow easily into the fractures of the formation and will remain in the fissured spaces. A good thickening agent, therefore, yields a high viscosity at a low concentration, reduces friction pressure, is inexpensive, and degrades once it has carried the sand particles into the fractures. Preferably, it should also not leave insoluble precipitates or residues when it is degraded, as these precipitates or residues tend to plug the formations. The amount of oil which can be obtained from a well depends to a great extent upon how extensively the rock formations can be fractured. This, in turn, depends upon the degree of pressure that is applied to the rock. Due to friction between the fracturing fluid and the pipe or rock and within the fracturing fluid itself because of turbulent flow, a significant amount of energy may be lost as the fluid travels from the earth's surface to the formation, and considerably less pressure may be actually applied to the rock than was originally applied at the top of the well. This problem is minimized by adding a friction reducer to the fracturing fluid.


A good friction reducer should cause a large decrease in friction when used in small concentrations, be inexpensive, have shear, temperature and pressure stability, work at all or most total dissolved solids (TDS) and not leave deposits which plug the formation.


There remains a need in the art for good friction reducers that would satisfy these characteristics and for fracturing fluid compositions containing these friction reducers.


SUMMARY OF THE INVENTION

In one embodiment, the invention provides a friction reducer comprising a reacted product of natural gum and partially hydrolyzed polyacrylamide (PHPA) having a molecular weight between 300,000 and 30,000,000, wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.




embedded image


In one embodiment, the invention provides a friction reducer comprising of partially hydrolyzed polyacrylamide (PHPA) grafted on natural gum having a molecular weight between 300,000 and 30,000,000, wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.




embedded image


In one embodiment, the invention provides a friction reducer comprising a blend of natural gum and partially hydrolyzed polyacrylamide (PHPA) having a molecular weight between 300,000 and 30,000,000, wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.




embedded image


In one embodiment, the ratio of natural gum and PHPA is from about 5:1 to about 1:0.01 by weight of the friction reducer.


In one embodiment, the natural gum is a galactomannan gum.


In one embodiment, the galactomannan gum is guar gum.


In one embodiment, the guar gum is derivatized.


In one preferred embodiment, the friction reducer comprises a locust bean gum.


In another preferred embodiment, the friction reducer comprises a karaya gum.


In another preferred embodiment, the friction reducer comprises a cassia tora gum.


In one embodiment, the friction reducer comprises a cellulose polymer.


In one embodiment, the friction reducer comprises a starch polymer.


In another embodiment, the friction reducer comprises a combination of two or more ingredients selected from guar gum, guar gum derivatives, locust bean gum, karaya gum, cassia tora, carrageenan gum, xanthan gum, starch, cellulose or any natural gum.


In another embodiment, the friction reducer comprises copolymers of acrylamides.


In another embodiment, the friction reducer comprises acrylic acids.


In another embodiment, the friction reducer comprises acrylic acids salts.


In another embodiment, the friction reducer comprises a combination of PHPA, copolymers of acrylamides, acrylic acid and its salts.


In one embodiment, the friction reducer can be prepared by reacting a natural gum, either a guar gum or another gum or a combination of gums with a PHPA, either a copolymer of acrylamides or acrylic acids and its salts.




embedded image


In one embodiment, the friction reducer can be prepared by grafting PHPA either a copolymer of acrylamides or acrylic acids and its salts, on a natural gum, either a guar gum or another gum or a combination of gums.




embedded image


In one embodiment, the friction reducer can be prepared by combining a natural gum, either a guar gum or another gum or a combination of gums and a PHPA, either a copolymer of acrylamides or acrylic acids and its salts.


The invention is particularly suited for slick water fracturing applications, wherein a low viscosity aqueous fluid is pumped into subterranean formations to induce the subterranean fractures. The hydrated polymer suppresses the turbulence present in high velocity gradient water.


In one embodiment, the invention provides a fracturing fluid comprising: an aqueous base fluid, a dry blend or a liquid slurry; a friction reducer, wherein the friction reducer is either a reacted compound of natural gum and PHPA or a grafted PHPA on a natural gum or a blend of natural gum and PHPA having a molecular weight between 300,000 and 30,000,000 wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.


In one embodiment, the concentration of the friction reducer in the fracturing fluid is from about 0.2% to about 0.5% and more preferably from about 0.1% to about 0.2% by weight of the fracturing fluid.


In one embodiment, the concentration of the PHPA in the fracturing fluid is from about 0.02% to about 0.05% by weight of the fracturing fluid.


In one embodiment, the fracturing fluid of the invention has a viscosity of from 1 cp to 10 cps; and more preferably from 2 cps to 4 cps.


In one embodiment, the fracturing fluid of the invention has a viscosity of from 50 cps to 500 cps; and more preferably from 50 cps to 250 cps when crosslinked.


In one embodiment, the temperature of the fracturing fluid of the invention is less than 150° C., preferably 120° C. or less, and even more preferably 100° C. or less.


In one embodiment, the temperature of the fracturing fluid of the invention is less than 120° C.


In one embodiment, the concentration of the friction reducer is about 0.1% or less by weight of the fracturing fluid.


In another embodiment, fresh water comprises 95% or more, preferably, 97% or more, and even more preferably 99% or more by weight of the aqueous base fluid.


In one embodiment, the aqueous base fluid is a fresh water or brine or flowback water or a combination of water sources.


Brine comprising one or more dissolved inorganic salts in a total concentration between 0.1 and 20 weight percent of the total weight of the aqueous base fluid.


In another embodiment, the inorganic salt comprises one or more monovalent or divalent or trivalent cations.


In another embodiment, the trivalent cations comprise iron cations.


In another embodiment, the trivalent cations comprise boron cations.


In another preferred embodiment, the trivalent cations comprise both iron and boron cations.


In another embodiment, the divalent cations comprise calcium cations.


In another embodiment, the divalent cations comprise iron cations.


In another embodiment, the divalent cations comprise strontium cations.


In one preferred embodiment, the divalent cations comprise magnesium cations.


In another preferred embodiment, the divalent cations comprise of calcium, iron, strontium and magnesium cations.


In one preferred embodiment, the monovalent cations comprise sodium cations.


In another preferred embodiment, the monovalent cations comprise potassium cations.


In another preferred embodiment, the monovalent cations comprise both sodium and potassium cations.


In another embodiment, the inorganic salt comprises one or more monovalent or divalent anions.


In another embodiment, the divalent anions comprise sulfates.


In another embodiment, the divalent anions comprise sulfides.


In another embodiment, the divalent anions comprise oxides.


In another embodiment, the divalent anions comprise carbonates.


In another preferred embodiment, the divalent anions comprise of sulfates, sulfides, carbonates and oxides.


In one preferred embodiment, the monovalent anions comprise of chlorides.


In another preferred embodiment, the monovalent anions comprise of bicarbonates.


In another preferred embodiment, the monovalent anions comprise both of chlorides and bicarbonates anions.


In one embodiment, at least a portion of the aqueous base fluid is flowback water.


In another embodiment, the aqueous base fluid comprises fresh fracturing fluid, recycled fracturing fluid, flowback fracturing fluid or back-produced fracturing fluid, or combinations thereof.


In one embodiment, the friction reducer can act as hybrid fracturing fluid and eliminate the need to use two products for different stages of fracturing.


In one embodiment, the friction reducer can also be used for carrying proppants from 20 mesh to 100 mesh.


In one embodiment, the friction reducer can also be crosslinked with boron and other group 4 metals likes zirconium, titanium and hafnium.


In another embodiment, the friction reducer can be used without any additional crosslinkers. Thus, in one embodiment, the fracturing fluid of the invention does not include any additional cross-linker (because there is no need to use other cross-linkers due to the advantages of the provided synergistic compound).


In one embodiment, the friction reducer is biodegradable.


In one embodiment, the friction reducer is breakable into small particles with strong oxidizers.


In one embodiment, the friction reducer does not block the screen with iron present.


In one embodiment, the friction reducer is slurriable in mineral oil and other non-sheen forming oils and solvents.





BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.



FIG. 1 is a graph demonstrating friction reduction performance of various modified friction reducer (MFR) in Houston Tap Water (HTW) and 7% (KCl).



FIG. 2 is another graph demonstrating friction reduction performance of MFR at different concentrations 0.25%, 0.125% and 0.0625% in HTW and 7% KCl solution.



FIG. 3 is a graph demonstrating friction reduction performance of various MFR in HTW, 7% KCl solution, and 150K synthetic brine.



FIG. 4 is a graph demonstrating friction reduction performance of various MFR in HTW and 231K synthetic brine.



FIG. 5 is a graph of viscosity vs time for guar gum 0.375% solution at 120° C. cross-linked with a delayed borate crosslinker using 0.25% oxygen scavenger.



FIG. 6 is a graph of viscosity vs time for MFR-210 0.375% solution at 120° C. cross-linked with a delayed borate crosslinker using 0.25% oxygen scavenger sodium thiosulfate.



FIG. 7 is a graph of viscosity vs time for MFR-212 0.375% solution at 120° C. cross-linked with zirconium based crosslinker using 0.25% oxygen scavenger.



FIG. 8 is a graph of viscosity vs time for MFR-210 0.25% solution in 5% KCl at 120° C. cross-linked with delayed boron based crosslinker.



FIG. 9 is a bar graph of sand volume of 0.24% solution of various blends of the invention in a sand settling test.



FIG. 10 is a graph demonstrating friction reduction performance of MFR in HTW and 150K synthetic brine compared with a Cationic FR.





DETAILED DESCRIPTION OF THE INVENTION

The invention is directed to a surprising and unexpected discovery that a reacted, grafted or blended mixture of natural gum and polyacrylamide having a molecular weight between 300,000 and 30,000,000 can serve as an effective friction reducer at a very low concentration of less than 0.1% by weight (when this blend is used in a combination with an aqueous base fluid, a dry blend, or a liquid slurry) or as a thickening agent when used at higher concentrations of greater than 0.2% by weight, wherein “by weight” refers to the total weight of the aqueous base fluid, dry blend or liquid slurry.


The polyacrylamides currently used as friction reducers are essentially linear homopolymers. In contrast, the synergetic blend of the present invention is a reacted compound or mixture of mainly a natural gum (a carbohydrate with soluble fiber) with small amounts of (1-20% and preferably 1-10% and more preferably 1-5% by total weight of the friction reducer) partially hydrolyzed polyacrylamides (PHPAs). One of the key advantages of the friction reducers of the present invention is that when they are utilized as friction reducers, they provide more viscous aqueous solutions than conventional friction reducers while maintaining the friction reducing properties. Therefore, the synergetic compounds of the present invention are more economically utilizable as friction reducers than conventional linear galactomannans and homo polyacrylamides because they provide the desired solution properties at lower concentrations, such as 0.1% or less by weight of the fracturing fluid.


The synergistic compounds of the present invention effectively reduce friction in all Total Dissolved Solids (TDS) brines. Utilizing friction reducers of the present invention allows to avoid the need for separate friction reducers for fresh water, mid brine, high brine, cationic liquid friction reducer, or high viscosity liquid friction reducer.


At higher concentrations of greater than 0.2% by weight of the fracturing fluid, this blend is effective as a thickening agent. The synergistic blend of the present invention has improved shear and temperature stability, is easily degradable, and does not leave any insoluble residues when degraded.


The term “natural gum” refers to polysaccharides of natural origin, capable of causing a large increase in a solution's viscosity, even at small concentrations. This term includes, but is not limited to, galactomannan gums.


In one embodiment, the invention provides a friction reducer comprising a reacted, a grafted or a blend of natural gum and partially hydrolyzed polyacrylamide (PHPA) having a molecular weight between 300,000 and 30,000,000, wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.


In one embodiment, the ratio of natural gum and PHPA is from about 5-1 to about 1:0.01 by weight of the fraction reducer.


In one embodiment, the natural gum is a galactomannan gum.


In one embodiment, the galactomannan gum is guar gum.


In one preferred embodiment, the friction reducer comprises a locust bean gum.


In another preferred embodiment, the friction reducer comprises a karaya gum.


In another preferred embodiment, the friction reducer comprises a cassia tora gum.


In one embodiment, the friction reducer comprises a cellulose polymer.


In one embodiment, the friction reducer comprises a starch polymer.


In another embodiment, the friction reducer comprises a combination of two or more ingredients selected from guar gum, guar gum derivatives, locust bean gum, karaya gum, cassia tora, carrageenan gum, xanthan gum, starch, cellulose or any natural gum.


In another embodiment, the friction reducer comprises copolymers of acrylamides.


In another embodiment, the friction reducer comprises acrylic acids.


In another embodiment, the friction reducer comprises acrylic acids salts.


In another embodiment, the friction reducer comprises a combination of PHPA, copolymers of acrylamides, acrylic acid and its salts.


In one embodiment, the friction reducer can be prepared by combining a natural gum and a PHPA. The combination can be a reacted product, or a grafted polymer or a simple blend.


The invention is particularly suited for slick water fracturing applications, wherein a low viscosity aqueous fluid is pumped into subterranean formations to induce the subterranean fractures. The hydrated polymer suppresses the turbulence present in high velocity gradient water.


In one embodiment, the invention provides a fracturing fluid comprising: an aqueous base fluid, a dry blend or a liquid slurry; a friction reducer, wherein the friction reducer is a reacted blend of natural gum and PHPA having a molecular weight between 300,000 and 30,000,000 wherein the PHPA and/or natural gum has an average particle size of 150 μm or less.


In one embodiment, the concentration of the friction reducer in the fracturing fluid is from about 0.1% to about 0.5% and more preferably from about 0.1% to about 0.2% by weight of the fracturing fluid.


In one embodiment, the concentration of the PHPA in the fracturing fluid is from about 0.02% to about 0.05% by weight of the fracturing fluid.


In one embodiment, the fracturing fluid of the invention has a viscosity of from 1 cp to 10 cps; and more preferably from 2 cps to 4 cps.


In one embodiment, the temperature of the fracturing fluid of the invention is less than 150° C., preferably 120° C. or less and even more preferably 100° C. or less.


In one embodiment, the concentration of the friction reducer is about 0.1% or less by weight of the fracturing fluid.


In another embodiment, fresh water comprises 95% or more, preferably, 97% or more, and even more preferably 99% or more by weight of the aqueous base fluid.


In one embodiment, the aqueous base fluid is a brine comprising one or more dissolved inorganic salts in a total concentration between 0.1 and 20 weight percent of the total weight of the aqueous base fluid.


In another embodiment, the inorganic salt comprises one or more monovalent or divalent or trivalent cations and monovalent and divalent anions.


In another embodiment, the trivalent cations comprise iron cations.


In another embodiment, the trivalent cations comprise boron cations.


In another preferred embodiment, the trivalent cations comprise both iron and boron cations.


In another embodiment, the divalent cations comprise calcium and iron cations.


In one preferred embodiment, the divalent cations comprise magnesium and strontium cations.


In another preferred embodiment, the divalent cations comprise both calcium, iron, strontium and magnesium cations.


In one preferred embodiment, the monovalent cations comprise sodium cations.


In another preferred embodiment, the monovalent cations comprise potassium cations.


In another preferred embodiment, the monovalent cations comprise both sodium and potassium cations.


In another embodiment, the divalent anions comprise of sulfates, sulfides and oxides.


In another preferred embodiment, the monovalent anions comprise of chlorides and bicarbonates.


In one embodiment, at least a portion of the aqueous base fluid is flowback water.


In another embodiment, the aqueous base fluid comprises fresh fracturing fluid recycled fracturing fluid, flowback fracturing fluid or back-produced fracturing fluid, or combinations thereof.


In one embodiment, the friction reducer can act as hybrid fracturing fluid and eliminate the need to use two products for different stages of fracturing.


In one embodiment the friction reducer can be used as iron control. It doesn't block the screen when iron is present in produced water.


In one embodiment, the friction reducer can also be used for carrying proppants from 20 mesh to 100 mesh.


In one embodiment, the friction reducer can also be crosslinked with boron and other group 4 metals likes zirconium, titanium and hafnium.


In another embodiment, the friction reducer of the invention can be used without any additional crosslinkers. Thus, in one embodiment, the fracturing fluid of the invention does not include any additional cross-linker (because there is no need to use other cross-linkers due to the advantages of the provided synergistic blend and because viscosity of the fracturing fluid does not need to be high for slick water applications).


In one embodiment, the friction reducer is biodegradable.


In one embodiment, the friction reducer is breakable with strong oxidizers.


In one embodiment, the friction reducer is slurriable in mineral oil and other non-sheen forming oils and solvents.


Hydraulic fracturing is an unconventional drilling method used due to increasing scarcity of retrieving oil and gas using conventional methods. It allows to drill down, drill horizontally and fracturing happens, which enables oil and gas to be flowing from tight reservoirs. The general practice for treatments of reservoirs applies a sequence of pumping events where millions of gallons of water based fracturing fluids mixed with proppants and other chemicals are pumped in a controlled environment above fracture pressure. Proppants such as sand or ceramic beads are usually added to hold the fractures open after treatment is complete. The chemical additives typically account for only 0.5%-2% of the total fluid, the rest is water. The chemical additives include, but are not limited to, thickening agents, such as friction reducers, guar gum and its derivatives, crosslinkers, scale inhibitors, corrosion inhibitors, biocides, surfactants, acids, oxygen scavengers, breakers and clay control.


The main fluids currently used for fracturing are water-based friction reducing additives called slick water. This allows the fracturing additives to be pumped to the target zone at reduced pressure and higher rate. However, the choice of additives varies with water quality source, site specific needs of the target formation and including company preferences along with the design engineer.


The fracturing fluid of the invention may also contain other conventional additives common to the well service industry, including but not limited to, corrosion inhibitors, surfactants, demulsifying agents, scale inhibitors, asphaltene inhibitors, paraffin inhibitors, gas hydrate inhibitors, dispersants, oxygen scavengers, biocides and the like.


Suitable surfactants may act as surface active agents and function as emulsifiers, dispersants, foamers or defoamers. In some embodiments of the invention, the surfactant is an anionic surfactant. Examples of suitable anionic surfactants also include, but are not limited to, cationic surfactants such as alkyl amines, alkyl diamines, alkyl ether amines, alkyl quaternary ammonium, dialkyl quaternary ammonium and ester quaternary ammonium compounds. Examples of suitable ionic surfactants also include, but are not limited to, surfactants that are usually regarded as zwitterionic surfactants and in some cases as amphoteric surfactants such as alkyl betaines, alkyl amido betaines, alkyl imidazolines, alkyl amine oxides and alkyl quaternary ammonium carboxylates.


Examples of common additives that could be present in the friction reducers and/or fracturing fluids of the present invention, as well as a more detailed explanation how friction reducers and/or fracturing fluids may work can be found, for example, in U.S. Pat. No. 7,857,055 (Li), U.S. Patent Application Publication No. 2012/0157356, the contents of which are herein incorporated by reference in their entirety.


The following are some of the examples of the friction reducer melds of the invention:


FR: anionic PHPA: 100% by weight of the total composition.


MFR-210: fast hydrating guar gum reacted or grafted or blended with anionic PHPA or PAM.


MFR-211: premium guar gum reacted or grafted or blended with anionic PHPA or PAM


MFR-212: CMHPG: reacted or grafted or blended with anionic PHPA or PAM


Molecular weight of anionic PHPA was between 10,000,000 and 30,000,000. All tested anionic PHPAs worked for the purposes of the invention.


Hereinafter, the present invention will be further illustrated with reference to the following examples. However, these examples are only provided for illustrative purposes, and are not meant to limit the scope of the present invention.


EXAMPLES

The following is a list of abbreviations used throughout these Examples and the rest of the specification:















Additives



















cps
Centipoise



GG
Guar Gum



RT
Room Temperature



HPG
Hydroxy Propyl Guar



CMHPG
Carboxy Methyl Hydroxy Propyl Guar



SHI-057PB
Anionic PHPA Dry (FR)



HTW
Houston Tap Water



DIW
Deionized Water



KCl
Potassium Chloride



PAM
Polyacrylamide



PHPA
Partially Hydrolyzed Polyacrylamide



MFR-210
Modified Friction Reducer Fast hydrating



MFR-211
Modified Friction Reducer Premium



MFR-212
Modified Friction Reducer Derivatized










Example 1

Preparation of Natural Gum/Polyacrylamide Blends


To a 500 ml WARING blender jar 250 ml DIW was added and 1.2 gms of either guar gum or a friction reducer or a modified friction reducer for 0.5% solution and 0.6 gms for 0.25% solution was slowly added and mixed at 1100 rpm on Grace M3080 variable speed mixer for 2.5 minutes at room temperature.


Hydration viscosities in centipoise (cps) were compared between regular guar gum and regular anionic PHPA and between modified friction reducer. Hydration viscosities were measured on Grace 3600, at 3 minutes and 60 minutes. It was used as a stand-alone unit without the use of external equipment, as described in U.S. Pat. No. 6,571,609, the contents of which are hereby incorporated by reference in their entirety. The results are shown in Table 1 below, which shows that the polysaccharide blend with anionic PHPA produced higher hydration viscosities than regular guar gum or regular anionic PHPA. At the end of the experiment, pH was also measured.










TABLE 1







Hydra-



tion
Viscosity (cps)













Time
MFR-211
MFR-211
FR
FR
Guar Gum
Guar Gum


(min)
0.5%
0.25%
0.5%
0.25%
0.5%
0.25%
















3
43
16
20
11
39
12


30
52
20
45
17
44
14


pH
7.6
7.73
7.72
7.78
7.61
7.69









To test further concentrations, additional blends were prepared as follows. To a 500 ml WARING blender jar 250 ml DIW was added and guar gum or modified friction reducer blend, 0.6 gms for 0.25% solution and 0.3 gms for 0.125% solution and 0.15 gms for 0.0625% solution was slowly added and mixed at 1100 rpm on Grace M3080 variable speed mixer for 2.5 minutes at room temperature. Hydration viscosities were measured on Grace 3600, at 3 minutes and 60 minutes.


Hydration viscosities in centipoise (cps) were compared between guar gum and derivatized guar gum and between mixtures of guar gum and polyacrylamides. From 90.1% guar gum and 9.9% anionic polyacrylamide mixture was blended and compared. These samples were sent to a third-party lab to run friction loop test.


The results of the test are shown in Tables 2 and 3 below.










TABLE 2







Hydra-



tion
Viscosity (cps)













time
GG
GG
GG
MFR-210
MFR-210
MFR-210


(min)
0.063%
0.13%
0.25%
0.06%
0.13%
0.25%
















3
2.1
3.9
12.4
3.2
6.7
15


30
2.3
4.7
14.5
3.5
8.2
16.5

















TABLE 3







Hydra-



tion
Viscosity (cps)












time
CMHPG
CMHPG
CMHPG
MFR-212
MFR-212


(min)
0.063%
0.13%
0.25%
0.06%
0.13%















3
2.9
6
11.5
4.3
9.2


30
3.9
6
13.3
4.7
9.2









The results shown in Table 2 and 3 indicate that the current inventive compound MFR-210 and MFR-212 has higher viscosity than regular guar gum or CMHPG for the same concentration and same temperature.


To test whether there are variations based on a supplier of PHPA, we ran tests using different versions of PHPA received from different suppliers, referred to as FR-1; FR-2 and FR-3, FR-1, FR-2 and FR-3 are all PHPAs.


To a 500 ml WARING blender jar 250 ml DIW was added and guar gum and anionic PHPA from different vendors were blended for 0.25%, 0.125% and 0.0625% solutions and mixed at 1100 rpm on Grace M3080 variable speed mixer at 1100 rpm for 2.5 minutes. Hydration viscosities were measured on Grace 3600, at 3 minutes and 60 minutes.


The results of the tests are shown in Tables 4-6 below. Each of Tables 4-6 contains data for a different version of PHPA.










TABLE 4







Hydra-



tion
Viscosity (cps)













time
GG
GG
GG
MFR-210
MFR-210
MFR-210


(min)
0.63%
0.13%
0.25%
0.06%
0.13%
0.25%
















3
1.9
3.7
8.9
2.5
4.9
11.9


30
2
4.5
11.1
3
6.4
14.2

















TABLE 5







Hydra-
Viscosity (cps)













tion



FR2
FR2
FR2


time
GG
GG
GG
MFR-210
MFR-210
MFR-210


(min)
0.63%
0.13%
0.25%
0.06%
0.13%
0.25%

















1.9
3.7
8.9
2.9
5.6
15.5


30
2
4.5
11.1
3.1
7
18.8

















TABLE 6







Hydra-
Viscosity (cps)













tion



FR3
FR3
FR3


time
GG
GG
GG
MFR-210
MFR-210
MFR-210


(min)
0.63%
0.13%
0.25%
0.06%
0.13%
0.25%
















3
1.9
3.7
8.9
2.9
5.8
17.2


30
2
4.5
11.1
3
7.2
19.2









The results shown in Tables 4-6 indicate that PHPA choice is not limited to a particular vendor. All combinations of guar gum and PHPA resulted in higher hydration viscosities compared to regular guar gum.


Example 2

Testing of Various Natural Gum/Polyacrylamide Compound


The following compounds were tested to determine their effect on friction reduction: 0.25% solution of MFR-210; 0.125% solution of MFR-210; 0.25% solution of MFR-211 and 0.125% solution of MFR-210 in 7% KCl.


The experiment was conducted as follows.


The flow loop test was conducted at room temperature for 6 minutes. The fluid was flowing at 6 gallons per minute, average pressure in ⅜″ outside diameter (OD) flow loop was 60-65 PSI and for ½″ OD flow loop was 9-10 PSI.


Samples were tested with fresh water and different brines by measuring its friction reduction percentage though ⅜″ and 2″ OD pipe using Chandler Flow-Loop system. The water sample was circulated throughout the flow-loop at a rate of 6 gallons per minute.


Once rate was established for a total duration of three minutes, the loop was discharged and refilled with already hydrated solution of the friction reducer products at specific loadings. The solution was circulated to establish the new reduced friction pressures which were used to calculate the friction pressure percentages.


The Flow Loop (FL) pipe diameters were as follows:


¾ (OD) is 8 ft and 0.619 inch as inside diameter (ID)


½ (OD) is 8 ft and 0.404 inch as ID


⅜ (OD) is 5 ft and 0.251 inch as ID


The Flow Loop (FL) test is well known in the industry. Samples were tested with fresh water and different brines by measuring its friction reduction percentage though ⅜″ and 2″ OD pipe using Chandler Flow-Loop system. The water sample was circulated throughout the flow-loop at a rate of 6 gpm (gallons per minute). Once rate was established for a total duration of three minutes, the loop was discharged and refilled with already hydrated solution of the guar products at specific loadings. The solution was circulated to establish the new reduced friction pressures which were used to calculate the friction pressure percentages.


The results of this experiment are shown in FIG. 1. It shows a better friction reduction performance at a lower concentration (0.125%) of different grades compared to 0.25% of the modified friction reducer (MFR). The experiment also demonstrated that at this concentration, the friction reduction does not change when fresh water is replaced with 7% potassium chloride solution.


Then, the performance of 0.0625% solution of MFR-210 was evaluated in the same manner. The results of this experiment are shown in FIG. 2. It shows a better friction reduction performance at a lower concentration of 0.0625% solution as compared to the 0.25% solution or the 0.125% solution. The experiment also demonstrated that the friction reduction does not change when fresh water is replaced with 7% potassium chloride.


Then, the performance of 0.0625% solution MFR-210 was tested in 150K Synthetic Brine and the performance of 0.0325% solution MFR-210 was tested in HTW. The results of this experiment are shown in FIG. 3. It shows a better friction reduction performance at lower concentration of 0.0625% solution and 0.0325% solution compared to 0.125% and 0.25% solution and the friction reduction does not change when fresh water is replaced with 7% potassium chloride and 150K synthetic brine.


Finally, the following compounds were tested to determine their effect on friction reduction: 0.0625% solution of guar gum in HTW; 0.0625% solution of MFR-210 (vendor 2) in HTW; 0.0625% solution of MFR-210 (vendor 3) in HTW; 0.0625% solution of MFR-210 (vendor 4) in HTW; and 0.0625% solution of MFR-210 in 231K Brine.


150K Brine and 231K Brine refers to total dissolved solids (TDS) brines. TDS brine is a flow back water from gas wells, such as Marcellus shale region brine after hydraulic fracturing


The compositions of 150K and 213K Brine are listed below:













TABLE 7







Sample Name
150K TDS Brine
231K TDS Brine
















Physical Properties (mg/L)











TDS
194495.1988
220870.0000







Cations (mg/L)











Boron (B)
0.000
30.000



Barium (Ba+2)
4926.440
2.000



Calcium (Ca+2)
21442.504
9170.000



Iron (Fe+2)
189.363
5.000



Potassium (K+)
807.656
1317.000



Magnesium (Mg+2)
2916.590
1460.000



Manganese (Mn+2)
0.000
0.000



Sodium (Na+)
37995.469
74400.000



Strontium (Sr+2)
9684.440
785.000



Zinc (Zn+2)
0.000
0.000







Anions (mg/L)











Chlorides (Cl)
116483.346
132500.000



Sulfates (SO4−2)
0.000
515.000







Alkalinity (mg/L)











Bicarbonates (HCO3)
49.390
686.000










150K and 231K TDS Brines were provided by Premier Oilfield Group, which also did the Friction Loop test.


The results of this experiment are shown in FIG. 4. It shows premium friction reduction performance at lower concentration of 0.0625% solution of MFR from different vendors and at that same concentration the friction reduction does not change when fresh water is replaced with 231K Brine.


Example 3

Measuring Viscosity of Natural Gum/Polyacrylamide Blends


Viscosity of the friction reducer of the invention was tested using various cross-linking tests. These tests were also done to determine whether the guar gum properties were still intact in the friction reducer of the invention. The tests were done as follows:


All crosslink tests were done at high pressure around 400 PSI and a temperature from 93° C. to 120° C. on Grace M5600 HTHP Viscometer.


Test 1 was done using guar gum 0.375% solution at 120° C. and crosslinking with a delayed borate crosslinker, using 0.25% oxygen scavenger sodium thiosulfate.


The test was done as follows. Guar gum solution was hydrated for 30 minutes at room temperature. Then, 0.25-0.5 ml buffer (45-50% potassium carbonate solution) was added and mixed for 30 seconds. pH was measured to make sure it was above 10. The rest of the chemicals (clay control (1 gpt choline chloride), surfactants (1 gpt non emulsifier) and oxygen scavengers (20 ppt sodium thiosulphate)) in no particular order were added.


At the end, the crosslinker was added and mixed at high shear of 2500 rpm. 50 ml of the crosslink fluid was taken and added to the test cup to run Grace 5600 test.


The results of Test 1 are shown in FIG. 5. It shows guar gum performance at 120° C. temperature and 400 PSI pressure, when crosslinked with a delayed borate crosslinker. The plot shows apparent viscosity, cps @ 100 sec−1, versus time in minutes. The fluid was stable for 2 hours with above 400 cps viscosity. The plot shows apparent viscosity, cps @ 100 sec−1, versus time in minutes.


Test 2 was done using MFR-210 0.375% solution at 120° C. and crosslinking with a delayed borate crosslinker, using 0.25% oxygen scavenger sodium thiosulfate.


MFR-210 solution was hydrated for 30 minutes at room temperature. Then, 0.25-0.5 ml buffer (45-50% potassium carbonate solution) was added and mixed for 30 seconds. pH was measured to make sure it was above 10. The rest of the chemicals (clay control (1 gallon per thousand gallons (gpt) choline chloride), surfactants (1 gpt non-emulsifier) and oxygen scavengers (20 ppt sodium thiosulphate)) in no particular order were added.


At the end, the crosslinker was added and mixed at high shear of 2500 rpm. 50 ml of the crosslink fluid was taken and added to the test cup to run Grace 5600 test.


The results of Test 2 are shown in FIG. 6. It shows MFR-210 performance at 120° C. temperature and 400 PSI pressure, when crosslinked with a delayed borate crosslinker. The plot shows apparent viscosity, cps @ 100 sec−1, versus time in minutes. The fluid was stable for 2 hours with above 400 cps viscosity. The viscosity was determined on a Grace 5600HTHP Viscometer. This means that the inventive blend did not destroy the guar gum properties.


Test 3 was done using MFR-212 0.375% solution at 120° C. and crosslinking with zirconium based crosslinker, using 0.25% oxygen scavenger sodium thiosulfate.


MFR-212 solution was hydrated for 30 minutes at room temperature. Then, 0.25-0.5 ml buffer (45-50% potassium carbonate solution) was added and mixed for 30 seconds. pH was measured to make sure it was above 10. The rest of the chemicals (clay control (1 gpt choline chloride), surfactants (1 gpt non-emulsifier) and oxygen scavengers (20 ppt sodium thiosulphate)) in no particular order were added.


At the end, the crosslinker was added and mixed at high shear of 2500 rpm. 50 ml of the crosslink fluid was taken and added to the test cup to run Grace 5600 test.


The results of Test 3 are shown in FIG. 7. It shows MFR-212 performance at 120° C. temperature and 400 PSI pressure, when crosslinked with a zirconium crosslinker. The plot shows apparent viscosity, cps @ 100 sec−1, versus time in minutes. The fluid was stable for 2 hours with above 400 cps viscosity. The viscosity was determined on a Grace 5600HTHP Viscometer. This means that the inventive blend did not destroy the guar gum properties.


Test 4 was done using MFR-210 0.25% solution in 5% KCl at 93° C. and crosslinking with instant boron based crosslinker.


MFR-210 solution was hydrated for 30 minutes in 5% KCl solution at room temperature. Then, 0.25-0.5 ml buffer (45-50% potassium carbonate solution) was added and mixed for 30 seconds. pH was measured to make sure it was above 10. The rest of the chemicals (clay control (Igpt choline chloride), surfactants (1 gpt non emulsifier) and oxygen scavengers (20 ppt sodium thiosulphate)) in no particular order were added.


At the end crosslinker was added and mixed at high shear of 2500 rpm. 50 ml of the crosslink fluid was taken and added to the test cup to run Grace 5600 test.


The results of Test 4 are shown in FIG. 8. FIG. 8 shows MFR-210 in 5% KCl performance at 93° C. temperature and 400 PSI pressure, when crosslinked with a boron crosslinker. The plot shows apparent viscosity, cps @ 100 sec−1, versus time in minutes. The fluid was stable for 2 hours with above 300 cps viscosity. The viscosity was determined on a Grace 5600HTHP Viscometer. This means that the inventive blend did not destroy the guar gum properties.


Example 4

Using Natural Gum/Polyacrylamide Blends to Carry Proppants


A purpose of this experiment was to determine whether the friction reducer of the present invention can be used to carry proppants.


A sand settling test was conducted as follows


Different combinations of guar to PHPA were tested to make a 0.24% solution to determine the fluids capability to carry sand and how concentration/viscosity changes affected this ability.


The test was performed at a 3rd party lab as follows.


Sand 100 mesh was added at 3 ppa (pounds of proppant added) to 0.125% and 0.24% polymer fluids. It was then observed how sand falls in each solution. The slower the sand accumulates in the cylinder, the better is the sand carrying capacity of the fracturing fluid. A 50 ml cylinder was used.


Another sand settling test was conducted, using different combinations of guar to PHPA for a 20 ppt (0.24%) solution to determine the fluids capability to carry sand and how concentration/viscosity changes affected this ability. Sand (20/40) mesh was added at 10 ppa (pounds of proppant added) to 0.24% polymer fluids. The mixtures were shaken to homogenize the slurry and were then allowed to settle. Sand volumes accumulated at the bottom of the cylinder were measured over time approximately seven minutes. A 50 ml measuring cylinder was used. The results are shown in FIG. 9.


As FIG. 9 demonstrates, there was some delay in settling as ratio of guar gum to anionic PHPA increased (0%-30%. By the end of seven minutes, all the sand settled in every cylinder.


From this test, it can be concluded that the higher the ratio of guar gum to anionic PHPA, the better proppant carrying capability at the same concentration of 0.25%.


Example 5

Using Present invention in a Slurry


The purpose of this experiment was to test whether the present invention is slurriable.


The slurry was prepared as follows. 1.5% of the viscosifying agent was mixed with the 52% of the carrier fluid and mixed at 1000 rpm for 30 minutes on an overhead mixer. After the carrier fluid was viscosified, 0.5% of surfactant was added and mixed for 30 minutes. At the end, 46% of MFR-210 was added and mixed for an hour.


The neat slurry was put on Grace 3600 to measure viscosity which was below 250 cps.


To a 500 ml WARING blender jar, 250 ml DIW was added. Then, 5 ml of MFR-210 slurry was slowly added and mixed at 1100 rpm on Grace M3080 variable speed mixer for 2.5 minutes at room temperature to make a 0.5% hydrated polymer gel.


Hydration viscosities were measured on Grace 3600 at 3 minutes, 10 minutes and 60 minutes. pH of the solution was also measured.


The slurry had the following composition:












TABLE 8









Component
Weight %







Carrier solvent
52



Viscosifying agent
1.5



Surfactant
0.5



MFR 210
46



Neat slurry viscosity cps
<300 cpss













Hydrate gel 5 mls/500 gms
Guar Gum
MFR


DIW with 2% KCl at 2000 rpm
viscosities
Viscosities


mix for 2 minutes
(cps)
(cps)





 3 min viscosity
36-40
41


10 min viscosity
40-44
44


60 min viscosity
42-46
47


pH
7-8
7.52








Claims
  • 1. A friction reducer comprising a reacted, grafted or blend of a nonionic natural gum and a synthetic partially hydrolyzed polyacrylamide (PHPA) having a molecular weight between 300,000 and 30,000,000, wherein the PHPA and/or natural gum has an average particle size of 150 μm or less, wherein the friction reducer further comprises copolymers of acrylamides and acrylic acids, wherein the ratio of the natural gum and the synthetic PHPA is from about 5:1 to about 1:0.01 by weight relative to the friction reducer.
  • 2. The friction reducer of claim 1, wherein the natural gum is a galactomannan gum.
  • 3. The friction reducer of claim 2, wherein the galactomannan gum is guar gum.
  • 4. The friction reducer of claim 1, wherein the nonionic natural gum is selected from the group consisting of either a guar gum or a combination of gums.
  • 5. The friction reducer of claim 1, wherein the friction reducer further comprises a cellulose polymer.
  • 6. The friction reducer of claim 1, wherein the friction reducer further comprises a starch polymer.
  • 7. The friction reducer of claim 1, wherein the friction reducer further comprises acrylic acids.
  • 8. The friction reducer of claim 1, wherein the friction reducer further comprises a combination of one or more of a starch polymer and a cellulose polymer.
  • 9. The friction reducer of claim 1, wherein the friction reducer is crosslinkable.
  • 10. The friction reducer of claim 1, wherein the friction reducer is biodegradable.
  • 11. The friction reducer of claim 1, wherein the friction reducer is breakable into small particles with strong oxidizers.
  • 12. The friction reducer according to claim 1 further comprising an aqueous base fluid.
  • 13. The friction reducer of claim 12, wherein the concentration of the friction reducer is about 0.1% or less by weight of the aqueous base fluid.
  • 14. The friction reducer of claim 12, wherein the aqueous base fluid is fresh water 99.9 weight percent of the total weight of the aqueous base fluid.
  • 15. The friction reducer of claim 12, wherein the aqueous base fluid is a brine comprising one or more dissolved inorganic salts in a total concentration between 0.1 and 20 weight percent of the total weight of the aqueous base fluid.
  • 16. The friction reducer of claim 15, wherein inorganic salt comprises one or more monovalent or divalent or trivalent cations.
  • 17. The friction reducer of claim 16, where the trivalent cations comprise iron and boron cations.
  • 18. The friction reducer of claim 16, where the divalent cations comprise calcium, magnesium, iron and strontium cations.
  • 19. The friction reducer of claim 16, where the monovalent cations comprise of sodium and potassium cations.
  • 20. The friction reducer of claim 15, wherein the inorganic salt comprises one or more monovalent or divalent anions.
  • 21. The friction reducer of claim 20, wherein the monovalent anions comprise of chlorides and bicarbonates.
  • 22. The friction reducer of claim 20, wherein the divalent anions comprise of sulfates, sulfides, carbonate and oxides.
  • 23. The friction reducer of claim 12, wherein at least a portion of the aqueous base fluid is flowback water.
  • 24. The friction reducer of claim 12, wherein the aqueous base fluid comprises fresh fracturing fluid, recycled fracturing fluid, flowback fracturing fluid or back-produced fracturing fluid, or combinations thereof.
  • 25. The friction reducer of claim 1, wherein the friction reducer is used for carrying proppants wherein the proppants have a size range of from 20 mesh to 100 mesh.
US Referenced Citations (124)
Number Name Date Kind
4265311 Ely May 1981 A
4425241 Swanson Jan 1984 A
4688639 Falk Aug 1987 A
4701247 Kalonins et al. Oct 1987 A
5100932 Lockhart et al. Mar 1992 A
5129457 Sydansk Jul 1992 A
5133624 Cahill Jul 1992 A
5220938 Kley Jun 1993 A
5669456 Auibert et al. Sep 1997 A
5720347 Audibert et al. Feb 1998 A
5789349 Patel Aug 1998 A
5881825 Collee et al. Mar 1999 A
6230805 Vercaemer et al. May 2001 B1
6257336 Audibert et al. Jul 2001 B1
6281172 Warren et al. Aug 2001 B1
6309455 Skaggs et al. Oct 2001 B1
6605570 Miller et al. Aug 2003 B2
6720290 England et al. Apr 2004 B2
6793018 Dawson et al. Sep 2004 B2
6794340 Nguyen et al. Sep 2004 B2
6818596 Hayes Nov 2004 B1
6823939 Bouwmeester et al. Nov 2004 B2
6825152 Green Nov 2004 B2
6843841 Reddy et al. Jan 2005 B2
7007754 Fanguy et al. Mar 2006 B2
7131493 Eoff et al. Nov 2006 B2
7261158 Middaugh et al. Aug 2007 B2
7264054 Harris et al. Sep 2007 B2
7271133 Weaver et al. Sep 2007 B2
7275596 Willberg et al. Oct 2007 B2
7304098 Li et al. Dec 2007 B2
7373977 Berger et al. May 2008 B1
7384892 Melbouci et al. Jun 2008 B2
7407915 Jones et al. Aug 2008 B2
7528095 Maresh May 2009 B2
7541316 Maresh Jun 2009 B2
7549474 Valenziano et al. Jun 2009 B2
7578968 Nalepa et al. Aug 2009 B1
7622427 Sau et al. Nov 2009 B2
7637320 Howard et al. Dec 2009 B2
7687438 Munoz et al. Mar 2010 B2
7694739 Brothers et al. Apr 2010 B2
7703521 Sullivan et al. Apr 2010 B2
7784544 Lindvig et al. Aug 2010 B2
7798224 Huang et al. Sep 2010 B2
7814980 Bryant et al. Oct 2010 B2
7857055 Li Dec 2010 B2
8043999 Sullivan et al. Oct 2011 B2
8076270 Smith et al. Dec 2011 B2
8196660 Smith Jun 2012 B2
8338341 Ezzelarab et al. Dec 2012 B2
8360149 Hughes et al. Jan 2013 B2
8360152 Defosse et al. Jan 2013 B2
8413719 Milne et al. Apr 2013 B2
8720556 Todd May 2014 B2
8722588 Zamudio et al. May 2014 B2
8789592 Mason Jul 2014 B2
8871691 Rey et al. Oct 2014 B2
8946132 Chang et al. Feb 2015 B2
9034802 Ahrenst et al. May 2015 B2
9062242 Jiang et al. Jun 2015 B2
9296943 Ladva et al. Mar 2016 B2
9399729 Singh et al. Jul 2016 B2
9574127 Chapman Feb 2017 B2
9574131 Weaver et al. Feb 2017 B2
9598629 Morvan et al. Mar 2017 B2
9650299 Alwattari et al. May 2017 B2
9663707 Gupta et al. May 2017 B2
9714389 See et al. Jul 2017 B2
9790777 Nguyen et al. Oct 2017 B2
9890319 Ezell et al. Feb 2018 B2
20040209780 Harris et al. Oct 2004 A1
20050194142 Nguyen et al. Sep 2005 A1
20050227874 Berger et al. Oct 2005 A1
20060272816 Willberg et al. Dec 2006 A1
20080312108 Berger Dec 2008 A1
20090145607 Li Jun 2009 A1
20100184630 Sullivan et al. Jul 2010 A1
20100184631 Turner et al. Jul 2010 A1
20110265997 Miquilena Nov 2011 A1
20120152544 Parris et al. Jun 2012 A1
20120157356 Dawson et al. Jun 2012 A1
20120252707 Li et al. Oct 2012 A1
20130015115 Landis et al. Jan 2013 A1
20130015141 Landis et al. Jan 2013 A1
20130233546 Liang et al. Sep 2013 A1
20130306321 Lanctot-Downs et al. Nov 2013 A1
20140041944 Ewanek Feb 2014 A1
20140262275 Dean et al. Sep 2014 A1
20140305651 Hill et al. Oct 2014 A1
20140352961 Dobson et al. Dec 2014 A1
20150034315 Jiang et al. Feb 2015 A1
20150057196 Debord et al. Feb 2015 A1
20150060062 Shen et al. Mar 2015 A1
20150166870 Jain Jun 2015 A1
20150175877 Shindgikar et al. Jun 2015 A1
20150252252 Soane et al. Sep 2015 A1
20150252254 Zhang et al. Sep 2015 A1
20150275068 Shong et al. Oct 2015 A1
20150289530 Demazeau et al. Oct 2015 A1
20150307772 Zhang et al. Oct 2015 A1
20160009985 Brennan et al. Jan 2016 A1
20160137906 Guan et al. May 2016 A1
20160160118 Van Oort et al. Jun 2016 A1
20160177166 Reddy et al. Jun 2016 A1
20160264850 Okunola et al. Sep 2016 A1
20160298018 Medvedev Oct 2016 A1
20160298022 Chang Oct 2016 A1
20160347986 Nguyen et al. Dec 2016 A1
20160355726 Eoff et al. Dec 2016 A1
20160376881 Li et al. Dec 2016 A1
20170015893 Al-Yousef et al. Jan 2017 A1
20170044418 Lee et al. Feb 2017 A1
20170088769 Kesavan et al. Mar 2017 A1
20170088770 Kramer Mar 2017 A1
20170137702 Khlestkin et al. May 2017 A1
20170145302 Qin et al. May 2017 A1
20170198202 Shong et al. Jul 2017 A1
20170313931 Chopade et al. Nov 2017 A1
20170349817 Maberry et al. Dec 2017 A1
20170369767 Guo et al. Dec 2017 A1
20180112124 Conner et al. Apr 2018 A1
20180118992 May May 2018 A1
20190161673 McDaniel et al. May 2019 A1
Foreign Referenced Citations (12)
Number Date Country
2011012921 Feb 2011 WO
2014139037 Sep 2014 WO
2015080609 Jun 2015 WO
2015108929 Jul 2015 WO
2016088141 Jun 2016 WO
2016195525 Dec 2016 WO
2016201445 Dec 2016 WO
2017044953 Mar 2017 WO
2017069762 Apr 2017 WO
2017131525 Aug 2017 WO
2017184111 Oct 2017 WO
2018145065 Aug 2018 WO
Non-Patent Literature Citations (1)
Entry
International Search Report and Written Opinion for corresponding PCT Application No. PCT/US2019/035985 dated Aug. 16, 2019.
Related Publications (1)
Number Date Country
20200224083 A1 Jul 2020 US
Continuation in Parts (1)
Number Date Country
Parent 16004176 Jun 2018 US
Child 16818598 US