Superacid‐Catalyzed Oxygenation of Alkanes. [New synthetic methods (26)]

Olah, G. A.; Parker, David G.; Yoneda, Norihiko

doi:10.1002/anie.197809091

Cited by 77 publications

(34 citation statements)

References 88 publications

(1 reference statement)

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“…The reason is that the insertion of incipient " + OH" derived from H 3 O 2 + (protonated hydrogen peroxide) into a methane C-H bond via electrophilic oxygenation results in methanol in its protonated form, CH 3 OH 2 + , protecting it from thermodynamically favored further oxidation and accounting for the observed high selectivity. 70,71 Using hydrogen peroxide in superacids is, however, not suited for practical applications. When triflic acid was used as a superacid, methyl triflate was formed, protecting methanol from further oxidation.…”

mentioning

confidence: 98%

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

et al. 2015

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Catalysts based on suitable metal oxide supports, such as NiO/MgO and CoO/MgO, were shown to be active for single step bi-reforming, the combined steam and dry reforming of methane or natural gas with H2O and CO2 exclusively to metgas (CO-2H2) for efficient methanol synthesis. Reactions were carried out in a tubular flow reactor under pressures up to 42 bar at 830-910 °C. Using a CH4 to steam to CO2 ratio of ∼3:2:1 in the gas feed, the H2/CO ratio of 2:1 was achieved, which is desired for subsequent methanol synthesis. The needed 2/1 steam/CO2 feed ratio together with the reaction heat for the endothermic bi-reforming can be conveniently obtained by the complete combustion of a quarter part of the overall used methane (natural gas) with oxygen of the air (oxidative bi-reforming). Complete combustion of a part of methane followed by bi-reforming leads to the production of metgas (H2/CO in 2:1 mol ratio) for self-sufficient exclusive methanol synthesis. The long sought after but elusive efficient and selective oxygenation of methane to methanol is thus achieved in an effective and economic way without any oxidation byproduct formation according to CH4 + 1/2O2 → CH3OH.

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confidence: 98%

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

et al. 2015

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“…Neki od prvih postupaka aktivacije upotrebljavali su kao katalizatore organometalne sustave, [3][4][5][6] metalne ione u plinovitom stanju 7,8 i biokemijske sustave, 9 pri čemu se aktivacija metana može provesti heterogenom, [10][11][12] ili homogenom katalizom. 13,14 Metode izravne pretvorbe dijele se na oksidacijske i neoksidacijske, ovisno o prisutnosti oksidansa. U neoksidacijske metode spadaju spajanje metana u više ugljikovodike (engl.…”

Section: Izravna Pretvorba Metanaunclassified

Novi petrokemijski procesi na temelju izravne pretvorbe metana

Faraguna

Jukić

2015

Kem. Ind.

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Zavod za tehnologiju nafte i petrokemiju Fakultet kemijskog inženjerstva i tehnologije Sveučilišta u Zagrebu Marulićev trg 19, 10 000 Zagreb Sažetak Petrokemija je grana kemije i kemijskog inženjerstva koja proučava reakcije i procese dobivanja i svojstva proizvoda iz naftnih prerađevina i prirodnoga plina, a koji ne služe kao goriva ili maziva. U svojim početcima petrokemija, odnosno organska kemijska industrija, temeljila se na etinu i Reppeovim sintezama. Danas su osnovne petrokemikalije olefini i aromatski ugljikovodici, s težnjom razvoja novih procesa i sve veće uporabe sinteznog plina, metana i drugih alkana kao ishodnih sirovinskih komponenti. U ovom radu dan je pregled reakcija i novih procesa izravne pretvorbe metana u vrjednije petrokemijske proizvode. Kroz pojedina poglavlja u radu su detaljnije opisane reakcije parcijalne oksidacije metana, dehidroaromatizacije metana te oksidacijskog i neoksidacijskog spajanja metana u više ugljikovodike. Ključne riječi 28F. FARAGUNA i A. JUKIĆ: Novi petrokemijski procesi na temelju izravne pretvorbe metana, Kem. Ind. 64 (1-2) (2015) 27−37 iskoristi, teži se proizvodnji vrjednijih kemikalija na samom nalazištu.Metan je simetrična i stabilna molekula kojoj treba dovesti energiju da bi došlo do pucanja stabilne C−H veze (435 kJ mol −1 ) i daljnje reakcije za dobivanje željenog produkta. S obzirom na način dovođenja energije, reakcijski put može biti izravna (slika 1) i neizravna (slika 2) pretvorba metana u petrokemijske proizvode.Izravna pretvorba metana obuhvaća sljedeće reakcije: parcijalnu oksidaciju metana u metanol ili formaldehid, dehidroaromatizaciju metana u aromatske ugljikovodike (aromate) te oksidacijsko i neoksidacijsko spajanje metana u više ugljikovodike. Dobiveni petrokemijski proizvodi mogu se dalje prevesti u benzin, katalitičkim procesima pretvorbe metanola (engl. Methanol to Gasoline, MTG) i olefinskom oligomerizacijom viših ugljikovodika.Kod neizravne pretvorbe metana najprije se iz metana parnim reformiranjem proizvodi sintezni plin, smjesa CO i H 2 , koji je osnova za daljnju sintezu petrokemijskih proizvoda. Iz sinteznog plina Fischer-Tropschovom sintezom mogu se proizvesti alkani (parafini) i benzin, dimetil-eter, selektivnom sintezom olefini, selektivnom hidrogenacijom i oksosintezom viši alkoholi i karboksilne kiseline te metanol. Iz navedenih primarnih petrokemijskih proizvoda daljnjim reakcijama prema slici 2 mogu se proizvesti benzin i olefini iz metanola i dimetil-etera, dok se hidrokrekiranjem i hidroizomerizacijom iz parafina proizvodi benzin. Viši alkoholi i kiseline proizvode se iz metanola. Izravna pretvorba metanaRazvoj postupaka izravne pretvorbe metana od velikog je interesa jer bi se za dobivanje korisnih petrokemijskih proizvoda navedenim postupcima izbjegla uporaba energetski zahtjevnog procesa parnog reformiranja. Također bi se smanjila potreba za proizvodnjom olefina procesima parnog i katalitičkog krekiranja. Metan je kao stabilnu molekulu nepolarnog karaktera i bez funkcijskih skupina teško destabilizirati i potaknuti na ...

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“…Later on an original chemical approach in superacidic media was applied that could cause dramatic changes in the skeleton of these complex molecules. Superacids are able to protect functional groups by protonation and can induce modifications at non-activated bonds [11]. Via this approach a new family of fluorinated bisindoles were synthesized [12] from which vinflunine (20', 20'-difluoro-3',4'-dihydrovinorelbine) cf.…”

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confidence: 99%

New Anti-Mitotic Drugs with Distinct Anti-Calmodulin Activity

Orosz¹,

Horváth²,

Ovádi³

2006

MRMC

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Bisindole Vinca alkaloids target microtubule system causing anti-mitotic activity. The problem of their clinical application is the lack of selectivity resulting in toxic side effects. In this paper we review the late history of new bisindole derivatives focusing on KARs recognized as potent anti-cancer drugs with low side effect. KARs, just as other bisindoles, impede microtubule assembly of mitotic spindle, however, they display no anti-calmodulin activity. This new drug family appears to be less potent than vinblastine in vitro systems, but it shows high antitumor efficacy with considerably higher doses being well tolerated in the animal tumor models. 3D data of calmodulin complexed with KAR-2 explain the specificity and unique pharmacology of KAR derivatives.

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Superacid‐Catalyzed Oxygenation of Alkanes. [New synthetic methods (26)]

Cited by 77 publications

References 88 publications

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

Novi petrokemijski procesi na temelju izravne pretvorbe metana

New Anti-Mitotic Drugs with Distinct Anti-Calmodulin Activity

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Superacid‐Catalyzed Oxygenation of Alkanes. [New synthetic methods (26)]

Cited by 77 publications

References 88 publications

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H2) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H2) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

Novi petrokemijski procesi na temelju izravne pretvorbe metana

New Anti-Mitotic Drugs with Distinct Anti-Calmodulin Activity

Contact Info

Product

Resources

About

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H₂) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen