Naphthenic acids (NA) yog ib qho sib xyaw ntawm ob peb cyclopentyl thiab cyclohexylcarboxylic acids uas muaj qhov hnyav ntawm 120 txog 700 lossis ntau dua atomic mass units. Cov feem tseem ceeb yog carboxylic acids nrog ib tug carbon skeleton ntawm 9 mus rau 20 carbon atoms. Cov kws tshawb fawb tau hais tias naphthenic acids (NA) yog cycloaliphatic carboxylic acids nrog 10-16 carbon atoms, txawm hais tias cov kua qaub uas muaj txog li 50 carbon atoms tau pom hauv cov roj hnyav.
Etymology
Lub sij hawm muaj nws cov hauv paus hniav nyob rau hauv lub sij hawm archaic "naphthene" (cycloaliphatic tab sis tsis muaj ntxhiab), uas yog siv los faib cov hydrocarbons. Nws yog thawj zaug siv los piav qhia txog kev sib xyaw ntawm cov roj av-raws li cov kua qaub thaum cov txheej txheem tshuaj ntsuam muaj nyob rau thaum ntxov 1900s tuaj yeem txheeb xyuas qee qhov raug.naphthenic yam Cheebtsam. Niaj hnub no, naphthenic acid feem ntau yog siv los xa mus rau tag nrho cov carboxylic acids tam sim no nyob rau hauv roj av (txawm yog cyclic, acyclic, los yog aromatic compounds) thiab carboxylic acids uas muaj heteroatoms xws li N thiab S. Ntau cov kev tshawb fawb tau pom tias feem ntau cycloaliphatic acids kuj muaj ncaj thiab branched saw aliphatic acids thiab aromatic acids. Qee cov kua qaub muaj > 50% ua ke aliphatic thiab aromatic acids.
Formula
Naphthenic acids yog sawv cev los ntawm cov qauv dav dav CnH2n-z O2, qhov twg n yog cov pa roj carbon atoms thiab z yog homologous series. Z-tus nqi yog 0 rau saturated acyclic acids thiab nce mus rau 2 hauv monocyclic acids, mus rau 4 hauv bicyclic acids, mus rau 6 hauv tricyclic acids, thiab mus rau 8 hauv tetracyclic acids.
Cov ntsev ntawm cov kua qaub hu ua naphthenates tau dav siv los ua hydrophobic hlau ion qhov chaw hauv ntau yam kev siv. Cov txhuas thiab sodium ntsev ntawm naphthenic acid thiab palmitic acid tau ua ke thaum Ntiaj Teb Tsov Rog II los ua napalm. Thiab napalm tau ntse synthesized. Lo lus "napalm" los ntawm lo lus "naphthenic acid" thiab palmitic acid".
Oil txuas
Qhov xwm txheej, keeb kwm, kev rho tawm thiab kev lag luam siv ntawm naphthenic acid tau kawm rau qee lub sijhawm. Nws yog lub npe hu hais tias cov roj crude ntawm teb nyob rau hauv Romania, Russia, Venezuela, lub North Hiav txwv, Tuam Tshoj thiab West Africamuaj ntau cov acidic compounds piv rau feem ntau US cov roj crude. Cov ntsiab lus carboxylic acid ntawm qee cov khoom hauv Californian roj av tshwj xeeb yog siab (txog 4%), qhov twg cov chav kawm feem ntau ntawm carboxylic acids tau tshaj tawm tias yog cycloaliphatic thiab aromatic acids.
Composition
Cov muaj pes tsawg leeg sib txawv nyob ntawm seb muaj pes tsawg leeg ntawm cov roj crude thiab cov xwm txheej thaum ua thiab oxidation. Feem ntau cov nplua nuj nyob rau hauv naphthenic acids tuaj yeem ua rau corrosion puas rau cov khoom siv refinery, yog li cov kua qaub corrosion (NAC) tshwm sim tau kawm zoo. High acid crude roj feem ntau hu ua high tag nrho acid tooj (TAN) crude roj los yog siab acidity crude roj (HAC). Naphthenic acids yog cov kab mob loj hauv dej los ntawm kev rho tawm cov roj los ntawm Athabasca roj xuab zeb (AOS). Acids muaj ob qho tib si mob thiab mob toxicity rau ntses thiab lwm yam kab mob.
Environmental
Nyob rau hauv nws cov ntawv tshaj tawm hauv Toxicological Sciences, Rogers tau hais tias naphthenic acid sib tov yog qhov tseem ceeb tshaj plaws ntawm ib puag ncig cov pa phem los ntawm cov roj xuab zeb ntau lawm. Lawv pom tias nyob rau hauv qhov xwm txheej phem tshaj plaws, kev mob toxicity tsis zoo li rau cov tsiaj qus uas raug cov kua qaub hauv dej, tab sis kev rov raug dua tuaj yeem muaj kev cuam tshuam rau kev noj qab haus huv.
Nyob rau hauv nws tsab xov xwm 2002tau hais ntau dua 100 zaug, Rogers li al tau tshaj tawm cov txheej txheem kev kuaj xyuas hnyav uas tsim los kom tshem tawm cov kua qaub los ntawm cov ntim loj ntawm Athabasca Oil Sands Tailings Pond (TPW) dej. Naphthenic acids muaj nyob rau hauv AOS Tailings Dej (TPW) ntawm qhov kwv yees ntawm 81 mg / L, ib qib qis heev rau TPW yuav suav tias yog qhov muaj txiaj ntsig zoo rau kev lag luam rov qab.
Delete
Naphthenic acid raug tshem tawm los ntawm cov roj av tsis yog tsuas yog txo qis corrosion, tab sis kuj rov qab cov khoom lag luam zoo. Qhov loj tshaj plaws tam sim no thiab keeb kwm siv cov kua qaub no yog nyob rau hauv zus tau tej cov hlau naphthenates. Cov kua qaub yog muab rho tawm los ntawm roj av distillates los ntawm alkaline extraction, regenerated nyob rau hauv ib tug acid neutralization txheej txheem, thiab ces distilled kom tshem tawm impurities. Cov kua qaub muag muag yog cais los ntawm tus lej acid, qib impurity, thiab xim. Siv los tsim cov hlau naphthenates thiab lwm yam derivatives xws li esters thiab amides.
Napthhenates
Naphthenates yog cov ntsev ntsev zoo sib xws rau cov acetates sib xws, txhais tau zoo dua tab sis tsis muaj txiaj ntsig. Naphthenates, zoo li naphthenic acids hauv roj av, yog cov soluble hauv cov organic media xws li xim. Lawv yog siv nyob rau hauv kev lag luam, nrog rau zus tau tej cov tej yam tseem ceeb: hluavtaws detergents, lubricants, corrosion inhibitors, roj thiab lubricating roj additives, preservatives.rau ntoo, tshuaj tua kab, fungicides, acaricides, wetting agents, napalm thickeners thiab roj desiccants siv nyob rau hauv painting thiab ntoo nto kho.
Oil sands
Ib txoj kev tshawb fawb tau hais tias naphthenic acids yog qhov muaj kuab lom tshaj plaws ntawm ib puag ncig ntawm txhua yam khoom tau los ntawm kev rho tawm cov roj los ntawm cov roj xuab zeb. Txawm li cas los xij, nyob rau hauv cov xwm txheej ntawm kev xau thiab kev sib kis, kev mob toxicity tsis zoo li tshwm sim hauv cov tsiaj qus uas raug cov kua qaub nyob hauv cov pas dej hauv pas dej, tab sis rov ua dua tuaj yeem ua rau muaj kev phom sij rau tsiaj txhu. Cov kua qaub muaj nyob rau hauv cov roj xuab zeb thiab cov tailings dej ntawm qhov kwv yees ntawm 81 mg / L.
Siv Lub Koom Haum rau Kev Koom Tes Kev Lag Luam thiab Kev Txhim Kho (OECD) cov txheej txheem rau kev kuaj tshuaj lom neeg, Asmeskas cov kws tshawb fawb tau sib cav tias, raws li lawv cov kev tshawb fawb, ntxuav NAs, thaum noj hauv qhov ncauj, tsis yog genotoxic rau cov tsiaj txhu. Txawm li cas los xij, kev puas tsuaj los ntawm NDT los ntawm kev raug luv luv thaum lub sij hawm raug mob los yog cuam tshuam tuaj yeem sib sau ua ke nrog rov tshwm sim dua.
YCyclopentane
Cyclopentane yog ib qho hluav taws kub alicyclic hydrocarbon nrog cov tshuaj formula C5H10 thiab CAS naj npawb 287-92-3, muaj ib lub nplhaib ntawm tsib carbon atoms, txhua bonded rau ob hydrogen atoms saum toj no thiab hauv qab lub dav hlau. Nws feem ntau nthuav tawm hauv daim ntawvcov kua tsis muaj xim uas muaj ntxhiab tsw zoo ib yam li roj av. Nws cov ntsiab lus melting yog -94 ° C thiab nws qhov kub ntawm 49 ° C. Cyclopentane belongs rau chav kawm ntawm cycloalkanes thiab yog alkanes nrog ib lossis ntau lub nplhaib ntawm carbon atoms. Nws yog tsim los ntawm cracking cyclohexane nyob rau hauv lub xub ntiag ntawm alumina ntawm qhov kub thiab txias.
Kev tsim cov naphthenic acids, suav nrog cyclopentane, tau poob nws lub cim qub qub nyob rau xyoo tas los no.
Nws tau npaj thawj zaug hauv xyoo 1893 los ntawm German chemist Johannes Wieslikus. Tsis ntev los no, nws feem ntau hu ua naphthenic acids.
Role in production
Cyclopentane yog siv rau hauv kev tsim cov khoom siv hluavtaws thiab cov nplaum nplaum, thiab ua tus neeg sawv cev hauv kev tsim cov polyurethane insulating ua npuas ncauj, uas muaj nyob rau hauv ntau yam khoom siv hauv tsev xws li tub yees thiab lub tub yees, hloov lwm yam kev puas tsuaj xws li CFCs -11 thiab HCFC-141b.
Ntau yam cyclopentane alkylation (MAC) lubricants muaj qhov tsis muaj zog thiab siv rau qee qhov tshwj xeeb.
Tebchaws Asmeskas tsim ntau tshaj li ib nrab lab kilograms ntawm cov tshuaj no hauv ib xyoos. Nyob rau hauv Russia, naphthenic acids (xws li cyclopentane) yog tsim raws li ib tug natural khoom ntawm cov roj ua.
Cycloalkanes tuaj yeem tsim los siv cov txheej txheem hu ua catalytic hloov kho. Piv txwv li, 2-methylbutane tuaj yeem hloov mus rau cyclopentane siv platinum catalyst. Qhov no tshwj xeeb tshaj yog siv nyob rau hauvtsheb, raws li ceg alkanes yuav hlawv sai dua.
Lub cev thiab tshuaj yam ntxwv
Xav tsis thoob, lawv cov cyclohexanes pib boil 10 ° C siab dua hexahydrobenzene lossis hexanaphthene, tab sis qhov kev sib cav no tau daws nyob rau hauv 1895 los ntawm Markovnikov, N. M. Kishner thiab Nikolai Zelinsky thaum lawv repurposed hexahydrobenzene thiab hexanaphthene li methylcyclopentane - qhov tshwm sim ntawm ib qho kev npaj txhij txog backlash.
Txawm hais tias tsis yog-reactive, cyclohexane dhau los ua cov catalytic oxidation los ua cyclohexanone thiab cyclohexanol. Kev sib xyaw ntawm cyclohexanone-cyclohexanol, hu ua "KA roj", yog cov khoom siv raw rau adipic acid thiab caprolactam, precursors ntawm nylon.
Daim ntawv thov
Nws yog siv los ua cov kuab tshuaj hauv qee hom tshuaj kho kua. Cyclohexane qee zaum siv los ua cov kuab tshuaj tsis muaj polar organic, txawm hais tias n-hexane feem ntau siv rau lub hom phiaj no. Nws kuj yog feem ntau siv los ua cov kuab tshuaj recrystallization, ntau cov organic tebchaw pom zoo solubility hauv kub cyclohexane thiab tsis zoo solubility ntawm qhov kub thiab txias.
Cyclohexane kuj tseem siv los ntsuas qhov sib txawv scanning calorimetry (DSC) cov cuab yeej vim qhov yooj yim siv lead ua-rau-crystal hloov ntawm -87.1 ° C.
Cyclohexane vapors yog siv rau hauv lub tshuab nqus tsev carburizing rau hauv kev tsim cov khoom siv kho cua sov.
Deformation
Ib lub nplhaib nrog 6 vertices tsis phim cov duab ntawm hexagon zoo meej. Lub hom phiaj hexagon conformation muaj qhov tseem ceeb angular strain vim nws daim ntawv cog lus tsis yog 109.5 degrees. Torsional deformation kuj tseem ceeb vim tias txhua daim ntawv cog lus yuav ploj mus.
Yog li ntawd, txhawm rau txhawm rau txo qhov torsional deformation, cyclohexane tau txais cov qauv peb-dimensional hu ua "conformational chair". Kuj tseem muaj ob qhov sib txawv nruab nrab conformers - "ib nrab lub rooj zaum", uas yog qhov tsis ruaj khov tshaj plaws, thiab "twist nkoj", uas ruaj khov dua. Cov npe eccentric no tau npaj ua ntej thaum ntxov li 1890 los ntawm Hermann Sachs, tab sis tau lees paub ntau tom qab.
Ib nrab ntawm cov hydrogen atoms nyob rau hauv lub dav hlau ntawm lub nplhaib (equatorially), thiab lwm ib nrab yog perpendicular rau lub dav hlau (axially). Qhov kev sib haum xeeb no muab cov qauv cyclohexane ruaj khov tshaj plaws. Muaj lwm qhov kev sib haum xeeb ntawm cyclohexane hu ua "nkoj conformation", tab sis nws yuav hloov mus rau ib qho me ntsis ruaj khov "stool" tsim.
Cyclohexane muaj lub kaum sab xis qis tshaj plaws thiab torsional strain ntawm tag nrho cov cycloalkanes, ua rau cyclohexane raug suav tias yog 0 hauv tag nrho cov nplhaib. Tib yam muaj tseeb rau sodium ntsev ntawm naphthenic acids.
phase
Cyclohexane muaj ob theem crystalline. Kub kub theem I, ruaj khov ntawm +186 ° C thiab kubmelting point +280 ° C, yog cov yas siv lead ua, uas txhais tau hais tias cov molecules khaws qee qhov kev ywj pheej ntawm kev txav mus los. Qhov ntsuas kub qis (qis dua 186 ° C) theem II yog xaj ntau dua. Lwm ob qhov kub qis (metastable) theem III thiab IV tau txais los ntawm kev siv cov kev kub ntxhov siab tshaj 30 MPa, thiab theem IV tshwm tsuas yog hauv deuterated cyclohexane (nco ntsoov tias daim ntawv thov siab nce txhua qhov kev hloov pauv kub).
