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Kukula kwa shale m'malo osungiramo zinthu zakale kumabweretsa mavuto akulu, zomwe zimapangitsa kuti pakhale kusakhazikika kwa madzi. Pazifukwa zachilengedwe, kugwiritsa ntchito madzi obowola pogwiritsa ntchito madzi okhala ndi zoletsa zowonjezera za shale kumakondedwa kuposa madzi obowola pogwiritsa ntchito mafuta. Madzi a Ionic (ILs) akopeka chidwi kwambiri ngati zoletsa za shale chifukwa cha mphamvu zawo zosinthika komanso mawonekedwe amphamvu a electrostatic. Komabe, madzi a Ionic (ILs) ochokera ku imidazolyl, omwe amagwiritsidwa ntchito kwambiri mumadzi obowola, atsimikizira kuti ndi oopsa, osawonongeka komanso okwera mtengo. Zosungunulira za Deep Eutectic (DES) zimaonedwa kuti ndi njira yotsika mtengo komanso yopanda poizoni m'malo mwa madzi a Ionic, koma sizikukwaniritsa zofunikira pa chilengedwe. Kupita patsogolo kwaposachedwa m'munda uno kwapangitsa kuti pakhale zosungunulira zachilengedwe za deep eutectic (NADES), zomwe zimadziwika kuti ndi zabwino kwa chilengedwe. Kafukufukuyu adafufuza ma NADES, omwe ali ndi citric acid (monga cholandirira hydrogen bond) ndi glycerol (monga wopereka hydrogen bond) ngati zowonjezera zamadzi obowola. Madzi obowola opangidwa ndi NADES adapangidwa motsatira API 13B-1 ndipo magwiridwe antchito awo adayerekezeredwa ndi madzi obowola opangidwa ndi potassium chloride, madzi a ionic opangidwa ndi imidazolium, ndi madzi obowola opangidwa ndi choline chloride:urea-DES. Makhalidwe a physicochemical a NADES enieni afotokozedwa mwatsatanetsatane. Makhalidwe a rheological, kutayika kwa madzi, ndi mawonekedwe oletsa shale a madzi obowola adayesedwa panthawi ya kafukufukuyu, ndipo zidawonetsedwa kuti pa kuchuluka kwa 3% NADESs, chiŵerengero cha yield stress/plastic viscosity (YP/PV) chidawonjezeka, makulidwe a matope adachepetsedwa ndi 26%, ndipo voliyumu ya filtrate idachepetsedwa ndi 30.1%. Chodziwika bwino ndichakuti, NADES idapeza chiwopsezo chowonjezereka cha 49.14% ndikuwonjezera kupanga kwa shale ndi 86.36%. Zotsatirazi zikugwirizana ndi kuthekera kwa NADES kusintha ntchito ya pamwamba, zeta potential, ndi interlayer space ya dongo, zomwe zikukambidwa mu pepalali kuti timvetsetse njira zomwe zili pansi pake. Madzi obowola okhazikika awa akuyembekezeka kusintha makampani obowola mwa kupereka njira ina yopanda poizoni, yotsika mtengo, komanso yothandiza kwambiri m'malo mwa zoletsa zachikhalidwe za shale corrosion, zomwe zimapanga njira yobowola yosawononga chilengedwe.
Mwala wa Shale ndi mwala wosiyanasiyana womwe umagwira ntchito ngati gwero komanso nkhokwe ya ma hydrocarbon, ndipo kapangidwe kake ka mabowo1 kamapereka mwayi wopanga ndi kusunga zinthu zofunikazi. Komabe, shale ili ndi mchere wambiri wa dongo monga montmorillonite, smectite, kaolinite ndi illite, zomwe zimapangitsa kuti itukuke ikakumana ndi madzi, zomwe zimapangitsa kuti mabowo asamayende bwino panthawi yobowola2,3. Mavutowa angayambitse nthawi yosagwira ntchito (NPT) komanso mavuto ambiri ogwirira ntchito kuphatikizapo mapaipi otsekeka, kutayika kwa matope, kugwa kwa mabowo a wellbore ndi kuipitsidwa kwa bit, zomwe zimawonjezera nthawi yobwezeretsa ndi ndalama. Mwachikhalidwe, madzi obowola opangidwa ndi mafuta (OBDF) akhala chisankho chokondedwa cha mapangidwe a shale chifukwa amatha kukana kukula kwa shale4. Komabe, kugwiritsa ntchito madzi obowola opangidwa ndi mafuta kumabweretsa ndalama zambiri komanso zoopsa zachilengedwe. Madzi obowola opangidwa ndi zinthu zopangidwa (SBDF) amaonedwa ngati njira ina, koma kuyenerera kwawo kutentha kwambiri sikuli kokwanira. Madzi obowola pogwiritsa ntchito madzi (WBDF) ndi njira yokongola chifukwa ndi otetezeka, ochezeka kwambiri pa chilengedwe, komanso otsika mtengo kuposa OBDF5. Ma shale inhibitors osiyanasiyana agwiritsidwa ntchito kuonjezera mphamvu yoletsa shale ya WBDF, kuphatikizapo zoletsa zachikhalidwe monga potassium chloride, laimu, silicate, ndi polymer. Komabe, zoletsa izi zili ndi zoletsa pankhani yogwira ntchito bwino komanso kuwononga chilengedwe, makamaka chifukwa cha kuchuluka kwa K+ mu zoletsa potassium chloride komanso pH sensitivity ya silicates. 6 Ofufuza afufuza kuthekera kogwiritsa ntchito ionic liquids ngati zowonjezera zamadzimadzi obowola kuti akonze rheology yamadzimadzi obowola ndikuletsa kutupa kwa shale ndi kupanga hydrate. Komabe, madzi a ionic awa, makamaka omwe ali ndi imidazolyl cations, nthawi zambiri amakhala oopsa, okwera mtengo, osawonongeka, ndipo amafunika njira zovuta zokonzekera. Kuti athetse mavutowa, anthu anayamba kufunafuna njira ina yotsika mtengo komanso yochezeka pa chilengedwe, zomwe zinapangitsa kuti pakhale zosungunulira zakuya za eutectic (DES). DES ndi chisakanizo cha eutectic chomwe chimapangidwa ndi wopereka hydrogen bond (HBD) ndi hydrogen bond acceptor (HBA) pa chiŵerengero cha molar ndi kutentha. Zosakaniza za eutectic izi zimakhala ndi malo otsika osungunuka kuposa zigawo zake, makamaka chifukwa cha kuchotsedwa kwa mphamvu komwe kumachitika chifukwa cha ma hydrogen bond. Zinthu zambiri, kuphatikizapo lattice energy, kusintha kwa entropy, ndi kuyanjana pakati pa anions ndi HBD, zimathandiza kwambiri pakuchepetsa malo osungunuka a DES.
Mu kafukufuku wakale, zowonjezera zosiyanasiyana zinawonjezedwa ku madzi obowola pogwiritsa ntchito madzi kuti athetse vuto la kukula kwa shale. Mwachitsanzo, Ofei et al. adawonjezera 1-butyl-3-methylimidazolium chloride (BMIM-Cl), yomwe idachepetsa kwambiri makulidwe a keke yamatope (mpaka 50%) ndikuchepetsa YP/PV ndi 11 pa kutentha kosiyanasiyana. Huang et al. adagwiritsa ntchito zakumwa za ionic (makamaka, 1-hexyl-3-methylimidazolium bromide ndi 1,2-bis(3-hexylimidazol-1-yl)ethane bromide) kuphatikiza ndi tinthu ta Na-Bt ndipo idachepetsa kwambiri kutupa kwa shale ndi 86.43% ndi 94.17%, motsatana12. Kuphatikiza apo, Yang et al. adagwiritsa ntchito 1-vinyl-3-dodecylimidazolium bromide ndi 1-vinyl-3-tetradecylimidazolium bromide kuti achepetse kutupa kwa shale ndi 16.91% ndi 5.81%, motsatana. 13 Yang ndi anzake adagwiritsanso ntchito 1-vinyl-3-ethylimidazolium bromide ndipo adachepetsa kukula kwa shale ndi 31.62% pomwe adasungabe kuchira kwa shale pa 40.60%. 14 Kuphatikiza apo, Luo ndi anzake adagwiritsa ntchito 1-octyl-3-methylimidazolium tetrafluoroborate kuti achepetse kutupa kwa shale ndi 80%. 15, 16 Dai ndi anzake adagwiritsa ntchito ma ionic liquid copolymers kuti aletse shale ndipo adapeza kuwonjezeka kwa 18% pakuchira kwa mzere poyerekeza ndi ma amine inhibitors. 17
Madzi a Ionic okha ali ndi zovuta zina, zomwe zinapangitsa asayansi kufunafuna njira zina zotetezera chilengedwe m'malo mwa madzi a ionic, motero DES inabadwa. Hanjia anali woyamba kugwiritsa ntchito zosungunulira za deep eutectic (DES) zomwe zili ndi vinyl chloride propionic acid (1:1), vinyl chloride 3-phenylpropionic acid (1:2), ndi 3-mercaptopropionic acid + itaconic acid + vinyl chloride (1:1:2), zomwe zinaletsa kutupa kwa bentonite ndi 68%, 58%, ndi 58%, motsatana18. Mu kuyesera kwaulere, MH Rasul adagwiritsa ntchito chiŵerengero cha 2:1 cha glycerol ndi potassium carbonate (DES) ndipo adachepetsa kwambiri kutupa kwa zitsanzo za shale ndi 87%19,20. Ma adagwiritsa ntchito urea:vinyl chloride kuti achepetse kwambiri kukula kwa shale ndi 67%.21 Rasul et al. Kuphatikiza kwa DES ndi polymer kunagwiritsidwa ntchito ngati choletsa shale cha dual-action, chomwe chidapeza zotsatira zabwino kwambiri za shale inhibition22.
Ngakhale kuti ma deep eutectic solvents (DES) nthawi zambiri amaonedwa ngati njira ina yobiriwira m'malo mwa madzi a ionic, alinso ndi zinthu zomwe zingakhale zoopsa monga mchere wa ammonium, zomwe zimapangitsa kuti kusakhala bwino kwa chilengedwe kukhale kokayikitsa. Vutoli lapangitsa kuti pakhale ma deep eutectic solvents achilengedwe (NADES). Amagawidwabe ngati DES, koma amapangidwa ndi zinthu zachilengedwe ndi mchere, kuphatikizapo potassium chloride (KCl), calcium chloride (CaCl2), Epsom salts (MgSO4.7H2O), ndi ena. Kuphatikizana kosiyanasiyana kwa DES ndi NADES kumatsegula mwayi waukulu wofufuzira m'derali ndipo akuyembekezeka kupeza ntchito m'magawo osiyanasiyana. Ofufuza angapo apanga bwino kuphatikiza kwatsopano kwa DES komwe kwakhala kogwira ntchito m'magawo osiyanasiyana. Mwachitsanzo, Naser et al. 2013 adapanga DES yochokera ku potassium carbonate ndipo adaphunzira za mphamvu zake za thermophysical, zomwe pambuyo pake zidapeza ntchito m'magawo oletsa hydrate, zowonjezera pakubowola madzi, delignification, ndi nanofibrillation. 23 Jordy Kim ndi anzake adapanga ma NADES okhala ndi ascorbic acid ndipo adawunika momwe amagwiritsira ntchito ma antioxidant m'njira zosiyanasiyana. 24 Christer ndi anzake adapanga ma NADES okhala ndi citric acid ndipo adapeza kuthekera kwake ngati chowonjezera cha zinthu za collagen. 25 Liu Yi ndi anzake adafotokoza mwachidule momwe ma NADES amagwiritsidwira ntchito ngati chotsitsa ndi chromatography mu ndemanga yonse, pomwe Misan ndi anzake adakambirana za momwe ma NADES amagwiritsidwira ntchito bwino m'gawo la zakudya zaulimi. Ndikofunikira kuti ofufuza zamadzimadzi obowola ayambe kuyang'ana momwe ma NADES amagwirira ntchito. Mu 2023, Rasul ndi anzake adagwiritsa ntchito mitundu yosiyanasiyana ya zosungunulira zachilengedwe zochokera ku ascorbic acid26, calcium chloride27, potassium chloride28 ndi Epsom salt29 ndipo adapeza kuletsa kwa shale ndikubwezeretsa shale. Kafukufukuyu ndi umodzi mwa maphunziro oyamba kuyambitsa NADES (makamaka citric acid ndi glycerol-based formula) ngati choletsa shale choteteza chilengedwe komanso chogwira ntchito bwino m'madzi obowola pogwiritsa ntchito madzi, chomwe chili ndi kukhazikika kwabwino kwa chilengedwe, kuthekera koletsa shale komanso magwiridwe antchito abwino amadzimadzi poyerekeza ndi zoletsa zachikhalidwe monga KCl, zakumwa za ionic zochokera ku imidazolyl ndi DES zachikhalidwe.
Kafukufukuyu adzaphatikizapo kukonzekera mkati mwa nyumba kwa NADES yochokera ku citric acid (CA) kutsatiridwa ndi kufotokozera mwatsatanetsatane za physicochemical ndi kugwiritsidwa ntchito kwake ngati chowonjezera cha madzi obowola kuti aone momwe madzi obowola alili komanso momwe amalepheretsa kutupa. Mu kafukufukuyu, CA idzagwira ntchito ngati cholandirira hydrogen bond pomwe glycerol (Gly) idzagwira ntchito ngati chopereka hydrogen bond chosankhidwa kutengera njira zowunikira za MH za mapangidwe/kusankha kwa NADES mu maphunziro oletsa kutupa kwa shale30. Miyeso ya Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) ndi zeta potential (ZP) idzafotokoza momwe NADES imagwirira ntchito ndi dongo komanso njira yomwe imayambitsa kuletsa kutupa kwa dongo. Kuphatikiza apo, kafukufukuyu adzayerekeza madzi obowola ochokera ku CA NADES ndi DES32 kutengera 1-ethyl-3-methylimidazolium chloride [EMIM]Cl7,12,14,17,31, KCl ndi choline chloride:urea (1:2) kuti afufuze momwe amagwirira ntchito poletsa kutupa kwa shale ndikuwongolera magwiridwe antchito a madzi obowola.
Citric acid (monohydrate), glycerol (99 USP), ndi urea zinagulidwa ku EvaChem, Kuala Lumpur, Malaysia. Choline chloride (>98%), [EMIM]Cl 98%, ndi potassium chloride zinagulidwa ku Sigma Aldrich, Malaysia. Kapangidwe ka mankhwala a mankhwala onse akuwonetsedwa pa Chithunzi 1. Chithunzi chobiriwira chikuyerekeza mankhwala akuluakulu omwe agwiritsidwa ntchito mu kafukufukuyu: imidazolyl ionic liquid, choline chloride (DES), citric acid, glycerol, potassium chloride, ndi NADES (citric acid ndi glycerol). Gome lothandiza zachilengedwe la mankhwala omwe agwiritsidwa ntchito mu kafukufukuyu laperekedwa mu Gome 1. Mu tebuloli, mankhwala aliwonse amayesedwa kutengera poizoni, kuwonongeka kwa zinthu, mtengo, ndi kukhazikika kwa chilengedwe.
Kapangidwe ka mankhwala a zinthu zomwe zagwiritsidwa ntchito mu kafukufukuyu: (a) citric acid, (b) [EMIM]Cl, (c) choline chloride, ndi (d) glycerol.
Opereka ma hydrogen bond (HBD) ndi olandira ma hydrogen bond (HBA) omwe akufuna kupanga ma CA (natural deep eutectic solvent) ochokera ku ma NADES adasankhidwa mosamala malinga ndi njira zosankhidwa za MH 30, zomwe cholinga chake ndi kupanga ma NADES ngati zoletsa za shale. Malinga ndi muyezo uwu, zigawo zomwe zili ndi opereka ma hydrogen bond ambiri komanso olandira komanso magulu ogwira ntchito polar amaonedwa kuti ndi oyenera kupanga ma NADES.
Kuphatikiza apo, madzi a ionic [EMIM]Cl ndi choline chloride:urea deep eutectic solvent (DES) adasankhidwa kuti ayerekezedwe mu kafukufukuyu chifukwa amagwiritsidwa ntchito kwambiri ngati zowonjezera zamadzimadzi obowola33,34,35,36. Kuphatikiza apo, potaziyamu chloride (KCl) idayerekezeredwa chifukwa ndi choletsa chofala.
Citric acid ndi glycerol zinasakanizidwa m'magawo osiyanasiyana a molar kuti zipeze zosakaniza za eutectic. Kuyang'ana kowoneka bwino kunawonetsa kuti chosakaniza cha eutectic chinali madzi ofanana, owonekera bwino opanda turbidity, zomwe zikusonyeza kuti hydrogen bond donor (HBD) ndi hydrogen bond acceptor (HBA) zinasakanizidwa bwino mu eutectic composition iyi. Kuyesa koyambirira kunachitika kuti awone momwe kutentha kumayenderana ndi kachitidwe kosakanikirana kwa HBD ndi HBA. Malinga ndi mabuku omwe alipo, kuchuluka kwa zosakaniza za eutectic kunayesedwa pa kutentha katatu kopitilira 50 °C, 70 °C ndi 100 °C, zomwe zikusonyeza kuti kutentha kwa eutectic nthawi zambiri kumakhala pakati pa 50–80 °C. Mettler digital balance idagwiritsidwa ntchito poyeza molondola zigawo za HBD ndi HBA, ndipo mbale yotentha ya Thermo Fisher idagwiritsidwa ntchito kutenthetsa ndikusakaniza HBD ndi HBA pa 100 rpm pansi pa mikhalidwe yolamulidwa.
Kapangidwe ka thermophysical ka thermophysical solvent yathu yopangidwa ndi deep eutectic solvent (DES), kuphatikizapo kuchulukana, kupsinjika kwa pamwamba, refractive index, ndi kukhuthala, zinayesedwa molondola pa kutentha kuyambira 289.15 mpaka 333.15 K. Tiyenera kudziwa kuti kutentha kumeneku kunasankhidwa makamaka chifukwa cha zofooka za zida zomwe zilipo. Kusanthula kwathunthu kunaphatikizapo kuphunzira mozama za kapangidwe ka thermophysical ka NADES, kuwulula momwe amagwirira ntchito pa kutentha kosiyanasiyana. Kuyang'ana kwambiri kutentha kumeneku kumapereka chidziwitso cha kapangidwe ka NADES komwe ndikofunikira kwambiri pa ntchito zingapo.
Kuthamanga kwa pamwamba pa NADES komwe kwakonzedwa kunayesedwa kuyambira 289.15 mpaka 333.15 K pogwiritsa ntchito choyezera kuthamanga kwa interfacial (IFT700). Madontho a NADES amapangidwa m'chipinda chodzaza ndi madzi ambiri pogwiritsa ntchito singano ya capillary pansi pa kutentha ndi kupanikizika kwina. Makina amakono ojambulira zithunzi amayambitsa magawo oyenera a geometric kuti awerenge kuthamanga kwa interfacial pogwiritsa ntchito Laplace equation.
Chida choyezera kutentha cha ATAGO chinagwiritsidwa ntchito kudziwa kuchuluka kwa kuwala kwa ma NADES omwe angokonzedwa kumene pa kutentha kwa 289.15 mpaka 333.15 K. Chidachi chimagwiritsa ntchito gawo la kutentha kuti liwongolere kutentha kuti liyerekeze kuchuluka kwa kuwala kowala, kuchotsa kufunikira kwa madzi osambira otentha nthawi zonse. Pamwamba pa prism ya refractometer payenera kutsukidwa ndipo yankho la chitsanzo liyenera kugawidwa mofanana pamwamba pake. Linganizani ndi yankho lodziwika bwino, kenako werengani kuchuluka kwa kuwala kuchokera pazenera.
Kukhuthala kwa ma NADES omwe adakonzedwa kale kunayesedwa pa kutentha kwa 289.15 mpaka 333.15 K pogwiritsa ntchito Brookfield rotational viscometer (mtundu wa cryogenic) pa liwiro la 30 rpm ndi kukula kwa spindle ya 6. Viscometer imayesa kukhuthala mwa kudziwa mphamvu yomwe imafunika kuti spindle izungulire pa liwiro losasintha mu chitsanzo chamadzimadzi. Chitsanzocho chikayikidwa pazenera pansi pa spindle ndikumangiriridwa, viscometer imawonetsa kukhuthala mu centipoise (cP), kupereka chidziwitso chofunikira pa momwe madziwo alili.
Chida choyezera kuchuluka kwa madzi chonyamulika (DMA 35 Basic) chinagwiritsidwa ntchito kudziwa kuchuluka kwa madzi osungunuka achilengedwe (NDEES) omwe angokonzedwa kumene pa kutentha kwa 289.15–333.15 K. Popeza chipangizochi chilibe chotenthetsera chomangidwa mkati, chiyenera kutenthedwa kutentha komwe kwatchulidwa (± 2 °C) musanagwiritse ntchito NADES density meter. Kokani osachepera 2 ml ya chitsanzo kudzera mu chubu, ndipo kuchuluka kwake kudzawonetsedwa nthawi yomweyo pazenera. Ndikofunikira kudziwa kuti chifukwa cha kusowa kwa chotenthetsera chomangidwa mkati, zotsatira za muyeso zimakhala ndi cholakwika cha ± 2 °C.
Kuti tiyese pH ya NADES yokonzedwa kumene pa kutentha kwa 289.15–333.15 K, tinagwiritsa ntchito Kenis benchtop pH meter. Popeza palibe chipangizo chotenthetsera chomwe chili mkati, NADES poyamba idatenthedwa kufika kutentha komwe mukufuna (±2 °C) pogwiritsa ntchito hotplate kenako nkuyesedwa mwachindunji ndi pH meter. Imani mokwanira pH meter probe mu NADES ndikulemba mtengo womaliza pambuyo poti kuwerengako kwakhazikika.
Kusanthula kwa Thermogravimetric (TGA) kunagwiritsidwa ntchito poyesa kukhazikika kwa kutentha kwa zinthu zachilengedwe zozama za eutectic solvents (NADES). Zitsanzo zinasanthulidwa panthawi yotenthetsera. Pogwiritsa ntchito kulinganiza bwino kwambiri komanso kuyang'anira mosamala njira yotenthetsera, chithunzi cha kutayika kwa unyinji poyerekeza ndi kutentha chinapangidwa. NADES inatenthedwa kuyambira 0 mpaka 500 °C pa liwiro la 1 °C pamphindi.
Kuti ayambe ntchitoyi, chitsanzo cha NADES chiyenera kusakanikirana bwino, kusinthidwa kukhala homogeneous, ndikuchotsa chinyezi pamwamba. Chitsanzo chokonzedwacho chimayikidwa mu TGA cuvette, yomwe nthawi zambiri imapangidwa ndi zinthu zopanda mphamvu monga aluminiyamu. Kuti zitsimikizire zotsatira zolondola, zida za TGA zimayesedwa pogwiritsa ntchito zipangizo zofotokozera, nthawi zambiri miyezo ya kulemera. Akayesedwa, kuyesa kwa TGA kumayamba ndipo chitsanzocho chimatenthedwa mwanjira yowongoleredwa, nthawi zambiri pamlingo wokhazikika. Kuyang'anira kosalekeza ubale pakati pa kulemera kwa chitsanzo ndi kutentha ndi gawo lofunika kwambiri la kuyesaku. Zida za TGA zimasonkhanitsa deta pa kutentha, kulemera, ndi zina monga kuyenda kwa mpweya kapena kutentha kwa chitsanzo. Kuyesa kwa TGA kukatha, deta yosonkhanitsidwayo imasanthulidwa kuti idziwe kusintha kwa kulemera kwa chitsanzo ngati ntchito ya kutentha. Chidziwitsochi ndi chofunikira pozindikira mitundu ya kutentha yogwirizana ndi kusintha kwa thupi ndi mankhwala mu chitsanzo, kuphatikizapo njira monga kusungunuka, kusungunuka, kusungunuka, kapena kuwonongeka.
Madzi obowola pogwiritsa ntchito madzi adapangidwa mosamala motsatira muyezo wa API 13B-1, ndipo kapangidwe kake kalembedwa mu Table 2 kuti kagwiritsidwe ntchito. Citric acid ndi glycerol (99 USP) zidagulidwa ku Sigma Aldrich, Malaysia kuti akonze solvent yachilengedwe ya deep eutectic (NADES). Kuphatikiza apo, potassium chloride (KCl) yoletsa shale inhibitor (KCl) idagulidwanso ku Sigma Aldrich, Malaysia. 1-ethyl, 3-methylimidazolium chloride ([EMIM]Cl) yokhala ndi chiyero choposa 98% idasankhidwa chifukwa cha zotsatira zake zazikulu pakukweza rheology ya madzi obowola ndi kuletsa shale, zomwe zidatsimikiziridwa m'maphunziro am'mbuyomu. KCl ndi ([EMIM]Cl) zonse zidzagwiritsidwa ntchito poyesa kufananiza kuti aone momwe NADES imagwirira ntchito poletsa shale.
Ofufuza ambiri amakonda kugwiritsa ntchito ma bentonite flakes kuti aphunzire kutupa kwa shale chifukwa bentonite ili ndi gulu lomwelo la "montmorillonite" lomwe limayambitsa kutupa kwa shale. Kupeza zitsanzo zenizeni za shale core n'kovuta chifukwa njira yopangira shale imasokoneza shale, zomwe zimapangitsa kuti zitsanzo zomwe sizili za shale kwathunthu koma nthawi zambiri zimakhala ndi chisakanizo cha miyala yamchenga ndi miyala yamwala. Kuphatikiza apo, zitsanzo za shale nthawi zambiri zimakhalabe ndi magulu a montmorillonite omwe amayambitsa kutupa kwa shale ndipo chifukwa chake sizoyenera kuyesa zoletsa kutupa.
Mu kafukufukuyu, tinagwiritsa ntchito tinthu ta bentonite tomwe tinapangidwanso tokhala ndi mainchesi pafupifupi 2.54. Tinthu ta granule tinapangidwa pokanikiza magalamu 11.5 a sodium bentonite powder mu hydraulic press pa 1600 psi. Kukhuthala kwa tinthu ta granule kunayesedwa molondola tisanayikidwe mu linear dilatometer (LD). Kenako tinthu ta granule tinaviikidwa mu zitsanzo zamadzimadzi obowola, kuphatikizapo zitsanzo za maziko ndi zitsanzo zomwe zinabayidwa ndi zoletsa zomwe zimagwiritsidwa ntchito kupewa kutupa kwa shale. Kusintha kwa makulidwe a tinthu ta granule kunayang'aniridwa mosamala pogwiritsa ntchito LD, ndipo miyeso inalembedwa pamasekondi 60 kwa maola 24.
Kufalikira kwa X-ray kunasonyeza kuti kapangidwe ka bentonite, makamaka gawo lake la 47% la montmorillonite, ndi chinthu chofunikira kwambiri pakumvetsetsa mawonekedwe ake a geology. Pakati pa zigawo za montmorillonite za bentonite, montmorillonite ndiye gawo lalikulu, lomwe limawerengera 88.6% ya zigawo zonse. Pakadali pano, quartz imakhala ndi 29%, illite ndi 7%, ndi carbonate ndi 9%. Gawo laling'ono (pafupifupi 3.2%) ndi chisakanizo cha illite ndi montmorillonite. Kuphatikiza apo, lili ndi zinthu zochepa monga Fe2O3 (4.7%), siliva aluminosilicate (1.2%), muscovite (4%), ndi phosphate (2.3%). Kuphatikiza apo, pali Na2O yaying'ono (1.83%) ndi iron silicate (2.17%), zomwe zimapangitsa kuti zikhale zotheka kuyamikira mokwanira zinthu zomwe zili mu bentonite ndi kuchuluka kwake.
Gawo lophunzirirali lathunthu limafotokoza za momwe zinthu zilili komanso momwe zinthu zilili m'madzimadzi obowola zomwe zakonzedwa pogwiritsa ntchito natural deep eutectic solvent (NADES) ndipo zimagwiritsidwa ntchito ngati chowonjezera cha madzi obowola pamlingo wosiyanasiyana (1%, 3% ndi 5%). Kenako zitsanzo za NADES slurry zinayerekezeredwa ndikusanthulidwa ndi zitsanzo za slurry zomwe zili ndi potassium chloride (KCl), CC:urea DES (choline chloride deep eutectic solvent:urea) ndi ionic liquids. Mu kafukufukuyu, pali zinthu zingapo zofunika zomwe zafotokozedwa kuphatikizapo ma viscosity readings omwe adapezeka pogwiritsa ntchito FANN viscometer asanayambe komanso atakumana ndi ukalamba pa 100°C ndi 150°C. Miyeso idatengedwa pa liwiro losiyanasiyana lozungulira (3 rpm, 6 rpm, 300 rpm ndi 600 rpm) zomwe zimathandiza kusanthula kwathunthu momwe madzi obowola amagwirira ntchito. Deta yomwe yapezedwa ingagwiritsidwe ntchito kudziwa zinthu zofunika monga yield point (YP) ndi plastic viscosity (PV), zomwe zimapereka chidziwitso cha momwe madzi amagwirira ntchito pansi pa mikhalidwe yosiyanasiyana. Mayeso osefera kutentha kwambiri (HPHT) pa 400 psi ndi 150°C (kutentha kwanthawi zonse m'zitsime zotentha kwambiri) amatsimikiza momwe zosefera zimagwirira ntchito (kukhuthala kwa keke ndi kuchuluka kwa zosefera).
Gawoli likugwiritsa ntchito zida zamakono, Grace HPHT Linear Dilatometer (M4600), kuti liwunikire bwino momwe madzi athu obowolera madzi amagwirira ntchito pobowola zinthu amagwirira ntchito. LSM ndi makina apamwamba kwambiri okhala ndi zigawo ziwiri: plate compactor ndi linear dilatometer (chitsanzo: M4600). Ma Bentonite plates adakonzedwa kuti awunikidwe pogwiritsa ntchito Grace Core/Plate Compactor. Kenako LSM imapereka deta yofulumira yotupa pa ma plates awa, zomwe zimathandiza kuwunika kwathunthu momwe shale imagwirira ntchito pobowola zinthu. Mayeso okulitsa shale adachitika pansi pa nyengo yozungulira, mwachitsanzo, 25°C ndi 1 psia.
Kuyesa kukhazikika kwa shale kumaphatikizapo mayeso ofunikira omwe nthawi zambiri amatchedwa mayeso obwezeretsa shale, mayeso olowetsa shale kapena mayeso ogawa shale. Kuti ayambe kuwunikaku, zidutswa za shale zimalekanitsidwa pa sikirini ya #6 BSS kenako zimayikidwa pa sikirini ya #10. Kenako zidutswazo zimaperekedwa ku thanki yosungiramo zinthu komwe zimasakanizidwa ndi madzi oyambira ndi matope obowola okhala ndi NADES (Natural Deep Eutectic Solvent). Gawo lotsatira ndikuyika chisakanizocho mu uvuni kuti chizitenthe kwambiri, kuonetsetsa kuti zidutswazo ndi matope zasakanikirana bwino. Pambuyo pa maola 16, zidutswazo zimachotsedwa pakhungu polola shale kuti ivunde, zomwe zimapangitsa kuti kulemera kwa zidutswazo kuchepe. Kuyesa kobwezeretsa shale kunachitika pambuyo poti zidutswa za shale zasungidwa mu matope obowola pa 150°C ndi 1000 psi. inchi mkati mwa maola 24.
Kuti tiyese kubweza matope a shale, tinawasefa kudzera mu sikirini yabwino (maukonde 40), kenako tinawatsuka bwino ndi madzi, kenako tinawaumitsa mu uvuni. Njira yolimbikirayi imatithandiza kuyerekeza matope omwe abwezedwa poyerekeza ndi kulemera koyambirira, potsiriza kuwerengera kuchuluka kwa matope a shale omwe abwezedwa bwino. Magwero a zitsanzo za shale akuchokera ku Niah District, Miri District, Sarawak, Malaysia. Asanayesedwe kufalikira ndi kubweza, zitsanzo za shale zinayesedwa bwino ndi X-ray diffraction (XRD) kuti zitsimikizire kapangidwe kake ka dongo ndikutsimikizira kuti ndizoyenera kuyezedwa. Kapangidwe ka mchere wa dongo mu chitsanzocho ndi motere: illite 18%, kaolinite 31%, chlorite 22%, vermiculite 10%, ndi mica 19%.
Kuthamanga kwa pamwamba ndi chinthu chofunikira kwambiri chomwe chimayang'anira kulowa kwa madzi m'maselo a shale micropores kudzera mu capillary action, zomwe zidzaphunziridwa mwatsatanetsatane m'gawo lino. Pepalali likufotokoza za udindo wa kuthamanga kwa pamwamba pa chinthu chogwirizana cha madzi obowola, kuwonetsa kufunika kwake pa njira yobowola, makamaka kuletsa kwa shale. Tinagwiritsa ntchito interfacial tensiometer (IFT700) kuti tiyese molondola kuthamanga kwa pamwamba pa zitsanzo za madzi obowola, ndikuwulula mbali yofunika kwambiri ya khalidwe la madzi pokhudzana ndi kuletsa kwa shale.
Gawoli likukambirana mwatsatanetsatane za mtunda wa d-layer, womwe ndi mtunda wa pakati pa zigawo za aluminosilicate ndi gawo limodzi la aluminosilicate mu dongo. Kusanthulaku kunakhudza zitsanzo za matope onyowa okhala ndi 1%, 3% ndi 5% CA NADES, komanso 3% KCl, 3% [EMIM]Cl ndi 3% CC:urea based DES poyerekeza. Diffractometer ya X-ray yapamwamba kwambiri (D2 Phaser) yomwe imagwira ntchito pa 40 mA ndi 45 kV yokhala ndi radiation ya Cu-Kα (λ = 1.54059 Å) idagwira ntchito yofunika kwambiri polemba ma X-ray diffraction peaks a zitsanzo za Na-Bt zonyowa komanso zouma. Kugwiritsa ntchito Bragg equation kumathandiza kudziwa molondola mtunda wa d-layer, motero kumapereka chidziwitso chofunikira pa khalidwe la dongo.
Gawoli likugwiritsa ntchito chida chapamwamba cha Malvern Zetasizer Nano ZSP kuti chiyese molondola zeta potential. Kuwunikaku kunapereka chidziwitso chofunikira pa makhalidwe a mphamvu ya zitsanzo za matope osungunuka okhala ndi 1%, 3%, ndi 5% CA NADES, komanso 3% KCl, 3% [EMIM]Cl, ndi 3% CC:urea-based DES kuti tiwunikenso mofanana. Zotsatirazi zimathandiza kuti timvetse bwino kukhazikika kwa mankhwala a colloidal ndi momwe amagwirira ntchito m'madzimadzi.
Zitsanzo za dongo zinafufuzidwa asanayambe kukhudzidwa ndi chilengedwe chachilengedwe cha deep eutectic solvent (NADES) komanso atangokumana ndi zinthu zachilengedwe zakuya (NADES) pogwiritsa ntchito makina oyezera magetsi otchedwa Zeiss Supra 55 VP field emission scanning electron microscope (FESEM) omwe ali ndi mphamvu yogawa mphamvu (EDX). Kuzindikira kwa zithunzi kunali 500 nm ndipo mphamvu ya kuwala kwa electron inali 30 kV ndi 50 kV. FESEM imapereka chithunzithunzi chapamwamba cha mawonekedwe a pamwamba ndi kapangidwe ka zitsanzo za dongo. Cholinga cha kafukufukuyu chinali kupeza chidziwitso chokhudza momwe NADES imakhudzira zitsanzo za dongo poyerekezera zithunzi zomwe zapezeka asanayambe kukhudzidwa ndi zinthu zina.
Mu kafukufukuyu, ukadaulo wa field emission scanning electron microscopy (FESEM) unagwiritsidwa ntchito pofufuza momwe NADES imakhudzira zitsanzo za dongo pamlingo wa microscopic. Cholinga cha kafukufukuyu ndikufotokozera momwe NADES ingagwiritsire ntchito komanso momwe imakhudzira mawonekedwe a dongo komanso kukula kwa tinthu tating'onoting'ono, zomwe zipereka chidziwitso chofunikira pa kafukufukuyu.
Mu kafukufukuyu, mipiringidzo yolakwika idagwiritsidwa ntchito pofotokoza mwachiwonekere kusiyana ndi kusatsimikizika kwa cholakwika chapakati pa peresenti (AMPE) m'mikhalidwe yoyesera. M'malo mojambula mipiringidzo ya AMPE (popeza kujambula mipiringidzo ya AMPE kumatha kubisa zomwe zikuchitika ndikukokomeza kusiyana pang'ono), timawerengera mipiringidzo yolakwika pogwiritsa ntchito lamulo la 5%. Njirayi ikutsimikizira kuti mipiringidzo iliyonse yolakwika ikuyimira nthawi yomwe nthawi yodalirika ya 95% ndi 100% ya mipiringidzo ya AMPE ikuyembekezeka kutsika, motero kupereka chidule chomveka bwino komanso chofupikitsa cha kugawa deta pa vuto lililonse loyesera. Kugwiritsa ntchito mipiringidzo yolakwika kutengera lamulo la 5% motero kumawongolera kutanthauzira ndi kudalirika kwa zithunzi zowonetsera ndipo kumathandiza kupereka kumvetsetsa kwatsatanetsatane kwa zotsatira ndi zotsatira zake.
Pakupanga zinthu zachilengedwe zozama za eutectic solvents (NADES), magawo angapo ofunikira adaphunziridwa mosamala panthawi yokonzekera mkati. Zinthu zofunika izi zikuphatikizapo kutentha, chiŵerengero cha molar, ndi liwiro losakaniza. Kuyesa kwathu kukuwonetsa kuti HBA (citric acid) ndi HBD (glycerol) zikasakanizidwa pa chiŵerengero cha molar cha 1:4 pa 50°C, chisakanizo cha eutectic chimapangidwa. Chinthu chodziwika bwino cha chisakanizo cha eutectic ndi mawonekedwe ake owonekera, ofanana, komanso kusowa kwa sediment. Chifukwa chake, gawo lofunikali likuwonetsa kufunika kwa chiŵerengero cha molar, kutentha, ndi liwiro losakaniza, pakati pawo chiŵerengero cha molar chinali chinthu chofunikira kwambiri pakukonzekera DES ndi NADES, monga momwe zasonyezedwera pa Chithunzi 2.
Chizindikiro cha refractive index (n) chimasonyeza chiŵerengero cha liwiro la kuwala mu vacuum ndi liwiro la kuwala mu gawo lachiwiri, lolemera kwambiri. Chizindikiro cha refractive index ndi chofunikira kwambiri pa zosungunulira zachilengedwe zakuya za eutectic (NADES) poganizira ntchito zowunikira monga biosensors. Chizindikiro cha refractive index cha NADES chomwe chinaphunziridwa pa 25 °C chinali 1.452, chomwe ndi chotsika kwambiri kuposa cha glycerol.
Ndikofunikira kudziwa kuti refractive index ya NADES imachepa ndi kutentha, ndipo izi zitha kufotokozedwa molondola ndi fomula (1) ndi Chithunzi 3, pomwe absolute mean percentage error (AMPE) ikufika 0%. Khalidwe lodalira kutenthali limafotokozedwa ndi kuchepa kwa viscosity ndi density pa kutentha kwakukulu, zomwe zimapangitsa kuti kuwala kuyende pakati pa sing'anga pa liwiro lalikulu, zomwe zimapangitsa kuti refractive index (n) ikhale yochepa. Zotsatirazi zimapereka chidziwitso chofunikira pakugwiritsa ntchito bwino kwa NADES mu optical sensing, kuwonetsa kuthekera kwawo pakugwiritsa ntchito biosensor.
Kukanika kwa pamwamba, komwe kumasonyeza chizolowezi cha pamwamba pa madzi kuchepetsa malo ake, ndikofunikira kwambiri poyesa kuyenerera kwa zosungunulira zachilengedwe zakuya za eutectic (NADES) kuti zigwiritsidwe ntchito pogwiritsa ntchito kupanikizika kwa capillary. Kafukufuku wa kukanika kwa pamwamba pa kutentha kwa 25–60 °C amapereka chidziwitso chofunikira. Pa 25 °C, kukanika kwa pamwamba kwa NADES yokhala ndi citric acid kunali 55.42 mN/m, komwe kuli kotsika kwambiri kuposa kwa madzi ndi glycerol. Chithunzi 4 chikuwonetsa kuti kukanika kwa pamwamba kumachepa kwambiri kutentha kukakwera. Chochitikachi chikhoza kufotokozedwa ndi kuwonjezeka kwa mphamvu ya kinetic ya molekyulu ndi kuchepa kwa mphamvu zokopa pakati pa mamolekyulu.
Kutsika kwa mphamvu ya pamwamba pa nthaka komwe kwawonedwa mu NADES yophunziridwa kungafotokozedwe bwino ndi equation (2), yomwe ikuwonetsa ubale woyambira wamasamu pa kutentha kwa 25–60 °C. Chithunzi chomwe chili pa Chithunzi 4 chikuwonetsa bwino momwe mphamvu ya pamwamba pa nthaka imayendera ndi kutentha komwe kuli ndi cholakwika chapakati chapakati (AMPE) cha 1.4%, chomwe chimawerengera kulondola kwa mphamvu ya pamwamba yomwe yanenedwa. Zotsatirazi zili ndi tanthauzo lofunikira pakumvetsetsa machitidwe a NADES ndi momwe angagwiritsire ntchito.
Kumvetsetsa mphamvu ya kuchuluka kwa zinthu zosungunulira zamadzimadzi zakuya (NADES) n'kofunika kwambiri kuti zigwiritsidwe ntchito mosavuta m'maphunziro ambiri asayansi. Kuchuluka kwa NADES komwe kumachokera ku citric acid pa 25°C ndi 1.361 g/cm3, komwe ndi kwakukulu kuposa kuchuluka kwa glycerol yoyambirira. Kusiyana kumeneku kungafotokozedwe powonjezera cholandirira cha hydrogen bond (citric acid) ku glycerol.
Potengera chitsanzo cha NADES yokhala ndi citrate, kuchuluka kwake kumatsika kufika pa 1.19 g/cm3 pa 60°C. Kuwonjezeka kwa mphamvu ya kinetic pakatenthedwa kumapangitsa mamolekyu a NADES kufalikira, zomwe zimapangitsa kuti azikhala ndi voliyumu yayikulu, zomwe zimapangitsa kuti kuchulukana kuchepe. Kuchepa kwa kuchuluka komwe kwawonedwa kukuwonetsa kulumikizana kwina ndi kuwonjezeka kwa kutentha, komwe kungafotokozedwe bwino ndi fomula (3). Chithunzi 5 chikuwonetsa bwino mawonekedwe awa a kusintha kwa kuchuluka kwa NADES ndi cholakwika chapakati chapakati (AMPE) cha 1.12%, chomwe chimapereka muyeso wochuluka wa kulondola kwa kuchuluka kwa kuchuluka komwe kwanenedwa.
Kukhuthala ndi mphamvu yokoka pakati pa zigawo zosiyanasiyana za madzi omwe akuyenda ndipo imagwira ntchito yofunika kwambiri pomvetsetsa kugwiritsidwa ntchito kwa zosungunulira zachilengedwe zakuya (NADES) m'njira zosiyanasiyana. Pa 25 °C, kukhuthala kwa NADES kunali 951 cP, komwe ndi kokwera kuposa kwa glycerol.
Kuchepa kwa kukhuthala komwe kumawonedwa ndi kutentha kokwera kumachitika makamaka chifukwa cha kufooka kwa mphamvu zokopa zapakati pa mamolekyulu. Izi zimapangitsa kuti kukhuthala kwa madzi kuchepe, zomwe zawonetsedwa bwino mu Chithunzi 6 ndikuwerengedwa ndi Equation (4). Chodziwika bwino ndichakuti, pa 60°C, kukhuthala kumatsika kufika pa 898 cP ndi cholakwika chapakati pa peresenti (AMPE) cha 1.4%. Kumvetsetsa mwatsatanetsatane kudalira kwa kukhuthala ndi kutentha mu NADES ndikofunikira kwambiri pakugwiritsa ntchito kwake.
pH ya yankho, yomwe imatsimikiziridwa ndi logarithm yoyipa ya kuchuluka kwa ma ion a hydrogen, ndiyofunikira kwambiri, makamaka pakugwiritsa ntchito pH mosasamala monga kupanga DNA, kotero pH ya NADES iyenera kuphunziridwa mosamala musanagwiritse ntchito. Potengera NADES yokhala ndi citric acid mwachitsanzo, pH ya asidi ya 1.91 ikhoza kuwonedwa, yomwe ndi yosiyana kwambiri ndi pH ya glycerol yomwe ilibe mbali.
Chochititsa chidwi n'chakuti, pH ya natural citric acid dehydrogenase soluble solvent (NADES) inasonyeza kuchepa kosalekeza ndi kutentha kokwera. Izi zimachitika chifukwa cha kuchuluka kwa kugwedezeka kwa mamolekyu komwe kumasokoneza H+ balance mu yankho, zomwe zimapangitsa kuti pakhale ma [H]+ ion ndipo, motero, kusintha kwa pH. Ngakhale pH yachilengedwe ya citric acid imayambira pa 3 mpaka 5, kukhalapo kwa acidic hydrogen mu glycerol kumatsitsanso pH kufika pa 1.91.
Khalidwe la pH la ma NADES okhala ndi citrate pa kutentha kwa 25–60 °C likhoza kuyimiridwa moyenera ndi equation (5), yomwe imapereka chithunzi cha masamu cha momwe pH imaonekera. Chithunzi 7 chikuwonetsa bwino ubale wosangalatsawu, kuwonetsa momwe kutentha kumakhudzira pH ya ma NADES, yomwe ikunenedwa kuti ndi 1.4% ya AMPE.
Kusanthula kwa Thermogravimetric (TGA) kwa natural citric acid deep eutectic solvent (NADES) kunachitika mwadongosolo pa kutentha kuyambira kutentha kwa chipinda mpaka 500 °C. Monga momwe tikuonera pa Zithunzi 8a ndi b, kutayika koyamba kwa unyinji mpaka 100 °C makamaka chifukwa cha madzi omwe amalowa ndi madzi ogwirizana ndi citric acid ndi pure glycerol. Kusungidwa kwakukulu kwa unyinji pafupifupi 88% kunawonedwa mpaka 180 °C, komwe makamaka kunali chifukwa cha kuwonongeka kwa citric acid kukhala aconitic acid komanso kupangika kwa methylmaleic anhydride (III) pakutenthedwa kwina (Chithunzi 8 b). Pamwamba pa 180 °C, mawonekedwe omveka bwino a acrolein (acrylaldehyde) mu glycerol amathanso kuwonedwa, monga momwe zasonyezedwera pa Chithunzi 8b37.
Kusanthula kwa thermogravimetric (TGA) kwa glycerol kunavumbula njira yotaya kulemera kwa magawo awiri. Gawo loyamba (180 mpaka 220 °C) limaphatikizapo kupangidwa kwa acrolein, kutsatiridwa ndi kutayika kwakukulu kwa kulemera pa kutentha kwakukulu kuyambira 230 mpaka 300 °C (Chithunzi 8a). Pamene kutentha kukukwera, acetaldehyde, carbon dioxide, methane, ndi hydrogen zimapangidwa motsatizana. Chodziwika bwino, 28% yokha ya kulemerako idasungidwa pa 300 °C, zomwe zikusonyeza kuti katundu wa NADES 8(a)38,39 ukhoza kukhala wopanda pake.
Kuti apeze zambiri zokhudza kupangidwa kwa ma bond atsopano a mankhwala, ma suspensions atsopano a natural deep eutectic solvents (NADES) adawunikidwa ndi Fourier transform infrared spectroscopy (FTIR). Kusanthulaku kunachitika poyerekeza ma spectrum a NADES suspension ndi ma spectra a pure citric acid (CA) ndi glycerol (Gly). Ma CA spectrum adawonetsa ma peaks omveka bwino pa 1752 1/cm ndi 1673 1/cm, omwe akuyimira kugwedezeka kotambasuka kwa C=O bond ndipo ndi khalidwe la CA. Kuphatikiza apo, kusintha kwakukulu mu kugwedezeka kwa OH bending pa 1360 1/cm kudawonedwa m'dera la zala, monga momwe zasonyezedwera pa Chithunzi 9.
Mofananamo, pankhani ya glycerol, kusintha kwa kugwedezeka kwa OH ndi kugwedezeka kunapezeka pa mafunde a 3291 1/cm ndi 1414 1/cm, motsatana. Tsopano, pofufuza mtundu wa NADES wokonzedwa kale, kusintha kwakukulu kwa mtundu wa spectrum kunapezeka. Monga momwe zasonyezedwera pa Chithunzi 7, kugwedezeka kwa kugwedezeka kwa C=O bond kunasamuka kuchoka pa 1752 1/cm kufika pa 1720 1/cm ndipo kugwedezeka kwa -OH bond ya glycerol kunasamuka kuchoka pa 1414 1/cm kufika pa 1359 1/cm. Kusintha kumeneku kwa mafunde kumasonyeza kusintha kwa ma elekitironi, komwe kumasonyeza kupangidwa kwa ma bond atsopano a mankhwala mu kapangidwe ka NADES.