Dehydration of 2,3-butanediol over zeolite catalysts

Abstract

opment of the ethylene industry are such that ethylene producers are switchingt om ore efficient ethylene production technologies. This leads to al ack of butadiene on the market and therefore requires the development of alternative technologies leadingt ob utadiene.T herefore, the synthesis of MEK, BD, and 3B2OL from BDO appears to be achallenging goal.Synthesis of MEK from BDO has been reportedo ver strong solid catalysts such as H-Nafion, [10] heteropoly acids, [11] aluminosilicates, [12] and zeolites. [1f, 13, 14] Bucsi et al. [10] reported high conversions of BDO into MEK over H-Nafion catalysts at temperatures as low as 150 8C; the acetalization of MEK with BDO being the main side reaction. MEK and its acetals accounted for 94 %o ft he products over these catalysts. Other strong acids such as heteropoly acids have also demonstratedh igh conversion into MEK in the temperature range 150-180 8C. [11] The selectivity to MEK varied from 50 to 95 %, the main byproducts were the corresponding dioxolanes and 2-methylpropanal( MP). Zeolites were found to be active catalysts for transforming BDO into MEK in the temperature range 230-350 8C. [1f, 13-15] Differentz eolite structures, including FAU, MFI, MOR, and BEA, have also been tested. Whereas medium-pore zeolites favored MEK formation, the large-pore zeolitesy ielded acetals andk etals. [13] The selective synthesis of 3B2OL and BD from BDO has been achieved over less acidic solids and at higher temperatures. [8b, 16, 17] The first attempts for 3B2OL and BD synthesis go back to the 1940s.W infield [16] studied al arge number of metal oxidesa nd salts and found that the best catalyst for 3B2OL and BD production is ThO 2 .T hey disclosed that over ThO 2 , 3B2OL can be obtained with ay ield of 70 %a t3 50 8C, whereas 62 %y ield of BD can be reached at 500 8C. [16] Significant contribution to the synthesis of 3B2OL and BD from BDO has been madeb yt he group of Sato et al. [8b, 17, 18] during the few last years. These authors have investigated BDO dehydration over al arge range of rare-earth-oxidec atalysts. They disclosedt hat Sc 2 O 3 calcined at 800 8Cs hows excellent catalytic activity at 325 8Cw ith 85 %s electivity to 3B2OL at 2,3-Butanediol (BDO) is an excellent feedstock for expanding the network of bio-based chemicals through catalytic technologies. The dehydration of BDO provides an alternative green route to important chemicals such as methyl ethyl ketone (MEK) and1 ,3-butadiene (BD). In this contribution, we report on the catalytic performanceo fb oron (BP), aluminum (AlP), titanium (TiP), zirconium (ZrP), and niobium (NbP) phosphates in BDO dehydration.T he kinetic study points to three reaction pathways operating over phosphate catalysts, leading to MEK, 2-methyl-propanal( MP), and BD via intermediate 3-butene-2-ol (3B2OL) formation. The major reaction pathway is shownt oi nvolve pinacolr earrangementt oM EK. The reactivity of phosphates is found to increasei nt he order:B P< TiP < ZrP = NbP < AlP.T he best catalytic performance is achieved over Al...

A Polyethylenimine‐Functionalized Protic Ionic Liquid (PolyE‐IL) Catalyst for Conversion of Aqueous 2,3‐Butanediol into Methyl Ethyl Ketone (MEK)

“…[21][22][23][24][25][26][27] In spite of high conversion and yield, the reported catalytic systems are suffered from several economical and scientific barriers such as a) low yield and selectivity of catalyst b) stringent reaction conditions c) difficult product separation protocol and d) lower recyclability of catalyst e) Rigorous catalyst preparation f) limited number of active sites per gram etc. [22][23][24][25][26][27] In order to overcome the reported barriers, homogenous catalyst such as Ionic Liquid (IL)/ Polymeric Ionic Liquid (PIL) were explored as one of the most promising participate in the field of catalysis. [28] ILs/PILs have various characteristics properties such as solubility, polarity, and easy synthesis.…”

“…Even being the immobilized H 2 SO 4 is a heterogeneous catalyst but it is not recommended due to low recyclability due to stability and leaching characteristics. Various zeolites with different ratio of silica and alumina [19] and doped with different metals or acids like copper, [22] zirconium, [25] sodium phosphate, [27] phosphoric acid, [26] boric acid [19] were tested and operated between temperature range of 200 °C–400 °C and 70–90 % yield. In addition to zeolites metal oxides like zirconium oxide, [24] rare earth metal oxides, [28] were also studied for dehydration for 2,3‐BDO in a temperature range of 250–450 °C which resulted in complete conversion of 2,3‐BDO and yield of MEK vary from 10–80 % [21–27] …”

Bio-Based Solvents and Gasoline Components from Renewable 2,3-Butanediol and 1,2-Propanediol: Synthesis and Characterization

“…Hence, the noted compounds are of particular interest as renewable feedstocks for the production of chemicals. The majority of studies on 2,3-BD conversion are dedicated to its dehydrative conversion that yields methyl ethyl ketone (MEK) and isobutyraldehyde [9][10][11][12], 3-butene-2-ol [10,[13][14][15], butenes [16][17][18] and 1,3-butadiene [19][20][21]. Some 2,3-BD derivatives have been previously considered as potential motor fuel components and organic solvents.…”

Modeling of a Pilot-Scale Fixed-Bed Reactor for Dehydration of 2,3-Butanediol to 1,3-Butadiene and Methyl Ethyl Ketone

“…The catalysts are bentonite clay [4], metal and earth oxides [5][6][7][8][9], zeolites [10][11][12][13], a perfluorinated resin with sulfonic acid groups [10], heteropolyacids [11,14], calcium phosphates [15][16][17][18][19][20], Cs/SiO 2 [21], sodium phosphates [22] and so on. Research on old chemistry and new catalytic advances in the on-purpose synthesis of butadiene has been reviewed by Makshina et al [23].…”