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    US20170362497A1 - Easily Dispersible Pam

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    us) United States 2) Patent Application Publication co) Pub. No.: US 2017/0362497 A1 en @ (60) oy Tang et al. EASILY DISPERSIBLE POLYMER POWDER FOR HYDROCARBON EXTRACTION Applicant: ChemEOR, Ine., Covina, CA (US) Inventors: Yongehun Tang, Wolaut, CA (US); Allen Thomas Lyssy, Stockdale, TX (US); Yaser Asgarl, Chino ils, CA (US); Carl Wilhelm Aften, Magnolia, TX (US); Hongxin Tang, Walnut, CA ws) Appl. No. 151625988 Filed: Sun, 16, 2017 Related U.S. Application Data Provisional application No. 62/351,910, filed on Jua 17, 2016 Publication Classification Int. ¢ COOK 8168 (2006.01) COOK 8188 (2006.01) US 2017036249741 (43) Pub. Date: Dee. 21, 2017 CO9K 8/68 (2013.01): COOK 8/882 201301) on ABSTRACT A dry polymer powder for use in enhanced petroleum recovery without being prehydrated before being added 10 Water of brine to be inimdoced into a wellhead, The dry polymer powder consisting of atleast one of a polyoeryl- ‘amide, a copolymer of acrylamide and acrylic acid, a Functionalized derivatives thereof, galactomannan, oc Iulosie polymer or derivatives thereof, and the polymer eaa be crosslinked or not crosslinked, provided that if they are hhomo- or co-polymers of aerylie acid, they are not cross linked. The dry polymer powder is sized between 0 size Timits, namely’ atleast about 85 wt % of panicles ofa size smaller than about 40-mesh, sida least 75 wt % of particles ‘of a size greater than 200-mesh, which size range ensures that the dry polymer powder wil efficiently hydrate in the water of brine Wwithia about one minute without fomning fisheyes. US 2017/0362497 AI Dec. 21, 2017 Sheet 1 of 6 Patent Application Publication Told dawAjod Aup ~ 7 ‘duind ainssasd-ysiy ~ ¢ ‘duind - z Suey sarem — T < am ayy OL aqnuiw T apun —&) Patent Application Publication Dec. 21,2017 Sheet 2 of 6 US 2017/0362497 Al 1200 2 8 S FIG. 2 2 8 4 2 a oR HINpaY YON! 15 Patent Application Publication Dec. 21,2017 Sheet 3 of 6 US 2017/0362497 Al 1200 3 FIG. 3 200 0 50 9% ‘uoRONpay UO!’ Patent Application Publication Dec. 21,2017 Sheet 4 of 6 US 2017/0362497 Al ANTS in HEC Time, Sec FIG. 4 US 2017/0362497 AI Dec. 21, 2017 Sheet 5 of 6 Patent Application Publication s‘Old Dag ‘aul, oot 000r cog 909 oor oz IDyAz 4 SOT-KWWY Puno yeunse wedge Ont Ul BOs9GMT + SOL XYHY punOID gaMSe tH NRE UH ROSTEIME + SOT VN PU SST KYW punosD 0% of ob os 99 96 ‘uoRONpay “OND Patent Application Publication Dec. 21,2017 Sheet 6 of 6 US 2017/0362497 Al 2 8 8 3 3S 9 2 8 gE © a) z 2 8 2 S g ° geeReegaeeareg % ‘O}IONpay uORILY US 2017/0362497 AI EASILY DISPERSIBLE POLYMER POWDER FOR HYDROCARBON EXTRACTION CROSS-REFERENCE TO RELATED APPLICATION(S) 10001) This application claims priovty from U.S. Provi sional Patent Application No. 62/351,910 entitled "Man acting Dispersible Powder", and filed Jun. 17, 2016 FIELD OF THE INVENTION 10002] The invention relates tothe field of making and ‘easily hydrated polymer powder compositions useful in oll and gas well stimulation, ining being added 10 fresh wate or brinc to make a carrier fui to eartyproppants for hydraulic fracturing, and in related applications and for related purposes. BACKGROUND OF THE INVENTION [0003] Hydraulic frcturing of oil- and gas-bearing shale ormations for improving hydrocarbon production is. a celletive method to get more “rapped” oj and as out of the subsurface, in which ractring uid (fesh water, brine, et.) ‘containing a number of components, including proppant is injected via high-pressure pumps to increase the permeabil- ‘ty of formation, The pressure generated on the surface decreases significantly when the fracturing uid reaches subsurface friclring zones, primarily due tothe turbulent tendency of fracturing flow under very high Reynolds- umber noa-Newtonian flowing conditions. Addition of natural or synthetic polymers into the facturing Mid is @ practical way to reduce the pressure drop, also known as the “ition reduction.” The polymer additives serving for the purpose of friction reduction in an aquoous-based ‘well Stimulation operation are referred 0 38 “fraction retacers", ‘whereas those used inthe oil-based pipeline operations are ‘commonly referred to as “ag reducers”. The requirement for fiction reduction in hydraulic fracturing of oil- and as-bearing formations is very different than use of friction reducers in transport of oil though pipelines that curry oil ‘overlong distances, in which the ofl passes and is pumped through various substations. In hydraulic fracturing opers- tions, the fvid must be pumped down into the formation very quickly and under high pressure so thatthe proppants ate foreed into fissures in the Formation to physically hold ‘open the fissures so that petroleum may be allowed to more readily flow out ofthe formation. In these operations, the fiction reduction must occur very quickly and typically large volumes of water or brine must be prepared. In contrast, inthe fell of moving ol though pipelines, fiction reducers are added direct to oil o redoce the friction ofthe cil as it moves through the pipelines for many hours and as the oil passes repeatedly through pumping stations to keep the oil moving, The fition reducers mst optimally be able ‘o withstand the repeated action of pumping stations and ‘degradation over time, 10003} Polymer-based friction reducers are composed of high-molecolar weight, water-soluble polymers. Fxampes ‘of these polymers inelude polyaerylamide, hydrolyzed poly scrylamide, polyaerylamidelserylate copolymers or those based on sich a backbone or on poly(meth}acrylamide and poly(methjserylic acid backhones, polyethylene oxide and Uerivatives thereof, and semi-synthetic polymers such as Dee. 21, 2017 carboxymethyl cellulose or hydroxy-ethyl eelllose, or the ‘naural-occurring biopolymers sueh as guar gum. 0005} It has Jong been recognized that water-soluble Iietion roducors are easily degraded when exposed to water under high-temperature, high-pressure, high-salinity and/or high-shear conditions. Along with numerous laboratory and fick stds to improve the stability of polymers in voltion ‘Ma eta. also conducted systematic theoretical studies based fon quantum chemistry computational modeling to ins ‘0 of polymer hydrolysis and stability based on energetics calculations. See Ma, eta. in EI Sevier Polymer Degrada- sion and Stability, 121 (2015) 69-77, Theoretical stu of Iiydrolysis and stability of polyacrylamide polymers.) To preserve shelf life and for Storage purposes prior to use, Greet contact of friction reducers with water should be avoided. Several methods can be used to accomplish this. ‘One method is to keep the fetion reducer in the dy-powder form. That is, after being synthesized, polymers are sepa- rated from solution, dried, purified and often ground into powdered products, Products made by this appmoach can be refered to as “dry friction reducer”, or “DFR”. Another approach is synthesize polymers by inverse emulsion polymerization (cil-extenal), preserving the water-soluble polymer inside an oil phase. Because # majority of friction reducers are polyacrylamide (PAM), produets made by this approach ate often referred to as “emulsion PAM-bassd Iietion reducers", or “ePAM™ for short [0006] Friction reduction achieves its. maximum effect ‘when the friction reducing polymer is fully extended in the aqueous solution, but stats to decrease when the polymer degrades. The stability requirements ofa polymer depend on the type of field operation. Far example, in polymer-aug- mente! waterlooding enhanced oil recovery (EOR) open. tions, water-soluble polymers often are required to be stable ‘under high-temperature, high-pressure, or high-sainity con- ditions for several months, Whereas in hydraulic factoring ‘operations, a major cause of polymer degradation is ulti high shearing stemming from very high pumping rates, and the required time period for stability of a ition reducer such as use is often only one or two hours. Another impor fant timing eviterion for fiction reduction ia hydraulic fracturing operations is how fast the polymer ean achieve its ‘maximum finetionality, For an ePAM product, this is often referred to as “inversion time”, that iy the time it takes to beak the emulsion for release of the polymers when t PAM dispersion of suspension is died in water, For @ DER product, inversion time is related tothe time it takes t0 {or the polymer to be hydrated by water. [0007] The inversion and/or hydration time for of a fie- tion reducer in typieal hydraulic fracturing operations often is roqured tobe less than | minute, This as imposed a great challenge to the field application of many’ product ca ates, especially because the inversion and/or hydration time js alo influenced by a number of field conditions such as femperature and the type and concentration of dissolved salts i the Mui. Fas inversion times (less than 30 seconds} by ePAM can be achieved under lresh/tap water conditions ‘when the active polymer content is limited 10 30 weight percentage or less, Additional additives such as surfactants have boon used to shorten the inversion time. However, addtional mateeal and lopistieal costs as well as environ- ‘mental issves of including addtional chemicals in factoring ‘Tuids have been a great concern for the ePAM products. US 2017/0362497 AI {0008} _Hlydration of sotid powder polymers ean be ehal- Jenging for use in fricking operations as they tend not dissolve quickly enough. U.S. Pat, No, 9.334.438 provides, 1 good overview of the hydration problem and how current ‘il service industries have dealt with this issue, Pre-hydra- tion of the polymer powder ia a mixing unit is often required, A variety of mechanical deviees have been dis- ‘closed in previous work. Examples include, but not limited to, US. Pat. Nos. 5,190,374, 5382 411, 5,426,137, 5.947, ‘well as more complex commercial ‘units such as the precision continuous mixer or progran- ‘able optimum density blender disclosed in U.S. Pa. No. 9,334,438. In U.S. Pat. Publ 20120137386, Dawson et al ‘ako disclose conceptual designs for batch mixing in & ‘continuous process blending equipment 10009] For cost-effective application of DFR in hydraulic fracturing operations or stimulation operations, what is needed isthe direct feeding scheme of DER into the fiae- turing fluids without the prior art pre-hydration step, as illustrated in FIG. 1, procedure that is often referred to as addition “on-the-fly”, whieh is eurendy only available for solect PAM products. When using a dry powder product, the most dificult hurlle to overcome is achieving ultra-fast hyeration of DFR in an aqucous fui, ideally in les than 1 minute, in water, without, atthe same time, suering the ommation of so-called “isheyes", as described further below. [0010] Fuadameatsl flow theology theory teaches that the hydration ime of dry powders is proportional to ther active Water contact surface ares, and that the reduction of the panicle size can affect the hydration rate. US. Pat. No. 3,730,275 discloses that by including various sizes of par- ticles, the shear degradation rate of frition reducers can be ‘modified. In porticlar, U.S, Pat. No. 3,730,275 discloses @ ‘dry powder with prefered particle sizes as follows: At leat 20% by weight within 2 size range of 5 t0 30 mesh (or 4000-595 microns), at least 20% by weight within a size range of 40 © 90 mesh (or 420-163 microns), a least 20% by weight within a size range of 100 t0 200 mes (or 14974 microns), and with any remaining powder of O% wo 40% being ina size ringe ofS to 300 mes (or 4000-74 mirons). “The purpose fortis prior ar disclosure isto provide fetion reduction yet withstand shear degradation of polymer. Thus at least 20% by weight of the particles are greater than 30-mesh (~604 microns), while particles smaller than 440-mesh account for at most 80% by weight. The particle ize range is very broad, that is, from about 74 to 4040) microns. The 275 reference doesnot disclose or discuss any hydration times by its polymer mixtures, (The tem “miton” herein and thrighoxt is equivalent to the SI- recommended “micrometer.” abbreviated “jim.”) [0011] Atempts © simply reduce the particle size of fietion reducers do not necessarily result in the improve- ‘ment of the shortening hydration time. Indeed, it has been ound that particles with too fine a size tend to aggregate or ‘agglomerate upon contact with water to oma globules or the so-called “Tisheyes", which are very dificult to (ee-hhydate Pat, Nos. 5,849,862 and 6,682,351 disclose that the jomerated forms of precipitates of smaller particles dis- solve more slowly than those of larger panicles. US, Pat No, 3,839,500 discloses that in order to have very Fes hamps ‘during dissolution and have the powder well dispersed, the ‘dry powder mixture should have less than about 5% by weight of particles ofa size smaller than 44 mesh (~370 Dee. 21, 2017 rons), with most particles between 16 and 44 mesh (or '90-370 microns). and the polymer powders are made {rom “various block polymers of mixtures of ethylene and propylene oxides". Novwithstanding disclosures of particle sizes of polymer dry powders influencing thei dispersibility fr degradation (it has been unexpectedly discovered that & very short hydration time, viz. about I minute oF less, and ‘ear complete dispersbility lacing to significant maxim {ition reduction ficiency can be achieved simltaneous}y vusing # dry powder polymer, rendering direct injection of DFR possible. The direct or onthe-ly injection of DFR has ‘been believed to be very dlicul if no impossible to achieve. ‘in well stimlation operations, soch that PAM remains the major fietion redueer type in current markets SUMMARY OF THE INVENTION [0012] ‘The present invention provides a method to directly Teed a dry watersoluble polymer-based friction reducer as additive into the well stimulation ids without the use of special dilution equipmeat and methodologies. The hydr- sion time of the polymer powders in water is sufficiently shortened to les tha I minute, seh that the added ea-the- Aly operation mode ean be achieved, without any pre- hydration operations. The fast hydration rate of the polymer particles is achieved by carefully choosing the size of the polymer puricles to be within a narow range. [0013] In the preferred embodiment, this invention pro- vides a polymer in dry pranular form selected from poly- scrylamide, elated polymers comprising acrylamide unis, or other polymers: said polymer having at least 90% by ‘weight of particles sized smaller than 300 microns (~50 mesh), and sized greater than 100 mierons (~150 mesh). The polymers ofthe invention are not ePAM products, [0014] In the prefered embodiment, this invention further iscloses that the use of the dry friction reducer in the hydraulic fracturing operations not only could bave eos saving and logistical advantages, but also could have supe- rior fietion reduction performance, compared 10 the con- ventional oi-extemal emulsion-based friction reducers [015] In another embodiment the invention provides a try polymer powder for use inthe petroleum industry for enhanced petroleum recovery, comprising dry polymer pow er sized beoween two size limits, namely atleast about 8S \w1% of particles ofa size smaller than 40-mesh, and atleast 75 wi % of particles of a size greater than 200-mes [0016] In yet another embodiment, there is provided a dry polymer powder for use in the petroleum industry for enhanced petroleum recovery, comprising a dry polymer powder selected fom the group consisting ofa least one of 8 polyacrylamide, a copolymer of acrylamide and acrylic ‘acid, Functionalized derivative of said polyaerylanside oF copolymer, a galactomaanan, or a celitlosie polymer or derivatives thereof, wherein the polymer can be crosslinked for rot crosslinked, provided that if they are homo- or corpolymers” af acrylic acid, they’ are not crosslinked, ‘wherein the dry polymer powder is sized between twa size Timits, namely atleast about 85 wt % of particles of a size smaller than about 40-mesh, aid at least 75 wt % of particles of a size greater than 200-mesh. [0017] In a further embodiment, there is provided a method for using a dry polymer powder for use in the petroleum industry for enhanced petroleum recovery the dry powder comprising a dry polymer powder sized between {wo size limits, namely at east about 85 wt % of particles US 2017/0362497 AI ‘of size smaller than 40-mesh, and at least 75 wt Particles of a size greater than 200-mesh. a& a friction reducer in fracking water, the method comprising ading the dy polymer powder dirceily toa stream of fresh water oF brine without pre-hydrating the dry power before intodue- ing it to fresh Water or brine 10018] These and other features of the invention are described below, BRIBE DESCRIPTION OF THE DRAWINGS {0019} FIG. 1 is a diagrammatic sketch of the aed ‘onset operation mode to cet inteduce dy fetion reducer powder into main hydeoulic fracturing fis jst prioe to be pumped by high pressure pumps to 2 wells borchcad 10020] FG. 2 is» plot of friction rection performance ‘ers time ofthe ground MAX165 and its prevusor MAX 16s. 10021] FIG. 3 so pot offieton reduction performance Yerus time of the dry polymer powder at specifically Seleted parce size anes {0022} FIG. 4 is plot of feton reduction periormance ‘versus time of the ground MAX-165 at various concenta- tions mixing with 2% KCL 10023] FIG. $s plot of friction rection performance ‘ersus time ofthe gund MAX-I6S apd sat mxtue inthe presence of diferent concentrations of selected surfactant 10024] FIG. 6 so plot offeton reduction performance ters tine of the ground MAX-168 under varios pre- Iydation conditions DETAILED DESCRIPTION 10025] In certsin embodiments, the polymer powder is sizod between two size limits namely at least 86,90, oF 9S WE %, oF any WL % between any tWo of these values, of particles ofa size smaller than 40-mesh (~425 microns) and at least 76, 80, 85,90, 0 95 wi %, or any Wi % between any two of these values, of particles of a size greater than 200-mesh (~75 microns). All references used! herein for ‘mesh sizes of the invention are in ASTM/U.S. Standard [0026] In one embodiment, the polymer powder having at Feast 85 wt % of particles of a size smaller than 40-mesh (425 microns) and at least 75 wt % of particles ofa size srvater than 200-mesh (~75 microns) have panicles selected from ~40460 mesh (42S 10 -250 microns), ~60+100 mesh (205 to ~150 microns), =1004140 mesh (-150 © ~106 microns), or 1404200 mesh (106 to ~75 microns). In some embodiments, the proportion of polymer particles smaller than 100 mesh (-150 microns) is greater than 10%, 20%, 30%, 40%, oF 50% by weight of the total polymer Particles ora percentage between any two of these. In some ‘embodiments, the proportion of polymer particles between, O-mesh and 100-mesh (~205 to ~150 microns) is greater than 10°%, 20%, of 30% by weight of the total polymer particles or a percentage between any tWo ofthese 10027) In some embodiments, inversion time is less than about 60 s, 80, 40s, 30,205, oF 15s, ora valve between, ny two ofthese, In some embodiments, maximum friction reduction ellcieney achieved is greater than 40%, 42%, 449%, 4646, 48%, oF $08, or a percentage berwcen any two ‘of these. In some embodintents, riction reduction elliciency Dee. 21, 2017 at 20 minis areater than 25%, 269%, 27%, 28%, 29 30%, ora perventage between any two of these [0028] The dy polymer ean be polymerized by any su able method known inthe ar. In eeatain embodiments, the polymer is polyacrylamide or a copolymer of acrylamide and acrylic aid, or funetionalized derivatives thereof. The {unetonalization consists in incomporating charged (anion cationic, aniphoteie) or pendant hydrophilic or hydrophobic aroops onto the polymer backbone. This ean be achieved by adding specialty monomers during polymerization or cary ing_out further reactions post-polymerization, In. one cembodiment, the polymer is polyethylene oxide or deiva- tives thereof. In ancther embodiment, the polymer is a galactomuannan or ccliulosie polymer or derivatives thereof The polymers ean be crosslinked oF not crosslinked, pro- Vide! that if they are homo oF eo-polymers of acrylic aid they are not croslinked. Particles of mesh —40, +100 (between 125 and ~150 microns) may comprise greater than about 25% by weight of the total polymer in dry Form in cerain embodiments [0029] - While dey polymer inthe size anges noted above ‘ill provide exceptional functionality as friction reducer ‘without additives, the addition of water soluble eleewolytes salts and block polymers can be beneficial in the formila- ‘ions ofthe invention [0030] Accordingly. one or more water-soluble eletro- Ivtessut in finely divided form inelude without imitation salts of alkaline and alkaline earth metals and ammonia sats Or salts of water-soluble amines ean optionally be added to te formulation. In some embodiments the sats are the sax, potassium, and ammonium salts of anions such as chlorides, sulfates, phosphates, acetates, formates, and ‘methanesolionates, Salts should bein finely divided form ‘one aspect, salts in finely divide form have parle size Jess than about $00 microns. [0031] The optional block polymer is a block polymer ‘onionie surfactant that is, however, not a silicone surfae- tant. The block polymer should not be conised with the polymer in dey form, the latter being generally high ‘molecular weight polymer. In some embodiments, the block polymer isu wiblock copolymer composed of bh ethylene fxide and propylene oxide mits, and variously koown oF branded as Poloxamer, Pluronic? (BASF), Antamx (Golvay), Synperonie (Cross), Fpan (DKS), andl by other ‘ames from other suppliers. Certain embodiments of the invention can farther comprise surface ative agents other than block polymer nonionic surfactants [0032] Friction reduction efficiency is determined by Joop test wel known in the af using inventive compositions with a polymer concentration at for example around 1 pound Per thousand gallons (ppig) or around 0.012 wt %. Persons Skilled in the aet woukd understand that friction reduction can be achieved at othe dilute polymer concentrations. [0038] | Embodiments ofthe invention may futher contain ‘ther solid additives and chemicals known to be commonly ‘used in oiled applications by those skilled in the ar, sullicient amounts to be useful for @ treatment fhuid in such applications, These include, but are n0t necessarily limited to, materials such as oxygen scavengers, scale inhibitors, cormosion inhibitors, Hide-loss additives, bacter- cides, clay stabilizers, surfactants (in dry form, possibly absorbed or adsorbed onto an inetive support material) to reduce capillary presses or surface tension, and the like Now-limiting examples of some suitable scale inhibitor US 2017/0362497 AI include phospionate, phosphate esters, and the like. Any table biocides may be used in embodiments ofthe inven- 10034) The polymers of the present embodiments should have a molecular weight (MW) sufficient to provide @ desired dogree of friction reduction or ability 10 increase viscosity of the aqueous-hased hydraulic fracturing Mui. ‘They may have a weight average MW in the range fom, about $00,000 g/mol to about 60,000,000 pimol, as deter- ‘mined by intrinsic viseosity methods. The one or more block polymer surfactants may have a bydrophilie-lpophilie bal- ance (HLB) of at last 6, at least 12, ora least 20 (or values between these), and may he added as a mixture of surfac- tants having different HLB values 10035] In some embodiments of the invention the aeryl- ‘amide monomer accounts for 10 mole % 10 95 mole % ofthe polymer in the polymerization reaction, or 10 mole % to 70 mole % in some embodiments, and the one or more other ‘monomers, including. for example, (methacrylic acid of various acrylic sulfonic acids and salts thereo, account for 1 mole % to 60 mole % of the polymerization reaction, or 5 mole % to 40 mole % in some embodiments. In other ‘embodiments, the one or more specialty monomers wed for Tunedonlization, including hydrophobic monomers, sccount for 0.5 mole % to 20 mole % of the polymer in the polymerization reaction, of | mole % to 10 mole % in certain ‘embodiments. Acrylates can result from aerylamides by ‘caustic hydrolysis, and qustemary ammonium groups ca result from qustemization of tertiary amines. The mole percentages of polymer units ina polymerized produet ofthe present invention can be described by the same mole per- ‘centages provided herein to characterize monomer incorpo- ration. The polymerization reaction can be carried out by methods knowin in the at, for example free radical chain polymerization, employing suitable i tiation systems 0036) be included i suficent to provide the desired friction reduction or ether Tunetions in some embodiments, polymers comprise atleast (0.005% by weight of the solution or dispersion, In some ‘embosdiments, polymers acount fora percentage by weight ‘of the solution or dispersion total that is 0.006%, 0.008%, 0.01%, 0.012%, 0.014%, 0.016%, 0.018%, 0.02%, 0.022%, (0.028%, 0.026%, 0.028%, 0.08%, 0.035%, 0.04%, 0.045%, 10.05%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%, or any percentage by weight ins range delimited by any two ofthese. Dillerent relative amounts, or ratios, ofthe polymer in dry from to the Water-soluble salt or block polymer surfactant ae elective. none embodiment, the ratio by weight ofthe polymer to the ‘optional water-soluble salt is in the range of about 4:1 t0 about I: 10037] _Inother embodiments, the composition comprising polymer powder, Water soluble salts, and block polymer surfactants may be combined with an agueous diluent 10 orm a tectment fluid. Examples of the aqueous diluent include, but are not limited to, DI water, fresh water, brinc, seawater, flowhack water, produced water, and recycled ‘water. Present embodiments of both the composition and ‘method can be practiced ata temperature ranging from about 10° C. to about 120! Cand especialy from about 20°C. to about 95 Dee. 21, 2017 EXAMPLES [0038] Dette fition reduetion performance evaluation proces fas heca publish! in ob recent presentation to the Society of Petoleum Engineers (SPE-171025). Spec cally, faction rection was evalted using recirculating fo loop. A constant high Yat of flow is maintained fora testing uid in the loop, which ia Applicant's sppartas comprises two tubing ses, 1 inch (-2'34 em) and (-1.9 cm), Two dllerent se of pressure tansders on the lop ‘measure presse difforentials across 10 foot (~3 m) test Section of the % inch (1.9 em) tubing. Other han the loop ‘self the lop assembly consists ofone 69 US. gallon -26 ie With an overhead mixer a progressive cavity ily operated to soppy 65 psi of pressure, aloe nl dats acquisition unt Flas were pumped st 25 US. gallos per min (346 Limi). All tests were por formed at ‘armbient temperature. In tis procedure, the re rir was fit fills with op water, then KCI slowly added {0 2% by weight and recirculation allowed to conti forS ‘hin for compete salt dissolition, Thereafter the Applicant Started to collect pressure dflerence across the test Seton ‘versus time Data forthe untreated brine served as a base- Tine. sample was the loaded int the reservoiat 120 ppm, oer concentrations 3s specified in each ease, and pres Sure diference data again elected {0039} ‘Thee performance parameters ae calewated! fom the persntageIeton eduction (6 FR) vers ie, which js determined using the following equation: % FR-(GP Ssaveated fhid-aP weated MidaP unreated hid®100 ‘Eeuaton 1), where dP means the pressure dlference aeoss the loop's test section. These thete parameters are @) the maximum fetion reduction (Max FR), whic i the ma ‘num % FR that ean be atin (i) inversion/hydeation time (jaw), which i defined ay the time i takes to reach 50% of Max FR: and (i) the fieton reduction ater 20 ‘minutes (20), which isthe % FR sill mainsind ater 20 nes {0040} Inthe field of fracking the so-called base yd! carte is almost never fesh water alone, but typically i 3 tyne solution ined the formation water is bine. 2% KCl is simple way i Inborstory studies to mimic this reality, and is representa in Examples 1-5. Thus ths sma percentage sbould be considera as a ~base™ oF “back: round Teel of sal, nt extra salt In some studies 2 more complex mitre of sso total dissolved solids (TDS) ae ‘made or obiained, up 10 7 oF 186, However 20%6~28% ot Anke salt Nal (See Examples 4 and 5) would be considered extra sal, going above and Beyond a “base” or “back- sevund” Keel {0041} "The procedure forthe dissolution and fisheyes tests fare as follows: 2000 pom active sclected polymer was poured into 250 mL disiled water a S00 rpm an sired for {minut then the rwlting solution was pred through a sreen about 20 mesh), then rinsed with 2000 mi tp water the residual solid contents (iF any) on the sereen were collected and transfered onto a clean fil pam the ei pan Was dried for 2.5 hours in un 80° C. aven to observe the formation and the size or quantity of solid ge Gif any) Example 1 [0042] commercial polyaerylamide-hased dey polymer powder, MAX-165, aflered by the Applicant ChemPOR, Inc. was used as the baseline. Particulars on the particle size US 2017/0362497 AI distribution of the batelilot of MAX-165 tested are as follows: Mesh <40 mesh~$0.3%; 40 to 100 mesh-38.2%: 100 0 140 mesh10.9%; 140 0 200 mesh-0.2%: 200 10325, mesh-0.2%: and >325 mesh-.2%, Friction reduction per- formances of polymer povsders with selocted range of par~ ticle sizes were summarized as follows. AI] tests were ‘conducted with 120 ppm active polymer in 2% KCI solution (Go mimic a typical background level of salinity.) Pietioey eo ce ese o re Shs inet st re 10043] |The dissolution and fsheyes testing results as sum- marized as follow’ Taage of ari assed Dey Weigle of 10044} These data show that shorer hydration time ean be attained by reducing the particle sizes of polymers; and the smaller the particle sizes are, the shorter the hydration time ‘canbe attained. In particular, the hydration time isles than ‘minute whea the particle size of polymers is smaller than 40 mesh (420 microns). However, the dissolution rate and the tendency ofthe fsheyes formation are in confit, When the particle sizes become smaller, the tendency to fom fisheyes increases. These data also show that there exists @ narow range of the particle size, within whic the hydration time is less than 1 minute and there will not be formation of fisheyes. The mange is within 60-100 mesh, or 150-250 Example 2 10045] A polymer composition was tested for friction reduction performance having particles 93.4% by weight of smaller than 40 mesh (420 microns), and 92% by weight of a size greater than 200 mesh (74 microns). ‘wherein particles of sizes from 40 to 200 mesh comprise 85.49% by weight ofthe toil. A hydration time of less than 1 min wa attained, and no fsheyes formation observed. The test was conducted with 120 ppinaetive polymer in 2% KCL solution. Range of Pats Sze Mae Tw FR Dee. 21, 2017 [0046] ‘These data show that by eliminating lauer particle Sizes, that is, in particular, those of particle sizes greater than -4Onmesh, inthe dry polymer composition, a suiciently short hydration time of less than I miaute is achievable, By simultaneously also eliminating those very fine partite, in particular of sizes smaller than 200 mesh, the formation of fisheyes ean be avoided. Thus, dry polymer composition having a great majority of polymer particles sized betwen bout 40°t0 200 mesh results in a composition that has fexccodingly fast inversion times without formation of lisheyes. Example 3 [0047] The polymer composition of EXAMPLE 2, herein denoted $ "Ground MAX-165", is blended with various joncentrions of the NaCl sill. All percentages are by ‘weight, and all tests were conducted at 120 ppm active polymer in 2% KCI solution, No fisheye formation was ‘observed in any of these tests. These data show that the addition of sat substantially improves polymer hydration, Haneef Parice Se a tie A oe O65 Pxample 4 [00483] Various concentrations of @ surfactant, Pluronie® F.68, a nonionic oligomeric surfactant powder (olered by BASF Corporation), are added to a polymer-slt mixture ‘composition. The postive effect of the surfactant additive on polymer hydration as exhibited by shortened T_inv's is Surfactant concentration dependent. Adverse effect seen in fers of Max FR decrease is relatively small. A small amouat of this type of stefactant, up {0 39% at least, ean substantially improve polymer hydration. Range of Parise Sze Martine Gtousd MAX-LSS «29% Nace MASS wD Example § [049] Conventional dry polymer produets are also sub- ject to conventional handling, which oquites pre-hydeation In this example, an 80% Ground MAX-165420% NaCl mixture js ether added om the fly (inventive—frst ine in ‘able below) or pre-ydrated (and as part of the standard pre-hydation practice first sheared for varions times). Their performance is compared. Under fresh water condition, higher polymer concentrations (240-300 ppm) are used Runs lasted 400 seconds (~6.6 minutes) to test he effect of pre-hydation under shearing on Max FR and T_inv. FR20 ‘was not tested, US 2017/0362497 AI Cer doe cntion (RPM) FR Tow REDD Tabialontet= 1 iio predydraion = 240 HT Simin petodnson tad Sine pecteion Mt) ak = 0 mine petition ad TOS = ie mine pretointion 30d [0080] | Under low shearing conditions (1000-3000 RPM), the negative effect of hydration on decreased Max FR is relatively small. Even aller 5 hours of hydration at 1000 RPM shearing, ony about 10% in Max FR reduction was ‘observed. However, high shearing had more significant adverse effects on Max FR. At 9000 RPM shearing, even S ‘minute of pre-hydration significantly reduces MAX FR, by ‘more than 40%. Polymer powders begin to dissolve during the pre-hydration proces snd are subject to shear degrad- Example 6 {0081} The dry polymer powders (80% Ground MAX- 165+20% NaCI) is preydrated at 1000 RPM. for 300 minute (5 hours) then friction reduction performance tests ‘are carried out in API (American Petroleum Industry) brine (hich is water with 8% NaCl+2% CaCl, to mimie heavy brine) and compared with the performance of the same polymer powder added on-the-ly. The main focus ofthis ‘eximple is to compare inital fiction reduetion perfor. mance, only 400 seeonuls (-6.6 minutes) runs were con- “ducted in these tess, so thee are not FR20 data given, Under the API (American Petroleum Industry) brie condition, the ‘ackied on-the-fly mode has better fiction reduction perfor- mance than the long-time pre-hydration mode. After long- time exposure to various cationic compounds in the API brine, polymers degrade even under relatively slow shear ing. Therefore, under heavy brine conditions, such as those recycling the Nowback water or produced water, the added ‘on-the-fly mode of the dry friction reducer will perform better than the pre-hydration mode mae Pan Contin Nm ih Tay BE ry 7 preys 10052] Accordingly, as can be appreciatod from the Example above. The preferred embodiments of this inven- tion have been disclosed, however, so that one of ordinary skill in the art would recognize that certain modifications ‘would come within the seope of this invention ‘What is claimed is: 1. Adey polymer powder for use inthe petroteum industry for enhanced petroleum recovery, comprising dry polymer powder sized Between two size limits, namely atleast about KS wt 9 of particles of a size smaller than 40-mesh, and at least 75 wt 6 of particles of a size greater than 200-mesh, Dee. 21, 2017 2. The dry polymer powder of claim 1, the polymer size range ensures thatthe dry polymer powder will eicintly hydrate in the water or brine within about ope minute without forming fisheye. 3. The dry polymer powder ofelsim 1, further comprising at least one additive selocted from the group consisting of Water soluble elecrolyteislis, oxygen scavengers, scale inhibitors, corrosion inhibitors, fud-loss additives, bateri- ides, clay stabilizers, and surfactants 4. The dry polymer powder of claim 3, wherein the surTactant comprises a block polymer nonionie surfactant 8. The dry polymer powder of claim 3, wherein the water soluble elecroiytessalis comprise alkaline and alkaline ides, sulfites, phosphates, acetates, formates, and methane- sulfonates 6. The diy polymer power of csim 1, wherein the dry polymer powder comprises at est one of a polyacrylamide, ‘enpolymer of acrylamide and acrylic aid fnetionalized derivative theeo.agalctomannan or aclllosic polymer or derivatives thee, wherein the polymer can be cross Tinker ot eroslinked, provided tht i they are homo or co-polymers of acrylic ack, they are aot erossinked 7. The diy polymer powder of claim 4, wherein the proportion of polymer particles smaller than 100-nesh C180 microm) is baween 10% and 50% of the tal polymer parle 8. The diy polymer powder of claim 4, wherein the proportion of palymer picts between 6O-nesh ad 100- mesh (-205 19 ~150 meron s between 10% and 30% of the total polymer partic. 9. The dey polymer poser of claim 6, the dry polymer powder has 8 panicle size dntibation of 40 mesh-aboot £03%, 40.10. 100 mesh-about 382%, 100 to. 140 ‘mesh about 10.9%, 140 10 200 mesh-about 0.2%: 200 wo 325 mesh-about 02% an >328 mesh-about 0.2%. 10. A dry polymer powder for wse in the poole Indwity for enhanced petroleum recovery. comprising» dry polymer powder selected Irom the group conning oft Teast one of polyacrylamide, a copolymer of aerlamide an aeryic aid, netionalized derivative threo. gala: tomannan, of a cellulosic polymer or derivatives thereof ‘wherein the polymer canbe eeslnked o aot crosslinked Provided tat if they ae Bomo- oF co-poyers of aeryic Sci, they are aot resid, wherein the dry polyiner powder is sized betwoen two size limits, namely’ atleast Shout 85 WL % of particles of a size smaller than about O-mesh, and a east 75 wt % of panicles of size grwter than 200-mesh, and wherein the polymer size ange ensures the dry polymer powder will elicially hydrate in the water oe brine Within about one minute without forming Faheyes 11, The dry polymer powder of claim 10, farther com- prising at lest on ative selected fom the aoup con- Sisting of water soloble eleetolytessals, oxygen scaven- ae, scale iakbitors, omosion inhibit, ldlans ives, bctercies, clay sablizes, and surfactant 12. The dty polymer power of claim 1, wherein the surfictant comprises a bloek polymer nonionic surfactant 13. The dey polymer power of claim 11, wherein the water soluble cectytelsalts camprise alin and lke Tine earth meals and amavoni salts als of water soluble US 2017/0362497 AI ‘and smmoniuas salts of chlo acetates, Foemates, and methane- nines, sodium, potassi ides, sulfates, phosphate sulfonates 14. A method for using the dry polymer powder of elim 1 as a friction reducer in focking Water, comprising adding the dey polymer powder of claim I direely to a steam of fresh water or brine without pre-hydrating the dry power before introducing it to fresh Water of brine 18, The method for using the dry polymer powder of

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