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Kuyungizya kwa Shale mumaziba aa clastic kuletela mapenzi mapati, akupa kuti bulo butazungaani. Nkaambo kazyintu zizingulukide, kubelesya maanzi aakuboola aazwa mumaanzi antoomwe azintu zilesya shale nkubotu kwiinda maanzi aakuboola aabelesya mafuta. Ma Ionic liquids (ILs) akakwela maanu kapati mbuli zintu zilesya shale akaambo kakuti zilakonzya kucinca-cinca alimwi akuba anguzu zyakubelesya magesi. Nokuba boobo, imidazolyl-based ionic liquids (ILs), iibelesyegwa kapati mukubboola maanzi, yakatondezya kuti ilakola, taikonzyi kubola alimwi iladula. Ma deep eutectic solvents (DES) alabonwa kuti ngaabelesya mali masyoonto alimwi taakwe toxic kwiinda ma ionic liquids, pesi taakwe nachikonzya kukwabilila busena. Kuyaambele kwakachitika ino-ino mumulimo ooyu kwapa kuti kube nzila zyakupanga zintu zipangwa anyika (NADES), izizyibidwe kuti tazinyonganyi busena. Ooku kuvwuntauzya kwakavwuntauzya NADESs, eezyo zijisi asidi ya citric (mbuli chintu chitambula hydrogen bond) antoomwe a glycerol (mbuli hydrogen bond donor) mbuli zintu ziyungizya maanzi aakubboola. NADES-based drilling fluids zyakabambwa kweendelana a API 13B-1 mpawo kubeleka kwazyo kwakakozyanisyigwa a potassium chloride-based drilling fluids, imidazolium-based ionic liquids, antoomwe a choline chloride:urea-DES-based drilling fluids. Zibeela zya physicochemical zya NADESs zyaambwa mubufwaafwi. Bube bwa rheological, kusweekelwa kwamaanzi, antoomwe a shale inhibition bube bwamaanzi aakubboola zyakali kulinguwe muchiindi chakwiiya, mpawo kwakatondezyegwa kuti a 3% NADESs, yield stress/plastic viscosity ratio (YP/PV) yakayungizigwa, bupati bwa bulongo bwakacheya a 26%, mpawo filtrate volume yakacheya a 30%. Chazibinkene, NADES yakajana mweelwe mubotu wakulesya kuyaambele kwa 49.14% mpawo yakayungizya kupanga shale a 86.36%. Eezyi mpindu zyakajanwa akaambo kakukonzya kwa NADES kuchincha milimo yaatala, nguzu zya zeta, antoomwe akwaandaana kwabulongo, eezyo zyabandikwa mupepa eeli kuteelela nzila zibelesyegwa. Maanzi aaya aakubboola aatamani alalangilwa kuchincha makwebo aakubboola kwiinda mukupa nzila iitakwe toxic, iitayandiki mali manji, alimwi iibeleka kabotu kwiinda misamu iilesyela kubola kwa shale, ikujalula nzila yakubelesya nzila zyakubboola zitanyonganyi busena.
Shale ni bbwe likonzya kubelesegwa munzila zyiingi libeleka mbuli ntalisyo akubamba ma hydrocarbons, mpawo bupange bwalyo bujisi mapopwe1 bupa nguzu zyakupanga akubamba zintu eezyi ziyandisi. Nokuba boobo, shale ilijisi bulongo buvwubide mbuli montmorillonite, smectite, kaolinite antoomwe a illite, eezyo zipa kuti ifwambaane kuzimba aawo noili mumaanzi, eezi zipa kuti bulo butazungaani muchiindi chakusya2,3. Twaambo ootu tulakonzya kuleta chiindi chakutabeleka (NPT) antoomwe amapenzi manji aakubeleka mbuli mapaipi aajatikizyidwe, kusweeka kweenda kwamatope, kuwa kwamugoti akusofwaazya, ikuyungizya chiindi chakubambulula amali. Muchuyanza, mafuta abelesya mafuta (OBDF) ngaakali kusalwa kapati mukupanga mabwe aa shale akaambo kakukonzya kwawo kukazya kuvwula kwa shale4. Nokuba boobo, kubelesya mafuta aakusya kuleta mali manji alimwi ntenda kubusena. Maanzi aakubboola aapangidwe aabantu (SBDF) akayeeyelwa kuti nganzila imwi, asi kweelela kwawo muchiindi chakupya loko takukkuti pe. Maanzi aakuboola aamaanzi (WBDF) nchintu chibotu nkaambo alikwabilidwe, tachinyonganyi busena, mpawo tachibelesyi mali manji kwiinda OBDF5. Zisinkilizyo zyaandeene zya shale zyakabelesegwa kuyungizya nguzu zyakulesya shale zya WBDF, kubikkilizya azintu zyakale zilimbuli potassium chloride, lime, silicate, antoomwe a polymer. Nokuba boobo, eezyi zisinkilizyo zilaampindu zyakubeleka kabotu akujatikizya busena, ikapati akaambo kakuvwula kwa K+ muzisinkilizyo zya potassium chloride antoomwe a pH sensitivity ya silicates. 6 Basikuvwuntauzya bakavwuntauzya nzila zyakubelesya maanzi aa ionic mbuli zintu ziyungizyidwe mumaanzi aakubboola kutegwa maanzi aakubboola asumpukide akukwabilila kuzimba kwa shale akupanga maanzi. Nokuba boobo, aaya ma ionic liquids, ikapati aayo ajisi imidazolyl cations, kanjikanji alakola, aladula, taakonzyi kubola, alimwi ayanda nzila zikatazya zyakulibambila. Kumanizya mapenzi aaya, bantu bakatalika kuyandaula nzila imwi iitabelesyi mali manji alimwi iitanyonganyi busena, eecho chakasololela kukuzwa kwa deep eutectic solvents (DES). DES musanganisyo wa eutectic uchitwa a hydrogen bond donor (HBD) a hydrogen bond acceptor (HBA) a molar ratio a temperature imwi. Eeyi misanganisyo ya eutectic ilaa busena bwakunyenguluka buce kwiinda zibeela zyayo, ikapati akaambo kakugwisigwa kwamagesi akaambo ka hydrogen bonds. Twaambo tunji, kubikkilizya anguzu zya lattice, kuchincha kwa entropy, akujatana aakati ka anions a HBD, zilagwasya kapati mukucesya melting point ya DES.
Muziiyo zyakainda, zintu zyiingi zyakayungizigwa mumaanzi aakubboola aameenda kuchitila kuti kumanizye penzi lyakuvwula kwa shale. Mbuli chitondeezyo, Ofei abamwi. wakayungizya 1-butyl-3-methylimidazolium chloride (BMIM-Cl), walo wakacesya kapati bupati bwakkekke lyamatope (kusikila ku 50%) mpawo wakacesya mweelwe wa YP/PV a 11 kutempelecha zisiyene. Huang abamwi. wakabelesya maanzi aajisi ayoni (ikapati, 1-hexyl-3-methylimidazolium bromide a 1,2-bis(3-hexylimidazol-1-yl)ethane bromide) antoomwe atunsiyansiya twa Na-Bt mpawo wakachesya kuzimba kwa shale a 86.43% a 94.17%, kweendelana. Mukuyungizya, Yang abamwi. wakabelesya 1-vinyl-3-dodecylimidazolium bromide antoomwe a 1-vinyl-3-tetradecylimidazolium bromide kuchesya kuzimba kwa shale a 16.91% antoomwe a 5.81%, kweendelana. 13 Yang abamwi. alimwi wakabelesya 1-vinyl-3-ethylimidazolium bromide mpawo wakachesya kuvwula kwa shale a 31.62% mpawo wakabamba shale recovery a 40.60%. 14 Mukuyungizya, Luo abamwi. wakabelesya 1-octyl-3-methylimidazolium tetrafluoroborate kuchesya kuzimba kwa shale a 80%. 15, 16 Dai abamwi. wakabelesya ma ionic liquid copolymers kukasya shale mpawo wakajana 18% yakuyungizya mukubweedezya kweelanisigwa a amine inhibitors. 17
Maanzi aajisi ionic alikke alijisi zintu zimwi zitali kabotu, eezyo zyakapa kuti basayaansi bayandaule nzila zimbi zitanyonganyi busena kwiinda maanzi aajisi ionic, aboobo DES yakazyalwa. Hanjia wakaba wakusaanguna kubelesya misamu iikola (DES) iijisi vinyl chloride propionic acid (1:1), vinyl chloride 3-phenylpropionic acid (1:2), antoomwe a 3-mercaptopropionic acid + itaconic acid + vinyl chloride (1:1:2), eeyo yakalesya kuzimba kwa bentonite a 6%, a 8%, a 8%, a 8% 58%, kweendelana18. Mukusola kwaalubazu, MH Rasul wakabelesya mweelwe wa 2:1 wa glycerol a potassium carbonate (DES) mpawo wakachesya kuzimba kwa shale samples a 87%19,20. Ma wakabelesya urea:vinyl chloride kuchesya kuyaambele kwa shale a 67%.21 Rasul abamwi. Kusanganya DES a polymer kwakabelesegwa mbuli chintu chilesya shale, eecho chakapa kuti kube kukasya shale22.
Nikuba kuti ma deep eutectic solvents (DES) kanjikanji abonwa kuti nganzila imwi iitakwe busani kwiinda maanzi aajisi ionic, alimwi alijisi zintu zikonzya kujaya mbuli munyo wa ammonium, calo cipa kuti kutabi kunyonganya busena. Penzi eeli lyakapa kuti kube kuchitwa kwama deep eutectic solvents (NADES). Zichili muchibaka cha DES, pesi zilijisi zintu zyacilengwaleza amunyo, kubikkilizya a potassium chloride (KCl), calcium chloride (CaCl2), Epsom salts (MgSO4.7H2O), azimwi. Kusanganya kunjaanji kwa DES a NADES kujalula nzila mpati yakuvwuntauzya muchibaka eechi mpawo kulalangilwa kubelesegwa mumbazu zyiingi. Basikuvwuntauzya biingi bakazwidilila mukupanga nzila zipya zya DES eezyo zyakatondezya kuti zilagwasya muzintu zyiingi. Mbuli chitondeezyo, Naser abamwi. 2013 bakapanga potassium carbonate-based DES mpawo bakaiya thermophysical properties, eezyo zyakazoojana kubelesegwa mumbazu zyakulesya hydrate, drilling fluid additives, delignification, antoomwe a nanofibrillation. 23 Jordy Kim ababelesinyina bakapanga ascorbic acid-based NADES mpawo bakalanga-langa bube bwayo bwakulwana malwazi mumilimo yiindene-indene. 24 Christer abamwi. wakapanga NADES iijisi asidi ya citric mpawo wakabona kuti ilakonzya kugwasya mukupanga zintu zya collagen. 25 Liu Yi ababelesinyina bakapandulula kubelesyegwa kwa NADES mbuli nzila yakugwisya akubamba mubala mukulanga-langa koonse, mpawo Misan abamwi. bakabandika aatala akuzwidilila kwakubelesya NADES muchibaka chabulimi azyakulya. Nchintu chipati kuti basikuvwuntauzya zyamaanzi aakubboola batalike kubikkila maanu kukuzwidilila kwa NADES mumilimo yabo. lino lino. Mu 2023, Rasul abamwi. bakabelesya misamu yiindene-indene ya deep eutectic solvents zyeendelana a ascorbic acid26, calcium chloride27, potassium chloride28 antoomwe a Epsom salt29 mpawo bakazwidilila mukulesya shale akubweedezya shale. Ooku kuvwuntauzya nchimwi chaziiyo zyakusaanguna kuzyibya NADES (ikapati citric acid a glycerol-based formulation) mbuli musamu uukwabilila busena alimwi uubeleka kabotu mukulesya shale mumaanzi aakubboola, walo uujisi busena bubotu bwakukkalilila, kusumpula nguzu zyakulesya shale alimwi akusumpula mulimo wamaanzi kweelanisigwa azintu zyakale mbuli KCl, izoid-based DESs alimwi amaanzi aakaindi.
Chiiyo chiyoobikkilizya akubamba mukati ka citric acid (CA) based NADES kutobelwa akusalazya kwa physicochemical akubelesya kwayo mbuli chintu chiyungizyidwe mumaanzi aakubboola kulanga-langa bube bwamaanzi aakubboola akukonzya kwawo kulesya kuzimba. Mukuvwuntauzya ooku, CA iyoobeleka mbuli sikutambula ma hydrogen bond kakuli glycerol (Gly) iyoobeleka mbuli hydrogen bond donor yakasalwa kweendelanya a MH screening criteria ya NADES formation/kusala mu shale inhibition studies30. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) antoomwe a zeta potential (ZP) zipima ziyoopandulula kujatana kwa NADES-clay anzila zibelesyegwa kulesya kuzimba kwa clay. Kuyungizya waawo, chiiyo eechi chiyookozyanisya CA NADES based drilling fluid antoomwe a DES32 based a 1-ethyl-3-methylimidazolium chloride [EMIM]Cl7,12,14,17,31, KCl antoomwe a choline chloride:urea (1:2) kuti tuvwuntauzye mbozibeleka mukulesya shale drilling fluid.
Citric acid (monohydrate), glycerol (99 USP), antoomwe a urea zyakaulwa kuzwa ku EvaChem, Kuala Lumpur, Malaysia. Choline chloride (>98%), [EMIM]Cl 98%, antoomwe a potassium chloride zyakaulwa kuzwa ku Sigma Aldrich, Malaysia. Bupange bwamakemikalu woonse buli muchifanikisyo 1. Mufanikisyo uusalala pyu weezyanisya makemikalu mapati akabelesegwa muchiiyo eechi: imidazolyl ionic liquid, choline chloride (DES), citric acid, glycerol, potassium chloride, antoomwe a NADES (citric acid and glycerol). Chibeela chakukwabilila busena bwamakemikalu akabelesegwa muchiiyo eechi chitondezyedwe muchibeela 1. Muchibeela, musamu umwi aumwi ulapimwa kweendelanya abuti, kubola, muulo, akukwabilila busena.
Bupange bwazintu zyakabelesegwa mukwiiya ooku: (a) sitric acid, (b) [EMIM]Cl, (c) choline chloride, antoomwe a (d) glycerol.
Basikugwasizya ba hydrogen bond (HBD) aba hydrogen bond acceptor (HBA) bakonzya kupanga CA (natural deep eutectic solvent) based NADES bakasalwa kabotu-kabotu kweendelana anzila zyakusala zya MH 30, eezyo zyakabambilwa kupanga NADES kuti zibelesyegwe kukwabilila shale. Kweelana achiimo eechi, zibeela zili amweelwe mupati wabasikupa abasikutambula antoomwe a polar functional groups zilabonwa kuti zileelela mukupanga NADES.
Mukuyungizya, ionic liquid [EMIM]Cl antoomwe a choline chloride:urea deep eutectic solvent (DES) zyakasalwa kuti zyeelanisyigwe muchiiyo eechi nkaambo zilabelesyegwa kapati mbuli zintu ziyungizya maanzi aakubboola33,34,35,36. Mukuyungizya, potassium chloride (KCl) yakakozyanisyigwa nkaambo nchintu chidumide chakulesya.
Citric acid a glycerol zyakasanganyigwa muzibeela zya molar zisiyene kuchitila kuti kube kusanganya kwa eutectic. Kulangisisya kwakatondeezya kuti musanganisyo wa eutectic wakali uukozyenye, uusalala uutakwe busi, kutondezya kuti hydrogen bond donor (HBD) a hydrogen bond acceptor (HBA) zyakasanganizigwa kabotu mu eutectic composition eeyi. Kusola kwakusaanguna kwakachitwa kuti kuboneke kweendelana akupya kwakusanganya kwa HBD a HBA. Kweelana alugwalo luliwo, mweelwe wamisanganisyo ya eutectic wakalingulwa kutempelecha zyotatwe zili atalaa 50 °C, 70 °C a 100 °C, kutondezya kuti kupya kwa eutectic kanjikanji kuli akati ka 50–80 °C. Chipimyo cha Mettler chakabelesegwa kupima HBD a HBA, mpawo Thermo Fisher hot plate yakabelesegwa kupya akuzungaanya HBD a HBA a 100 rpm muchiimo chili kabotu.
Bube bwa thermophysical bwa deep eutectic solvent (DES) yesu, kubikkilizya abulemu, kuyuma kwaatala, mweelwe wakutontola, akuyuma, zyakali kupimwa kabotu-kabotu kuzwa ku 289.15 kusikila ku 333.15 K. Chileelela kuzyibwa kuti ooku kupya kwakasalwa akaambo kakubula zibelesyo. Buvwuntauzi buzulide bwakabikkilizya akuvwuntauzya kwamukati-kati kwazibeela zya thermophysical zya NADES eeyi, kutondezya mbozibeleka muzibeela zyakupya ziindene. Kubikkila maanu kuchiimo eechi chakupya kupa kumvwisisisya aatala abube bwa NADES oobo buyandika kapati mumilimo myiingi.
Kuyuma kwaatala kwa NADES yakabambilwa kwakapimwa kuzwa ku 289.15 kusika ku 333.15 K kubelesya chipimyo chakuyuma kwaatala (IFT700). Madonsi aa NADES apangwa mukaanda kazwide maanzi manji kubelesya nyeleti ya capillary mubukkale bumwi bwakupya akusinikizyigwa. Nzila zyakufotozya zyamazubaano zileta zyeelelo zya geometry zyeelede kuti zikonzye kubala kusiyana kwazibeela zyaatala kubelesya nzila ya Laplace.
I ATAGO refractometer yakabelesegwa kujana refractive index ya NADES yakabambwa bupya aakati kakupya kwa 289.15 kusika ku 333.15 K. Chibelesyo eechi chibelesya thermal module kweendelezya kupya kuchitila kweezyeezya mweelwe wakupya kwamumuni, akulesya kuyandika kwakusamba mumaanzi aapya lyoonse. Busena bwa prism bwa refractometer bweelede kusalazyigwa mpawo musamu wa musamu weelede kwaabwa kabotu-kabotu atala lyawo. Bikka nzila iizyibidwe, mpawo ubale refractive index kuzwa kuchipekupeku.
Kuyuma kwa NADES yakabambilwa kwakapimwa aawo 289.15 kusikila ku 333.15 K kubelesya Brookfield rotational viscometer (cryogenic type) a shear rate ya 30 rpm antoomwe abwaamba bwa spindle bwa 6. Viscometer ilapima viscosity kwiinda mukuziba torque iiyandika kuti spindle izungaane aawo mpoili maanzi. Nikwakamana kubikwa musamu aachipekupeku munsi aachipimyo akuyuminizyigwa, viscometer itondezya viscosity mu centipoise (cP), kupa makani aayandika aatala a rheological properties yamaanzi.
Chipimyo cha DMA 35 Basic chakabelesegwa kuzyiba bunji bwazintu zyakabambilwa bupya bwa deep eutectic solvent (NDEES) mumusela wakupya kwa 289.15–333.15 K. Mbwaanga chibelesyo eechi tachijisi chipya chakayakidwe mukati, cheelede kupya kusika aawo mpokupya (± 2 °C) kakutanabelesegwa mita ya NES. Kokwela 2 ml ya sampulu kwiinda mu tube, mpawo bunji bwawo buyootondezyegwa a screen. Nchintu chibotu kuzyiba kuti akaambo kakubula chakupya chakayakidwe mukati, mpindu zyakupima zili akulubizya kwa ± 2 °C.
Kulingula pH ya NADES yakabambwa bupya muchiimo chakupya kwa 289.15–333.15 K, twakabelesya Kenis benchtop pH meter. Mbwaanga taakwe chibelesyo chakupya chakayakidwe mukati, NADES yakasaanguna kupya kusika aawo mpaakali kuyanda (±2 °C) kubelesya chipekupeku mpawo yakapimwa a pH mita. Bika loko pH meter probe mu NADES mpawo ulembe mweelwe wamamanino nikwakamana kubala.
Kuvwuntauzya kwa Thermogravimetric (TGA) kwakabelesegwa kulanga-langa kukkalwa kwakupya kwama deep eutectic solvents (NADES). Zitondezyo zyakavwuntauzyigwa muchiindi chakupya. Kubelesya chipimyo chili kabotu loko akulangisisya oobotu nzila yakupya, chitondeezyo chakusweekelwa kwabunji kweendelanya akupya kwakapangwa. NADES yakapya kuzwa ku 0 kusika ku 500 °C amweelwe wa 1 °C muminiti yomwe.
Kutalika nzila, musamu wa NADES weelede kusanganyigwa oobotu, kuchitwa kuti ube mbuli mbukweelede, mpawo kugwisigwa busi bwaatala. Isampulu yakabambilwa mpawo yakabikkwa mu TGA cuvette, eeyo kanjikanji ichitwa azintu zitabeleki mbuli aluminiyamu. Kuchitila kuti kube mpindu ziluzi, zibelesyo zya TGA zilapimwa kubelesya zibelesyo zyakubelesya, kanjikanji zyeelelo zyabulemu. Nikuba kuti zyabikkwa kabotu, TGA yakatalika mpawo musamu ulapya munzila yeendelezyegwa, kanjikanji amweelwe uutacinci. Kuzumanana kulangisisya kujatana aakati kabulemu bwasampulu akupya nchintu chipati mukusola. Zibelesyo zya TGA ziyobolola data aatala akupya, kulema, azintu zimwi zilimbuli kweenda kwamuwo naakuti kupya kwasampulu. Nikuba kuti TGA yamana, data yakabungikwa ilalingulwa kuchitila kuziba kuchincha kwabulemu bwasampulu kweendelana akupya. Aaya makani alagwasya kapati mukuziba kupya kwamubili kweendelana akusanduka kwamubili akwamakemikalu muchikozyano, kubikkilizya anzila zilimbuli kunyenguluka, kuvwuuma, kuvwuuma, naa kubola.
Maanzi aakuboola aamaanzi akapangwa oobotu kweendelanya a API 13B-1, mpawo bupange bwawo bulilembedwe mu Table 2 kuti tubone. Citric acid a glycerol (99 USP) zyakaulwa kuzwa ku Sigma Aldrich, Malaysia kuti zipangwe musamu uuzwa mumubili (NADES). Mukuyungizya, musamu uukasya bbwe lya potassium chloride (KCl) wakaulwa kuzwa ku Sigma Aldrich, Malaysia. 1-ethyl, 3-methylimidazolium chloride ([EMIM]Cl) iisalala kwiinda 98% yakasalwa akaambo kakugwasya kwayo kupati mukusumpula rheology ya drilling fluid akulesyegwa kwa shale, eezyo zyakasinizyigwa muziiyo zyakainda. Zyoonse zyobile KCl a ([EMIM]Cl) ziyoobelesegwa mukweezyanisya kulanga-langa mulimo wakulesya shale wa NADES.
Basikuvwuntauzya biingi bayanda kubelesya zibeela zya bentonite kwiiya kuzimba kwa shale nkaambo bentonite ilijisi nkamu njiyonya ya "montmorillonite" eeyo iipa kuti shale kuzimbe. Kujana zitondezyo zya shale core ncobeni nchintu cikatazya nkaambo nzila yakupanga shale ilanyonganya shale, eezi zipa kuti zitondezyo zitabi zya shale zyoonse pesi kanjikanji zilijisi misanganisyo ya sandstone a limestone layers. Mukuyungizya, zitondezyo zya shale kanjikanji tazijisi tubunga twa montmorillonite tupa kuti shale kuzimbe aboobo tazyeelede pe kubelesyegwa mukusola kulesya kuzimba.
Mukuvwuntauzya ooku, twakabelesya zibeela zya bentonite zyakabambululwa zili abwamba bwa 2.54 cm. Ma granules akapangwa akusinikizya 11.5 grams ya sodium bentonite powder mu hydraulic press a 1600 psi. Bupati bwama granules bwakapimwa kabotu-kabotu kaatanabikkwa mu linear dilatometer (LD). Zibeela eezyo zyakabikkwa mumasampulo aamaanzi aakubboola, kubikkilizya amasampula aakusaanguna alimwi amasampulo aakabikkwa misamu iilesya kuzimba kwa shale. Kuchincha kwabupati bwama granule kwakalangwa-langwa kabotu-kabotu kubelesya LD, akupima kwakalembwa mumasekondi aali 60 kwamahola aali 24.
Kuvwuntauzya kwa X-ray kwakatondezya kuti bupange bwa bentonite, ikapati 47% ya montmorillonite, nchintu chipati mukumvwisisisya bube bwawo. Akati kazibeela zya montmorillonite zya bentonite, montmorillonite ncecibeela cipati, cijisi 88.6% yazibeela zyoonse. Aawo, quartz ilaa 29%, illite 7%, antoomwe a carbonate 9%. Kabeela kaniini (aasika ku 3.2%) nkusanganya kwa illite a montmorillonite. Mukuyungizya, ilijisi zintu zilimbuli Fe2O3 (4.7%), silver aluminosilicate (1.2%), muscovite (4%), antoomwe a phosphate (2.3%). Mukuyungizya, tuniini twa Na2O (1.83%) antoomwe a iron silicate (2.17%) ziliwo, eezyo zipa kuti cikonzyeke kumvwisisisya zintu zipangwa a bentonite antoomwe amweelwe wazyo.
Eechi chibeela chakwiiya chizulide chilapandulula zyintu zya rheological a filtration zyama sampuli aamaanzi aakubboola aakabambilwa kubelesya musamu uutegwa natural deep eutectic solvent (NADES) mpawo akabelesegwa mbuli chintu chakuyungizya maanzi aakubboola muzibeela ziindene-indene (1%, 3% a 5%). NADES based slurry samples mpawo yakakozyanisigwa akuvwuntauzyigwa a slurry yama potassium chloride (KCl), CC:urea DES (choline chloride deep eutectic solvent:urea) antoomwe a ionic liquids. Mweelwe wazyintu zipati zyakabandikwa muchiiyo eechi kubikkilizya akubalwa kwa viscosity kwakajanwa kubelesya FANN viscometer kakutanaba akumana kubikkwa mubukkale bwakuchembaala a 100°C a 150°C. Kupima kwakachitwa mumisela yiindene (3 rpm, 6 rpm, 300 rpm antoomwe a 600 rpm) ikuzumizya kuvwuntauzya kuzulide kwabukkale bwamaanzi aakubboola. Data yakajanwa ilakonzya kubelesegwa kujana zintu zipati zilimbuli yield point (YP) antoomwe a plastic viscosity (PV), eezyo zipa kumvwisisisya mbozibeleka maanzi mubukkale bwiindene-indene. Kusunkwa kwakusefa kwakupya kapati (HPHT) a 400 psi a 150°C (kupya kwachiindi chilamfu mumigodi iipya kapati) kulagwasya kusefa (bupati bwakkekke abwaamba bwakusefa).
Eechi chibeela chibelesya zibelesyo zyamazubaano, Grace HPHT Linear Dilatometer (M4600), kulanga-langa kabotu-kabotu bube bwakulesya kuzimba kwa shale mumaanzi eesu aakusya. LSM ninchina yachiindi chilamfu iijisi zibeela zyobile: chintu chakuvwumbilila mapuleti antoomwe a linear dilatometer (model: M4600). Mapuleti aa Bentonite akabambilwa kuti alingulwe kubelesya Grace Core/Plate Compactor. LSM mpawo ilapa data yakufwambaana kuzimba aamapuleti aaya, akupa kuti kube kulanga-langa kuzulide kwakulesya kuzimba kwa shale. Kusunkwa kwakuyungizya bbwe lya Shale kwakachitwa mubukkale buli afwaafwi, nkokuti, 25°C a 1 psia.
Kusunkwa kwakukkalwa kwa shale kulabikkilizya akusunkwa kupati kanjikanji kwiitwa kuti musunko wakubweedezya bbwe, musunko wakunjizya bbwe naa musunko wakumwaika kwabbwe. Kutalika kulanga-langa ooku, zibeela zya shale zilaandaanizyigwa a #6 BSS screen mpawo zyabikkwa a #10 screen. Zibeela eezyo mpawo zilabikkwa muchibbeeke chakuyobweda ooko nkozisanganyigwa amaanzi aakusaanguna abulongo bwakubboola bujisi NADES (Natural Deep Eutectic Solvent). Ntaamu itobela njakubikka musanganisyo muchitofu kuti ube aanguzu zyakuvwungulula, kusinizya kuti zisyango amatope zyaswaanganizyigwa obotu. Nikwakainda mawoola ali kkumi amusanu akamwi, zisyango zilagwisigwa kuzwa kumusamu kwiinda mukuleka kuti shale ibole, eezi zipa kuti zisyango ziche. Kusunkwa kwakujana bbwe lya shale kwakachitwa nikwakamana kutemwa bbwe lya shale mubulongo bwakubboola a 150°C a 1000 psi. inchi mukati ka mawoola aali makumi obilwe atune.
Kuti tubone bulongo bwa shale bwakabukuluka, twakabusefa kwiinda muchipekupeku chibotu (40 mesh), mpawo twakabusanzya aamaanzi, mpawo twakabuyuminizya muchitofu. Eeyi nzila iikatazya ilatuzumizya kweezyeezya bulongo bwakajanwa kweelanisigwa abulemu bwakusaanguna, kumamanino twabala mweelwe wabulongo bwa shale bwakajanwa. Nkozyakazwa zitondezyo zya shale kuzwa ku Niah District, Miri District, Sarawak, Malaysia. Kakutanaba kusunkwa kwakumwaika akubweedezya, zitondezyo zya shale zyakabikkwa mubuvwuntauzi bwa X-ray diffraction (XRD) kutegwa kuzyibwe bulongo bwazyo akusinizya kuti zilakonzya kusunkwa. Bulongo bwamabwe aamusamu mbuboobu: illite 18%, kaolinite 31%, chlorite 22%, vermiculite 10%, antoomwe a mica 19%.
Kuyuma kwaatala nchintu chipati cheendelezya kunjila kwama cations mumaanzi mu shale micropores kwiinda mukubelesya nzila zya capillary, eezyo ziyoovwuntauzyigwa mubufwaafwi muchibeela eechi. Pepa eeli lilalanga-langa mulimo wakuyuma kwaatala mubukkale bwakujatana kwamaanzi aakubboola, kutondezya nsungwaazyo mpati yayo mumulimo wakubboola, ikapati kulesyegwa kwa shale. Twakabelesya ntalisyo ya interfacial tensiometer (IFT700) kupima kabotu-kabotu buyumuyumu bwaatala bwazitondezyo zyamaanzi aakuboola, kutondezya cibeela ciyandika kapati cabukkale bwamaanzi mubukkale bwakulesyegwa kwa shale.
Eechi chibeela chibandika mubufwaafwi aatala a d-layer spacing, ooyo uuli akati-kati ka aluminosilicate layers a aluminosilicate layer yomwe mubulongo. Buvwuntauzi bwakavwumbilila bulongo buteteete bujisi 1%, 3% a 5% CA NADES, antoomwe a 3% KCl, 3% [EMIM]Cl antoomwe a 3% CC:urea based DES kuti kweezyanisye. Chibelesyo cha X-ray diffractometer (D2 Phaser) chibeleka a 40 mA a 45 kV a Cu-Kα radiation (λ = 1.54059 Å) chakagwasya kapati mukulemba X-ray diffraction peaks zya Na-Bt ziteteete aziyumu. Kubelesya equation ya Bragg kupa kuti kube kuzyiba kabotu-kabotu kwa d-layer spacing, aboobo kupa makani aayandika kapati kujatikizya mbobubede bulongo.
Eechi chibeela chibelesya chibelesyo cha Malvern Zetasizer Nano ZSP kuti chipimye kabotu nguzu zya zeta. Ooku kulanga-langa kwakapa makani aayandika kapati kujatikizya bube bwakujatikizyigwa kwamasampula aamatope aajisi 1%, 3%, alimwi a 5% CA NADES, alimwi a 3% KCl, 3% [EMIM]Cl, alimwi a 3% CC:urea-based DES kutegwa kube kweezyanisya. Eezyi mpindu zilagwasya kumvwisisisya kwesu kwakukkalikana kwa colloidal compounds akuswaangana kwazyo mumaanzi.
Zitondezyo zyabulongo zyakali kulinguwe kakutanaba alubo nikwakamana kubikkwa muchintu chiyumu (NADES) kubelesya Zeiss Supra 55 VP field emission scanning electron microscope (FESEM) iijisi nguzu zya X-ray (EDX). Kuboneka kabotu kwachifanikisyo kwakali 500 nm mpawo manguzu aamumuni wamagesi akali 30 kV a 50 kV. FESEM ilapa kubona kabotu-kabotu kwabupange bwaatala abukkale bwabulongo. Makanze aachiiyo aaya akali aakujana makani aatala akugwasya kwa NADES kumasampulo aabulongo kwiinda mukweezyanisya zifwanikiso zyakajanwa kakutanaba alubo nikwakamana kutondezyegwa.
Mukuvwuntauzya ooku, nzila yakubelesya magesi (FESEM) yakabelesegwa kulanga-langa mulimo wa NADES kumasampulo aabulongo aawo mpaali ma microscopic. Makanze aachiiyo aaya ngakupandulula nzila zikonzya kubelesegwa a NADES akugwasya kwayo kubulongo bwabulongo abupati bwazibeela, eezyo ziyoopa makani aayandika kapati mukuvwuntauzya mumulimo ooyu.
Mukuvwuntauzya ooku, zibeela zyakulubizya zyakabelesegwa kupandulula kusiyana akudooneka kwamweelwe waakati-kati wakulubizya (AMPE) mubukkale bwakusunka. Muciindi chakulemba mweelwe wa AMPE omwe-omwe (nkaambo kubamba mweelwe wa AMPE kulakonzya kusisa zyintu zicitika akuyungizya kusiyana kusyoonto), tulabala tumpenda twakulubizya kubelesya mulawu wa 5%. Eeyi nzila ilasinizya kuti bbaala lyakulubizya lyomwe lyomwe liyiminina chiindi eecho 95% yachiindi chakusyoma a 100% ya AMPE mpozilangilwa kuwa, aboobo kupa mubufwiifwi busalala alimwi bufwaafwi bwakwaabila kwa data mubukkale buli boonse bwakusunka. Kubelesya tumpenda twakulubizya kweendelanya amulawu wa 5% aboobo kusumpula bupanduluzi akusyomeka kwazifwanikiso mpawo kugwasya kupa kumvwisisisya kuzulide kwazyazwa anzyozyaamba.
Mukupanga ma deep eutectic solvents (NADES), zintu zyiingi zipati zyakavwuntauzyigwa oobotu muchiindi chakulibambila. Twaambo ootu tuyandika kapati tubikkilizya kupya, mweelwe wa molar, akufwambaana kusanganya. Kusola kwesu kutondezya kuti eelyo HBA (citric acid) a HBD (glycerol) nozisanganyigwa a molar ratio ya 1:4 a 50°C, kusanganya kwa eutectic kulapangwa. Cintu cipa kuti kube kwaandaana kwamusanganisyo wa eutectic nkuboneka kwawo kusalala, kulibonya mbuli chintu chomwe, akubula bulongo. Aboobo, ntaamu eeyi iiyandika kapati itondezya mbociyandika mweelwe wa molar, kupya, akufwambaana kusanganya, akati kazyeezyo mweelwe wa molar ngowakali kugwasya kapati mukubamba DES a NADES, mbuli mbokutondezyedwe muchifanikisyo 2.
I refractive index (n) itondezya mweelwe wakufwambaana kwamumuni mubusena butakwe chintu kusikila kukufwambaana kwamumuni mubusena bwabili, bupati. I refractive index ilayandika kapati kuzintu zipangwa ansi kapati (NADES) notulanga-langa nzila zikonzya kubelesegwa mbuli zintu zipona. Ikuboneka kwa NADES yakavwuntauzyigwa a 25 °C kwakali 1.452, eecho nchaansi loko kwiinda cha glycerol.
Nchintu chibotu kuzyiba kuti mweelwe wa NADES ulaselemuka akupya, mpawo eezi zilakonzya kupandululwa kabotu-kabotu afoomu (1) aMufanikisyo 3, aawo kulubizya kwamweelwe waakati-kati (AMPE) kusika ku 0%. Ooku kulilemeka kweendelanya akupya kupandululwa akucheya kwa viscosity a density muchiindi chakupya kapati, kupa kuti mumuni weende mukati kachintu eechi chakufwambaana, eezi zipa kuti kube kucheya kwa refractive index (n) value. Eezyi mpindu zipa mizeezo iiyandika kapati kujatikizya nzila zyakubelesya NADES mukuzyiba zintu ziboneka, kutondezya mbozikonzya kubelesyegwa muzintu zipona.
Kuyuma kwaatala, ooko kutondezya kuti busena bwamaanzi bulakonzya kucesya busena bwabo, nchintu chipati loko mukulanga-langa kweelela kwama deep eutectic solvents (NADES) kuti abelesyegwe kubelesya nguzu zya capillary. Buvwuntauzi bwakuyuma kwaatala aakati kakupya kwa 25-60 °C bupa makani aayandika. A 25 °C, kusinikizyigwa kwa NADES iijisi asidi ya citric kwakali 55.42 mN/m, ooko kwakali munsi kapati kwiinda kwamaanzi a glycerol. Cifwanikiso 4 chitondeezya kuti kusima kwaatala kulaselemuka loko aawo kupya nokwatanta. Eechi chintu chilakonzya kupandululwa akuyungizya nguzu zya molecule mpawo akucheya kwanguzu zyakukwela akati kama molecule.
Ikucheya kwakutontola kwakabonwa mu NADES yakavwuntauzyigwa kulakonzya kwaambwa kabotu a equation (2), eeyo itondezya kujatana kwa nsamu aakati kakupya kwa 25-60 °C. Igilafu muchifanikisyo 4 itondezya antangalala kweenda kwakuyuma kwaatala aawo mpaali kupya kakuli kulubizya kwamweelwe waakati-kati (AMPE) wa 1.4%, ooko kupima buluzi bwazibeela zyaatala zyaambwa. Eezyi mpindu zilaampindu mpati mukumvwisisisya nzila zya NADES anzila zyayo zikonzya kubelesegwa.
Kumvwisisisya bupati bwama deep eutectic solvents (NADES) nchintu chipati loko mukugwasya kubelesegwa muziiyo zyiingi zyasayaansi. Bunji bwa citric acid-based NADES a 25°C mbu 1.361 g/cm3, oobo bupati kwiinda bupati bwa glycerol. Ooku kwiimpana kulakonzya kupandululwa akuyungizyigwa kwa hydrogen bond acceptor (citric acid) ku glycerol.
Kubweza citrate-based NADES mbuli chitondezyo, bunji bwayo bwaseluka kusika ku 1.19 g/cm3 a 60°C. Kuyungizya kwanguzu zyakunyamuna zintu aawo nozipya kupa kuti ma molecule aa NADES amwaike, akupa kuti abweze busena bupati, mpawo akucheya kwabunji. Ikuceya kwabunji bwazintu kwakabonwa kutondezya kweendelana kumwi akuyungizya kwakupya, ooko kukonzya kwaambwa kabotu afomula (3). Cifwanikiso 5 chitondeezya munzila iitondezya zitondezyo zyakusanduka kwabunji bwa NADES akulubizya kwa mweelwe waakati-kati (AMPE) wa 1.12%, ooko kupa mweelwe wakululama kwabunji bwazintu zyaambwa.
Kuyuma ninguzu zikwela aakati kazibeela zyamaanzi zili mukweenda mpawo zilagwasya kapati mukumvwisisisya kubelesegwa kwama deep eutectic solvents (NADES) mumilimo yiindene. A 25 °C, busi bwa NADES bwakali 951 cP, oobo buli atala kwiinda bwa glycerol.
Ikuceya kwa viscosity kwabonwa aawo kupya nokwatanta kupandululwa akucheya kwanguzu zyakukwela zili akati kama molecule. Eechi chintu chipa kuti busi bwamaanzi buche, eezi zitondezyedwe kabotu-kabotu muchifanikisyo 6 mpawo zyaambwa a Equation (4). Chazibinkene, a 60°C, kuvwumbilila kwaseluka kusika ku 898 cP antoomwe akulubizya kwa mweelwe waakati-kati (AMPE) wa 1.4%. Kumvwisisisya kabotu-kabotu kwakuyuma kwa viscosity a temperature mu NADES nchintu chipati loko mukubelesegwa kwayo.
I pH ya musamu, iijanwa a negative logarithm ya hydrogen ion concentration, ilayandika kapati, ikapati mumilimo iijatikizya pH mbuli kupanga DNA, aboobo pH ya NADES yeelede kuvwuntauzyigwa kabotu-kabotu kaitanabelesyegwa. Kubweza citric acid-based NADES mbuli chitondezyo, pH ya 1.91 ilakonzya kubonwa, eeyo yiindene a pH ya glycerol.
Chakugambya, pH ya citric acid dehydrogenase soluble solvent (NADES) yakatondeezya kuseluka kutali kwamulongo aawo kupya nokwatanta. Eechi chintu chakachitika akaambo kakuyungizya kuzungaana kwama molecule ooko kunyonganya kweendelana kwa H+ mumusamu, mpawo eezi zisololela kukupangwa kwa [H]+ ions mpawo, kuchincha kwa pH value. Nikuba kuti pH yacitric acid ili akati ka 3 kusikila ku 5, kubako kwa acidic hydrogen mu glycerol kulayungizya kusezya pH kusika ku 1.91.
I pH ya citrate-based NADES muchiimo chakupya kwa 25-60 °C ilakonzya kutondezyegwa kabotu a equation (5), eeyo iipa chitondezyo cha pH chakabonwa. Cifwanikiso 7 chitondeezya kujatana ooku kubotu, kutondeezya mulimo wakupya a pH ya NADES, eeyo yaambwa kuti ili 1.4% ya AMPE.
Kuvwuntauzya kwa Thermogravimetric (TGA) kwa citric acid deep eutectic solvent (NADES) kwakachitwa munzila iilondokede mumusela wakupya kuzwa ku 500 °C. Mbuli mbokukonzya kubonwa kuzwa kuzifwanikiso 8a a b, kusweekelwa kwabunji bwakusaanguna kusika ku 100 °C kwakali akaambo kamaanzi aakanyonyooka alimwi amaanzi aakali kunywa aajatikizyidwe a citric acid alimwi a pure glycerol. Kukwabililwa kupati kwa 88% kwakabonwa kusika ku 180 °C, ooko kwakachitika akaambo kakubola kwa citric acid kuya ku aconitic acid mpawo akupangwa kwa methylmaleic anhydride(III) nikwakazumanana kupya (Chitondeezyo 8 b). Atala a 180 °C, kulibonya antangalala kwa acrolein (acrylaldehyde) mu glycerol akwalo kwakali kukonzya kubonwa, mbuli mbokutondezyedwe muchifanikisyo 8b37.
Kuvwuntauzya kwa thermogravimetric (TGA) kwa glycerol kwakatondeezya nzila zyobile zyakusweekelwa kwabunji. Chiindi chakusanguna (180 kusika ku 220 °C) chibikkilizya kupanga kwa acrolein, mpawo kutobelwa akusweekelwa kupati kwakupya kapati kuzwa ku 230 kusika ku 300 °C (Mufanikisyo 8a). Mbuli kupya mbokuyaambele, acetaldehyde, carbon dioxide, methane, antoomwe a hydrogen zilapangwa munzila zitobelana. Chazibinkene, 28% luzutu lwabupati bwakajatwa a 300 °C, kutondeezya kuti zintu zyamukati zya NADES 8(a)38,39 zilakonzya kuba zilubide.
Kuti tujane makani aatala akupanga zijatikizyo zyamakemikalu zipya, zintu zyakabambilwa zipya zyakabambilwa zyintu zyakalengwa buya (NADES) zyakali kuvwuntauzyigwa a Fourier transform infrared spectroscopy (FTIR). Kuvwuntauzya kwakachitwa kwiinda mukkozyanisya mubala wa NADES amumuni wa citric acid (CA) a glycerol (Gly). I CA spectrum yakatondezya nsumbu zisalala a 1752 1/cm a 1673 1/cm, eezyo ziiminina kuzungaana kwakutandabala kwa C=O bond alimwi azyalo zili a CA. Mukuyungizya, kucinca kupati mukuzungaana kwa OH a 1360 1/cm kwakabonwa muchibaka chaminwe, mbuli mbokutondezyedwe achifanikisyo 9.
Mbubwenya buyo, muchiimo cha glycerol, kuchincha kwa OH kutandabika akukotama kwakajanwa ku wavenumbers zya 3291 1/cm antoomwe a 1414 1/cm, kweendelana. Lino, kwiinda mukulanga-langa nzila zya NADES zyakabambilwa, kwakajanwa kucinca kupati mumulengalenga. Mbuli mbokutondezyedwe achifanikisyo 7, kuzungaana kwakutandabala kwa C=O kwakasanduka kuzwa ku 1752 1/cm kusika ku 1720 1/cm mpawo kuzungaana kwakukotama kwa -OH bond ya glycerol kwakasanduka kuzwa ku 1414 1/cm kusika ku 1359 1/cm. Ooku kuchincha kwanamba zyamayuwe kutondeezya kuchincha kwa electronegativity, ooko kutondeezya kupangwa kwamakemikalu mapya mubupange bwa NADES.