Acidity effects of Hβ zeolite on olefin alkylation of thiophenic sulfur in gasoline

Olefin alkylation of thiophenic sulfur process was carried out in model gasoline, using Hβ zeolites with different Si/Al2 ratios as catalysts. In particular, the influence of acid properties of Hβ zeolites on its catalytic ability for the thiophene alkylation, xylene alkylation and hexene oligomerization was investigated. The results showed that the acidity of the Hβ zeolite was increased with the decrease of Si/Al2 ratio, but its catalytic ability was not always increased. In fact, it reached the maximal catalytic ability at Si/Al2 ratio of 66, and under the reaction conditions of 60 ℃, 1.5 MPa, WHSV 3.0 h^-1 and time on stream 2 h. At the ratio, the conversion of thiophene, xylene, and oligomerized hexene were 96.6%, 2.7% and 2.8%, respectively. An optimal Si/Al2 ratio exists for the catalytic performance of Hβ zeolite. By investigating the coke deposition of the used Hβ zeolite catalysts, it has been found that the optimal Si/Al2 ratio is attributed to the combined effect of the carbocation activation capability and the hydrogen transformation capability of the Hβ zeolite catalyst.

Novel Synthetic Method for the Vilsmeier-Haack Reagent and Green Routes to Acid Chlorides, Alkyl Formates, and Alkyl Chlorides

An environmentally benign and practical preparation method for the Vilsmeier-Haack reagent (VH) has been developed by using phthaloyl dichloride with DMF in toluene or 2-chlorotoluene. Phthalic anhydride as the byproduct was recovered in high yield by simple filtration. Some aromatic acids have been transformed into the corresponding acid chlorides in good yields by employing the isolated VH. Treatment of primary or secondary alcohols with VH gave alkyl formates or alkyl chlorides by depending on the reaction conditions.

One-pot Synthesis of Lewis Acidic Ionic Liquids for Friedel-Crafts Alkylation

Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.

Alkylation of Isobutane and Isobutene in Acidic Polyether Ionic Liquids

The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.

Long-chain alkanol-alkyl carboxylic acid-based low-viscosity hydrophobic deep eutectic solvents for one-pot extraction of anthraquinones from Rhei Radix et Rhizoma

Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low polarity(lower than that of methanol,ChCl-based deep eutectic solvents and other reported HDESs),and low density(<0.928 g/mL).A simple one-pot method based on a novel HDES-water two-phase extraction system was constructed for the extraction of weak-polarity bioactive components,anthraquinones,from Rhei Radix et Rhizoma.This HDES-based new extraction method does not consume hazardous organic solvents and can obtain a total anthraquinone yield of 21.52 mg/g,which is close to that obtained by the Chinese pharmacopoeia method(21.22 mg/g)and considerably higher than those by other reported HDESs-based extraction methods(14.20-20.09 mg/g,p<0.01).The high extraction yield can be mainly attributed to the severe destruction of the RRR cell walls by the extraction system and the excellent dissolving ability of novel HDESs for anthraquinones.

Alkylation of Catechol with tert-Butyl Alcohol Catalyzed by Mesoporous Acidic Montmorillonite Heterostructure Catalysts

The liquid phase alkylation of catechol with tert-butyl alcohol to produce 4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite and novel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is the main product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the side products. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBC compared to other solid acid catalysts tested. Over the PMHs derived from H-exchanged montmorillonite through template extraction processes, the suitable reaction temperature is ca 410 K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lower weight hourly space velocity) can improve the conversion of catechol and influence the selectivity slightly. The reasonable reaction time is ca 8 h.The type and strength of acidity of H-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammonia temperature-programmed desorption techniques. The medium and strong acid sites are conducive to producing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences between the PMHs from calcination and those fi'om extraction are attributed to proton migration and acidity change in the gallery surface.

Surface Acidity of Aluminum Phosphate and Its Catalytic Performance in Benzene Alkylation with Long Chain Olefin

铝磷酸盐( AlPO4-5 )的酸的性质稳固的酸催化剂被温度描绘氨( NH3 )的规划解吸附作用( TPD )， n-propylamine ( n-C3H7NH2 )， iso-propylamine [( CH3 ) 2CHNH2 ]并且 n-dipropylamine [( C3H7 ) 2NH ]独立，并且它在有长链石蜡的苯完化的催化表演在一个改正床反应堆被学习。催化剂的描绘的酸数量与被吸附物质的盐基度增加了。随催化剂的激活温度的增加，然而， NH3-TPD 描绘的酸数量减少了什么时候用三种另外的被吸附物质由 TPD 描绘了，增加了。TPD 过程的解吸附作用动力学和催化剂的释放动力学被调查。酸味和催化剂的催化性能也被相关。结果证明酸数量和力量很好与显示 NH3 是一种更好基本的被吸附物质的分别地，把 NH3 用作被吸附物质的活动和稳定性被相关。有更高的酸的催化剂总计，这也被发现，表面上的更低的酸力量展出了更好催化的表演和稳定性。

A STUDY ON THE DEGRADATION MECHANISM OF PHOTOCROSSLINKING PRODUCTS FORMED BY CYCLIZED POLYISOPRENE-DIAZIDE SYSTEM UNDER THE INFLUENCE OF ALKYL BENZENE SULFONIC ACIDS

The degradation mechanism of photocrosslinking products formed by cyclized polyisoprene-diazide system under the influence of the different alkyl benzene sulfonic acids was studied. The effects of alkyl chain length and the concentration of alkyl benzene sulfonic acids on the rate of degradation reaction were discussed. It was found that in the initial stage of degradation, the cyclicity ratio and the average fused ring number did not change considerably, but the percentage of uncyclized parts content varied significantly. The suitable mechanism was supposed.

Mild and Highly Selective Preparation of Alkylate Gasoline Promoted by Using Polyetheramine-Based Acidic Ionic Liquid

A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants,but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse.The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity.Under the conditions covering a VIL/VTfOH ratio of 10:3,a temperature of 25°C,and a reaction time of 25 min,the C8-product selectivity reaches 86.63%.The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance.After many operating cycles,the hydrophobic PEA-IL can be easily regenerated by simply adding water.This study provides a green,economic,and highly efficient method for producing high-octane alkylate gasoline.

Preparation, Characterization and Catalytic Activity of Alkyl Benzene Sulfonic Acid Carbon-Based Acid Catalyst

Based on starch and series of alkyl benzene sulfonic acid as the materials, a novel carbon-based solid acid catalyst is synthesized using hydrothermal method. This catalyst exhibits much higher catalytic activity in the reaction of esterification of Mono-fatty alcohol polyoxyethylene maleate esters with 1,4-butanediol. The structure of carbon-based solid acid catalyst was charactered by IR and XRD, characterizations showed that this catalyst exhibited high –SO3H loading. Reusability of the carbon-based solid acid catalyst for esterification showed that after recycling five times the activity remained unchanged.

First-in-China Sulphuric Acid Alkylation Unit Passed Technical Appraisal with Its Technology Reaching Internationally Advanced Level

On November 15,2018 the sulfuric acid alkylation(SINOALKY)technology,jointly developed by RIPP,SINOPEC’s Shijiazhuang Refining and Chemical Branch Company,and the Luoyang Engineering Co.Ltd.,had passed the technical appraisal organized by the SINOPEC Science and Technology Division.The experts attending the appraisal meeting have recognized that the said technology,featuring low reaction temperature,low acid consumption and good products distribution,has entirely on a par with the internationally advanced level.The successful commercialization of SINOALKY technology has symbolized that China does possess the first sulfuric acid alkylation unit with fully independent intellectual property right after breaking through foreign technical barriers.

PERFLUOROOCTANESULFONIC ACID CATALYZED FRIEDEL-CRAFTS ALKYLATION WITH OLEFINS IN GAS-LIQUID PHASE

Solid superacid perfluorooctanesulfonic acid(POSA)catalyzed Friedel-Crafts alkylation of aromatic hydrocarbons with olefins in gas-liquid phase.The alkylations gave good yields with simple operation and easy work up.The amount of the catalyst used in the reactions was small and could be reused.The optimum temperature of the reactions and the effect of the amount of the catalyst used in the reactions are also discussed.

SYNTHESES OF HINDERED ALKYL PHOSPHONATES AND PHOSPHONIC & PHOSPHINIC ACIDS

A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.

An Anionic Polymer Incorporating Low Amounts of Hydrophobic Residues Is a Multifunctional Surfactant. Part 2: Emulsification, Moisture Absorption, and Moisture Retention of Alkyl Esterified Poly-γ-Glutamic Acid

In the accompanying paper (Part 1), we showed that the fatty acid moiety and the acidity of the polysaccharide-backbone of a fatty acid-containing polysaccharide might be involved in its emul-sification, moisture absorption, and moisture retention abilities. In this study, we synthesized alkyl esterified poly-γ-glutamic acid (PGA) with various chain lengths and degrees of substitution of the alkyl moieties to examine how hydrophobic groups incorporated in the anionic polymer contribute to enhanced emulsification, moisture absorption, and moisture retention. With a low degree of alkylation of PGA, these abilities were drastically improved. To improve the moisture absorption of PGA, alkylation with a short chain length is effective in forming interspaces between PGA chains to trap water molecules. Hydrophobic-hydrophilic balance may also be important to improve the emulsification and moisture retention abilities of PGA alkylates. To the best of our knowledge, this is the first report of the relationship between the structure and the multifunctional abilities of an anionic polymer incorporated with a small amount of hydrophobic residue. PGA alkylates, as well as fatty acid-containing polysaccharides, have potential use as multifunctional surfactants throughout various industries.

ASYMMETRIC SYNTHESIS Ⅻ:HIGHLY ENANTIOSELECTIVE SYNTHESIS OF α-AMINO ACIDS BY ALKYLATION OF THE KETIMINE FROM 2-HYDROXY-PINAN-3-ONE AND MENTHYL GLYCIN-ATE A DOUBLE ASYMMETRIC INDUCTION SYSTEM

A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates with mineral acid.The double asymmetric induction are explained by the transition model of lithium enolate.

Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

Novel organo-inorganic hybrid materials(MTW-x-SO_(3)H) have been fabricated by immobilizing 3-mercap topropyltriethoxysilane onto mesopore MTW zeolites, which is treated via a simple oxidation process with hydrogen peroxide as the oxidant to transform sulfhydryl group into sulfonic acid group. The organic sulfhydryl groups are covalently bonded to the external surface of MTW zeolites through the condensation between siloxane arising from organic fragments with silanol groups on the surface of MTW zeolites, the hybrids contain sulfonic acid group within the external surface of MTW zeolites and an opened mesoporous system in the matrix of MTW zeolites, which provide enough accessible Brùnsted acid sites for the alkylation between phenol with tert-butyl alcohol. Through this methodology it's possible to prepare multifunctional materials where the plenty of mesopores are benefit for the introduction of larger numbers of sulfonic acid groups that contributes to activity during reactions, resulting in high activity(>55%) of MTW-4-SO_(3)H and desired selectivity(>56%) of 2-TBP(2-tert-butyl phenol) in the alkylation between phenol with tert-butyl alcohol.

Hydrothermal conversion of fructose to lactic acid and derivatives:Synergies of metal and acid/base catalysts

With increasing strict regulation on single-use plastics,lactic acid(LA)and alkyl lactates,as essential monomers for bio-degradable polylactic acid(PLA)plastic products,have gained worldwide attention in both academia and industry.While LA is still dominantly produced through fermentation processes from start,chemical synthesis from cellulosic biomass remains a grand challenge,owing to poor selectivity in activating CAH and CAC bonds in sugar molecules.To our best knowledge,recent publications have been focused on hydrothermal conversion of glucose to LA,while this review summarizes the highlights on direct thermal conversion of fructose as starting material to LA and derivatives.In particular,the synergies of metal/metal cations and acid/base catalysts will be critically revised on retro-aldol and dehydration reactions.This work will provide insights into rational design of active and selective catalysts for the production of carboxylic acids from biomass feedstocks.

硫酸法烷基化工艺的专用过程模拟系统开发

为了实现硫酸法烷基化工艺装置的准确模拟计算,在Visual Studio2010开发环境下,采用SQLite数据库管理系统建立烷基化物性数据库;基于CAPE-OPEN标准,在已开发的通用过程模拟系统OPEN的基础上,建立烷基化反应模块,采用C++语言实现与通用过程模拟系统OPEN的集成,形成完整的硫酸法烷基化工艺的专用过程模拟系统。通过实例对所开发的模拟系统进行检验,并将计算结果与实际值进行对比。结果表明:产品质量均满足工业生产需求,计算结果与实际工业生产中的主要工艺指标基本吻合,各流股中关键组分模拟值与实际值的相对偏差都控制在2.0%以内,满足计算精度要求,说明开发的硫酸法烷基化工艺的专用过程模拟系统可进行较为准确的模拟计算。