- A high-yield approach to the sulfonation of methane to methanesulfonic acid initiated by H2O2 and a metal chloride
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Low temperatures and low pressures suffice for the sulfonation of methane with a suitable free-radical initiator and promoter [Eq. (1)]. Since the RhCl3 promoter can be recycled, and the initiator complex is stable and easy to handle, development of this reaction into an industrial process is promising. MSA = methanesulfonic acid.
- Mukhopadhyay, Sudip,Bell, Alexis T.
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- Direct catalytic sulfonation of methane with SO2 to methanesulfonic acid (MSA) in the presence of molecular O2
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Methane is transformed selectively to methanesulfonic acid at low temperature by liquid-phase sulfonation of methane with SO2 and O2 in the presence of Pd- and Cu-salts as the catalysts.
- Mukhopadhyay, Sudip,Bell, Alexis T.
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- A novel method for the direct sulfonation of CH4 with SO 3 in the presence of KO2 and a promoter
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Direct sulfonation of methane with SO3 to methanesulfonic acid (MSA) is accomplished in sulfuric acid in the presence of a small amount of KO2 as the free radical initiator and a metal chloride. Of the several metal chlorides examined, RhCl3 was found to be the most effective promoter. While KO2 alone can activate methane, the conversion of SO3 to MSA increases 2.3-fold when KO2 and RhCl3 are both present in the reaction mixture. The effects of different process parameters such as temperature, SO3 concentration, methane pressure, KO2 concentration, and RhCl3 concentration have been examined on the rate of reaction. The reaction is optimized at a KO2-to-RhCl3 molar ratio of 3.16. Strongly acidic solvents such as H2SO4 or CF3SO 3H are necessary for the reaction. No MSA was formed when the reaction was carried out in DMSO. A mechanism is proposed to explain the activation of CH4 to form MSA. A critical part of the sequence is in situ formation of a metal-peroxo species via the reaction of KO2, acid solvent, and RhCl3.
- Mukhopadhyay, Sudip,Bell, Alexis T.
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- Direct liquid-phase sulfonation of methane to methanesulfonic acid by SO3 in the presence of a metal peroxide
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Activation of methane by metal peroxides: Calcium peroxide serves as an effective radical initiator in the liquid-phase sulfonation of methane to methansulfonic acid (MSA) by SO3 [Eq. (1)]. Under the best reaction conditions a 91% conversion of SO3 to MSA was achieved.
- Mukhopadhyay, Sudip,Bell, Alexis T.
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- Activation of methane to CH3 +: A selective industrial route to methanesulfonic acid
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Direct methane functionalization to value-added products remains a challenge because of the propensity for overoxidation in many reaction environments. Sulfonation has emerged as an attractive approach for achieving the necessary selectivity. Here, we report a practical process for the production of methanesulfonic acid (MSA) from only two reactants: methane and sulfur trioxide. We have achieved >99% selectivity and yield of MSA. The electrophilic initiator based on a sulfonyl peroxide derivative is protonated under superacidic conditions, producing a highly electrophilic oxygen atom capable of activating a C–H bond of methane. Mechanistic studies support the formation of CH3 + as a key intermediate. This method is readily scalable with reactors connected in series for prospective production of up to 20 metric tons per year of MSA.
- Díaz-Urrutia, Christian,Ott, Timo
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Read Online
- AgII-Mediated Electrocatalytic Ambient CH4 Functionalization Inspired by HSAB Theory
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Although most class (b) transition metals have been studied in regard to CH4 activation, divalent silver (AgII), possibly owing to its reactive nature, is the only class (b) high-valent transition metal center that is not yet reported to exhibit reactivities towards CH4 activation. We now report that electrochemically generated AgII metalloradical readily functionalizes CH4 into methyl bisulfate (CH3OSO3H) at ambient conditions in 98 % H2SO4. Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol?1, a high pseudo-first-order rate constant of CH4 activation up to 2.8×103 h?1 at room temperature and a CH4 pressure of 85 psi, and two competing reaction pathways preferable towards CH4 activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH4 at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.
- Deng, Jiao,Guan, Xun,I?iguez, Jesus A.,Liu, Chong,Martinez, Antonio,Xiang, Danlei
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- Direct sulfonation of methane to methanesulfonic acid by sulfur trioxide catalyzed by cerium(IV) sulfate in the presence of molecular oxygen
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Direct sulfonation of methane with SO3 to methanesulfonic acid (MSA) is accomplished in sulfuric acid with almost 100% selectivity in the presence of a catalyst, namely, Ce and Rh salts and molecular oxygen as the catalyst regenerator. In the absence of O2, the catalyst remains effective but the selectivity to MSA decreases to 53% and byproducts, principally CH3OSO3H, are formed. The effects of O 2 pressure, catalyst concentration, temperature, SO3 concentration, and methane pressure have been examined on the rate of SO 3 conversion to MSA. The conversion of SO3 to MSA was the same when CF3SO3H was used as the solvent instead of H2SO4.
- Mukhopadhyay, Sudip,Bell, Alexis T.
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Read Online
- Direct sulfonation of methane to methanesulfonic acid with SO2 using Ca salts as promoters
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Direct liquid-phase sulfonation of methane to methanesulfonic acid (MSA) with SO2 has been achieved in triflic acid using K2S2O8 as the oxidant and a small amount of a Ca salt as the promoter. The effects of reaction conditions on the conversion of SO2 to MSA were examined. Included were the influence of solvent acidity, reaction duration, reaction temperature, amount of K2S2O8, and composition and amount of promoters. Copyright
- Mukhopadhyay, Sudip,Bell, Alexis T.
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- PROCESS FOR MANUFACTURING ALKANESULFONIC ACIDS
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The present invention relates to an improved process for manufacturing of alkanesulfonic acids.
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Page/Page column 16-18
(2021/04/10)
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- PROCESS FOR THE PRODUCTION OF ALKANESULFONIC ACIDS
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A process for the manufacturing of alkanesulfonic acid by reaction of an alkane with an anhydride in the presence of sulfuric acid and a starter at ambient temperature or higher and under pressure.
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Page/Page column 7-8
(2021/02/12)
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- METHOD FOR THE PRODUCTION OF ALKANE SULFONIC ACID AT SUPERACIDIC CONDITIONS
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The present invention refers to a method for the production of alkane sulfonic acid, in which SO3 and an alkane are contacted with each other in the presence of a solvent, said solvent does constitute a superacid and the combination of said solvent with one or more of the reactants also gives rise to a superacid.
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Page/Page column 12
(2020/10/09)
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- PROCESSES AND SYSTEMS FOR RECOVERING METHANESULFONIC ACID IN PURIFIED FORM
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Aspects of the invention relate to systems and processes for recovering methanesulfonic acid, in a purified form, from a composition additionally including sulfur trioxide. In accordance with one aspect, the invention provides a process that includes separating a feed stream comprised of hydrocarbons, methanesulfonic acid, sulfur trioxide, and optionally sulfuric acid to produce a light stream comprised of hydrocarbons and a heavy stream comprised of methanesulfonic acid and sulfur trioxide; contacting (e.g., by mixing) the heavy stream with a reactive additive capable of reacting with sulfur trioxide, under conditions effective to cause reaction of the reactive additive with the sulfur trioxide to produce a heavy reaction product having a boiling point higher than the boiling point of methanesulfonic acid; and separating the heavy stream using a distillation column to produce a distillate stream consisting essentially of methanesulfonic acid and a bottoms stream comprising the heavy reaction product.
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Paragraph 0058-0067
(2020/02/19)
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- Preparation method of high-purity methanesulfonic acid
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The invention relates to a preparation method of high-purity methanesulfonic acid. The method comprises the following steps: adding sodium sulfite, an organic solvent and a catalyst into a mixed reactor, adding a pH regulator to regulate the pH value of the system to 3-6, uniformly stirring, and slowly dropwise adding a methylation reagent; after dropwise adding the methylation reagent, implementing reaction at 10-40 DEG C for 5-8 hours, and then stopping the reaction; extracting the organic solvent under reduced pressure, adding a small amount of water, stirring for 5-10 minutes, and performing ion exchange through an exchange column filled with strongly acidic cationic resin to obtain a crude product; and removing water from the obtained crude product under 0.098 MPa, and taking a fraction at 180-200 DEG C to obtain the high-purity methanesulfonic acid. The preparation method provided by the invention is carried out under an anhydrous condition, so that decomposition of a methylationreagent or incompatibility with a reaction system is avoided. The method is simple in process, high in yield, low in cost and suitable for industrial large-scale production.
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Paragraph 0034-0057
(2020/12/30)
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- Preparation method of methanesulfonic acid (by machine translation)
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The invention discloses a preparation method of methanesulfonic acid. The preparation method comprises the following steps: reacting sodium methylsulfonate and an acidic reagent in water to obtain the methanesulfonic acid. The acidic reagent is one or more of hydrochloric acid solution, hydrogen chloride gas, thionyl chloride and sulfuric acid. The acid reagent can be dissolved in water or can react with water to form H. + H-H. + The initial concentration in the reaction system was ≥ 3.76 μM/L. H+ The molar ratio of sodium to sodium methanesulfonate ≥ 1.5: 1. The method can obtain methanesulfonic acid with high yield, and has good economic benefits. (by machine translation)
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Paragraph 0057-0116
(2020/12/30)
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- PROCESS FOR PROVIDING ANHYDROUS ALKANE SULFONIC ACIDS IN PURIFIED FORM
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The present application refers to a process for providing anhydrous alkane sulfonic acid in purified form.
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Page/Page column 10; 11
(2020/10/27)
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- REGULATOR FOR THE PRODUCTION OF ALKANE SULFONIC ACIDS
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The present invention relates to a process for the production of alkane sulfonic acid with a regulator as well as two specific compounds which can be used as regulator in a respective process.
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Page/Page column 6
(2019/01/16)
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- DIRECT SYNTHESIS OF ALKANE SULFONIC ACIDS FROM ALKANE AND SULFUR TRIOXIDE EMPLOYING HETEROGENEOUS CATALYSIS
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The present invention relates to a process for the direct synthesis of alkanesulfonic acids, particularly methanesulfonic acid, from sulfur trioxide and alkanes employing heterogeneous catalysts, particularly transition metals such as rhodium. Particularly the synthesis is carried out in a tube furnace and the resultant product is isolated by quenching the resultant gas mixture in aqueous concentrated sulfuric acid at room temperature.
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Page/Page column 5; 11
(2019/09/06)
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- CATALYSTS FOR THE SYNTHESIS OF ALKANESULFONIC ACIDS
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The present invention relates to novel uses of stable inorganic peroxoacids as catalysts in the preparation of alkanesulfonic acids from alkanes and sulfur tri- oxide, methods for the production of alkanesulfonic acids employing said cata- lysts as well as reaction mixtures comprising said catalysts. The invention par- ticularly relates to the production of methanesulfonic acid from methane and sulfur trioxide employing stable inorganic peroxoacids as catalysts.
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Page/Page column 11; 12
(2019/09/04)
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- COMPOUNDS, PROCESSES, AND MACHINERY FOR CONVERTING METHANE GAS INTO METHANE-SULFONIC ACID
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Improved initiators, solvents, and processing equipment and methods are disclosed for improving the yields and efficiency of a manufacturing process which uses a radical chain reaction to convert methane (CH4), which is a gas under any normal conditions, into methane sulfonic acid (MSA), a liquid. MSA is useful and valuable in its own right, and it also can be processed to create desulfured fuels and other valuable chemicals. A preferred type of initiator combination has been identified, comprising at least two different peroxide sulfate compounds. One will act as a "primary" initiator for the chain reaction, while the other will act as a "chain-lengthening oxidant", which can eliminate chain-terminating species, such as sulfur Di-oxide, in the MSA-forming reactor. Integrated continuous-loop processing systems also are disclosed, including a first variant which uses a mixture of sulfuric acid and MSA as the solvent, and a second variant which completely avoids sulfuric acid and uses MSA only, as the solvent. Options are also disclosed which can avoid any need for distillation, to create reduced-cost "rough grades" of MSA with purity levels which will be entirely adequate for various types of uses in bulk.
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Page/Page column 55-56
(2019/11/19)
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- Selective Late-Stage Sulfonyl Chloride Formation from Sulfonamides Enabled by Pyry-BF4
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Reported here is a simple and practical functionalization of primary sulfonamides, by means of a pyrylium salt (Pyry-BF4), with nucleophiles. This simple reagent activates the poorly nucleophilic NH2 group in a sulfonamide, enabling the formation of one of the best electrophiles in organic synthesis: a sulfonyl chloride. Because of the variety of primary sulfonamides in pharmaceutical contexts, special attention has been focused on the direct conversion of densely functionalized primary sulfonamides by a late-stage formation of the corresponding sulfonyl chloride. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides, sulfonates, sulfides, sulfonyl fluorides, and sulfonic acids. The mild reaction conditions and the high selectivity of Pyry-BF4 towards NH2 groups permit the formation of sulfonyl chlorides in a late-stage fashion, tolerating a preponderance of sensitive functionalities.
- Gómez-Palomino, Alejandro,Cornella, Josep
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supporting information
p. 18235 - 18239
(2019/11/13)
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- Mechanistic and Synthetic Implications of the Diol-Ritter Reaction: Unexpected Yet Reversible Pathways in the Regioselective Synthesis of Vicinal-Aminoalcohols
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The Ritter reaction of 1,2-diolmonoesters with nitriles to 1-vic-amido-2-esters proceeds through dioxonium and nitrilium cation intermediates. To provide the basis for the reaction mechanism, novel forms of these cations were isolated, characterized, and studied by spectroscopic methods and single crystal X-ray analysis. Ground and transition state energies were determined both experimentally and theoretically. Taken together, these data suggest that the reaction proceeds via rapid formation of the dioxonium cation 9, followed by rate determining yet reversible ring opening by acetonitrile to the corresponding nitrilium cation 10 (computed ΔG∞ = 24.7 kcal at 50 °C). Rapid, irreversible hydration of the latter affords the corresponding vic-acetamido ester. Controlled addition of H2O to the dioxonium cation 9 in acetonitrile-d3 results in near-quantitative production of deuterated acetamido ester 13a. Kinetics of this conversion (9 to 13a) are biphasic, and the slow phase is ascribed to either direct cation 9 attack by acetamide to form cation 16 via O-alkylation or by reversible ether formation. Deuterium labeling studies suggest O-alkylated cation 16 does not directly isomerize to N-alkylated cation 18; instead, it reverts to vic-amidoester 13a via the nitrilium pathway. Preliminary results indicate high regioselectivity for primary amide formation in the diol-Ritter sequence.
- Ondari, Mark E.,Klosin, Jerzy,Froese, Robert D. J.,Kruper, William R.,Macdonald, Jason,Arriola, Dan J.,Bell, Bruce M.,Briggs, John R.,Kruper, William J.
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supporting information
p. 4715 - 4722
(2018/12/14)
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- Method for synthesizing methyl sulfonic acid
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The invention discloses a method for synthesizing methyl sulfonic acid. According to the method disclosed by the invention, dithioether and a nitric acid water solution are used as raw materials and are directly synthesized into the methyl sulfonic acid under the reaction temperature of 30 DEG C to 160 DEG C; generated tail gas is absorbed by water to form the raw material for recycling. A crude product containing the methyl sulfonic acid is subjected to normal-pressure distillation and then a compound with a low boiling point, such as water, is removed; furthermore, the crude product is decompression and distillation to obtain the high-quality methyl sulfonic acid. The method disclosed by the invention is short in technological flow and simple to operate, no polluting gas is emitted and pollution to the environment is not caused, so that the method is suitable for being applied to the production field of the methyl sulfonic acid.
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Paragraph 0026; 0027; 0030; 0031; 0032; 0033; 0034
(2018/03/24)
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- CATALYST FOR OXIDATION REACTIONS, A METHOD FOR ITS PREPARATION AND THE USE THEREOF
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The present invention relates to a catalyst for oxidation reactions, particularly for oxidation of mercaptan dialkyldisulfides and/or dialklypolysulfides with oxygen to alkanesulfonic acids.
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Paragraph 0132
(2018/05/26)
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- SOLVENT-FREE ALKANE SULFONATION
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The present invention relates to an alkane-sulfonation process using alkane and sulfur trioxide, especially pure sulfur trioxide (100%) under solvent-free conditions in the presence of an initiator. It further relates to the use of a precursor which forms "in-situ" an initiator for manufacturing of alkanesulfonic acids, especially methanesulfonic acids.
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Page/Page column 10
(2018/06/12)
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- METHOD FOR THE PRODUCTION OF ALKANE SULFONIC ACIDS
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The present invention relates to methods for the production of alkane sulfonic acids, especially methane sulfonic acid, from alkane, especially methane, in which a carbocation, particularly a carbenium ion, is formed, as well as to the use of carbocations, particularly carbenium ions, for the production of alkane sulfonic acids, especially methane sulfonic acid.
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Page/Page column 12; 13; 18; 19; 20
(2018/09/08)
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- Preparation process of methyl sulfonic acid (by machine translation)
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The present invention discloses a process for preparing methyl sulfonic acid, the methyl mercaptan and nitric acid aqueous solution as the raw material, and the pressure is 0.01 mpa - 1 mpa, reaction temperature at 20 °C -160 °C directly synthesizing methyl sulfonic acid, generating the exhaust gas through the water absorption to form a nitric acid aqueous solution is recycled. The crude product containing methyl sulfonic acid first by atmospheric distillation to remove low boiling point compounds such as water, to carry out further distilled under reduced pressure to obtain high-quality methyl sulfonic acid; the process of the invention the procedure is short, the operation is simple, mild reaction conditions, there is no exhaust emission, realize zero pollution to the environment, and is suitable for methyl sulfonic acid industrial for production application. (by machine translation)
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Paragraph 0027; 0028; 0029; 0030; 0031
(2018/03/26)
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- Chlorination of florfenicol (FF): reaction kinetics, influencing factors and by-products formation
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Florfenicol (FF) is a widely used antibiotic, which is commonly found in natural waters. In this study, we investigated the removal fate of FF in two different drinking water treatment plants (DWTPs), which suggest that FF was easily transformed by free available chlorine (FAC) and the potential reactions of FF with FAC was the focus of this study. The oxidation kinetics of FF by FAC (7 × 10?4 mol) are very rapid with large pseudo-first-order rate constants kobs = 0.31 min?1, while FF (5 mg L?1) can be completely transformed in 30 min. The results showed that high Cl? (the dominant seawater constituent), Br?, and lower humic acid (HA, main constituents in freshwater) favor the FF oxidation. 21 degradation products were identified by liquid chromatography-tandems mass spectrometry (LC-MS/MS) and the possible routes for FF chlorination were proposed. These results are of importance toward the goal of assessing the persistence of FF in water chlorination.
- Zhang, Yansen,Shao, Yisheng,Gao, Naiyun,Chu, Wenhai,Chen, Juxiang,Li, Shuo,Wang, Yue,Xu, Shuaixian
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p. 107256 - 107262
(2016/11/25)
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- Study of the Paternò–Büchi type photolabile protecting group and application to various acids
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An efficient photolabile protecting group, thiochromone S,S-dioxides with the diazomethyl group for phosphate derivatives, amino acids and sulfonic acids was developed. Protection and photodeprotection reactions proceeded smoothly under mild conditions without any catalyst.1H NMR and HPLC spectra studies demonstrated the photolysis properties of the photolabile protecting group and gave an exact quantification of the released substrates. Specially, the photoproduct derived from the thiochromone derivatives following Paternò–Büchi type photo-cycloaddition showed high fluorescence intensity. This fluorescent characteristic demonstrated the photodeprotection progress also can be monitored by fluorescence spectra.
- Zhang, Youlai,Zhang, Huan,Ma, Chi,Li, Junru,Nishiyama, Yasuhiro,Tanimoto, Hiroki,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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supporting information
p. 5179 - 5184
(2016/11/13)
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- A recycled by-product hydrochloric acid method of preparing methyl sulfonic acid
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The invention relates to a method for preparing methanesulfonic acid by recycling a byproduct, namely hydrochloric acid. The method is characterized in that a method of hydrogen chloride, chlorine gas, methanesulfonic acid and hydrogen chloride is adopted, and the byproduct, namely the hydrochloric acid is recycled in the preparation process of the methanesulfonic acid to prepare the methanesulfonic acid. The method has the advantages that the byproduct, namely the hydrochloric acid is adopted for preparing chlorine gas and directly reacted with dimethyl disulfide, so that the safety risk and the logistics cost in purchase, transportation and storage of the chlorine gas with severe toxicity can be avoided; the byproduct, namely the hydrochloric acid, which is difficult to sell can be locally digested and utilized, and turned into treasure, so that the byproduct, namely the hydrochloric acid becomes a main raw material for preparing the methanesulfonic acid and the recycling of chlorine element is realized. Simultaneously, leftover manganese dioxide waste after oxidation reaction of potassium permanganate is utilized to prepare manganese chloride, and the manganese chloride can be used for electrolytic manganese, so that the production cost and the safety risk of the methanesulfonic acid are greatly reduced, and two major restricting factors, namely the chlorine gas and the byproduct, namely the hydrochloric acid in the preparation method of the methanesulfonic acid are simultaneously eliminated.
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Paragraph 0060
(2016/10/07)
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- PROCESS FOR PREPARING ALKANESULPHONIC ACIDS
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A process for preparing alkanesulphonic acids from dialkyl disulphides with nitric acid and oxygen is provided.
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Page/Page column 28-33
(2015/06/25)
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- PROCESS FOR PREPARING ALKANESULFONIC ACIDS
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The present invention relates to a process for preparing alkanesulfonic acids from dialkyl disulfides with nitric acid and oxygen.
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Page/Page column 26-29
(2015/06/25)
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- NOVEL INITIATOR FOR PREPARING ALKANESULFONIC ACIDS FROM ALKANE AND OLEUM
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A compound of the formula (I) ALK-SO2-O-O-SO2OX, wherein ALK is a branched or unbranched alkyl group, especially a methyl, ethyl, propyl, butyl, isopropyl, isobutyl group, or a higher alkyl group, and X = hydrogen, zinc, aluminium, an alkali or alkaline earth metal.
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Page/Page column 7
(2015/06/03)
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- PROCESS FOR PREPARING ALKANESULFONIC ACIDS FROM SULFUR TRIOXIDE AND AN ALKANE
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A process for preparing alkanesulfonic acids from sulfur trioxide and an alkane, wherein sulfur trioxide, the alkane and dialkylsulfonoyi peroxide (DASP) react as components, characterized in that the following steps are performed : a) sulfur trioxide is charged in a high-pressure reactor in a condensed phase; b) a temperature of at least 25 °C is set; c) the gaseous alkane is introduced to the high-pressure reactor until a pressure of at least 10 bar is reached; d) dialkylsulfonoyi peroxide (DASP) is added; and e) after a duration of at least 5 hours, the produced alkanesulfonic acid is withdrawn.
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Page/Page column 4-5
(2015/06/03)
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- 1-Acetylferroceneoxime-based photoacid generators: Application towards sol-gel transformation and development of photoresponsive polymer for controlled wettability and patterned surfaces
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A newsworthy class of carboxylate and sulfonate esters of 1-acetylferroceneoxime has been demonstrated as non-ionic photoacid generators (PAGs). PAGs based on 1-acetylferroceneoxime were synthesized in good yields by simple treatment of 1-acetylferroceneoxime with various carboxylic and sulfonyl chlorides. Newly developed PAGs of 1-acetylferroceneoxime showed good absorbance >350 nm. On irradiation using UV light (≥365 nm), carboxylates and sulfonates of 1-acetyl ferroceneoxime in aqueous acetonitrile solvent underwent efficient homolytic cleavage of N-O bond, resulting in the generation of carboxylic and sulphonic acids, respectively, with high chemical and good quantum yields. Further, we demonstrated the application of our newly developed 1-acetylferroceneoxime-based PAGs for gelation of biopolymer alginate on UV irradiation. More interestingly, we synthesized a ferroceneoxime bound photoresponsive polymer, 1-acetylferroceneoxime-polycaprolactone (AFO-PCL), and demonstrated its controlled surface wettability and generation of patterned surfaces.
- Ikbal, Mohammed,Banerjee, Rakesh,Barman, Shrabani,Atta, Sanghamitra,Dhara, Dibakar,Singh, N.D. Pradeep
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p. 4622 - 4630
(2014/06/09)
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- Synthesis, photophysical and photochemical properties of photoacid generators based on N-hydroxyanthracene-1,9-dicarboxyimide and their application toward modification of silicon surfaces
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We have introduced a series of nonionic photoacid generators (PAGs) for carboxylic and sulfonic acids based on N-hydroxyanthracene-1,9-dicarboxyimide (HADI). The newly synthesized PAGs exhibited positive solvachromatic emission (λmax(hexane) 461 nm, λmax(ethanol) 505 nm) as a function of solvent polarity. Irradiation of PAGs in acetonitrile (ACN) using UV light above 410 nm resulted in the cleavage of weak Na-O bonds, leading to the generation of carboxylic and sulfonic acids in good quantum and chemical yields. Mechanism for the homolytic Na-O bond cleavage for acid generation was supported by time-dependent density functional theory (TD-DFT) calculations. More importantly, using the PAG monomer N-(p-vinylbenzenesulfonyloxy)anthracene- 1,9-dicarboxyimide (VBSADI), we have synthesized N-(p-vinylbenzenesulfonyloxy) anthracene-1,9-dicarboxyimidea-methyl methacrylate (VBSADI-MMA) and N-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimidea-ethyl acrylate (VBSADI-EA) copolymer through atom transfer radical polymerization (ATRP). Finally, we have also developed photoresponsive organosilicon surfaces using the aforementioned polymers.
- Ikbal, Mohammed,Banerjee, Rakesh,Atta, Sanghamitra,Dhara, Dibakar,Anoop, Anakuthil,Singh, N. D. Pradeep
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p. 10557 - 10567
(2013/02/22)
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- Development of 1-Hydroxy-2(1H)-quinolone-Based Photoacid Generators and Photoresponsive Polymer Surfaces
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A new class of carboxylate and sulfonate esters of 1-hydroxy-2(1H)- quinolone has been demonstrated as nonionic photoacid generators (PAGs). Irradiation of carboxylates and sulfonates of 1-hydroxy-2(1H)-quinolone by UV light (γ≥310 nm) resulted in homolysis of weak N-O bond leading to efficient generation of carboxylic and sulfonic acids, respectively. The mechanism for the homolytic N-O bond cleavage was supported by time-dependent DFT calculations. Photoresponsive 1-(p-styrenesulfonyloxy)-2-quinolone-methyl methacrylate (SSQL-MMA) and 1-(p-styrenesulfonyloxy)-2-quinolone-lauryl acrylate (SSQL-LA) copolymers were synthesized from PAG monomer 1-(p-styrenesulfonyloxy) -2-quinolone, and subsequently controlled surface wettability was demonstrated for the above-mentioned photoresponsive polymers. Copyright
- Ikbal, Mohammed,Banerjee, Rakesh,Atta, Sanghamitra,Jana, Avijit,Dhara, Dibakar,Anoop, Anakuthil,Singh, N. D. Pradeep
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p. 11968 - 11975
(2012/10/29)
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- Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates
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The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates. The Royal Society of Chemistry and Owner Societies 2011.
- Terpolilli, Marco,Merli, Daniele,Protti, Stefano,Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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experimental part
p. 123 - 127
(2012/01/03)
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- Photoacid generators (PAGs) based on N-acyl-N-phenylhydroxylamines for carboxylic and sulfonic acids
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Simple and efficient photoacid generators (PAGs) for carboxylic and sulfonic acids based on N-acyl-N-phenylhydroxylamines have been demonstrated. Irradiation of o-carboxylates and thermally rearranged o-arenesulfonates of N-acyl-N-phenylhydroxylamines using UV light (≥254 nm) in aqueous methanolic solution resulted in efficient generation of carboxylic and sulfonic acids, respectively. The carboxylic acid generation ability of N-acyl-N- phenylhydroxylamines was found to be dependent on their N-acyl substituents. Further, polymer bearing o-arenesulfonates of N-acyl-N-phenylhydroxylamine was synthesized and demonstrated as PAG for sulfonic acids.
- Ikbal, Mohammed,Jana, Avijit,Singh, N.D. Pradeep,Banerjee, Rakesh,Dhara, Dibakar
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experimental part
p. 3733 - 3742
(2011/06/21)
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- Removal of electrophilic potential genotoxic impurities using nucleophilic reactive resins
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Potential genotoxic impurities (PGI) are chemical compounds that could potentially damage DNA and lead to mutation. Controlling the occurrence of PGIs in active pharmaceutical ingredients (APIs) poses a big challenge for chemists, as levels of these compounds must be reduced well below the amounts required for other types of less toxic impurities. In situations where formation of PGIs cannot be avoided, an ideal solution would allow the complete removal of PGIs after the synthesis is complete, for example, by recrystallization, preparative chromatography or other downstream processing approaches. Some disadvantages of using these approaches are potential high yield loss, high solvent consumption, and additional time and resources required for process development. In this work, we present a simple and rapid approach to remove electrophilic PGIs from APIs. A selected nucleophilic resin can be added to the final API solution to reduce or totally remove the PGI. Esters of methanesulfonic acid (MSA), benzenesulfonic acid (BSA), and ρ-toluenesulfonic acid (pTSA) were used as model electrophilic PGIs. Several nucleophilic resins were screened, and the resins with the highest efficiency of PGI removal were chosen. A recommended procedure is presented for the removal of MSA, BSA, and pTSA esters. The kinetics of PGI removal, resin loading capacity, solvent effects, and API matrix effects are demonstrated.
- Lee, Claire,Helmy, Roy,Strulson, Christopher,Plewa, Jolanta,Kolodziej, Elizabeth,Antonucci, Vincent,Mao, Bing,Welch, Christopher J.,Ge, Zhihong,Al-Sayah, Mohammad A.
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experimental part
p. 1021 - 1026
(2011/03/20)
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- Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions
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A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Bronsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1′-binaphthalene-2,2′-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.
- Denmark, Scott E.,Kalyani, Dipannita,Collins, William R.
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supporting information; experimental part
p. 15752 - 15765
(2011/02/22)
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- PROCESS FOR RECOVERING SULFONIC ACID CATALYST AND NOBLE PRODUCTS FROM ACRYLATE HEAVY ENDS
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Sulfonic acid catalyst, e.g., methanesuifonic acid (MSA), and noble products, e.g., acrylic acid, butanol and butyl acrylatε, are recovered from acrylatc reactor blowdown. The blowndown comprises, among oilier things, the Michael ad ducts of the sulfonic acid and acrylate esters. The blowdown is mixed with water, subjected to conditions sufficient to crack or hydrolyze the Michael addυcts into their constitueut parts. These cracking conditions are also sufficient to allow the recovery of the sulfonic acid and constituent parts, as well as other light components of the heavy ends, e.g., unreacted acrylic acid and butanol,
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Page/Page column 14-17
(2009/08/16)
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- Process for oxidation of methane to acetic acid
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Acetic acid or derivatives such as methyl acetate and acetyl sulfate, are produced from methane by contacting a methane-containing feed with an oxygen-containing gas in the presence of a palladium-containing catalyst and an acid selected from concentrated sulfuric acid and fuming sulfuric acid. The process is carried out using an oxygen partial pressure of from about 30 to about 300 psi and most preferably from about 60 to about 200 psi, a methane partial pressure of from about 100 to about 1000 psi, and most preferably from about 100 to about 400 psi, and a total pressure of oxygen and methane of from about 130 to about 1300 psi, preferably from about 200 to about 600 psi. The process is carried out in the absence of a catalyst promoter.
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Page/Page column 3-5; sheet 1-3
(2008/06/13)
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- Manufacture of higher hydrocarbons from methane, via methanesulfonic acid, sulfene, and other pathways
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Hydrocarbon liquids and olefins can be made from methane with greater efficiency than previously available, by converting methane into methanesulfonic acid (MSA), then converting the MSA into a reactive anhydride called sulfene, H2C═SO2. Sulfene will exothermically form ethylene, an olefin. It also can insert methylene groups (—CH2—) into hydrocarbon liquids, to make heavier and more valuable liquids. Other options are disclosed for improved methods of making MSA (such as by using di(methyl-sulfonyl) peroxide as a radical initiator), for converting MSA into products such as dimethyl ether (DME), and for using DME as a “peak shaving” gas that can be injected into natural gas supply pipelines with no disruptions to end-use burners.
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Page/Page column 25
(2008/06/13)
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- Process for the conversion of methane
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A process for the facile two-step synthesis of methanol from methane is disclosed. In accordance with the invention, an appropriate combination of initiator and reaction medium is employed to achieve methane conversion in very high selectivity and yield under near-ambient temperature.
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Page/Page column 1
(2008/06/13)
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- Removal of alkyl alkanesulfonate esters from alkanesulfonic acids and other organic media
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Methods of removing alkyl alkanesulfonate esters from aqueous or anhydrous compositions are provided. The invention provides methods for the conversion of alkyl alkanesulfonate esters of the formula RSO3R′ to the corresponding acids of the formula RSO3H. The alkyl alkanesulfonate esters are present in an organic medium, which may contain significant amounts of water or which may be anhydrous or substantially anhydrous. In some embodiments, the invention provides methods for purifying aqueous or anhydrous alkanesulfonic acids by removing alkyl alkanesulfonate esters.
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Page/Page column 6; 7
(2008/06/13)
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- PROCESS FOR DIRECT OXIDATION OF METHANE TO ACETIC ACID
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Acetic acid is produced by oxidation of methane with an oxygen-containing gas in the presence of an acid selected from concentrated sulfuric acid and fuming sulfuric acid, a palladium-containing catalyst and a promoter, preferably a copper or iron salt. The addition of a promoter and O2 to a system that includes a palladium-containing catalyst such as PdCl2 increases the rate of acetic acid formation from methane by more than an order of magnitude as compared with prior art and, in addition, inhibits the precipitation of Pd black.
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Page/Page column 3
(2008/06/13)
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- A high-yield, liquid-phase approach for the partial oxidation of methane to methanol using SO3 as the oxidant
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A direct approach for producing methanol from methane in a three-step, liquid phase process is reported. In the first step, methane is reacted with SO3 to form methanesulfonic acid (MSA) at 75°C using a free-radical initiator and MSA as the solvent. Urea-H2O2 in combination with RhCl3 is found to be the most effective initiator (57% conversion of SO3; 7.2% conversion of CH4). MSA is then oxidized by SO3 at 160°C in a second step to produce a mixture containing methyl bisulfate and some methyl methanesulfonate (87% conversion of MSA). In the third step, the mixture of methyl bisulfate and methyl methanesulfonate is hydrolyzed in the presence of an organic solvent, to produce an organic phase containing methanol and an aqueous phase containing sulfuric acid and some MSA (63% conversion of methyl bisulfate; 72% conversion of methyl methanesulfonate). Overall, 58% of the MSA (of which 23% is derived from methane) is converted to methanol.
- Mukhopadhyay, Sudip,Zerella, Mark,Bell, Alexis T.
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p. 1203 - 1206
(2007/10/03)
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- Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds
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Anhydrous processing to convert methane into oxygenates (such as methanol), liquid fuels, or olefins uses an initiator to create methyl radicals. These radicals combine with sulfur trioxide to form methyl-sulfonate radicals. These radicals attack fresh methane, forming stable methane-sulfonic acid (MSA) while creating new methyl radicals to sustain a chain reaction. This system avoids the use or creation of water, and liquid MSA is an amphoteric solvent that increasing the solubility and reactivity of methane and SO3. MSA from this process can be sold or used as a valuable chemical with no mercaptan or halogen impurities, or it can be heated and cracked to release methanol (a clean fuel, gasoline additive, and chemical feedstock) and sulfur dioxide (which can be oxidized to SO3 and recycled back into the reactor). MSA also can be converted into gasoline, olefins, or other valuable chemicals.
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Page/Page column 11
(2008/06/13)
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- Wet oxidation process and system
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A process and system for the destruction of compounds having a carbon-hetero atom bond. The process includes wet oxidation at elevated temperature and pressure of an aqueous mixture of at least one compound having a carbon-hetero atom bond to substantially destroy the carbon-hetero atom bond of the at least one compound. The resulting oxidized material may be further treated in an advanced oxidation process to destroy any residual carbon-hetero atom bonds remaining.
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Page/Page column 5
(2008/06/13)
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- PROCESS FOR PRODUCTION OF ALKANESULFONIC ACID
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The present invention relates to a process for the production of alkanesulfonic acid. More particularly, the present invention relates to a process for the production of alkanesulfonic acid from alkyl mercaptan effluents generated in chemical industries. The process of the invention comprises the oxidation of the entire alkyl mercaptan generated as an effluent in the chemical industries to serve two concomitant purposes: (1) complete removal of obnoxious odour, and (2) value addition by the production of alkanesulfonic acids selectively in quantitative yields.
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- Process for production of alkanesulfonic acid
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The present invention relates to a process for the production of alkanesulfonic acid. More particularly, the present invention relates to a process for the production of alkanesulfonic acid from alkyl mercaptan effluents generated in chemical industries. The process of the invention comprises the oxidation of the entire alkyl mercaptan generated as an effluent in the chemical industries to serve two concomitant purposes: (1) complete removal of obnoxious odour, and (2) value addition by the production of alkanesulfonic acids selectively in quantitative yields.
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