Catalyst rau nce Octane Number nyob rau hauv Isomerization units
Hydrogen-Containing Unit
Peb lub hauv paus txheej txheem txheej txheem, qhov ntsuas kub, thiab kev xaiv catalyst
✅ Catalyst: platinum txhawb chlorinated alumina (aluminium chloride hom)
Reactor kub: 120 ~ 175℃(reactor inlet), txaj kub nce 10-25 degree
Siab: 2.8-3.8 MPa; kua teev qhov chaw tshaj tawm LHSV=1.0–3.0 h⁻¹; hydrogen hydrocarbon molar ratio 0.1-0.5
Cov khoom siv raw: nruj lub cev qhuav dej, desulfurization, thiab denitrification; dej / sulfur yuav mus tas li tshuaj lom acidic chlorine qhov chaw; yuav tsum tau chlorine supplementation thaum lub sijhawm ua haujlwm
Muaj feem xyuam: C₅/C₆ lub teeb naphtha, lub hom phiaj siab RON (ib qho dhau RON≈82–84, voj voog mus txog 87–93)
Nta: Kev ua haujlwm siab tshaj plaws, zoo tshaj plaws hloov pauv tus nqi; heev corrosive, nruab nrog alkali tu system, complex ua hauj lwm thiab txij nkawm
✅Catalyst: Pt-loaded acidic molecular sieve (zeolite hom, chlorine-dawb)
Cov tshuaj tiv thaiv kub: 240-280 degree
Siab: 2.0-3.2 MPa; LHSV=0.5–2.5 h⁻¹; hydrogen rau hydrocarbon ratio 0.1-1.0
Ntau dua cov khoom siv siab ntev: rhiab heev rau cov sulfur thiab dej qis dua li cov tshuaj chlorine - txhuas catalyst, tsis tas yuav ntxiv chlorine
Muaj feem xyuam: C₅ / C₆, kuj tuaj yeem siv rau C₄butane isomerization; cov cuab yeej yooj yim dua, muaj kev ruaj ntseg zoo, thiab yooj yim rau rov tsim dua tshiab
Qhov tsis zoo: qhov kub thiab txias, tsis muaj qhov sib npaug, ib zaug - kis tau tus nqi hloov dua siab tshiab qis dua - cov txheej txheem kub ntawm aluminium chloride, feem ntau nruab nrog cov khoom fractionation + unconverted n-alkane ncig voj
✅ Catalyst: Tshwj xeeb molecular sieve / txhuas chloride system
Cov tshuaj tiv thaiv kub: 160-210 degree
Siab: 1.5-2.0 MPa; hydrogen rau hydrocarbon ratio 0.07-0.15
Qhov ib zaug -hloov pauv tus nqi yog 50% – 55%, thiab ib tug deisobutane ntauwd yuav tsum tau ntsia kom circulated unreacted n-butane rov qab mus rau lub reactor.
Hydrogen{0}}Free Unit
Plaub pawg loj ntawm hydrogen-dawb isomerization catalysts
Hloov pauv hlau- hloov kho acidic ZSM-5 zeolites (Zn-ZSM-5, Ga-ZSM-5, Ni-ZSM-5)
Kev them nyiaj yug: ZSM-5 (MFI zeolite); Cov khoom xyaw nquag: Zn, Ga, Ni (tsis yog platinum hlau)
Kev ua haujlwm siab: 340-460 degree, 0-1.2 MPa; zoo kawg nkaus phim rau cov neeg siv khoom xav tau
Cov yam ntxwv tshwm sim: Ib txhij isomerization, aromatization, thiab me me tawg; nce roj av octane naj npawb; tsim propane thiab butane (cov pa qhuav); kua tawm los ntawm 82-90%; Kev tsim dua tshiab tsuas yog N₂ thiab huab cua rau coke hlawv -tawm (tsis muaj hydrogen txo)
Cov qib sib npaug ntawm Lavxias: KT-10, KT-17, KT-18 (Zn-Ce-ZSM-Al₂O₃); txhim kho naphtha tsis muaj hydrogen; roj av octane tooj mus txog 85-87 ntawm 400 degree
Hloov kho mordenite (MOR) (Ni-MOR, Fe-MOR; Pt-dawb)
Kev them nyiaj yug: Mordenite (MOR); Cov khoom xyaw nquag: Ni/Fe (platinum{0}}dawb)
Qhov kub thiab txias: 320-420 degree; Siab: 0.3-1.0 MPa
Yam ntxwv: Isomerization selectivity superior rau ZSM-5; tsawg aromatization kev ua; nquag coking ntawm qhov kub thiab txias; nruab nrab n-alkane conversion; regeneration ntawm huab cua calcination (coke hlawv-tawm) nkaus xwb; tsis xav tau hydrogen
Solid superacids (platinum{0}}dawb): SO₄²⁻/ZrO₂, SO₄²⁻/TiO₂-Al₂O₃
Kev them nyiaj yug: Zirconia / Titania-alumina composite oxide; tsis muaj Pt loading
Kub: 300-400 degree; siab: atmospheric rau 1 MPa
Cov yam ntxwv: siab acid zog heev; kev ua haujlwm zoo isomerization; drawbacks: sulfate pawg nquag mus leaching ntawm kub kub; tsis zoo dej stability; ceev coking; regeneration ntawm huab cua calcination nkaus xwb; txwv tsis pub hydrogen txo qis
10- nplhaib puab- xaiv molecular sieves (Ni-SAPO-11, Ni-ZSM-22; platinum-dawb)
Kev them nyiaj yug: SAPO-11 / ZSM-22; Cov khoom xyaw nquag: Ni (tsis muaj Pt)
Kub: 330-430 degree; Siab: 0.4-1.0 MPa
Yam ntxwv: Zoo li- xaiv isomerization; siab selectivity rau ntau-branched alkanes; drawbacks: hloov dua siab tshiab kuj tsawg; tseem ceeb roj tsim vim tawg; high coking tus nqi; regeneration ntawm huab cua calcination nkaus xwb; tsis muaj hydrogen kauj ruam koom nrog.
Lub teb ntawm Petroleum Refining
Isomerization ntawm n-butane rau isobutane
Platinum-raws li catalysts (xws li Pt/Al₂O₃-Cl system) yog siv los hloov n-butane rau hauv isobutane, cov khoom noj tseem ceeb rau kev tsim cov khoom siv roj av octane siab (piv txwv li, methyl tert-butyl MTBE). Hauv cov chaw tsim khoom, cov khoom siv sib xyaw C4 tau txais hydro-isomerization, ua rau 1-butene tsim muaj peev xwm mus txog qhov ntsuas ntawm ntau pua tons hauv ib hnub.
Isomerization ntawm C5-C6 alkanes
Khoom superacid catalysts (xws li RISO-C los yog Pt/SO₄²⁻-ZrO₂-Al₂O₃) yog ua hauj lwm los hloov ncaj- saw alkanes rau hauv ceg isomers. Piv txwv li, tom qab isomerization ntawm lub teeb naphtha (los ntawm kev hloov pauv catalytic), C5 thiab C6 isomerization tus nqi nce mus txog 70% thiab 85% raws li, nce cov khoom siv roj av Kev Tshawb Fawb Octane Number (RON) mus rau saum toj 85 thiab ua kom zoo dua roj zoo.
Aromatization Catalyst
Piv nrog rau kev hloov kho thev naus laus zis, cov txheej txheem no tsis txwv los ntawm qhov muaj peev xwm aromatic cov ntsiab lus ntawm feedstock; nws feem ntau yuav tsum tsis muaj ua ntej - feem ntau los yog ua kom zoo ntawm cov khoom siv raw thiab muaj ntau yam kev siv tau. Cov khoom lag luam tsim nyog rau kev tsim cov tshuaj tsw qab los ntawm cov txheej txheem no suav nrog cov roj av coker, ncaj-khiav roj av, roj av condensate, hloov kho lub teeb xaus (topped naphtha), hloov kho raffinate, pyrolysis roj av, thiab olefin- nplua nuj roj av roj (LPG).
When using olefin-rich LPG (olefin content >50%) raws li cov khoom noj khoom haus, cov ntsiab lus uas muaj ntxhiab hauv cov khoom ua kua mus txog 100%, tshem tawm qhov xav tau rau cov khoom muaj ntxhiab extraction; qhov ib zaug - kis tau tus ntxhiab tsw tshaj 48.2%, thiab BTX tawm los tshaj 42.2%. Lub catalyst muaj ib zaug xwb - dhau lub voj voog ua haujlwm ntawm Ntau dua lossis sib npaug rau 20 hnub thiab tag nrho cov kev pabcuam lub neej ntawm Ntau dua lossis sib npaug rau 3.0 xyoo.
Thaum siv naphtha li feedstock, ib zaug - kis aromatic yield tshaj 35.0%, thiab BTX tawm los tshaj 32.0%; tus catalyst muaj ib zaug xwb - dhau lub voj voog ua haujlwm ntawm 20–30 hnub thiab tag nrho cov kev pabcuam lub neej ntawm Ntau dua lossis sib npaug rau 3.0 xyoo.
Cov roj hluav taws xob generated yog nplua nuj nyob rau hauv hydrogen, uas tuaj yeem rov qab tau thiab siv los ua hydrogen qhov chaw.
Technical nta
① Tsawg aromatization tshuaj tiv thaiv kub
Advanced catalyst shaping thiab modification technologies pab kom cov tshuaj tiv thaiv mus rau ntawm qhov kub thiab txias. Hauv kev siv tshuaj tsw qab, cov tshuaj tiv thaiv kub yog 30℃-50℃qis dua li kev sib tw thev naus laus zis, txo qis kev siv zog. Cov tshuaj tiv thaiv qis dua kuj txo cov khoom siv zog uas yuav tsum tau ua thiab ua rau cov pa roj qhuav qis dua.
② Cov tshuaj tiv thaiv tshwj xeeb kub- siv tshuab ntxiv
Naphtha aromatization-tshwj xeeb tshaj yog nrog alkane- nplua nuj feedstocks- yog cov txheej txheem endothermic heev. Kev siv cov cua sov tshwj xeeb- cov cuab yeej siv ntxiv tshem tawm qhov kev xav tau ntawm cov cua sov nruab nrab ntawm cov cua sov, yog li txo cov peev peev thiab kev siv hluav taws xob.
Aromatization Catalyst rau Octane Number Enhancement
Aromatization muaj kev kub siab -kub dehydrogenation, cyclization, thiab hloov hydrogen; Nws yog feem ntau ua nyob rau hauv tsis muaj hydrogen ntxiv, thiab kev khiav hauj lwm kub yog siab dua li cov isomerization. ZSM-5 (MFI) yog qhov kev txhawb nqa tseem ceeb, categorized ua plaub yam tseem ceeb raws li kev hloov kho hlau:
Cov khoom xyaw nquag: Zn (1-3 wt%); P lossis tsawg lub ntiaj teb cov ntsiab lus tuaj yeem raug ntxiv los kho acidity thiab txo qis kev tsim coke.
Cov kev mob tshwm sim: 500-550 degree, atmospheric siab rau 0.3 MPa, WHSV 0.4-1.2 h⁻¹.
Mechanism: Zn chaw pab txhawb kev dehydrogenation, thaum zeolite acid qhov chaw catalyze cyclization; Kev hloov pauv hydrogen yog txoj hauv kev tseem ceeb, yielding me me ntawm H₂.
Cov khoom noj uas tsim nyog: C4 liquefied gas, C5, tawg C5, lub teeb naphtha.
Cov qib lag luam: NKC-5, DLP series, LHA hom.
Yam ntxwv: Tus nqi qis, zoo BTX xaiv; Kev tsim cov coke sai yuav tsum tau rov tsim dua tshiab, ua rau ib qho luv luv - dhau lub neej thaum siv cov khoom noj olefinic.
Cov khoom xyaw nquag: Ga (0.5-2 wt%)
Cov kev mob tshwm sim: 520-580 degree, atmospheric siab
Mechanism: Ga muaj zog dehydrogenation muaj peev xwm; ua tiav ntawm txoj kev ncaj qha dehydrogenation, yielding ntau hydrogen.
Cov txheej txheem: BP-UOP Cyclar; domestic M2-forming
Cov yam ntxwv: siab dua aromatics tawm los piv rau Zn-raws li catalysts; qis qhuav roj ntau lawm; tus nqi siab dua; ntau rhiab heev rau sulfur.
Pt/Cl-Al₂O₃ (Catalytic hloov kho; hydrogen- huab cua nplua nuj)
Cov xwm txheej: 480-530 degree, 0.8-2.0 MPa; ua haujlwm hauv hydrogen- huab cua nplua nuj.
Khoom noj khoom haus: C6+ naphtha; ua kom siab - octane roj av + BTX; zoo tiv thaiv coking, tab sis yuav tsum tau chlorine ntxiv thiab ua rau muaj kev pheej hmoo corrosion.
Pt/KL zeolite: Chlorine{0}} hloov kho dawb; haum rau n-hexane aromatization; heev rhiab heev rau sulfur; tsis tshua muaj siv nyob rau hauv loj industrial scale.
⚠ Nco tseg: Catalytic hloov kho ≠ lub teeb hydrocarbon aromatization. Reforming ua haujlwm nyob rau hauv hydrogen- huab cua nplua nuj, whereas Zn/Ga-ZSM-5 systems tau hais los saum no tsis yog -hydrogen- nplua nuj aromatization txheej txheem; ob lub tshuab tsis tuaj yeem siv sib hloov tau . 4. Lwm cov kev hloov kho (Mo, Ag, tsis tshua muaj ntiaj teb sib xyaw)
Mo/HZSM-5: Methane aromatization, >700 degree; haum rau methane xwb, tsis yog rau LPG / C5.
Ag/ZSM-5: me me dehydrogenation, nruab nrab BTX xaiv; txwv kev thov kev lag luam.
Tsis tshua muaj -lub ntiaj teb + phosphorus- hloov kho Zn-ZSM-5: Txhawb nqa / ntxiv es tsis yog ib qho catalyst standalone; siv los retard coke tsim thiab ncua ib zaug - khiav lub sij hawm (xws li, DLP-1 nano-ZSM-5).
Kev qhia ceev ceev
LPG, C4 / C5 feedstocks; pob nyiaj siv tsawg; atmospheric siab, tsis yog -hydrogen cua → Zn/ZSM-5 (NKC-5, DLP)
Nrhiav ntau dua aromatics tawm los thiab hydrogen co- ntau lawm; Kev noj zaub mov kom txaus muaj → Ga/ZSM-5 (Cyclar)
C6+ naphtha feedstock; hydrogen- chav tsev muaj peev xwm; cov khoom lag luam yog siab -octane roj av → Pt-chlorinated alumina hloov pauv catalyst
Methane feedstock → Mo/ZSM-5 (high temperature, >700 degree)
Catalyst rau Roj Hmab Ntau Lawm Ntawm Lub Teeb Hydrocarbon Aromatization
Siv lub teeb hydrocarbons-xws li refinery qhuav roj, post-etherification C4 feem, ncaj-khiav naphtha, oilfield condensate, los yog coker gasoline- ua feedstock, cov txheej txheem no ntiav proprietary catalysts los tsim high- octane gasoline cov kauj ruam, kev sib xyaw ua ke, thiab kev sib xyaw ua ke. dehydrogenation. Cov txiaj ntsig tau hloov kho roj av yog tus cwj pwm los ntawm cov ntsiab lus qis olefin thiab sulfur thiab qhov ntsuas octane siab, ua rau nws yog ib qho kev sib xyaw ua ke zoo heev rau kev tsim cov roj av tsheb uas ua tau raws li qib 92 thiab 95 cov qauv.
Technical nta
Cov txheej txheem siv ntau yam ntawm cov khoom noj khoom haus thiab tau txais txiaj ntsig zoo - roj av zoo, nrog cov khoom lag luam uas tuaj yeem hloov kho tau yooj yim raws li kev hloov pauv hauv khw. Cov roj roj yog nplua nuj nyob rau hauv hydrogen, uas tuaj yeem rov qab tau thiab siv los ua qhov chaw hydrogen. Lub tsev lag luam muaj cov txheej txheem ntws yooj yim thiab cov nqi peev qis, nrog rau kev siv nyiaj tsawg thiab kev siv hluav taws xob.
When using olefin-rich refinery dry gas or liquefied gas as feedstock: olefin conversion >95%; gasoline selectivity for olefins >90%; gasoline octane number (RON) >92; thiab catalyst ib zaug - khiav voj voog Ntau dua lossis sib npaug li 45 hnub.
Thaum siv naphtha uas muaj peev xwm tsis tshua muaj ntxhiab (xws li hloov kho raffinate, lub teeb -end naphtha, lossis thee-raws li naphtha): roj av octane tooj (RON) yog 85–92; qhuav roj yield yog 2-4%; cov catalyst ua kom muaj zog adaptability (txo cov khoom sulfur rau<10 ppm even with a feedstock sulfur content of 300 ppm); and the single-run cycle is 30–90 days, with a total catalyst lifespan of ≥3.0 years.
Muab piv rau cov thev naus laus zis zoo sib xws:
① Lub catalyst nthuav tawm kev ua haujlwm zoo thiab kev xaiv aromatics.
② Lub catalyst muaj zog tiv thaiv coking, uas ua rau cov roj qhuav qhuav.
③ Nws pioneers siv cov txheej txheem ua haujlwm siab:
--- Tshem tawm qhov kev xav tau ntawm cov khoom siv roj nplua nuj, yog li txo cov nqi khoom siv thiab cov nqi khiav lag luam.④ Optimized catalyst regeneration technology
---Lub regeneration gas-to-catalyst ratio (ntim piv ntawm circulating gas rau catalyst) yog txo los ntawm 20-30%; seem kev tsim dua tshiab yuav tsum tau nqis peev tsawg thiab cov nqi khiav lag luam thaum ua tiav cov txiaj ntsig zoo dua qub.
Olefin-Produce Catalyst
Tsim nyob rau hauv xyoo tas los no, thev naus laus zis los tsim cov olefins ntawm catalytic cracking ntawm lub teeb hydrocarbons ua ke qhov zoo ntawm ob qho tib si chav cracking thiab kua catalytic cracking (FCC). Nws qhib txoj hauv kev tshiab uas tseem ceeb heev rau kev txuag hluav taws xob thiab kev txo qis hauv cov nroj tsuag petrochemical, nrog rau kev ua kom tau raws li qhov xav tau loj hlob rau lub teeb olefins. Siv cov khoom noj xws li olefin- nplua nuj C4–C8 lub teeb hydrocarbons, ncaj-khiav naphtha, lossis thee-raws li naphtha, thev naus laus zis siv cov khoom siv hluav taws xob los xaiv los hloov lub teeb hydrocarbon rau hauv ethylene, propylene, thiab siab -octane roj.
Technical nta
Piv nrog rau cov tsoos ncu cracking, qhov no catalytic cracking tshuab ua hauj lwm nyob rau hauv qis kub, siv tsawg zog, siv ib tug ntau yam ntawm feedstocks, thiab tso cai rau kom saj zawg zog cov khoom faib. Piv rau FCC-raws li olefin cov thev naus laus zis, nws ua tiav qhov tob dua qhov tawg thiab ntau dua cov txiaj ntsig ntawm ethylene thiab propylene. Tsis tas li ntawd, cov txheej txheem ntws yog yooj yim, thiab qhov yuav tsum tau nqis peev tsawg.
Thaum siv cov roj liquefied C4 (nrog rau cov ntsiab lus ntawm butene ntau dua lossis sib npaug li 60%) raws li cov khoom noj, qhov sib xyaw ua ke ntawm ethylene thiab propylene tshaj 40%, thaum cov roj av tawm los ntawm kwv yees li 15-20%.