- Preparation method and application of polysubstituted ethyl alkane
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The preparation method comprises the following steps: in an inert atmosphere, adding a raw material alcohol to a reaction kettle, then adding a solvent, a dehydration catalyst and a stabilizer to carry out reaction, carrying out rectification after reaction, and dividing the distillate to obtain olefin. The olefin is added to the hydrogenation kettle, and then water and a hydrogenation catalyst are added to replace the nitrogen to be hydrogenated and hydrogenated, and after the hydrogenation is finished, the catalyst is removed by filtration. The polysubstituted ethane alkane prepared by the invention does not generate waste in the production process, and all materials other than the main materials in the production process can be used for multiple times. The added water can greatly reduce the generation of static electricity in the production process, so that the product production safety is greatly improved. The yield of the polysubstituted ethane alkane is higher than 98%, and the purity is greater than 99.8%.
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Paragraph 0038-0041; 0043-0048; 0050-0055; 0057-0058
(2021/10/05)
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- STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS
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Metal-organic framework (MOFs) compositions based on post?synthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic C—H bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Paragraph 0338
(2019/01/07)
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- Alkene Hydrogenations by Soluble Iron Nanocluster Catalysts
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The replacement of noble metal technologies and the realization of new reactivities with earth-abundant metals is at the heart of sustainable synthesis. Alkene hydrogenations have so far been most effectively performed by noble metal catalysts. This study reports an iron-catalyzed hydrogenation protocol for tri- and tetra-substituted alkenes of unprecedented activity and scope under mild conditions (1–4 bar H2, 20 °C). Instructive snapshots at the interface of homogeneous and heterogeneous iron catalysis were recorded by the isolation of novel Fe nanocluster architectures that act as catalyst reservoirs and soluble seeds of particle growth.
- Gieshoff, Tim N.,Chakraborty, Uttam,Villa, Matteo,Jacobi von Wangelin, Axel
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supporting information
p. 3585 - 3589
(2017/03/21)
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- PROCESS OF MAKING OLEFINS OR ALKYLATE BY REACTION OF METHANOL AND/OR DME OR BY REACTION OF METHANOL AND/OR DME AND BUTANE
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Methods of simultaneously converting butanes and methanol to olefins over Ti-containing zeolite catalysts are described. The exothermicity of the alcohols to olefins reaction is matched by endothermicity of dehydrogenation reaction of butane(s) to light olefins resulting in a thermo- neutral process. The Ti-containing zeolites provide excellent selectivity to light olefins as well as exceptionally high hydrothermal stability. The coupled reaction may advantageously be conducted in a staged reactor with methanol/DME conversion zones alternating with zones for butane(s) dehydrogenation. The resulting light olefins can then be reacted with iso-butane to produce high-octane alkylate. The net result is a highly efficient and low cost method for converting methanol and butanes to alkylate.
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Page/Page column 15; 25; 26; 31; 32
(2017/05/10)
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- Single-Site Cobalt Catalysts at New Zr8(μ2-O)8(μ2-OH)4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles
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We report here the synthesis of robust and porous metal-organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M8(μ2-O)8(μ2-OH)4 and octahedral M6(μ3-O)4(μ3-OH)4. While the M6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M8-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ2-oxo and four μ2-OH groups. The metalation of Zr-MTBC SBUs with CoCl2, followed by treatment with NaBEt3H, afforded highly active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr8-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis.
- Ji, Pengfei,Manna, Kuntal,Lin, Zekai,Urban, Ania,Greene, Francis X.,Lan, Guangxu,Lin, Wenbin
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supporting information
p. 12234 - 12242
(2016/09/28)
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- Enhancement of dehydrogenation and hydride transfer by La3+ cations in zeolites during acid catalyzed alkane reactions
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La3+ cations exchanged into ultrastable zeolite Y and zeolite X promote catalytic isomerization, cracking, and alkylation of alkanes. La 3+ cations stabilize the zeolite lattices and, more importantly, polarize alkane C-H bonds to enhance the rates of all three reactions. This unique activity leads to stable cracking and isomerization of reactive alkanes, with polarizable C-H bonds with adjacent tertiary or quaternary carbon atoms below 370 K. The presence of La3+ cations also enhances the zeolite catalyzed hydride transfer rate for isobutane alkylation with 2-butene leading to high catalyst stability. Solid state MAS NMR shows that the strongest positive effects are associated with nonhydroxylated La3+ cations accessible to the reacting molecules in supercages of the zeolite. The high activity is the result of a cooperative polarization of C-H bonds of alkanes by La3+ cations and the presence of stable and strong Bronsted acid sites.
- Schuessler, Florian,Schallmoser, Stefan,Shi, Hui,Haller, Gary L.,Ember, Erika,Lercher, Johannes A.
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p. 1743 - 1752
(2014/06/24)
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- Ionic liquid enhanced alkylation of iso-butane and 1-butene
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The alkylation of iso-butane with 1-butene was catalyzed by triflic acid (TFOH) coupled with a series of protic ammonium-based ionic liquids (AMILs), and the addition of the AMILs dramatically enhanced the efficiency of TFOH for the alkylation reaction. Up to 85.1% trimethylpentanes (TMP) selectivity and 98 research octane number (RON) were achieved with the optimized TFOH/AMIL catalyst (75 vol.% triflic acid and 25 vol.% triethylammonium hydrogen sulfate), which were much better than that with the commercial H2SO4 catalyst (65% TMP selectivity, 97 RON) and pure triflic acid. The addition of AMILs increased the I/O ratio dissolved in the catalyst system and adjusted the acidity of the TFOH/AMILs catalyst system, which were highly beneficial to the alkylation reaction and resulted in high TMP selectivity and high RON.
- Cui, Peng,Zhao, Guoying,Ren, Hailing,Huang, Jun,Zhang, Suojiang
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- DIMERIZATION PROCESS
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A process for the dimerization of isoolefins is disclosed. The process may include: contacting an isoolefin with sulfurous acid in a reaction zone at conditions of temperature and pressure sufficient to dimerize at least a portion of the isoolefin
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Page/Page column 4-5
(2011/04/18)
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- Alkylation of isobutane with 2-butene using ionic liquids as catalyst
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Alkylation of isobutane with 2-butene was performed in a batch reactor using the ionic liquid 1-n-octyl-3-methylimidazolium bromide aluminium chloride ([OMIM]Br-AlCl3) pure, and in a mixture with compounds containing SO3H-groups. The acidity of the ionic liquid (IL) was modified by the addition of acid cation exchange resins (dry or with a small amount of water), or by the addition of a second IL ([(HO3SBu)MIM]HSO4). A high content of the desired trimethylpentanes (up to 64%) and thus a high research octane number (RON up to 96) of the alkylate was obtained. The reusability of the IL systems was studied and compared with a catalyst commercially used at present (H2SO4).
- Bui, Thi Le Thuy,Korth, Wolfgang,Aschauer, Stephan,Jess, Andreas
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scheme or table
p. 1961 - 1967
(2010/06/15)
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- Zeolites as the modern catalysts for the high octane gasoline component production
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Processes of isobutane with butenes alkylation with the purpose of obtaining the high octane gasoline'component (alkylate), being environmentally detrimental due to use of concentrated H2SO4 or HF acids as catalysts, are nevertheless of great industrial importance supplying the world market with approximately 80 mln tons of alkylate yearly. The perspective of zeolite catalysts as the substitutes of the above concentrated acids in the modern alkylation process has been considered. The most effective today's solid alkylation catalyst of the narrow acid spectrum has been found. Such acidity spectrum is considered to be responsible for the essential prolongation of the effective catalyst lifetime.
- Patrylak,Patrylak,Ionin,Voloshyna,Skubiszewska-Zieba,Repetskyi
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p. 101 - 106
(2008/09/19)
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- Process for the production of hydrocarbons
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A process for the production of a hydrocarbon comprises reacting methanol, dimethyl ether, methyl acetate or mixtures thereof, with an olefin in the presence of methyl halide and/or hydrogen halide and at least one compound selected from the group consisting of ruthenium carbonyl halides, osmium carbonyl halides and mixtures thereof.
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Page/Page column 4-6
(2008/06/13)
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- Stages of aging and deactivation of zeolite LaX in isobutane/2-butene alkylation
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The formation of carbonaceous deposits and their effect on aging and deactivation of zeolite LaX during isobutane/2-butene alkylation at 348 K were investigated by stopping the reaction at different times on stream. Four stages of the reaction were identified: (1) stable alkylation, (2) deposit transformation, (3) slow deactivation, and (4) rapid deactivation. Deposits consist mostly of bicyclic compounds and branched carbenium ions, which are formed already at the beginning of the reaction and block Bronsted acid sites. During the deposit transformation, migration of smaller entities toward the pore mouth occurs. These cyclic compounds are further alkylated and lead to pore mouth plugging. In the final stage of rapid deactivation, the catalyst stops producing alkylate, and butene oligomerization is the main reaction leading to olefin desorption and massive deposit formation at the outside of the zeolite particles.
- Sievers, Carsten,Zuazo, Iker,Guzman, Alexander,Olindo, Roberta,Syska, Hitrisia,Lercher, Johannes A.
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p. 315 - 324
(2008/02/13)
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- Paraffin alkylation
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A liquid acid process is disclosed in which a hydrocarbon component containing an olefin, an olefin precursor or mixture and an isoalkane and a liquid acid catalyst is fed to a downflow reaction zone containing a disperser, under conditions to induce pulse flow at or near the outlet to react the isoalkane and olefin to produce a reaction product and feeding the reaction product to a vaporization zone containing a disperser under conditions to induce pulse flow at or near the outlet of the vaporization zone. A pressure drop across the disperser in the vaporization zone causes partial vaporization of the hydrocarbon which quench es the heat reaction and cooling the unvaporized portion of said reaction product, which is recovered and allowed to separate into an acid phase and hydrocarbon phase containing the alkylate. The acid catalyst and hydrocarbons may be fractally fed to the reaction zone.
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Page/Page column 7
(2008/06/13)
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- Alkylation process with recontacting in settler
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A system and/or process for decreasing the level of at least one organic fluoride present in a hydrocarbon phase contained in an alkylation settler by contacting the hydrocarbon phase with an HF containing stream, containing greater than about 80 wt. % and less than about 94 wt. % HF, in the intermediate portion of the settler which contains at least one tray system, with each tray system comprising a perforated tray defining a plurality of perforations and a layer of packing below the perforated tray, are disclosed.
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Page/Page column 3-5
(2008/06/13)
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- Catalyst and process for contacting a hydrocarbon and ethylene
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A process of contacting at least one feed hydrocarbon, containing three to about seven carbon atoms per molecule, and ethylene in a hydrocarbon-containing fluid in the presence of a catalyst composition to provide at least one product hydrocarbon isomer containing about four to about nine carbon atoms per molecule is provided. The at least one feed hydrocarbon can be selected from paraffins, isoparaffins, and the like and combinations thereof. The catalyst composition contains a hydrogen halide component, a sulfone component, and a metal halide component.
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- Disproportionation of hydrocarbons
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A novel hydrocarbon disproportionation process is provided and includes contacting a hydrocarbon feed comprising at least one paraffin with a disproportionation catalyst comprising a support component, a metal, and a halogen in a disproportionation reaction zone under disproportionation reaction conditions.
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- Alkene oligomerization process
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A process for oligomerising alkenes having from 3 to 6 carbon atoms which comprises contacting a feedstock comprising a) one or several alkenes having x carbon atoms, and, b) optionally, one or several alkenes having y carbon atoms, x and y being different, with a catalyst containing a zeolite of the MFS structure type, under conditions to obtain selectively oligomeric product containing predominant amounts of certain oligomers. The process is carried out at a temperature comprised between 125 and 175° C. when the feedstock contains only alkenes with 3 carbon atoms and between 140 and 240° C., preferably between 140 and 200° C. when the feedstock contains comprises at least one alkene with 4 or more carbon atoms.
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- Mechanism of reaction of n-butane with but-2-enes in the presence of LaCaX faujasites
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The reactions of n-butane and an n-butane (80 mol. percent)-isobutane (20 mol. percent) mixture with but-2-enes in the presence of polycationic PdLaCaX faujasites were studied. Quantum-chemical calculation of the enthalpies of formation of alkanes C4-C8 a
- Bachurikhin, A. L.,Mortikov, E. S.,Gribanov, V. Yu.,Abronin, I. A.
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p. 783 - 788
(2007/10/03)
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- Formation of trimethylpentanes from isobutane and 1-butene catalyzed by sulfated metal oxides
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The gas-phase alkylation of 1-butene with isobutane was carried out over superacids of sulfated metal oxides, SO4/Fe2O3, SO4/Al2O3, SO4/TiO2, SO4/SnO2, and SO4/ZrO2, at 0 °C; SO4/SnO2 gave the highest yield of trimethylpentane (TMP). It was proved from relationship between the catalyst acidities and the yields of C8 paraffins that the first intermediate species was a t-butyl cation formed on the superacidic Lewis site by abstraction of H- followed by the alkylation with butenes to form TMP.
- Satoh, Kunihiko,Matsuhashi, Hiromi,Arata, Kazushi
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p. 231 - 232
(2007/10/03)
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- MxOy/SO42--/dealuminated zeolite β (M=Ti, Fe) as novel catalysts for alkylation of isobutane with 1-butene
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A new kind of MxOy/SO42--/H-form dealuminated β (DHβ) catalysts prepared here were applied to alkylation of isobutane with 1-butene. The group of MxCy/SO42-/DHβ (M = Ti, Fe) catalysts has a lower rate of deactivation and higher selectivity of this alkylation than other group of Hβ and DHβ. It is proposed that the strong acid sites corresponding to the active sites for this alkylation can be formed by the interaction among DHβ, MxOy, and SO42-.
- Sun, Mingxing,Sun, Jianwei,Li, Quanzhi
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p. 519 - 520
(2007/10/03)
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- Isobutane/2-Butene Alkylation on Ultrastable Y Zeolites: Influence of Zeolite Unite Cell Size
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The alkylation reaction of isobutane with trans-2-butene has been carried out on a series of steam-dealuminated Y zeolites with unit cell sizes ranging from 2.450 to 2.426 nm.A fixed-bed reactor connected to an automatized multiloop sampling system allowed us to make differential product analysis from very short (1 min or less) to longer times on stream.A maximum in the initial 2-butene conversion was found on samples with unit cell sizes between 2.435 and 2.450 nm.However, the TMP/DMH ratio, i.e., the alkylation-to-oligomerization ratio, continuously increased withzeolite unit cell size.The concentration of reactants in the pores, the strength distribution of Broensted acid sites, and the extent of hydrogen transfer reactions, which in turn depend on the framework Si/Al ratio of a given zeolite, were seen to affect activity and product distribution of the catalysts.Finally, the influence of these factors on the aging characteristics of the samples was also discussed.
- Corma, A.,Martinez, A.,Martinez, C.
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p. 185 - 192
(2007/10/02)
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- Isomerisation des radicaux insatures. III. Radicaux α,α,β-, α,β,γ- et α,α,γ-trimethallyles
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α,α,β-, α,β,γ-, and α,α,γ-trimethallyl radicals have been generated in the 147.0-nm gas phase photolysis of 2,3,3-trimethyl-1-butene, 3,4-dimethyl-2-pentene, and 2,4-dimethyl-2-pentene, respectively.Under these conditions, the majority of allyl radicals have an internal energy sufficient for further decomposition: they give rise to the formation of various 1,3-dienes and small amounts of either 1,2- or 2,3-dienes.An internal sigmatropic 1,2-hydrogen atom transfer process is part of the proposed mechanism to explain such products.Moreover, the fragmentation of the trimethyl substituted allyl radicals involves the split of one β(C-C) bond, then one β(C-H), and, to a lesser extent, one central C-CH3 bond.
- Deslauriers, Helene,Collin, Guy J.
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p. 3168 - 3173
(2007/10/02)
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