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Faɗaɗar shale a cikin ma'ajiyar clastic yana haifar da matsaloli masu yawa, wanda ke haifar da rashin kwanciyar hankali a cikin rijiyoyin ruwa. Saboda dalilai na muhalli, amfani da ruwan haƙa mai tushen ruwa tare da ƙarin masu hana shale an fi fifita shi akan ruwan haƙa mai tushen mai. Ruwan ionic (ILs) sun jawo hankali sosai a matsayin masu hana shale saboda halayensu masu iya canzawa da kuma ƙarfin halayen electrostatic. Duk da haka, ruwan ionic mai tushen imidazolyl (ILs), wanda aka fi amfani da shi sosai a cikin ruwan haƙa, ya tabbatar da cewa yana da guba, ba ya lalacewa kuma yana da tsada. Ana ɗaukar ruwan eutectic mai zurfi (DES) a matsayin madadin mafi araha kuma mara guba ga ruwan ionic, amma har yanzu ba su kai matsayin dorewar muhalli da ake buƙata ba. Ci gaban da aka samu kwanan nan a wannan fanni ya haifar da gabatar da ruwan eutectic mai zurfi na halitta (NADES), wanda aka san shi da kyawun muhalli. Wannan binciken ya binciki NADESs, waɗanda ke ɗauke da citric acid (a matsayin mai karɓar haɗin hydrogen) da glycerol (a matsayin mai ba da gudummawar haɗin hydrogen) a matsayin ƙarin ruwan haƙa. An ƙera ruwan haƙo mai tushen NADES daidai da API 13B-1 kuma an kwatanta aikinsu da ruwan haƙo mai tushen potassium chloride, ruwan ionic mai tushen imidazolium, da ruwan haƙo mai tushen choline chloride:urea-DES. An bayyana dalla-dalla game da halayen sinadaran NADES na mallakar NADES. An kimanta halayen rheological, asarar ruwa, da halayen hana shale na ruwan haƙowa a lokacin binciken, kuma an nuna cewa a cikin yawan NADESs 3%, an ƙara yawan damuwa/rabobin ɗanko na amfani (YP/PV), kauri na cake ɗin laka ya ragu da kashi 26%, kuma an rage girman tacewa da kashi 30.1%. Abin lura shi ne, NADES ya sami babban ƙimar hana faɗaɗawa na kashi 49.14% kuma ya ƙara yawan samar da shale da kashi 86.36%. Waɗannan sakamakon an danganta su da ikon NADES na canza ayyukan saman, ƙarfin zeta, da tazara tsakanin layukan yumbu, waɗanda aka tattauna a cikin wannan takarda don fahimtar hanyoyin da ke ƙasa. Ana sa ran wannan ruwa mai dorewa zai kawo sauyi a masana'antar haƙar ma'adinai ta hanyar samar da madadin da ba shi da guba, mai araha, kuma mai inganci sosai ga magungunan gargajiya na lalata shale, wanda hakan zai share fagen ayyukan haƙar ma'adinai masu kyau ga muhalli.
Dutse mai siffar shale dutse ne mai amfani wanda ke aiki a matsayin tushen hydrocarbons da kuma ma'ajiyar su, kuma tsarinsa mai ramuka1 yana ba da damar samarwa da adana waɗannan albarkatu masu mahimmanci. Duk da haka, shale yana da wadataccen ma'adanai na yumbu kamar montmorillonite, smectite, kaolinite da illite, wanda ke sa shi ya zama mai saurin kumburi lokacin da aka fallasa shi ga ruwa, wanda ke haifar da rashin kwanciyar hankali a cikin rijiyoyin ruwa yayin ayyukan haƙa rami2,3. Waɗannan matsalolin na iya haifar da lokacin da ba ya aiki (NPT) da kuma matsaloli da yawa na aiki ciki har da bututun da suka makale, asarar zagayawar laka, rugujewar rijiyoyin ruwa da gurɓataccen ƙasa, ƙara lokacin murmurewa da farashi. A al'ada, ruwan haƙa mai tushen mai (OBDF) shine zaɓin da aka fi so don samuwar shale saboda ikonsu na tsayayya da faɗaɗa shale4. Duk da haka, amfani da ruwan haƙa mai tushen mai yana haifar da tsada mai yawa da haɗarin muhalli. Ana ɗaukar ruwan haƙa mai tushen roba (SBDF) a matsayin madadin, amma dacewarsu a yanayin zafi mai yawa ba ta gamsarwa ba. Ruwan haƙa mai tushen ruwa (WBDF) mafita ce mai kyau domin suna da aminci, sun fi dacewa da muhalli, kuma sun fi OBDF5 inganci. An yi amfani da wasu magungunan shale don haɓaka ikon hana shale na WBDF, gami da magungunan hana ruwa na gargajiya kamar potassium chloride, lemun tsami, silicate, da polymer. Duk da haka, waɗannan magungunan hana ruwa suna da iyakoki dangane da inganci da tasirin muhalli, musamman saboda yawan sinadarin K+ a cikin magungunan hana ruwa na potassium chloride da kuma yanayin pH na silicates. 6 Masu bincike sun bincika yiwuwar amfani da ruwan ionic a matsayin ƙarin ruwan haƙa don inganta ilimin haƙa ruwa da hana kumburin shale da samuwar hydrate. Duk da haka, waɗannan ruwan ionic, musamman waɗanda ke ɗauke da cations na imidazolyl, gabaɗaya suna da guba, masu tsada, ba sa lalacewa, kuma suna buƙatar hanyoyin shiri masu rikitarwa. Don magance waɗannan matsalolin, mutane sun fara neman madadin da ya fi araha da aminci ga muhalli, wanda ya haifar da fitowar sinadaran eutectic mai zurfi (DES). DES cakuda ne na eutectic wanda mai ba da gudummawar hydrogen bond (HBD) da mai karɓar hydrogen bond (HBA) suka samar a wani takamaiman rabo da zafin jiki. Waɗannan gaurayawan eutectic suna da ƙananan wuraren narkewa fiye da abubuwan da ke cikinsu, galibi saboda raguwar caji da haɗin hydrogen ya haifar. Abubuwa da yawa, gami da kuzarin lattice, canjin entropy, da hulɗa tsakanin anions da HBD, suna taka muhimmiyar rawa wajen rage wurin narkewar DES.
A cikin binciken da aka yi a baya, an ƙara wasu ƙarin abubuwa daban-daban a cikin ruwan haƙa mai tushen ruwa don magance matsalar faɗaɗa shale. Misali, Ofei da abokan aikinsa sun ƙara 1-butyl-3-methylimidazolium chloride (BMIM-Cl), wanda ya rage kauri na laka (har zuwa 50%) kuma ya rage ƙimar YP/PV da 11 a yanayin zafi daban-daban. Huang da abokan aikinsa sun yi amfani da ruwa ionic (musamman, 1-hexyl-3-methylimidazolium bromide da 1,2-bis(3-hexylimidazol-1-yl)ethane bromide) a haɗe da ƙwayoyin Na-Bt kuma sun rage kumburin shale da 86.43% da 94.17%, bi da bi12. Bugu da ƙari, Yang da abokan aikinsa sun yi amfani da 1-vinyl-3-dodecylimidazolium bromide da 1-vinyl-3-tetradecylimidazolium bromide don rage kumburin shale da 16.91% da 5.81% bi da bi. 13 Yang da abokan aikinsa sun kuma yi amfani da 1-vinyl-3-ethylimidazolium bromide kuma sun rage faɗaɗa shale da kashi 31.62% yayin da suke ci gaba da murmurewa daga shale a kashi 40.60%. 14 Bugu da ƙari, Luo da abokan aikinsa sun yi amfani da 1-octyl-3-methylimidazolium tetrafluoroborate don rage kumburin shale da kashi 80%. 15, 16 Dai da abokan aikinsa sun yi amfani da ionic liquid copolymers don hana shale kuma sun sami ƙaruwa da kashi 18% a murmurewa daga layi idan aka kwatanta da amine inhibitors. 17
Ruwan ionic da kansu suna da wasu rashin amfani, wanda hakan ya sa masana kimiyya suka nemi madadin ruwan ionic masu kyau ga muhalli, don haka aka haifi DES. Hanjia ita ce ta farko da ta yi amfani da sinadarin eutectic mai zurfi (DES) wanda ya ƙunshi vinyl chloride propionic acid (1:1), vinyl chloride 3-phenylpropionic acid (1:2), da 3-mercaptopropionic acid + itaconic acid + vinyl chloride (1:1:2), wanda ya hana kumburin bentonite da kashi 68%, 58%, da 58%, bi da bi18. A cikin wani gwaji kyauta, MH Rasul ya yi amfani da rabon glycerol da potassium carbonate (DES) na kashi 2:1 kuma ya rage kumburin samfuran shale da kashi 87%19,20. Ma ya yi amfani da urea:vinyl chloride don rage faɗaɗa shale da kashi 67%.21 Rasul et al. An yi amfani da haɗin DES da polymer azaman mai hana shale mai aiki biyu, wanda ya sami kyakkyawan tasirin hana shale22.
Duk da cewa ana ɗaukar sinadarin eutectic mai zurfi (DES) a matsayin madadin ruwan ionic mai kore, suna kuma ɗauke da abubuwan da ke iya zama guba kamar gishirin ammonium, wanda hakan ke sa rashin lafiyarsu ta zama abin tambaya game da muhalli. Wannan matsalar ta haifar da haɓakar sinadaran eutectic mai zurfi na halitta (NADES). Har yanzu ana rarraba su a matsayin DES, amma sun ƙunshi abubuwa na halitta da gishiri, gami da potassium chloride (KCl), calcium chloride (CaCl2), Epsom gishirin (MgSO4.7H2O), da sauransu. Haɗuwar da ake da su da yawa na DES da NADES suna buɗe fa'ida mai faɗi don bincike a wannan yanki kuma ana sa ran za su sami aikace-aikace a fannoni daban-daban. Masu bincike da yawa sun sami nasarar ƙirƙirar sabbin haɗin DES waɗanda suka tabbatar da inganci a aikace-aikace iri-iri. Misali, Naser et al. 2013 sun haɗa DES na tushen potassium carbonate kuma sun yi nazarin halayen thermophysical, wanda daga baya ya sami aikace-aikace a fannoni na hana hydrate, ƙarin ruwa mai haƙa, cirewa, da nanofibrillation. 23 Jordy Kim da abokan aikinsa sun haɓaka NADES na tushen ascorbic acid kuma sun kimanta kaddarorin antioxidant a aikace-aikace daban-daban. 24 Christer da abokan aikinsa sun haɓaka NADES mai tushen citric acid kuma sun gano yuwuwar sa a matsayin mai taimakawa ga samfuran collagen. 25 Liu Yi da abokan aikinsa sun taƙaita amfani da NADES a matsayin kafofin watsa labarai na cirewa da chromatography a cikin cikakken bita, yayin da Misan da abokan aikinsa suka tattauna nasarar amfani da NADES a fannin abinci na noma. Yana da mahimmanci masu binciken ruwa na haƙa rami su fara mai da hankali kan ingancin NADES a aikace-aikacen su. kwanan nan. A cikin 2023, Rasul da abokan aikinsa sun yi amfani da haɗuwa daban-daban na abubuwan narkewar eutectic na halitta waɗanda suka dogara da ascorbic acid26, calcium chloride27, potassium chloride28 da Epsom salt29 kuma sun sami nasarar hana shale da murmurewa mai ban mamaki. Wannan binciken yana ɗaya daga cikin binciken farko da ya gabatar da NADES (musamman citric acid da glycerol-based formulation) a matsayin mai hana shale mai kyau ga muhalli kuma mai tasiri a cikin ruwan haƙa rami, wanda ke da kyakkyawan kwanciyar hankali na muhalli, ingantaccen ikon hana shale da ingantaccen aikin ruwa idan aka kwatanta da masu hana ruwa na gargajiya kamar KCl, ruwa ionic na tushen imidazolyl da DES na gargajiya.
Binciken zai ƙunshi shirya NADES na citric acid (CA) a cikin gida, sannan kuma cikakken bayanin yanayin sinadaran jiki da amfani da shi azaman ƙarin ruwa don haƙa don kimanta halayen ruwan haƙa da ikon hana kumburinsa. A cikin wannan binciken, CA za ta yi aiki a matsayin mai karɓar haɗin hydrogen yayin da glycerol (Gly) zai yi aiki a matsayin mai ba da gudummawar haɗin hydrogen da aka zaɓa bisa ga ka'idojin tantance MH don ƙirƙirar/zaɓin NADES a cikin nazarin hana shale30. Ma'aunin Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) da zeta potential (ZP) za su bayyana hulɗar NADES-clay da kuma hanyar da ke ƙarƙashin hana kumburin laka. Bugu da ƙari, wannan binciken zai kwatanta ruwan haƙa mai tushen CA NADES tare da DES32 bisa ga 1-ethyl-3-methylimidazolium chloride [EMIM]Cl7,12,14,17,31, KCl da choline chloride:urea (1:2) don bincika ingancinsu a hana shale da inganta aikin ruwan haƙa.
An sayi sinadarin citric acid (monohydrate), glycerol (99 USP), da urea daga EvaChem, Kuala Lumpur, Malaysia. An sayi sinadarin choline chloride (>98%), [EMIM]Cl 98%, da potassium chloride daga Sigma Aldrich, Malaysia. An nuna tsarin sinadarai na dukkan sinadarai a Hoto na 1. Zane-zanen kore yana kwatanta manyan sinadarai da aka yi amfani da su a wannan binciken: ruwa mai kama da imidazolyl ionic, choline chloride (DES), citric acid, glycerol, potassium chloride, da NADES (citric acid da glycerol). An gabatar da teburin sinadarai masu kyau ga muhalli na wannan binciken a cikin Tebur na 1. A cikin teburin, an kimanta kowane sinadarai bisa ga guba, lalacewar halittu, farashi, da dorewar muhalli.
Tsarin sinadarai na kayan da aka yi amfani da su a wannan binciken: (a) citric acid, (b) [EMIM]Cl, (c) choline chloride, da (d) glycerol.
An zaɓi masu ba da gudummawar haɗin hydrogen (HBD) da masu karɓar haɗin hydrogen (HBA) don haɓaka NADES mai tushen CA (natural deep eutectic solvent) bisa ga ka'idojin zaɓi na MH 30, waɗanda aka yi niyya don haɓaka NADES a matsayin masu hana shale masu tasiri. Dangane da wannan ƙa'idar, an ɗauki sassan da ke da adadi mai yawa na masu ba da gudummawar haɗin hydrogen da masu karɓa da kuma ƙungiyoyin aiki na polar da suka dace da haɓaka NADES.
Bugu da ƙari, an zaɓi ruwan ionic [EMIM]Cl da choline chloride:urea deep eutectic solvent (DES) don kwatantawa a cikin wannan binciken saboda ana amfani da su sosai azaman ƙarin ruwa mai haƙa 33,34,35,36. Bugu da ƙari, an kwatanta potassium chloride (KCl) saboda yana hana ci gaba.
An haɗa sinadarin citric acid da glycerol a cikin rabo daban-daban na molar don samun gaurayen eutectic. Dubawar gani ya nuna cewa gaurayen eutectic ruwa ne mai kama da juna, mai haske ba tare da turbidity ba, wanda ke nuna cewa an haɗa mai ba da gudummawar hydrogen bond (HBD) da mai karɓar hydrogen bond (HBA) cikin wannan haɗin eutectic. An gudanar da gwaje-gwaje na farko don lura da halayen tsarin haɗa HBD da HBA dangane da zafin jiki. Dangane da wallafe-wallafen da ake da su, an kimanta rabon gaurayen eutectic a takamaiman yanayin zafi guda uku sama da 50 °C, 70 °C da 100 °C, wanda ke nuna cewa zafin eutectic yawanci yana cikin kewayon 50-80 °C. An yi amfani da ma'aunin dijital na Mettler don auna abubuwan HBD da HBA daidai, kuma an yi amfani da farantin zafi na Thermo Fisher don dumama da motsa HBD da HBA a 100 rpm a ƙarƙashin yanayin da aka sarrafa.
An auna halayen thermophysical na sinadarin eutectic mai zurfi (DES), wanda ya haɗa da yawan abu, tashin hankali a saman, ma'aunin refractive, da kuma ɗanko, daidai a kan zafin jiki daga 289.15 zuwa 333.15 K. Ya kamata a lura cewa an zaɓi wannan kewayon zafin jiki ne musamman saboda iyakokin kayan aikin da ake da su. Cikakken binciken ya haɗa da bincike mai zurfi game da halaye daban-daban na thermophysical na wannan tsari na NADES, yana bayyana halayensu a kan yanayin zafi daban-daban. Mai da hankali kan wannan takamaiman kewayon zafin jiki yana ba da haske game da halayen NADES waɗanda ke da mahimmanci musamman ga aikace-aikace da yawa.
An auna matsin lamba na saman NADES da aka shirya a tsakanin 289.15 zuwa 333.15 K ta amfani da na'urar auna matsin lamba ta fuska (IFT700). Ana samar da digo-digo na NADES a cikin ɗaki cike da babban adadin ruwa ta amfani da allurar capillary a ƙarƙashin takamaiman yanayin zafi da matsin lamba. Tsarin hoto na zamani yana gabatar da sigogin lissafi masu dacewa don ƙididdige matsin lamba ta fuska ta amfani da lissafin Laplace.
An yi amfani da na'urar auna zafin jiki ta ATAGO don tantance ma'aunin zafin jiki na NADES da aka shirya a cikin zafin jiki na 289.15 zuwa 333.15 K. Kayan aikin yana amfani da na'urar auna zafin jiki don daidaita zafin jiki don kimanta matakin hasken, yana kawar da buƙatar wanka na ruwa mai yawan zafin jiki. Ya kamata a tsaftace saman prism na na'urar auna zafin jiki kuma samfurin maganin ya kamata a rarraba shi daidai gwargwado. A daidaita shi da wani bayani na yau da kullun da aka sani, sannan a karanta ma'aunin haske daga allon.
An auna danko na NADES da aka shirya a cikin zafin jiki daga 289.15 zuwa 333.15 K ta amfani da na'urar juyawa ta Brookfield (nau'in cryogenic) a saurin yankewa na 30 rpm da girman spindle na 6. Viscometer yana auna danko ta hanyar tantance karfin juyi da ake buƙata don juya spindle a cikin saurin da ba ya canzawa a cikin samfurin ruwa. Bayan an sanya samfurin a kan allo a ƙarƙashin spindle kuma an matse shi, viscometer yana nuna danko a cikin centipoise (cP), yana ba da bayanai masu mahimmanci game da halayen rheological na ruwan.
An yi amfani da na'urar auna yawan amfani da na'urar DMA 35 Basic don tantance yawan sinadarin eutectic mai narkewa (NDEES) da aka shirya a cikin zafin jiki na 289.15–333.15 K. Tunda na'urar ba ta da na'urar dumama ruwa a ciki, dole ne a sanyaya ta zuwa zafin da aka ƙayyade (± 2 °C) kafin amfani da na'urar auna yawan amfani da na'urar NADES. Zana aƙalla 2 ml na samfurin ta cikin bututun, kuma za a nuna yawan amfani nan take akan allon. Ya kamata a lura cewa saboda rashin na'urar dumama ruwa a ciki, sakamakon aunawa yana da kuskuren ± 2 °C.
Domin tantance pH na NADES da aka shirya sabo a cikin kewayon zafin jiki na 289.15–333.15 K, mun yi amfani da na'urar auna pH ta Kenis benchtop. Tunda babu na'urar dumama da aka gina a ciki, an fara dumama NADES zuwa zafin da ake so (±2 °C) ta amfani da farantin zafi sannan a auna kai tsaye da mitar pH. A nutsar da na'urar auna pH gaba ɗaya a cikin NADES kuma a rubuta ƙimar ƙarshe bayan karatun ya daidaita.
An yi amfani da nazarin thermogravimetric (TGA) don kimanta daidaiton zafi na sinadarai masu narkewar eutectic na halitta (NADES). An yi nazarin samfura yayin dumama. Ta amfani da daidaitaccen daidaito da kuma sa ido sosai kan tsarin dumama, an samar da wani yanki na asarar taro idan aka kwatanta da zafin jiki. An dumama NADES daga 0 zuwa 500 °C a ƙimar 1 °C a minti ɗaya.
Don fara aikin, dole ne a haɗa samfurin NADES sosai, a haɗa shi daidai gwargwado, sannan a cire danshi daga saman samfurin. Sannan a sanya samfurin da aka shirya a cikin wani akwati na TGA, wanda yawanci ana yin sa ne da kayan da ba su da aiki kamar aluminum. Don tabbatar da sahihan sakamako, ana daidaita kayan aikin TGA ta amfani da kayan da aka yi amfani da su, galibi ma'aunin nauyi. Da zarar an daidaita shi, gwajin TGA zai fara kuma ana dumama samfurin ta hanyar da aka tsara, yawanci a kan lokaci. Ci gaba da sa ido kan alaƙar da ke tsakanin nauyin samfurin da zafin jiki muhimmin ɓangare ne na gwajin. Kayan aikin TGA suna tattara bayanai kan zafin jiki, nauyi, da sauran sigogi kamar kwararar iskar gas ko zafin samfurin. Da zarar an kammala gwajin TGA, ana nazarin bayanan da aka tattara don tantance canjin nauyin samfurin a matsayin aikin zafin jiki. Wannan bayanin yana da mahimmanci wajen tantance kewayon zafin jiki da ke da alaƙa da canje-canje na zahiri da na sinadarai a cikin samfurin, gami da hanyoyin kamar narkewa, ƙafewa, iskar shaka, ko ruɓewa.
An tsara ruwan haƙa mai tushen ruwa a hankali bisa ga ƙa'idar API 13B-1, kuma an jera takamaiman abun da ke cikinsa a cikin Jadawali na 2 don tunani. An sayi Citric acid da glycerol (99 USP) daga Sigma Aldrich, Malaysia don shirya sinadarin eutectic na halitta mai zurfi (NADES). Bugu da ƙari, an kuma sayi maganin hana shale na gargajiya potassium chloride (KCl) daga Sigma Aldrich, Malaysia. An zaɓi 1-ethyl, 3-methylimidazolium chloride ([EMIM]Cl) tare da tsarkin fiye da 98% saboda tasirinsa mai mahimmanci wajen inganta rheology na ruwan haƙa da hana shale, wanda aka tabbatar a cikin binciken da ya gabata. Za a yi amfani da KCl da ([EMIM]Cl) a cikin nazarin kwatantawa don kimanta aikin hana shale na NADES.
Masu bincike da yawa sun fi son amfani da flakes na bentonite don nazarin kumburin shale saboda bentonite yana ɗauke da ƙungiyar "montmorillonite" iri ɗaya da ke haifar da kumburin shale. Samun ainihin samfuran shale core yana da ƙalubale saboda tsarin coring yana lalata shale, yana haifar da samfuran da ba shale gaba ɗaya ba ne amma yawanci suna ɗauke da cakuda yashi da yadudduka na dutse mai laushi. Bugu da ƙari, samfuran shale yawanci ba su da ƙungiyoyin montmorillonite waɗanda ke haifar da kumburin shale kuma saboda haka ba su dace da gwaje-gwajen hana kumburi ba.
A cikin wannan binciken, mun yi amfani da barbashi na bentonite da aka sake haɗawa waɗanda diamitansu ya kai kimanin cm 2.54. An yi granules ɗin ta hanyar danna gram 11.5 na sodium bentonite foda a cikin injin matse ruwa a 1600 psi. An auna kauri granules ɗin daidai kafin a sanya su a cikin layin dilatometer (LD). Daga nan aka nutsar da ƙwayoyin a cikin samfuran ruwa masu haƙa, gami da samfuran tushe da samfuran da aka allura da masu hana kumburin shale. Daga nan aka sa ido sosai kan canjin kauri granule ta amfani da LD, tare da yin rikodin ma'auni a tazara na daƙiƙa 60 na tsawon awanni 24.
Rarraba hasken X-ray ya nuna cewa abun da ke cikin bentonite, musamman bangaren montmorillonite na 47%, muhimmin abu ne wajen fahimtar halayensa na ƙasa. Daga cikin sassan montmorillonite na bentonite, montmorillonite shine babban bangaren, wanda ya kai kashi 88.6% na jimillar sassan. A halin yanzu, quartz ya kai kashi 29%, illite ya kai kashi 7%, da kuma carbonate ya kai kashi 9%. Wani ƙaramin sashi (kimanin 3.2%) cakuda illite ne da montmorillonite. Bugu da ƙari, yana ɗauke da abubuwan da ba su da tushe kamar Fe2O3 (4.7%), aluminosilicate na azurfa (1.2%), muscovite (4%), da phosphate (2.3%). Bugu da ƙari, ƙananan adadin Na2O (1.83%) da silicate na ƙarfe (2.17%) suna nan, wanda hakan ke sa ya yiwu a fahimci abubuwan da ke cikin bentonite da kuma rabonsu.
Wannan cikakken sashen nazari ya yi bayani dalla-dalla game da halayen rheological da tacewa na samfuran ruwan haƙowa da aka shirya ta amfani da sinadarin eutectic na halitta (NADES) kuma ana amfani da su azaman ƙarin ruwan haƙowa a cikin ma'auni daban-daban (1%, 3% da 5%). Daga nan aka kwatanta samfuran slurry bisa NADES kuma aka yi nazari da samfuran slurry waɗanda suka ƙunshi potassium chloride (KCl), CC:urea DES (choline chloride deep eutectic solvent:urea) da ruwa ionic. An rufe wasu mahimman sigogi da dama a cikin wannan binciken, gami da karatun danko da aka samu ta amfani da na'urar auna zafin jiki ta FANN kafin da bayan fallasa ga yanayin tsufa a 100°C da 150°C. An ɗauki ma'auni a saurin juyawa daban-daban (3 rpm, 6 rpm, 300 rpm da 600 rpm) wanda ke ba da damar yin cikakken bincike game da halayen ruwan haƙowa. Bayanan da aka samu za a iya amfani da su don tantance mahimman halaye kamar wurin samarwa (YP) da dankowar filastik (PV), waɗanda ke ba da haske game da aikin ruwan a ƙarƙashin yanayi daban-daban. Gwaje-gwajen tacewa na zafin jiki mai ƙarfi (HPHT) a 400 psi da 150°C (zafin jiki na yau da kullun a cikin rijiyoyin zafi mai zafi) suna ƙayyade aikin tacewa (kauri na kek da girman tacewa).
Wannan sashe yana amfani da kayan aiki na zamani, Grace HPHT Linear Dilatometer (M4600), don kimanta halayen hana kumburin shale na ruwan haƙoranmu na ruwa sosai. LSM injin zamani ne wanda ya ƙunshi sassa biyu: mai haɗa faranti da kuma mai auna dilatometer mai layi (samfuri: M4600). An shirya faranti na Bentonite don yin bincike ta amfani da Grace Core/Plate Compactor. Daga nan LSM yana ba da bayanai kan kumburi nan take akan waɗannan faranti, wanda ke ba da damar yin cikakken kimantawa game da halayen hana kumburin shale. An gudanar da gwaje-gwajen faɗaɗa shale a ƙarƙashin yanayi na yanayi, watau, 25°C da 1 psia.
Gwajin daidaiton shale ya ƙunshi babban gwaji wanda galibi ake kira gwajin dawo da shale, gwajin shale dip ko gwajin watsa shale. Don fara wannan kimantawa, ana raba yanke shale akan allon #6 BSS sannan a sanya shi akan allon #10. Sannan ana ciyar da yanke zuwa tankin riƙewa inda ake haɗa su da ruwa mai tushe da laka mai haƙawa wanda ke ɗauke da NADES (Natural Deep Eutectic Solvent). Mataki na gaba shine a sanya cakuda a cikin tanda don yin birgima mai zafi, don tabbatar da cewa yanke da laka sun haɗu sosai. Bayan awanni 16, ana cire yanke daga ɓangaren litattafan ta hanyar barin shale ya ruɓe, wanda hakan ke haifar da raguwar nauyin yankewa. An gudanar da gwajin dawo da shale bayan an riƙe yanke shale a cikin laka mai haƙa a 150°C da inci 1000 psi. cikin awanni 24.
Domin auna murmurewa daga laka mai laushi, mun tace ta ta hanyar wani kyakkyawan tsari (rami 40), sannan muka wanke ta sosai da ruwa, sannan a ƙarshe muka busar da ita a cikin tanda. Wannan tsari mai wahala yana ba mu damar kimanta laka da aka gano idan aka kwatanta da nauyin farko, a ƙarshe muna ƙididdige kashi na laka mai laushi da aka samu nasarar dawo da shi. Tushen samfuran shale daga gundumar Niah, gundumar Miri, Sarawak, Malaysia. Kafin gwaje-gwajen warwatsewa da murmurewa, an yi wa samfuran shale cikakken nazarin X-ray diffraction (XRD) don auna yawan abin da ke cikin laka da kuma tabbatar da dacewarsu don gwaji. Tsarin ma'adinan laka na samfurin kamar haka: illite 18%, kaolinite 31%, chlorite 22%, vermiculite 10%, da mica 19%.
Tashin hankali a saman ruwa muhimmin abu ne da ke sarrafa shigar da cations na ruwa cikin ƙananan ramukan shale ta hanyar aikin capillary, wanda za a yi nazari dalla-dalla a cikin wannan sashe. Wannan takarda ta yi nazarin rawar da tashin hankali a saman ruwa ke takawa a cikin haɗin gwiwar ruwan haƙowa, tana nuna mahimmancin tasirinsa akan tsarin haƙowa, musamman hana shale. Mun yi amfani da na'urar auna zafin fuska (IFT700) don auna daidaiton matsin lamba a saman samfuran ruwan haƙowa, wanda ke bayyana wani muhimmin al'amari na halayen ruwa a cikin mahallin hana shale.
Wannan sashe ya yi bayani dalla-dalla game da tazara tsakanin layukan aluminosilicate da kuma layi ɗaya na aluminosilicate a cikin yumbu. Binciken ya ƙunshi samfuran laka mai danshi waɗanda ke ɗauke da 1%, 3% da 5% CA NADES, da kuma 3% KCl, 3% [EMIM]Cl da 3% CC:urea DES don kwatantawa. Wani na'urar auna hasken X-ray diffractometer ta zamani (D2 Phaser) wacce ke aiki a 40 mA da 45 kV tare da hasken Cu-Kα (λ = 1.54059 Å) ta taka muhimmiyar rawa wajen yin rikodin kololuwar diffraction na X-ray na samfuran Na-Bt da suka jike da bushewa. Amfani da lissafin Bragg yana ba da damar tantance tazara tsakanin layukan d, ta haka yana ba da bayanai masu mahimmanci game da halayen yumbu.
Wannan sashe yana amfani da kayan aikin Malvern Zetasizer Nano ZSP na zamani don auna ƙarfin zeta daidai. Wannan kimantawa ta ba da bayanai masu mahimmanci game da halayen caji na samfuran laka mai narkewa waɗanda ke ɗauke da 1%, 3%, da 5% CA NADES, da kuma 3% KCl, 3% [EMIM]Cl, da 3% CC:urea-based DES don nazarin kwatantawa. Waɗannan sakamakon suna ba da gudummawa ga fahimtarmu game da kwanciyar hankali na mahaɗan colloidal da hulɗarsu a cikin ruwa.
An duba samfuran yumbu kafin da kuma bayan fallasa su ga sinadarin eutectic na halitta (NADES) ta amfani da na'urar duba iskar gas ta Zeiss Supra 55 VP (FESEM) wacce aka sanye da na'urar X-ray mai rarraba makamashi (EDX). Matsakaicin ƙudurin hoton shine 500 nm kuma ƙarfin hasken lantarki shine 30 kV da 50 kV. FESEM yana ba da hangen nesa mai kyau na yanayin saman da fasalin tsarin samfuran yumbu. Manufar wannan binciken ita ce samun bayanai game da tasirin NADES akan samfuran yumbu ta hanyar kwatanta hotunan da aka samu kafin da kuma bayan fallasa.
A cikin wannan binciken, an yi amfani da fasahar duba fitar da iskar gas ta filin (FESEM) don bincika tasirin NADES akan samfuran yumbu a matakin ƙananan ƙwayoyin cuta. Manufar wannan binciken ita ce bayyana yuwuwar amfani da NADES da tasirinsa akan yanayin yumbu da matsakaicin girman ƙwayoyin cuta, wanda zai samar da bayanai masu mahimmanci don bincike a wannan fanni.
A cikin wannan binciken, an yi amfani da sandunan kuskure don bayyana bambancin da rashin tabbas na matsakaicin kashi na kuskuren (AMPE) a cikin yanayin gwaji. Maimakon tsara ƙimar AMPE ɗaya (tunda tsara ƙimar AMPE na iya ɓoye yanayin da kuma ƙara girman ƙananan bambance-bambance), muna ƙididdige sandunan kuskure ta amfani da ƙa'idar 5%. Wannan hanyar tana tabbatar da cewa kowace sandar kuskure tana wakiltar tazara a cikin abin da ake sa ran tazara ta amincewa ta 95% da 100% na ƙimar AMPE za su faɗi, ta haka ne ke samar da taƙaitaccen bayani game da rarraba bayanai don kowane yanayin gwaji. Yin amfani da sandunan kuskure bisa ƙa'idar 5% don haka yana inganta fassarar da amincin wakilcin zane kuma yana taimakawa wajen samar da cikakken fahimtar sakamakon da tasirinsu.
A cikin haɗakar sinadaran eutectic na halitta mai zurfi (NADES), an yi nazari sosai kan wasu muhimman sigogi da dama a lokacin shirye-shiryen cikin gida. Waɗannan muhimman abubuwan sun haɗa da zafin jiki, rabon molar, da saurin haɗuwa. Gwaje-gwajenmu sun nuna cewa lokacin da aka haɗa HBA (citric acid) da HBD (glycerol) a rabon molar na 1:4 a 50°C, ana samar da cakuda eutectic. Siffar da ke bambanta cakuda eutectic ita ce bayyanarsa mai haske, kamanni, da rashin laka. Don haka, wannan muhimmin mataki yana nuna mahimmancin rabon molar, zafin jiki, da saurin haɗuwa, wanda rabon molar shine mafi tasiri a cikin shirye-shiryen DES da NADES, kamar yadda aka nuna a Hoto na 2.
Ma'aunin haske (n) yana bayyana rabon saurin haske a cikin injin daskarewa zuwa saurin haske a cikin matsakaici na daƙiƙa ɗaya mai kauri. Ma'aunin haske yana da matuƙar sha'awa ga sinadaran da ke da zurfin eutectic na halitta (NADES) idan aka yi la'akari da aikace-aikacen da ke da saurin haske kamar na'urorin auna haske. Ma'aunin haske na NADES da aka yi nazari a kai a 25 °C shine 1.452, wanda abin sha'awa ya fi ƙasa da na glycerol.
Ya kamata a lura cewa ma'aunin refractive na NADES yana raguwa da zafin jiki, kuma ana iya bayyana wannan yanayin daidai ta hanyar dabara (1) da Hoto na 3, tare da matsakaicin kuskuren kashi (AMPE) ya kai 0%. Wannan ɗabi'ar da ta dogara da zafin jiki an bayyana ta ta hanyar raguwar danko da yawa a yanayin zafi mai yawa, wanda ke haifar da hasken ya yi tafiya ta cikin matsakaici a cikin sauri mafi girma, wanda ke haifar da ƙarancin ƙimar refractive (n). Waɗannan sakamakon suna ba da fahimta mai mahimmanci game da amfani da dabarun NADES a cikin na'urar hangen nesa, yana nuna yuwuwar su ga aikace-aikacen biosensor.
Tashin hankali a saman, wanda ke nuna yanayin da saman ruwa ke ɗauka don rage yankinsa, yana da matuƙar muhimmanci wajen tantance dacewa da sinadaran eutectic na halitta masu zurfi (NADES) don aikace-aikacen da ke dogara da matsin lamba na capillary. Nazarin tashin hankali a saman a cikin kewayon zafin jiki na 25-60 °C yana ba da bayanai masu mahimmanci. A 25 °C, tashin hankali a saman NADES mai tushen citric acid ya kasance 55.42 mN/m, wanda ya fi ƙasa da na ruwa da glycerol. Hoto na 4 ya nuna cewa tashin hankali a saman yana raguwa sosai tare da ƙaruwar zafin jiki. Ana iya bayanin wannan lamari ta hanyar ƙaruwar kuzarin motsi na kwayoyin halitta da raguwar ƙarfin jan hankali na intermolecular.
Ana iya bayyana yanayin raguwar layi na tashin hankali a saman da aka lura a cikin NADES da aka yi nazari a kai ta hanyar lissafi (2), wanda ke nuna alaƙar lissafi ta asali a cikin kewayon zafin jiki na 25-60 °C. Jadawalin da ke cikin Hoto na 4 ya nuna yanayin tashin hankali a saman tare da zafin jiki tare da kuskuren kashi na cikakke (AMPE) na 1.4%, wanda ke ƙididdige daidaiton ƙimar tashin hankali a saman da aka ruwaito. Waɗannan sakamakon suna da mahimman tasiri don fahimtar halayen NADES da yuwuwar amfani da su.
Fahimtar yawan sinadaran da ke cikin sinadarin eutectic mai zurfi (NADES) yana da matuƙar muhimmanci don sauƙaƙa amfani da su a cikin binciken kimiyya da yawa. Yawan NADES mai tushen citric acid a 25°C shine 1.361 g/cm3, wanda ya fi yawan glycerol na iyaye. Ana iya bayyana wannan bambanci ta hanyar ƙara mai karɓar haɗin hydrogen (citric acid) zuwa glycerol.
Idan aka yi la'akari da NADES mai tushen citrate a matsayin misali, yawansa ya ragu zuwa 1.19 g/cm3 a 60°C. Ƙaruwar kuzarin motsi lokacin dumama yana sa ƙwayoyin NADES su watse, wanda ke haifar da mamaye babban girma, wanda ke haifar da raguwar yawan. Raguwar yawan da aka lura yana nuna wata alaƙa mai layi tare da ƙaruwar zafin jiki, wanda za a iya bayyana shi yadda ya kamata ta hanyar dabara (3). Hoto na 5 a zane yana gabatar da waɗannan halaye na canjin yawan NADES tare da kuskuren kashi na matsakaici (AMPE) na 1.12%, wanda ke ba da ma'aunin adadi na daidaiton ƙimar yawan da aka ruwaito.
Danko shine ƙarfin jan hankali tsakanin layuka daban-daban na ruwa a cikin motsi kuma yana taka muhimmiyar rawa wajen fahimtar amfani da sinadaran eutectic na halitta masu zurfi (NADES) a cikin aikace-aikace daban-daban. A zafin jiki na 25 °C, danko na NADES shine 951 cP, wanda ya fi na glycerol girma.
Raguwar da aka lura a cikin danko tare da karuwar zafin jiki galibi ana bayyana ta ne ta hanyar raunin ƙarfin jan hankali na intermolecular. Wannan lamari yana haifar da raguwar danko na ruwan, wani yanayi da aka nuna a fili a Hoto na 6 kuma an auna shi ta hanyar Lissafi (4). Abin lura, a 60°C, danko ya ragu zuwa 898 cP tare da matsakaicin kashi na kuskuren (AMPE) na 1.4%. Cikakken fahimtar danko da dogaro da zafin jiki a NADES yana da matukar muhimmanci ga aikace-aikacensa a aikace.
pH na maganin, wanda aka ƙaddara ta hanyar logarithm mara kyau na yawan sinadarin hydrogen ion, yana da matuƙar muhimmanci, musamman a aikace-aikacen da ke da alaƙa da pH kamar haɗakar DNA, don haka dole ne a yi nazarin pH na NADES a hankali kafin amfani. Idan aka ɗauki NADES mai tushen citric acid a matsayin misali, ana iya lura da pH mai acidic na 1.91, wanda ya bambanta da pH mai tsaka tsaki na glycerol.
Abin sha'awa, pH na sinadarin citric acid dehydrogenase mai narkewa (NADES) ya nuna raguwar da ba ta layi ba tare da ƙaruwar zafin jiki. Wannan lamari yana da alaƙa da ƙaruwar girgizar kwayoyin halitta wanda ke wargaza daidaiton H+ a cikin maganin, wanda ke haifar da samuwar ions [H]+, sannan kuma, canji a ƙimar pH. Yayin da pH na halitta na citric acid ya kama daga 3 zuwa 5, kasancewar hydrogen mai acidic a cikin glycerol yana ƙara rage pH zuwa 1.91.
Ana iya wakiltar halayen pH na NADES mai tushen citrate a cikin kewayon zafin jiki na 25-60 °C ta hanyar lissafi (5), wanda ke ba da bayanin lissafi don yanayin pH da aka lura. Hoto na 7 ya nuna wannan alaƙa mai ban sha'awa a cikin zane, yana nuna tasirin zafin jiki akan pH na NADES, wanda aka ruwaito shine 1.4% ga AMPE.
An gudanar da nazarin thermogravimetric (TGA) na sinadarin citric acid mai zurfi (NADES) a cikin yanayin zafi daga zafin ɗaki zuwa 500 °C. Kamar yadda aka gani daga Hotuna 8a da b, asarar farko ta taro har zuwa 100 °C ta faru ne saboda ruwan da aka sha da kuma ruwan da ke da alaƙa da citric acid da glycerol mai tsarki. An lura da riƙe taro mai mahimmanci na kusan kashi 88% har zuwa 180 °C, wanda ya faru ne saboda rugujewar citric acid zuwa aconitic acid da kuma samuwar methylmaleic anhydride (III) bayan an ƙara dumamawa (Hoto na 8 b). Sama da 180 °C, ana iya ganin bayyanar acrolein (acrylaldehyde) a cikin glycerol, kamar yadda aka nuna a Hoto na 8b37.
Binciken thermogravimetric (TGA) na glycerol ya nuna tsarin asarar taro mai matakai biyu. Matakin farko (180 zuwa 220 °C) ya ƙunshi samuwar acrolein, sannan kuma babban asarar taro a yanayin zafi mai yawa daga 230 zuwa 300 °C (Hoto na 8a). Yayin da zafin jiki ke ƙaruwa, acetaldehyde, carbon dioxide, methane, da hydrogen suna samuwa a jere. Abin lura shi ne, kashi 28% ne kawai na nauyin aka riƙe a 300 °C, wanda ke nuna cewa halayen NADES 8(a)38,39 na iya zama nakasassu.
Domin samun bayanai game da samuwar sabbin haɗin sinadarai, an yi nazarin sabbin dakatarwar da aka shirya na sinadaran eutectic na halitta masu zurfi (NADES) ta hanyar amfani da Fourier transform infrared spectroscopy (FTIR). An gudanar da binciken ta hanyar kwatanta bakan dakatarwar NADES da bakan citric acid mai tsarki (CA) da glycerol (Gly). Bakan CA ya nuna kololuwa masu haske a 1752 1/cm da 1673 1/cm, waɗanda ke wakiltar girgizar haɗin C=O kuma suma halayen CA ne. Bugu da ƙari, an lura da gagarumin canji a cikin girgizar lanƙwasa ta OH a 1360 1/cm a yankin yatsan hannu, kamar yadda aka nuna a Hoto na 9.
Hakazalika, idan aka yi amfani da glycerol, an gano canjin girgizar OH da lankwasawa a lambobin raƙuman ruwa na 3291 1/cm da 1414 1/cm, bi da bi. Yanzu, ta hanyar nazarin bakan NADES da aka shirya, an sami babban canji a cikin bakan. Kamar yadda aka nuna a Hoto na 7, girgizar shimfiɗar haɗin C=O ta canza daga 1752 1/cm zuwa 1720 1/cm kuma girgizar lankwasawar haɗin -OH na glycerol ta canza daga 1414 1/cm zuwa 1359 1/cm. Waɗannan canje-canjen a cikin lambobin raƙuman ruwa suna nuna canjin electronegativity, wanda ke nuna samuwar sabbin haɗin sinadarai a cikin tsarin NADES.