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Supercritical alkylation

One example of normal-phase liquid chromatography coupled to gas chromatography is the determination of alkylated, oxygenated and nitrated polycyclic aromatic compounds (PACs) in urban air particulate extracts (97). Since such extracts are very complex, LC-GC is the best possible separation technique. A quartz microfibre filter retains the particulate material and supercritical fluid extraction (SPE) with CO2 and a toluene modifier extracts the organic components from the dust particles. The final extract is then dissolved in -hexane and analysed by NPLC. The transfer at 100 p.1 min of different fractions to the GC system by an on-column interface enabled many PACs to be detected by an ion-trap detector. A flame ionization detector (PID) and a 350 p.1 loop interface was used to quantify the identified compounds. The experimental conditions employed are shown in Table 13.2. [Pg.362]

The tuning of solubility with a relatively small jump or fall in pressure can possibly bestow many benefits with respect to rates, yields, and selectivity. Reaction parameters can be changed over a wide range. Replacement of solvents with high boiling points by supercritical (SC) fluids offers distinct advantages with respect to removal of the solvent. SC fluids like CO2 are cheap and environmentally friendly the critical temperature of CO2 is 31 C and the critical pressure 73.8 atm (Poliakoff and Howdle, 1995). Eckert and Chandler (1998) have given many examples of the use of SC fluids. Alkylation of phenol with tcrt-butanol in near critical water at 275 °C allows 2- erf-butyl phenol to be formed (a major product when the reaction is kinetically controlled 4-rert-butyl phenol is the major product, when the reaction is... [Pg.172]

The catalyst can be treated with a solvent to extract hydrocarbon deposits. The most straightforward solvent to use is isobutane, which has been shown to restore catalytic activity only partially. Supercritical solvents have been tested, but they also lead to only partial restoration of the activity. Supercritical alkylation to remove the deposits in situ has been shown in Section III.D.l to be less effective. It is unlikely that this method of operation will lead to a competitive process. [Pg.306]

P. G. Jessop, Y. Hsiao, T. Ikariya, R. Noyori, Homogeneous Catalysis in Supercritical Fluids Hydrogenation of Supercritical Carbon Dioxide to Formic Acid, Alkyl Formates, and Formamides ,J. Am Chem Soc 1996,118, 344-355. [Pg.25]

S. Hadida, M. S. Super, E. J. Beckman, D. P. Curran, Radical Reactions with Alkyl and Fluoroalkyl (Fluorous) Tin Hybride Reagents in Supercritical C02 , J. Am. Chem. Soc 1997,119,7406. [Pg.37]

Non-ionic surfactants of a commercial washing powder were separated by supercritical fluid chromatography (SFC) and determined by APCI-MS. The constituents were first extracted by supercritical fluid extraction (SFE) using C02 with or without methanol as a modifier. Variations of the conditions resulted in a selective extraction of the analytes, which could be determined without further purification. Six groups of surfactants were observed, four of which are alkyl-polyethoxylates. The presence of APEO could be excluded by identification recording SFC-FTIR (Fourier transform infrared) spectra [31]. [Pg.264]

The use of a polyfunctional catalyst could enhance the life of the catalyst. A clear example is the use of H3PWi2O40-SO4 /ZrO2 mixtures for isobutane/ butenes alkylation (Table 13.4-). However, modifications of the t) pe of reactor could also favor extended catalyst longevity." During the last few years, other alternatives have been proposed that favor a better catalyst regeneration and/or lower catalyst deactivation the use of supercritical isobutene regeneration or dense-C02 enhanced the reaction media. ... [Pg.261]

M.C. Clark and B. Subramaniam. Extended alkylate production activity during fixed-bed supercritical 1-butene/isobutane alkylation on solid-acid catalyst using carbon dioxide as a diluent. Ind. Eng. Chem,. Res., 37(4) 1243-1250, 1998. [Pg.50]

N. (2008) Continuous supercritical iC4/ C4= alkylation over H-Beta and H-USY Influence of the zeolite strudure. Appl. Catal A, 336, 51-71. [Pg.396]

Petkovic, L.M. and Ginosar, D.M. (2004) The efiect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation. Appl. Catal. A, 275, 235-245. [Pg.397]

Burch, K.C., and Zalewski, D.J. (2005) Extended catalyst longevity via supercritical isobutane regenerafion of a partially deactivated USY alkylation catalyst. Ind. Eng. Chem. Res., 44, 4534 542. [Pg.529]

A continuous procedure for the alkylation of mesitylene and anisole with supercritical propene, or propan-2-ol in supercritical carbon dioxide, with a heterogeneous polysiloxane-supported solid acid Deloxan catalyst has been reported giving 100% selectivity for monoalkylation of mesitylene with 50% conversion at 250 °C and 150 bar by propan-2-ol in supercritical carbon dioxide. p-Toluenesulfonic acid monohydrate has been demonstrated as an efficient catalyst for the clean alkylation of aromatics using activated alkyl halides, alkenes or tosylates under mild conditions. Cyclohexene, for example, reacts with toluene to give 100% cyclohexyltoluenes (o m p-29 18 53) under these circumstances. [Pg.291]

Low-valent palladium complex, for example, Pd(0), is readily prepared in situ by reaction of PdCl2(PPh3)2/Zn. This is shown to induce the similar homocoupling polycondensation of metaphenylene 183 at 95 °C in DMF. Fluorinated alkyl esters 180 polymerize smoothly in supercritical CO2 1,4-dichlorophenylene 184 having a keto group also reductively polymerized similarly. [Pg.686]

Yonker, C. R. and Linehan, J. C., A high-pressure NMR investigation of reaction chemistries in a simple salt hydrate,. Supercrit. Fluids, 29, 257 2004. Mehnert, C. R, Supported ionic liquid catalysis, Chem. Eur. ]., 11,50,2005. Giernoth, R. and Bankmann, D., Transition-metal free synthesis of perdeuter-ated imidazolium ionic liquidsby alkylation and H/D exchange, Eur. J. Org. Chem., 2008 (in print). DOT 10.1002/ejoc.200700784. [Pg.370]

In work by Hanrath and Korgel, H-terminated Ge nanowires were exposed to hexene in a supercritical fluid reactor at 220 °C, and the resulting hexyl-terminated nanowires appear resistant to oxidation in either air or water. The image reveals an abrupt interface for the alkyl-terminated Ge nanowire (Figure 5.12(b)) compared to the nanowires removed from the reactor without termination (Figure 5.12(a)) [103]. [Pg.349]

Mesitylene was alkylated with propylene or 2-propanol in supercritical CO2 using Deloxane, a polysiloxane-supported solid acid catalyst in a continuous flow reactor.406 Monoisopropylation with 100% selectivity occurred with 2-propanol. [Pg.265]

Well-controlled polymerization of substituted acetylenes was also reported. A tetracoordinate organorhodium complex induces the stereospecific living polymerization of phenylacetylene.600 The polymerization proceeds via a 2-1 -insertion mechanism to provide stereoregular poly(phenylacetylene) with m-transoidal backbone structure. Rh complexes were also used in the same process in supercritical C02601 and in the polymerization of terminal alkyl- and arylacetylenes.602 Single-component transition-metal catalysts based on Ni acetylides603 and Pd acet-ylides604 were used in the polymerization of p-diethynylbenzene. [Pg.784]

Supercritical hydrogenation is just one example of continuous reactions which can be carried out in SCCO2 solution. Other reactions which have been carried out successfully include Friedel-Crafts alkylation of aromatics by alcohols [64], the dehydration of alcohols to form ethers [65] (using acid catalysts), and the hydroformylation of alkenes [52] (using rhodium catalysts immobilized on Si02). In each of these reactions, it is possible to obtain a selectivity which is at least as good, and often better, than with conventional solvents. However, the precise role of the scCC>2 in these reactions is not as obvious as in supercritical hydrogenation. [Pg.481]

The isobutane-1 -butene alkylation was studied in dense CO2 in both fixed-bed and slurry reactors.165-167 Both Nafion SAC-13 and Nation SAC-25 exhibited steady-state conversions and selectivities for 50 h. Enhanced Cg alkylate selectivity could be achieved at near total butene conversion. The maximum value attained, however, was only about 40%. The higher effective alkylation rate constant for SAC-25 compared to SAC-13 indicates improved accessibility of the acid sites. Nafion SAC-13 and SAC-25 applied in a study to test the effect of supercritical fluids on alkylation exhibited only modest activities.168... [Pg.552]

A mixed reaction medium, composed of scC02 and ILs, has been defined as a new biphasic system by Advanced Industrial Science and Technology (AIST), and used for selective and efficient CC synthesis. For example, 1-alkyl-3-methylimidazolium salts represent a suitable system when used under supercritical conditions for the synthesis of CCs [156] from epoxides and C02. Kanawami et al. [159] have reported that the use of 1-octyl-3-methylimidazolium tetrafluoroborate under supercritical conditions resulted in a 100% conversion into PC, with 100% selectivity, within only a few minutes (Equation 7.15). [Pg.185]

Recently, Ikarya has reported the use of imidazolin-2-ylidenes with N-alkyl and N-aryl substituents and their C02 adducts as catalyst of the carboxylative cydiza-tion of internal and terminal propargylic alcohols [215], The reaction of internal propargyl alcohols with C02 has been carried out also under supercritical conditions. Ikariya et al. have developed a synthetic process to afford Z-alkylidene cyclic carbonates promoted by P( -C4H9)3 with high efficiency [216],... [Pg.192]


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See also in sourсe #XX -- [ Pg.209 ]




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