Pakati peasiri-siliceous oxides, alumina ine yakanaka mechanicha zvivakwa, yakakwirira tembiricha kuramba uye corrosion kuramba, nepo mesoporous alumina (MA) ine inogadziriswa pore saizi, hombe chaiyo nzvimbo, hombe pore vhoriyamu uye yakaderera mutengo wekugadzira, iyo inoshandiswa zvakanyanya mu catalysis. kudzorwa kusunungurwa kwezvinodhaka, adsorption uye mamwe minda, zvakadai sekuputika, hydrocracking uye hydrodesulfurization ye petroleum raw materials.Microporous alumina inowanzoshandiswa mumhizha, asi ichakanganisa zvakananga basa realuminium, hupenyu hwebasa uye kusarudza kwekugadzirisa.Semuyenzaniso, mukuita kwekucheneswa kwemoto wemoto, izvo zvinosvibisa zvakaiswa kubva kune einjini ekuwedzera zvinogadzira coke, izvo zvinozotungamira kuvharika kwecatalyst pores, nekudaro kudzikisa chiitiko checatalyst.Surfactant inogona kushandiswa kugadzirisa chimiro chealumina mutakuri kuti aite MA.Kuvandudza kuita kwayo kunobatsira.
MA ine constraining effect, uye simbi dzinoshanda dzinodzimwa mushure mekupisa kwepamusoro-tembiricha calcination.Mukuwedzera, mushure mekupisa kwepamusoro-tembiricha, iyo mesoporous chimiro inodonha, iyo MA skeleton iri mune amorphous state, uye iyo acidity yepamusoro haigone kuita zvinodiwa mumunda wekushanda.Kugadziriswa kwekugadzirisa kunowanzodiwa kuti uvandudze basa rinokonzera, mesoporous chimiro kugadzikana, kugadzikana kwekushisa kwepamusoro uye acidity yepamusoro yezvinhu zveMA.Mapoka ekugadzirisa akajairika anosanganisira metal heteroatoms (Fe, Co, Ni, Cu, Zn, Pd, Pt, Zr, nezvimwewo. ) uye masimbi oxides (TiO2, NiO, Co3O4, CuO, Cu2O, RE2O7, zvichingodaro)Yakaiswa pamusoro peMA kana kudonhedzwa muskeleton.
Iyo yakakosha erekitironi kumisikidzwa kwezvinhu zvisingawanzo zvepasi zvinoita kuti makomisheni ayo ave akakosha ekuona, magetsi uye magineti zvimiro, uye anoshandiswa muzvinhu zvinokonzeresa, mafotoelectric zvinhu, adsorption zvinhu uye magineti zvinhu.Rare earth modified mesoporous materials inogona kugadzirisa asidhi (alkali) pfuma, kuwedzera okisijeni vacancy, uye synthesize simbi nanocrystalline catalyst pamwe yunifomu dispersion uye yakagadzikana nanometer scale.Appropriate porous zvinhu uye zvisingawanzoitiki mavhu anogona kuvandudza pamusoro kupararira kwesimbi nanocrystals uye kugadzikana uye kabhoni deposition. kushorwa kwezvinokonzeresa.Mune pepa iri, isingawanzo kugadziridzwa pasi uye kushanda kweMA kuchaunzwa kuvandudza mashandiro anoita catalytic, kugadzikana kwekupisa, kugona kweokisijeni, nzvimbo chaiyo uye chimiro chepore.
1 MA kugadzirira
1.1 kugadzirira kwealumina mutakuri
Nzira yekugadzirira yealumina carrier inosarudza kugoverwa kwayo kwepore, uye nzira dzayo dzekugadzirira dzinosanganisira pseudo-boehmite (PB) dehydration method uye sol-gel nzira.Pseudoboehmite (PB) yakatanga kutaurwa naCalvet, uye H + yakasimudzira peptization kuti iwane γ-AlOOH colloidal PB ine interlayer mvura, iyo yakaverengerwa uye yakapera mvura pakupisa kwepamusoro kuita alumina.Maererano nemhando dzakasiyana-siyana dzakasvibirira, inowanzogoverwa kuva precipitation method, carbonization method uye alcoholaluminium hydrolysis method.Iyo colloidal solubility yePB inokonzerwa nekristallinity, uye inogadziriswa nekuwedzera kwekristallinity, uye inobatwawo nekushanda kwemaitiro parameters.
PB inowanzogadzirwa nenzira yekunaya.Alkali inowedzerwa mune aluminate mhinduro kana asidhi inowedzerwa mune aluminate mhinduro uye precipitated kuwana hydrated alumina (alkali precipitation), kana asidhi inowedzerwa mune aluminate precipitation kuwana alumina monohydrate, iyo inobva yashambidzwa, yakaomeswa uye calcined kuwana PB.Kunaya kwemvura nzira iri nyore kushanda uye yakaderera mumutengo, iyo inowanzoshandiswa mukugadzirwa kwemaindasitiri, asi inopesvedzerwa nezvinhu zvakawanda (mhinduro pH, concentration, tembiricha, etc.).Uye iyo mamiriro ekuwana particle ane nani dispersibility yakasimba.Munzira ye carbonization, Al (OH) 3 inowanikwa nekuita kwe CO2 uye NaAlO2, uye PB inogona kuwanikwa mushure mekukwegura.Iyi nzira ine mabhenefiti ekushanda kuri nyore, mhando yechigadzirwa chepamusoro, hapana kusvibiswa uye mutengo wakaderera, uye inogona kugadzirira alumina ine yakakwira catalytic chiitiko, yakanakisa corrosion resistance uye yakakwirira chaiyo nzvimbo ine yakaderera mari uye yakakwirira return.Aluminium alkoxide hydrolysis nzira inowanzoshandiswa. kugadzirira yakakwirira-kuchena PB.Aluminium alkoxide inonzi hydrolyzed kuti igadzire aruminiyamu oxide monohydrate, uye yozobatwa kuti iwane yakakwirira-kuchena PB, iyo ine yakanaka crystallinity, yunifomu particle size, concentrated pore size distribution uye high integrity of spherical particles.Zvisinei, maitiro acho akaoma, uye zvakaoma kupora nekuda kwekushandiswa kwezvimwe zvinonyungudutsa zvine chepfu.
Mukuwedzera, munyu kana organic compounds yesimbi inowanzoshandiswa kugadzirira alumina precursors ne-sol-gel nzira, uye mvura yakachena kana organic solvents inowedzerwa kugadzirira mhinduro dzekugadzira sol, iyo inobva yaiswa gelled, yakaomeswa uye yakagochwa.Parizvino, nzira yekugadzirira yealuminium ichiri kuvandudzwa pahwaro hwePB dehydration nzira, uye carbonization nzira yave nzira huru yekugadzirwa kwealuminium yeindasitiri nekuda kwehupfumi hwayo uye kuchengetedza kwezvakatipoteredza.Alumina yakagadzirwa ne-sol-gel nzira yakakwezva pfungwa dzakawanda nekuda kweiyo yakawanda yunifomu pore saizi yekugovera, inova nzira inogona, asi inoda kuvandudzwa kuti iite kushandiswa kwemaindasitiri.
1.2 MA kugadzirira
Yakajairika alumina haigone kusangana nezvinodiwa zvinoshanda, saka zvinodikanwa kugadzirira yepamusoro-inoshanda MA.Nzira dzekubatanidza dzinowanzobatanidza: nano-casting nzira ne carbon mold se template yakaoma;Synthesis yeSDA: Evaporation-induced self-assembly process (EISA) pamberi pezvinyoro zvinyoro zvakadai seSDA uye mamwe cationic, anionic kana nonionic surfactants.
1.2.1 EISA maitiro
Iyo yakapfava template inoshandiswa mune acidic mamiriro, iyo inodzivirira iyo yakaoma uye inopedza nguva maitiro eyakaoma membrane nzira uye inogona kuona inoenderera modulation yeaperture.Kugadzirira kweMA neEISA kwakwezva kutarisisa zvakanyanya nekuda kwekuwanikwa kwayo kuri nyore uye kuberekazve.Yakasiyana mesoporous zvimiro zvinogona kugadzirwa.Iyo pore size ye MA inogona kugadziriswa nekushandura hydrophobic chain urefu hwe surfactant kana kugadzirisa molar ratio ye hydrolysis catalyst kune aluminium precursor in solution.Naizvozvo, EISA, inozivikanwawo seimwe-nhanho synthesis uye kugadziridza sol-gel nzira yepamusoro pepamusoro. nzvimbo MA uye akarayira mesoporous alumina (OMA), yakashandiswa akasiyana-siyana akapfava templates, akadai P123, F127, triethanolamine (tii), etc. EISA anogona kutsiva co-assembly muitiro organoaluminium precursors, akadai aruminiyamu alkoxides uye surfactant templates. , kazhinji aruminiyamu isopropoxide uye P123, yekupa mesoporous zvinhu.Kubudirira kubudirira kweEISA maitiro kunoda kunyatsogadziriswa kwehydrolysis uye condensation kinetics kuwana sol yakagadzikana uye kubvumira kukura kwemesophase kuumbwa ne surfactant micelles mu sol.
Muchirongwa cheEISA, kushandiswa kweasiri-aqueous solvents (senge ethanol) uye organic complexing agents anogona kudzikamisa hydrolysis uye condensation rate ye organoaluminium precursors uye kupesvedzera kuzvibatanidza kweOMA zvinhu, seAl(OR)3and. aluminium isopropoxide.Nekudaro, mune zvisiri-aqueous volatile solvents, surfactant templates kazhinji inorasikirwa ne hydrophilicity / hydrophobicity.Mukuwedzera, Nekuda kwekunonoka kwehydrolysis uye polycondensation, chigadzirwa chepakati chine hydrophobic boka, izvo zvinoita kuti zviome kupindirana nesurfactant template.Chete apo chiyero che surfactant uye dhigirii ye hydrolysis uye polycondensation yealuminium zvishoma nezvishoma inowedzerwa mukuita kwekunyungudika kwekunyungudika ndiko kugona kuzvibatanidza kwetemplate nealuminium kuitika.Naizvozvo, akawanda ma paramita anobata mamiriro evaporation ezvinonyungudutsa uye iyo hydrolysis uye condensation reaction ye precursors, Senge tembiricha, hunyoro hunyoro, catalyst, solvent evaporation rate, nezvimwewo, ichakanganisa yekupedzisira gungano chimiro.Sezvinoratidzwa mufig.1, zvinhu zveOMA zvine kugadzikana kwakanyanya kwekupisa uye kuita kwepamusoro kwekuita kwakagadzirwa nesolvothermal yakabatsira evaporation induced self-assembly (SA-EISA).solvothermal treatment yakasimudzira hydrolysis yakakwana yealuminium precursors kuti iite madiki-sized cluster aluminum hydroxyl mapoka, ayo akawedzera kupindirana pakati pemasurfactants nealuminium.Two-dimensional hexagonal mesophase yakaumbwa muEISA process uye yakaverengerwa pa400 ℃ kuita OMA zvinhu.Muchinyakare EISA maitiro, iyo evaporation process inoperekedzwa neiyo hydrolysis ye organoaluminium precursor, saka mamiriro evaporation ane simba rakakosha pakuita uye chimiro chekupedzisira cheOMA.Iyo solvothermal yekurapa nhanho inosimudzira yakazara hydrolysis yealuminium precursor uye inogadzira chikamu chakanyungudutswa chakabatanidzwa aruminiyamu hydroxyl mapoka.OMA inoumbwa pasi pehuwandu hwakasiyana hwemamiriro evaporation.Kuenzaniswa neMA yakagadzirirwa neyakajairwa EISA nzira, OMA yakagadzirwa neSA-EISA nzira ine yakakwira pore vhoriyamu, iri nani yakananga nzvimbo uye nani kugadzikana kwekupisa.Mune ramangwana, EISA nzira inogona kushandiswa kugadzirira yekupedzisira-yakakura aperture MA ine yakanyanya kutendeuka mwero uye yakanakisa selectivity pasina kushandisa reaming agent.
Fig. 1 inoyerera chati yeSA-EISA nzira yekugadzira OMA zvinhu
1.2.2 mamwe maitiro
Kugadzirira MA kugadzirira kunoda kunyatso kudzora kweiyo synthesis paramita kuti uwane yakajeka mesoporous chimiro, uye kubviswa kwezvinhu zvetemplate kunonetsawo, izvo zvinokanganisa maitiro ekubatanidza.Parizvino, zvinyorwa zvakawanda zvakashuma kusanganiswa kweMA nematemplate akasiyana.Mumakore achangopfuura, tsvakurudzo yainyanya kutarisa kuumbwa kweMA neglucose, sucrose uye starch sema templates nealuminium isopropoxide mune aqueous solution.Zvizhinji zvezvinhu izvi zveMA zvinogadzirwa kubva kualuminium nitrate, sulfate uye alkoxide sealuminium zvinyorwa.MA CTAB inowanikwawo nekugadziriswa kwakananga kwePB sealuminium sosi.MA ine maitiro akasiyana ezvimiro, kureva Al2O3) -1, Al2O3)-2 uye al2o3Uye ine yakanaka kugadzikana kwekupisa.Kuwedzerwa kweiyo surfactant hakuchinji iyo yekuzvarwa crystal chimiro chePB, asi inoshandura iyo stacking modhi yezvimedu.Mukuwedzera, kuumbwa kweAl2O3-3 kunoumbwa nekubatanidzwa kwe nanoparticles yakagadziriswa ne organic solvent PEG kana kuunganidza kwakapoteredza PEG.Nekudaro, iyo pore saizi yekugovera yeAl2O3-1 yakatetepa.Mukuwedzera, palladium-based catalysts yakagadzirirwa nekugadzira MA semutakuri.Mu methane combustion reaction, iyo catalyst inotsigirwa neAl2O3-3 yakaratidza kuita kwakanaka kwekuita.
Kekutanga, MA ine yakatetepa pore saizi yekugovera yakagadziriswa nekushandisa yakachipa uye aruminiyamu-yakapfuma aluminium nhema slag ABD.Maitiro ekugadzira anosanganisira kudhirowa maitiro pakudziya kwakadzika uye kudzvanywa kwakajairika.Zvimedu zvakasimba zvakasiiwa mukuita zvekubvisa hazvisvibise nharaunda, uye zvinogona kuunganidzwa nenjodzi yakaderera kana kushandiswa zvakare sekuzadza kana kuunganidza mukongiri yekushandisa.Iyo chaiyo nzvimbo yeyakaitwa MA i123 ~ 162m2/g, Iyo pore saizi yekugovera idiki, peak radius i5.3nm, uye porosity i0.37 cm3/g.Izvo zvinhu zvine nano-saizi uye saizi yekristaro inenge 11nm.Solid-state synthesis inzira nyowani yekugadzira MA, inogona kushandiswa kugadzira radiochemical inonwisa kuti ishandiswe mukiriniki.Aluminium chloride, ammonium carbonate uye glucose raw materials zvinosanganiswa mu molar ratio ye 1: 1.5: 1.5, uye MA inogadzirwa nehutsva hwakasimba-state mechanochemical reaction.Nekuisa pfungwa pa131I mumidziyo yebhatiri inopisa, goho rose re131I mushure mekugadzirisa ndeye 90. %.
Kupfupisa, mune ramangwana, madiki mamorekuru matemplate anogona zvakare kugadzirwa kuti agadzire akawanda-level akarairwa pore zvimiro, zvinobudirira kugadzirisa chimiro, morphology uye pamusoro pemakemikari zvimiro zvezvinhu, uye kugadzira hombe yepamusoro nzvimbo uye yakaraira wormhole MA.Ongorora zvakachipa matemplate uye aruminiyamu masosi, shongedza iyo synthesis maitiro, jekesa iyo synthesis michina uye tungamira maitiro.
Kushandura nzira ye2 MA
Nzira dzekugovera zvakafanana zvikamu zvinoshanda paMA mutakuri anosanganisira kusamira, in-situ synthe-sis, kunaya kwemvura, ion exchange, mechanical mixing uye kunyunguduka, pakati payo maviri ekutanga ndiwo anonyanya kushandiswa.
2.1 in-situ synthesis nzira
Mapoka anoshandiswa mukugadzirisa kwekushanda anowedzerwa mukugadzirisa MA kugadzirisa uye kudzikamisa skeleton chimiro chezvinyorwa uye kunatsiridza mashandiro anoita.Iyo nzira inoratidzwa muMufananidzo 2. Liu et al.synthesized Ni/Mo-Al2O3in situ ine P123 setemplate.Vese Ni naMo vakaparadzirwa mune akarairwa MA chiteshi, pasina kuparadza iyo mesoporous chimiro cheMA, uye kuita kwekuita kwakagadziridzwa pachena.Kutora in-situ yekukura nzira payakagadzirwa gamma-al2o3substrate,Kuenzaniswa neγ-Al2O3, MnO2-Al2O3ine yakakura BET yakananga nzvimbo uye pore vhoriyamu, uye ine bimodal mesoporous chimiro chine nhete pore saizi yekugovera.MnO2-Al2O3 ine kukurumidza adsorption chiyero uye kushanda kwakanyanya kweF-, uye ine yakafara pH application renji (pH = 4 ~ 10), iyo inokodzera anoshanda maindasitiri ekushandisa.Iko kudzokorodza kuita kweMnO2-Al2O3 kuri nani pane kuya kweγ-Al2O.Kugadzikana kweStructural kunoda kuwedzeredzwa.Kupfupisa, iyo MA yakagadziridzwa zvinhu zvakawanikwa ne-situ synthesis zvine kurongeka kwakanaka, kudyidzana kwakasimba pakati pemapoka uye vatakuri vealuminium, musanganiswa wakaoma, mutoro mukuru wezvinhu, uye hazvisi nyore kukonzeresa kudururwa kwezvinhu zvinoshanda mukugadzirisa maitiro. , uye iyo catalytic performance inovandudzwa zvakanyanya.
Fig. 2 Kugadzirira kwekushanda MA ne-in-situ synthesis
2.2 nzira yekudzivirira
Kunyudza iyo MA yakagadzirirwa muboka rakagadziridzwa, uye nekuwana yakagadziridzwa MA zvinhu mushure mekurapwa, kuitira kuti uone mhedzisiro yecatalysis, adsorption nezvimwe zvakadaro.Cai et al.yakagadzirirwa MA kubva kuP123 ne-sol-gel nzira, uye yakanyura mu ethanol uye tetraethylenepentamine mhinduro kuti iwane amino yakagadziridzwa MA zvinhu zvine simba adsorption performance.Mukuwedzera, Belkacemi et al.yakanyikwa muZnCl2solution nenzira imwechete kuti uwane yakaodha zinc doped yakagadziridzwa MA zvinhu. Iyo chaiyo nzvimbo uye pore volume ndeye 394m2/g uye 0.55 cm3/g, zvichiteerana.Kana ichienzaniswa neye in-situ synthesis nzira, nzira yekumirisa ine zvirinani kuparadzira, yakagadzikana mesoporous chimiro uye yakanaka adsorption kuita, asi simba rekudyidzana pakati pezvinhu zvinoshanda uye mutakuri wealuminium harina simba, uye chiitiko chinokonzeresa chinokanganiswa zviri nyore nezvinhu zvekunze.
3 kufambira mberi kwebasa
Iyo synthesis yerare Earth MA ine yakakosha zvivakwa ndiyo maitiro ekusimudzira mune ramangwana.Parizvino, kune nzira dzakawanda dze synthesis.Iyo maitiro paramita anokanganisa mashandiro eMA.Iyo chaiyo nzvimbo, pore vhoriyamu uye pore dhayamita yeMA inogona kugadziriswa nemhando yetemplate uye aluminium precursor kuumbwa.Iyo tembiricha yecalcination uye polymer template concentration inokanganisa chaiyo nzvimbo uye pore vhoriyamu yeMA.Suzuki uye Yamauchi vakawana kuti kutonhora kwecalcination kwakawedzera kubva ku500 ℃ kusvika ku900 ℃. Iyo aperture inogona kuwedzerwa uye nzvimbo yepamusoro inogona kuderedzwa.Uye zvakare, iyo isingawanzo kugadziridzwa kwepasi kurapwa inovandudza chiitiko, pamusoro pekushisa kugadzikana, kugadzikana kwechimiro uye acidity yepasi yezvinhu zveMA mune catalytic process, uye inosangana nekuvandudzwa kweMA functionalization.
3.1 Defluorination Adsorbent
Iyo fluorine mumvura yekunwa muChina inokuvadza zvakanyanya.Pamusoro pezvo, kuwedzera kweiyo fluorine muindasitiri zinc sulfate mhinduro inotungamira mukuora kwe electrode plate, kushata kwenzvimbo yekushanda, kudzikira kwemhando yezinc yemagetsi uye kudzikira kwehuwandu hwemvura inodzokororwa mugadziriro yekugadzira acid. uye electrolysis muitiro we fluidized bed choto kugocha flue gasi.Parizvino, nzira yeadsorption ndiyo inonyanya kunakidza pakati pemaitiro akajairika ekunyorova defluorination.Zvisinei, pane zvimwe zvikanganiso, zvakadai sekushaya adsorption simba, nhete inowanikwa pH range, kusvibiswa kwechipiri nezvimwe zvakadaro.Activated kabhoni, amorphous alumina, activated alumina uye mamwe adsorbents akashandiswa defluorination yemvura, asi mutengo adsorbents wakakwira, uye adsorption simba reF-in neutral solution kana high concentration yakaderera.Activated alumina yava yakanyanya kupararira. yakadzidza adsorbent yekubvisa fluoride nekuda kwehukama hwayo hwepamusoro uye kusarudzwa kune fluoride payakarerekera pH kukosha, asi inoganhurwa neiyo yakashata adsorption kugona kwefluoride, uye chete papH <6 inogona kuve yakanaka fluoride adsorption performance.MA yakakwezva kutarisisa kwakakura. mukudzora kusvibiswa kwezvakatipoteredza nekuda kwenzvimbo yayo yakakura chaiyo, yakasarudzika pore saizi maitiro, acid-base performance, thermal uye mechanical kugadzikana.Kundu et al.yakagadzirirwa MA ine huwandu hwefluorine adsorption huwandu hwe62.5 mg/g.Iyo fluorine adsorption capacity yeMA inopesvedzerwa zvakanyanya neayo maitiro ezvimiro, akadai seakananga nzvimbo, pamusoro peanoshanda mapoka, pore saizi uye yakazara pore saizi.Kugadziriswa kwemaitiro uye kushanda kweMA inzira yakakosha yekuvandudza kwayo adsorption performance.
Nekuda kweiyo yakaoma asidhi yeLa uye iyo yakaoma basicity yefluorine, pane hukama hwakasimba pakati peLa uye fluorine ions.Mumakore achangopfuura, zvimwe zvidzidzo zvakawana kuti La semugadziriso anogona kuvandudza adsorption kugona kwefluoride.Nekudaro, nekuda kwekudzikama kwakadzikama kweasingawanzo pasi adsorbents, nyika zhinji isingawanzo nyuchirwa mumhinduro, zvichikonzera kusvibiswa kwechipiri kwemvura uye kukuvadza hutano hwevanhu.Nekune rimwe divi, Kukwirisa aluminium munzvimbo yemvura ndeimwe yehupfu kuhutano hwevanhu.Naizvozvo, zvinodikanwa kugadzirira rudzi rwecomposite adsorbent nekugadzikana kwakanaka uye pasina leaching kana kushoma leaching yezvimwe zvinhu mu fluorine kubvisa maitiro.MA yakagadziridzwa naLa uye Ce yakagadziridzwa neiyo impregnation nzira (La/MA uye Ce/MA).zvisingawanzoitiki pasi oxides zvakabudirira kutakurwa paMA pamusoro pekutanga, iyo yaive nepamusoro defluorination performance.Nzira huru dzekubvisa fluorine ndeye electrostatic adsorption uye chemikemikari adsorption, iyo electron inokwezva yepasi yakanaka charge uye ligand exchange reaction inosanganiswa nepamusoro hydroxyl, iyo hydroxyl inoshanda boka pane adsorbent pamusoro inogadzira hydrogen bond neF-, kugadziridzwa kweLa neCe kunovandudza adsorption kugona kwefluorine, La/MA ine mamwe hydroxyl adsorption nzvimbo, uye adsorption yeF iri muhurongwa hweLa/MA. >Ce/MA>MA.Nekuwedzera kwekutanga kusungirirwa, iyo adsorption kugona yefluorine inowedzera.Iyo adsorption mhedzisiro yakanakisa kana pH iri 5 ~ 9, uye adsorption process yefluorine inowirirana neLangmuir isothermal adsorption modhi.Mukuwedzera, kusvibiswa kwe sulfate ions mu alumina kunogonawo kukanganisa zvakanyanya kunaka kwemasampuli.Kunyangwe tsvagiridzo yakabatana pamusoro pepasi isingawanzo gadziriso alumina yakaitwa, mazhinji ekutsvagisa anotarisa pakuita kwe adsorbent, iyo yakaoma kushandiswa mumaindasitiri. Mune ramangwana, tinogona kudzidza nzira yekuparadzanisa yefluorine yakaoma mu zinc sulfate solution. uye hunhu hwekufamba kweiyo fluorine ion, kuwana inoshanda, yakaderera-inodhura uye inogona kudzokororwa fluorine ion adsorbent ye defluorination ye zinc sulfate mhinduro mu zinc hydrometallurgy system, uye kumisikidza maitiro ekudzora maitiro ekurapa yakakwirira fluorine mhinduro yakavakirwa isingawanzo pasi MA nano adsorbent.
3.2 Catalyst
3.2.1 Dry reforming ye methane
Rare Earth inogona kugadzirisa acidity (basicity) yezvinhu zvinoputika, kuwedzera oxygen vacancy, uye synthesis catalysts neuniform dispersion, nanometer scale uye kugadzikana.Inowanzo shandiswa kutsigira simbi dzakanaka uye shanduko yesimbi yekukonzeresa methanation ye CO2.Parizvino, ivhu risingawanzo gadziridzwa mesoporous zvinhu zviri kusimukira kune methane dry reforming (MDR), photocatalytic degradation yeVOCs uye miswe gasi kucheneswa. Zvichienzaniswa nesimbi dzakanaka (sePd, Ru, Rh, etc.) uye mamwe masimbi ekuchinja (akadai se Co, Fe, nezvimwewo), Ni/Al2O3catalyst inoshandiswa zvakanyanya pakuita kwayo kwepamusoro kwekuita uye kusarudza, kugadzikana kwakanyanya uye mutengo wakaderera wemethane.Nekudaro, iyo sintering uye kabhoni deposition yeNi nanoparticles pamusoro peNi / Al2O3 inotungamira kukurumidza kudzima kweiyo catalyst.Naizvozvo, zvinodikanwa kuti uwedzere kukurumidza, shandura catalyst mutakuri uye kugadzirisa nzira yekugadzirira kuvandudza catalytic chiitiko, kugadzikana uye kupisa kuramba.Kazhinji, zvisingawanzo pasi oxides zvinogona kushandiswa sezvimiro uye zvemagetsi zvinosimudzira mune heterogeneous catalysts, uye CeO2 inovandudza kupararira kweNi uye inoshandura zvimiro zvesimbi Ni kuburikidza nesimbi yakasimba tsigiro yekudyidzana.
MA inoshandiswa zvakanyanya kuwedzera kupararira kwesimbi, uye inopa kuzvidzora kune inoshanda simbi kudzivirira kuungana kwavo.La2O3 ine yakakwira okisijeni yekuchengetedza inosimudzira iyo kabhoni kuramba mukutendeuka, uye La2O3 inosimudzira kupararira kweCo pamesoporous alumina, iyo ine yakanyanya kugadzirisa chiitiko uye kusimba.La2O3promoter inowedzera basa reMDR reCo/MA catalyst, uye Co3O4and CoAl2O4phases inoumbwa pane catalyst surface.Zvisinei, La2O3 yakapararira zvikuru ine zviyo zviduku zve8nm ~ 10nm.Muchirongwa cheMDR, kupindirana kwe-in-situ pakati peLa2O3 neCO2formed La2O2CO3mesophase, iyo yakakonzera kubviswa kunobudirira kweCxHy panzvimbo inokonzeresa.La2O3 inosimudzira kudzikiswa kwehaidhirojeni nekupa huwandu hwemaerekitironi yepamusoro uye kuwedzera nzvimbo yeokisijeni mu10% Co/MA.Kuwedzerwa kweLa2O3 kunoderedza iyo inooneka activation simba yeCH4consumption.Nokudaro, kutendeuka kweCH4 kwakawedzera kusvika ku93.7% pa1073K K. Kuwedzerwa kweLa2O3 kwakavandudza basa rekugadzirisa, kwakakurudzira kuderedzwa kweH2, kwakawedzera nhamba yeCo0 inoshanda nzvimbo, yakabudisa kabhoni shoma shoma uye yakawedzera nzvimbo yeokisijeni kusvika 73.3%.
Ce naPr vakatsigirwa paNi/Al2O3catalyst nenzira yakaenzana yevhoriyamu yekumisa muLi Xiaofeng.Mushure mekuwedzera Ce uye Pr, kusarudza kuH2 kwakawedzera uye kusarudza kuCO kwakadzikira.Iyo MDR yakagadziridzwa naPr yaive yakanakisa catalytic kugona, uye kusarudza kuH2 kwakawedzera kubva ku64.5% kusvika 75.6%, nepo kusarudzwa kuCO kwakaderera kubva ku31.4% Peng Shujing et al.yakashandiswa sol-gel nzira, Ce-modified MA yakagadzirwa nealuminium isopropoxide, isopropanol solvent uye cerium nitrate hexahydrate.Iyo chaiyo nzvimbo yechigadzirwa yakawedzera zvishoma.Kuwedzerwa kweCe kwakaderedza kuunganidzwa kwetsvimbo-yakafanana nanoparticles pane MA pamusoro.Mamwe mapoka e-hydroxyl pamusoro pe-γ- Al2O3 ainyatsofukidzwa neCe makomponi.Kugadzikana kwekupisa kweMA kwakagadziridzwa, uye hapana crystal phase shanduko yakaitika mushure mecalcination pa 1000 ℃ kwemaawa 10. Wang Baowei et al.yakagadzirirwa MA zvinhu CeO2-Al2O4by coprecipitation nzira.CeO2ine cubic zviyo zvidiki zvakaparadzirwa zvakafanana mualuminium.Mushure mekutsigira Co naMo paCeO2-Al2O4, kudyidzana pakati pealumina uye inoshanda chikamu Co naMo kwakanyatso kudziviswa neCEO2.
Iwo asingawanzo kusimudzira pasi (La, Ce, y uye Sm) akasanganiswa neCo/MA catalyst yeMDR, uye maitiro anoratidzwa mufig.3. iyo isingawanzo kusimudzira pasi inogona kuvandudza kupararira kweCo paMA mutakuri uye inhibit agglomeration ye co particles.diki diki saizi yechikamu, kusimba kwekubatana kweCo-MA, kusimba kwekugona uye kugona muYCo/MA catalyst, uye nemhedzisiro yevazhinji vanosimudzira pane MDR chiitiko uye kabhoni deposition.Fig.4 iHRTEM iMage mushure mekurapa kweMDR pa1023K, Co2: ch4: N2 = 1 ∶ 1 ∶ 3.1 kwemaawa masere.Co particles aripo muchimiro chemavara matema, nepo MA vatakuri varipo muchimiro chegrey, zvinoenderana nemusiyano wemagetsi density.mumufananidzo weHRTEM une 10% Co/MA (fig. 4b), iyo agglomeration yeCo metal particles inoonekwa pane ma carriersKuwedzerwa kwepasi risingawanzosimudziri kunoderedza Co particles kusvika 11.0nm ~ 12.5nm.YCo/MA ine kuwirirana kwakasimba kweCo-MA, uye kuita kwayo sintering kuri nani pane zvimwe zvinokonzeresa.kuwedzera, sezvinoratidzwa mumaonde.4b kusvika 4f, hollow carbon nanowires (CNF) inogadzirwa pane zvinogadzirisa, izvo zvinoramba zvichisangana nekuyerera kwegasi uye kudzivirira iyo catalyst kubva pakudzima.
Fig. 3 Mhedzisiro yeisingawanzo kuwedzera kwepasi pane zvemuviri nemakemikari zvivakwa uye MDR inokonzeresa kuita kweCo/MA catalyst.
3.2.2 Deoxidation catalyst
Fe2O3/Meso-CeAl, Ce-doped Fe-based deoxidation catalyst, yakagadzirwa neoxidative dehydrogenation ye1-butene ine CO2as soft oxidant, uye yakashandiswa mukugadzirwa kwe1,3-butadiene (BD).Ce yakaparadzirwa zvakanyanya mualuminium matrix, uye Fe2O3/meso yakaparadzirwa zvakanyanyaFe2O3/Meso-CeAl-100 catalyst haina kungova nemhando dzesimbi dzakapararira kwazvo uye zvimiro zvakanaka zvechimiro, asiwo ine yakanaka yekuchengetedza okisijeni, saka ine yakanaka adsorption uye activation kugona. ye CO2.Sezvinoratidzwa muMufananidzo 5, mifananidzo yeTEM inoratidza kuti Fe2O3/Meso-CeAl-100 iri nguva dzoseInoratidza kuti iyo honye-yakaita senge chiteshi chimiro cheMesoCeAl-100 yakasununguka uye ine porous, iyo inobatsira kupararira kwezvinhu zvinoshanda, nepo zvakanyanya kupararira Ce. inobudirira doped mu alumina matrix.Iyo yakanakisa simbi inokonzeresa yekubatisa zvinhu inosangana neyekupedzisira-yakaderera emission standard yemota mota yakagadzira pore chimiro, yakanaka hydrothermal kugadzikana uye hombe yekuchengetedza okisijeni.
3.2.3 Catalyst yeMotokari
Pd-Rh yakatsigira quaternary aluminium-based rare earth complexes AlCeZrTiOx uye AlLaZrTiOx kuti iwane zvigadziriso zvekuputira zvemotokari.mesoporous aluminium-based rare earth complex Pd-Rh/ALC inogona kushandiswa zvinobudirira seCNG motokari inopedza tsvina yekuchenesa catalyst nekugara kwakanaka, uye kutendeuka kwekushanda kweCH4, chikamu chikuru cheCNG motokari yekupedza gasi, yakakwirira se97.8%.Gamuchira hydrotherMAl imwe-nhanho nzira yekugadzirira iyo isingawanzo pasi ma composite zvinhu kuti uzvione-wega, Yakarairwa mesoporous precursors ine metastable mamiriro uye yakakwirira aggregation akagadzirwa, uye synthesis yeRE-Al inoenderana nemuenzaniso we "compound growth unit" , nokudaro nekuona kucheneswa kwemotokari exhaust post-yakaiswa matatu-nzira catalytic converter.
Fig. 4 HRTEM mifananidzo yema (a), Co/ MA(b), LaCo/MA(c), CeCo/MA(d), YCo/MA(e) uye SmCo/MA(f)
Mufananidzo 5 TEM mufananidzo (A) uye EDS element diagram (b,c) yeFe2O3/Meso-CeAl-100
3.3 inopenya kuita
Maerekitironi ezvisingawanzo zvinhu zvepasi anonakidzwa zviri nyore kuchinjika pakati pesimba rakasiyana siyana uye anoburitsa chiedza.Mayoni epasi asingawanzo anowanzo shandiswa seanomisikidza kugadzira luminescent zvinhu.Rare Earth ions inogona kutakurwa pamusoro pealuminium phosphate hollow microspheres necoprecipitation nzira uye ion exchange nzira, uye luminescent zvinhu AlPO4∶RE(La,Ce,Pr,Nd) inogona kugadzirwa.Iyo luminescent wavelength iri pedyo ne ultraviolet region.MA inogadzirwa kuita mafirimu matete nekuda kwe inertia yayo, yakaderera dielectric inogara uye yakaderera conductivity, iyo inoita kuti ishande kune magetsi uye optical zvishandiso, matete mafirimu, zvipingamupinyi, sensors, nezvimwe. Inogonawo zvakare. inoshandiswa pakunzwa mhinduro one-dimensional photonic crystals, kugadzirwa kwesimba uye anti-reflection coatings.Midziyo iyi yakarongedzerwa mafirimu ane hurefu hwakajeka hwenzira, saka zvakafanira kudzora refractive index uye ukobvu.Parizvino, titanium dioxide uye zirconium oxide ine high refractive index uye silicon dioxide ine low refractive index inowanzoshandiswa kugadzira nekuvaka michina yakadaro. .Kuwanikwa kwemhando yezvigadzirwa zvine akasiyana epamusoro emakemikari ehupfumi anowedzerwa, izvo zvinoita kuti zvikwanise kugadzira advanced photon sensors.Kuiswa kwemafirimu eMA uye oxyhydroxide mukugadzirwa kwezvigadzirwa zvemaziso zvinoratidza kukwanisa kukuru nokuti refractive index yakafanana nesilicon dioxide.Asi makemikari emakemikari akasiyana.
3.4 kugadzikana kwekupisa
Nekuwedzera kwekushisa, sintering inokanganisa zvakanyanya kushandiswa kweMA catalyst, uye nzvimbo chaiyo inoderera uye γ-Al2O3in crystalline phase inoshandura kuva δ uye θ kusvika χ zvikamu.Zvishandiso zvepasi zvisingawanzo zvine kugadzikana kwakanaka kwemakemikari uye kugadzikana kwekupisa, kuchinjika kwakanyanya, uye kuwanikwa nyore uye zvakachipa zvigadzirwa.Kuwedzerwa kwezvinhu zvisingawanzoitiki zvepasi zvinogona kuvandudza kugadzikana kwekupisa, kupisa kwepamusoro oxidation kuramba uye mechanical properties yemutakuri, uye kugadzirisa pasi acidity yemutakuri.La uye Ce ndiyo inonyanya kushandiswa uye yakadzidza kugadzirisa zvinhu.Lu Weiguang nevamwe vakaona kuti kuwedzera kwezvinhu zvisingawanzo pasi pasi zvakadzivirira kupararira kukuru kwealumina particles, La neCe vakadzivirira mapoka ehydroxyl pamusoro pealuminium, inhibited sintering uye shanduko yechikamu, uye yakaderedza kukuvadzwa kwekushisa kwepamusoro kune mesoporous chimiro. .Iyo alumina yakagadzirwa ichine yakakwirira chaiyo nzvimbo uye pore vhoriyamu.Zvisinei, yakawandisa kana yakawandisa isingawanzo yepasi chinhu chinoderedza kugadzikana kwekupisa kwealuminium.Li Yanqiu et al.yakawedzera 5% La2O3to γ-Al2O3, iyo yakavandudza kugadzikana kwekupisa uye yakawedzera vhoriyamu yepore uye chaiyo nzvimbo yealumina mutakuri.Sezvinoonekwa kubva kuMufananidzo 6, La2O3 yakawedzerwa kuγ-Al2O3, Kuvandudza kugadzikana kwekupisa kweiyo isingawanzo pasi inoumbwa inotakura.
Mukuita doping nano-fibrous particles neLa kusvika MA, iyo BET pamusoro nzvimbo uye pore vhoriyamu yeMA-La yakakwirira kupfuura iya yeMA kana tembiricha yekurapa kupisa ichiwedzera, uye doping neLa ine mhedzisiro yekudzoreredza pakunyura pakakwirira. tembiricha.sezvaratidzwa muonde.7, nekuwedzera kwekushisa, La inhibits maitiro ekukura kwezviyo uye shanduko yechikamu, nepo maonde.7a uye 7c inoratidza kuunganidzwa kwe nano-fibrous particles.mumuonde.7b, iyo dhayamita yezvimedu zvakakura zvinogadzirwa necalcination pa 1200 ℃ inenge 100nm.Inoratidza kukosha kwakakosha kweMA.Mukuwedzera, kana ichienzaniswa neMA-1200, MA-La-1200 haina kuunganidza mushure mekupisa kurapwa.Nekuwedzera kweLa, nano-fiber zvimedu zvine zvirinani sintering kugona.kunyangwe pakakwirira calcination tembiricha, doped La ichiri yakaparadzirwa zvakanyanya pamusoro MA pamusoro.La yakagadziridzwa MA inogona kushandiswa semutakuri wePd catalyst muC3H8oxidation reaction.
Fig. 6 Chimiro modhi ye sintering alumina ine uye isina zvisingawanzo zvinhu zvepasi
Mufananidzo 7 TEM mifananidzo yeMA-400 (a), MA-1200(b), MA-La-400(c) uye MA-La-1200(d)
4 Mhedziso
Kufambira mberi kwekugadzirira uye kushandiswa kwekushanda kwezvinhu zvisingawanzo pasi zvakagadziridzwa MA zvinhu zvinounzwa.Rare Earth modified MA inoshandiswa zvakanyanya.Kunyangwe kutsvagisa kwakawanda kwakaitwa mucatalytic application, kugadzikana kwemafuta uye adsorption, zvinhu zvakawanda zvine mutengo wakakwira, yakaderera doping huwandu, kurongeka kwakashata uye zvakaoma kuve maindasitiri.Iri rinotevera basa rinofanirwa kuitwa mune ramangwana: gadzirisa kuumbwa uye chimiro chepasi isingawanzo yakagadziridzwa MA, sarudza iyo yakakodzera maitiro, Sangana nekuvandudzwa kwebasa;Gadzira maitiro ekudzora modhi yakavakirwa pane inoshanda maitiro ekudzikisa mutengo uye kuona kugadzirwa kwemaindasitiri;Kuti tiwedzere mabhenefiti ezviwanikwa zvepasi zveChina zvisingawanzo, isu tinofanirwa kuongorora magadzirirwo erare Earth MA gadziriso, kuvandudza dzidziso uye maitiro ekugadzirira isingawanzo pasi yakagadziridzwa MA.
Fund Project: Shaanxi Science and Technology Overall Innovation Project (2011KTDZ01-04-01);Purovhinzi yeShaanxi 2019 Special Scientific Research Project (19JK0490);2020 yakakosha tsvagiridzo yesainzi chirongwa cheHuaqing College, Xi 'an University of Architecture uye Technology (20KY02)
Kwakabva: Rare Earth
Nguva yekutumira: Jul-04-2022