1-9 A-D E-G H-M N-P Q-S T-Z

SOLKETAL

SOLKETAL

 

synonyms:
Solketal; 100-79-8; 2,2-Dimethyl-1,3-dioxolane-4-methanol; (2,2-Dimethyl-1,3-dioxolan-4-yl)methanol; Glycerolacetone;Dioxolan; 1,2-O-Isopropylideneglycerol; Isopropylidene glycerol; 1,2-Isopropylideneglycerol; 1,3-Dioxolane-4-methanol, 2,2-dimethyl-; Glycerol dimethylketal; 2,3-Isopropylideneglycerol; DL-1,2-Isopropylideneglycerol;Acetone monoglycerol ketal; 1,2-Isopropylideneglycerin; Glycerinisopropylidene ether; Acetone glycerol; 2,2-Dimethyl-1,3-dioxolan-4-ylmethanol; Glycerol acetonide;2,3-(Isopropylidenedioxy)propanol; 2,3-O-Isopropylideneglycerol; 2,2-Dimethyl-4-hydroxymethyldioxolane; 2,2-Dimethyl-4-(hydroxymethyl)-1,3-dioxacyclopentane; 1,2-O,O-Isopropylideneglycerin; Glycerol, 1,2-O-isopropylidene; Glycerol acetonide (VAN); 2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane; 2,2-Dimethyl-5-hydroxymethyl-1,3-dioxolane; 4-Hydroxymethyl-2,2-dimethyl-1,3-dioxolane; NSC 59720; 2,2-Dimethyl-4-oxymethyl-1,3-dioxolane; alpha,beta-Isopropylideneglycerol; 2,2-Dimethyl-1,3-dioxolan-4-yl methanol; Acetone, cyclic (hydroxymethyl)ethylene acetal; (R)-(ı)-2,2-Dimethyl-1,3-dioxolane-4-methanol; 2,2-dimethyl-1,3-dioxolane-4-methanol (solketal); Q2968854; W-108939; [(4R/S)-2,2-Dimethyl-1,3-dioxolan-4-yl]methanol; F0001-0027; Z1262396033; (+/-)-2,2-Dimethyl-1,3-dioxolane-4-methanol (Glycerol acetonide); 2,3-dioxolan-4-yl methanol; 5-19-02-00362 (Beilstein Handbook Reference); DL-1,2-isoproylideneglycerol; 1,2-o-isopropylidene glycerol; 2,2-dimethyl-1,3-dioxolan-4-methanol; 2,2-dimethyl-1,3-dioxolane4-methanol; solketal; sol ketal; sol-ketal; Q2968854; W-108939; Solketal; 100-79-8; 2,2-Dimethyl-1,3-dioxolane-4-methanol;(2,2-Dimethyl-1,3-dioxolan-4-yl)methanol; Glycerolacetone; Dioxolan; 1,2-O-Isopropylideneglycerol; Isopropylidene glycerol; solket al; sol ketal;1,2 Isopropylideneglycerol; 1,3-Dioxolane-4-methanol, 2,2-dimethyl-; Glycerol dimethylketal; 2,3-Isopropylideneglycerol; DL-1,2-Isopropylideneglycerol; Acetone monoglycerol ketal; 1,2-Isopropylideneglycerin; Glycerinisopropylidene ether; Acetone glycerol; 2,2-Dimethyl-1,3-dioxolan-4-ylmethanol; Glycerol acetonide; 2,3-(Isopropylidenedioxy)propanol; 2,3-O-Isopropylideneglycerol; 2,2-Dimethyl-4-hydroxymethyldioxolane; 2,2-Dimethyl-4-(hydroxymethyl)-1,3-dioxacyclopentane; 1,2-O,O-Isopropylideneglycerin; Glycerol, 1,2-O-isopropylidene; Glycerol acetonide (VAN); 2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane; 2,2-Dimethyl-5-hydroxymethyl-1,3-dioxolane; 4-Hydroxymethyl-2,2-dimethyl-1,3-dioxolane; NSC 59720; 2,2-Dimethyl-4-oxymethyl-1,3-dioxolane; alpha,beta-Isopropylideneglycerol; 2,2-Dimethyl-1,3-dioxolan-4-yl methanol; Acetone, cyclic (hydroxymethyl)ethylene acetal; (R)-(ı)-2,2-Dimethyl-1,3-dioxolane-4-methanol; 2,2-dimethyl-1,3-dioxolane-4-methanol (solketal); Q2968854; W-108939; [(4R/S)-2,2-Dimethyl-1,3-dioxolan-4-yl]methanol; SOLKETAL; Sol KEtal; Sol ketal; solketal;SOL KETAL; Sol Ketal

 

 

 

SOLKETAL
N° CAS 100-79-8
Formule moléculaire C6H12O3
Molecular Weight (g/mol) 132.16
Numéro MDL MFCD00063238
InChI Key RNVYQYLELCKWAN-UHFFFAOYSA-N
Synonyme solketal, 2,2-dimethyl-1,3-dioxolane-4-methanol, 2,2-dimethyl-1,3-dioxolan-4-yl methanol, glycerolacetone, dioxolan, isopropylidene glycerol, 1,2-isopropylideneglycerol, 1,2-o-isopropylideneglycerol, 1,3-dioxolane-4-methanol, 2,2-dimethyl, glycerol dimethylketalAfficher plus
PubChem CID 7528
IUPAC Name (2,2-diméthyl-1,3-dioxolan-4-yl)méthanol
SMILES CC1(OCC(O1)CO)C

 

 

Abstrait
Au cours de la dernière décennie, une attention considérable a été accordée au développement des biocarburants, surtout le biodiesel, en tant qu'alternative prometteuse aux combustibles fossiles. La réaction de transestérification pour produire du biodiesel donne comme sous-produit une quantité de glycérol qui représente environ 10% en poids de la production totale de biodiesel. Avec l'augmentation de la production de biodiesel, le glycérol est désormais considéré comme un déchet et des solutions pour son utilisation efficace sont nécessaires. Une voie prometteuse est représentée par la condensation du glycérol avec de l'acétone pour produire du solketal, un produit à valeur ajoutée avec plusieurs applications telles que tensioactif, agent aromatisant, agent plastifiant, solvant sûr ou en mélange avec du biodiesel pour améliorer ses propriétés. Une manière durable d'effectuer cette réaction envisage l'utilisation de catalyseurs hétérogènes présentant des acidités de Brønsted et Lewis. Les silicates poreux présentant un métal inséré en tant que site unique dans l'ossature peuvent être des catalyseurs actifs et sélectifs de cette réaction. En particulier, il a déjà été rapporté que les nanoparticules de Ga-MCM-41 sont l'un des catalyseurs les plus efficaces dans la conversion du glycérol en solketal. Ici, le processus sol-gel assisté par aérosol a été utilisé comme un outil puissant pour synthétiser des solides à base de silice avec du Ga inséré comme site unique dans la structure. L'influence de différents paramètres sur les propriétés morphologiques et l'activité catalytique, comme le rapport Si / Ga ou la nature de l'agent de modélisation, a été étudiée. De plus, pour optimiser la conception des catalyseurs, le rôle joué par l'équilibre hydrophobe / hydrophile de la surface du catalyseur a été étudié. Le processus d'aérosol a été utilisé avec succès pour synthétiser une série de Ga-silicates avec différents degrés de fonctionnalisation méthyle en utilisant une approche co-synthétique à un seul pot. Tous les matériaux synthétisés ont été entièrement caractérisés et testés pour la conversion du glycérol en solketal avec des résultats prometteurs.

 

 

Conversion catalytique du glycérol en solketal par des gallo-silicates préparés via le procédé aérosol

Résumé
Les réactions sans solvants sont des systèmes de choix en matière de chimie verte. En plus de contribuer à réduire l'impact environnemental des procédés chimiques, les systèmes sans solvants peuvent réduire les coût de production, les temps de réaction et les dimensions du réacteur, ce qui va diminuer les coûts d'investissement. Nous avons développé un procédé amélioré pour préparer des esters gras du 2,2-diméthyl-4-hydroxyméthyl-1,3-dioxolane (solcétal) à partir de graines de soja. Des rendements supérieurs à 90% ont été obtenus en combinant 15 h d'hydrolyse à 6 h d'estérification avec addition par étapes de solketal. La synthèse a été réalisée dans un milieu exempt de solvants, et l'extraction finale a été effectuée en utilisant du CO2 supercritique. Par conséquent, nous avons préparé avec succès ces esters à partir de fèves de soja sans utiliser de solvants organiques. En outre, compte tenu de la non-toxicité de R. oryzae et de la composition du solide restant, ce cernier peut être utilisé comme matière première pour la production d'autres matières premières.

 

 

 


SOLKETAL

 

 

Names
IUPAC name
(2,2-Dimethyl-1,3-dioxolan-4-yl)methanol
Other names
Isopropylidene glycerol
Identifiers
CAS Number
100-79-8 Racemic ☑
14347-78-5 R enantiomer ☒
22323-82-6 S enantiomer 
Properties
Chemical formula
C6H12O3
Molar mass 132.159 g·mol-1
Appearance clear colorless liquid
Density 1.063 g/mL at 25 °C
Boiling point 188 to 189 °C (370 to 372 °F; 461 to 462 K)
Solubility in water
Miscible
Solubility Miscible in most organic solvents (alcohols, ethers, hydrocarbons)

 

 

Solketal is a protected form of glycerol with an isopropylidene acetal group joining two neighboring hydroxyl groups. Solketal contains a chiral center on the center carbon of the glycerol backbone, and so can be purchased as either the racemate or as one of the two enantiomers. Solketal has been used extensively in the synthesis of mono-, di- and triglycerides by ester bond formation. The free hydroxyl groups of solketal can be esterified with a carboxylic acid to form the protected monoglyceride, where the isopropylene group can then be removed using an acid catalyst in aqueous or alcoholic medium. The unprotected diol can then be esterified further to form either the di- or triglyceride.
Abstract
Commercial solketal is known as AugeoTM SL 191 s which stands out as a slow evaporation solvent derived from glycerin which is considered a renewable source. It has low toxicity to human health and the environment. It is a good solvent for resins and polymers, replacing solvents derived from petroleum, and can be used as an additive of (bio) fuels. This work aimed to study acidy zeolites (H-BEA, H-MOR, H-MFI, and H-FER) as new heterogeneous catalysts of solketal production, through the ketalization reaction of glycerol with acetone. The catalytic activity showed H-BEA > H-MOR = H-MFI > H-FER after 180 min, in kinetics study. The major conversion was 85% for H-BEA. It was also verified that all the catalysts can be reused four times without washing or pretreatment among reactions in batch reactor. The solketal produced in this work was characterized by comparing it with its commercial standard, obtaining very similar characteristics
transformation of glycerol into solketal (isopropylidene glycerol or 2,2-dimethyl-1,3-dioxolan-4-yl methanol) (green solvent) through the ketalization reaction of glycerol with acetone. The reaction for solketal production is facilitated by major homogeneous and heterogeneous acid catalysts (Figure 3). The ketalization of glycerol with ketones generates branched oxygenates, solketal (2,2-dimethyl-[1,3] dioxan-4-yl methanol), and 2,2-dimethyl-[1,3] dioxane-5-ol; however, when the reaction is carried out with acetone, the selectivity is higher for the solketal molecule, which has a five-membered ring [5].
Solketal is an excellent component for the formulation of gasoline, diesel, and biodiesel. 
it occurs that the output of the remaining acetone and water between 70 and 120°C plus a fraction containing solketal is distilled. Glycerol is only removed when the system reaches 200°C. The yield of the distillation was 60% by mass of solketal over the initial blend (solketal-water-glycerol-traces of acetone). The solketal fraction is colorless but with a lower viscosity than glycerol.

 

 

Figure 12 shows the appearance of the solketal GreenTec fraction after distillation of the initial blend.
FTIR analysis was used to confirm the presence of solketal in the distilled product and to compare it with its Sigma-Aldrich standard. The FTIR spectrum of the solketal GreenTec and solketal Sigma-Aldrich samples is shown in Figure 13.
When analyzing Table 4, it is observed that both solketal Sigma-Aldrich and solketal GreenTec present very close densities and viscosities.

 

Table 5 shows that only in the analysis of humidity a significant difference between the solketal samples was noticed.

 

Solketal GreenTec presents 56.41% more humidity than solketal Sigma-Aldrich. To remove this moisture, anhydrous sodium sulfate may be added among other drying agents, and/or the solketal GreenTec fraction is withdrawn from 75°C.
Glycerol to solketal transformation is possible to carry out using zeolite acidic catalysts, such as H-BEA, H-MOR, H-MFI, and H-FER, showing a very good activity (conversion 85%) and selectivity (98%). H-BEA presented a larger area, major SAR, and a bigger ratio of the strong:weak sites than the other zeolites. This characteristic contributes to a higher catalytic activity for H-BEA catalyst. All the catalysts can be reused for four times without washing or pretreatment among reactions in batch reactor, but the best catalyst is still the H-BEA zeolite for being more active and showing constant solketal selectivity. The solketal produced in this work was characterized by comparing it with its commercial standard, obtaining very similar characteristics.
Solketal: Green and catalytic synthesis and its classification as a solvent - 2,2-dimethyl-4-hidroxymethyl-1,3-dioxolane, an interesting green solvent produced through heterogeneous catalysis
Most solvents have been labelled as toxic or hazardous substances, but the use of glycerol derivatives could help solve these and other problems. An alternative, green synthesis of 2,2dimethyl-4-hidroxymethyl-1,3-dioxolane (solketal), using solid acid catalysts, has been developed. It is shown that using auxiliary solvents is not essential to get good results, and that the solid catalyst can be recovered and reused, improving the productivity. Moreover solketal has been characterized by determining its polarity and hydrophobicity parameters, which allow identifying possible solvent substitution applications more easily.

 

 

Abstract
Solvent-free reactions are the systems of choice in green chemistry. In addition to contributing to lowering the environmental impact of chemical processes, solvent-free systems can reduce production costs, reaction times, and the dimensions of reactors, thereby decreasing investment costs. An improved procedure to prepare 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane (solketal) fatty esters from soybean seeds has been developed. Yields higher than 90% were achieved by combining 15 h of hydrolysis with 6 h of esterification with a stepwise addition of solketal. The synthesis was performed in a solvent-free medium, and the final extraction was accomplished using supercritical CO2 . Hence, we have successfully prepared these esters from soybean beans without using organic solvents. In addition, given the non-toxicity of Rhizopus oryzae and the composition of the remaining solid, it might be used as a raw material for feedstock production.
Applications
Solketal is useful for synthesis of mono-, di- and triglycerides. It is used as the starting reagent for synthesis of tulipaline derivatives. It acts as a fuel additive in gasoline. It is an inhibitor of Methyl ethyl ketone .

 

 

Notes
Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Incompatible materials are acids, Strong oxidizing agents.
Références bibliographiques
Claudio J. A. Mota; Carolina X. A. da Silva;Nilton Rosenbach; Jair Costa and Flávia da Silva. Glycerin Derivatives as Fuel Additives: The Addition of Glycerol/Acetone Ketal (Solketal) 
Ketalization of glycerol with acetone to synthesize solketal-a potential fuel additive is one of the most promising routes for valorization of glycerol. In this article, state-of-the-art of glycerol ketalization is reviewed, focusing on innovative and potential technologies towards sustainable production of solketal. The glycerol ketalization processes developed in both batch and continuous reactors and performance of some typical catalysts are compared. The mechanisms for the acid-catalyzed conversion of glycerol into solketal are presented. The main operation issues related to catalytic conversion of crude glycerol in a continuous-flow process and the direct use of crude glycerol are discussed.

 

Glycerol to Solketal for Fuel Additive: Recent Progress in Heterogeneous Catalysts

 

Abstract: Biodiesel has been successfully commercialized in numerous countries. Glycerol, as a byproduct in biodiesel production plant, has been explored recently for fuel additive production. One of the most prospective fuel additives is solketal, which is produced from glycerol and acetone via an acetalization reaction. This manuscript reviewed recent progress on heterogeneous catalysts used in the exploratory stage of glycerol conversion to solketal. The effects of acidity strength, hydrophobicity, confinement effect, and others are discussed to find the most critical parameters to design better catalysts for solketal production. Among the heterogeneous catalysts, resins, hierarchical zeolites, mesoporous silica materials, and clays have been explored as effective catalysts for acetalization of glycerol. Challenges with each popular catalytic material are elaborated. Future works on glycerol to solketal will be improved by considering the stability of the catalysts in the presence of water as a byproduct. The presence of water and salt in the feed is certainly destructive to the activity and the stability of the catalysts.
Keywords: fuel additives; biodiesel; glycerol; solketal; solid acid catalysts.
1. Introduction
The exploration of renewable energy to supplement limited fossil fuels in the next few years is one the most concerned research topics. Among some renewable energy resources, biofuels are receiving intensive attention, especially for some countries with a large production of vegetable oils and bio-oils for biodiesel production [1,2,3,4]. Annual production and consumption of biodiesel is likely to increase significantly in the coming few years. Numerous sources of abundant edible and potential non-edible oils have been identified [5]. Regardless, this fact leads to increasing glycerol production as the byproduct of biodiesel conversion [2]. Due to the chemical process of the biodiesel production, the molar ratio of glycerol to the methyl ester is 3:1, or about 10% to 20% of the total volume of biodiesel produced is made up of glycerol. The rapid growth of biodiesel production has contributed much to the increasing glycerol production since it was reported that the worldwide production of glycerol increased from 7.8 billion liters in 2006 to 36 billion liters in 2018 [6,7]. This fact revealed that glycerol is an abundant renewable chemical feedstock in the world. The conversion of glycerol into more valuable chemicals is the best option to create a new market for glycerol and improve the sustainability of biodiesel production [7,8,9,10,11,12,13,14].
This mini review paper aims to emphasize the potential exploration of catalytic materials for the conversion of glycerol to solketal by analyzing recent papers, especially open literature from after 2010. Rahmat et al. (2010) [15] wrote an overview of glycerol conversion to fuel additives, with an emphasis on reaction parameters (catalyst, reactant, temperature, and reaction time). In the range of 2009 to 2018, Cornejo et al. [16] wrote a review in 2017 on glycerol valorization to fuel additives over different co-reactants. These included second feeds, such as formaldehyde, acetaldehyde, butanal, and acetone, and many others. Nanda et al. [17] published a review on solketal as a fuel additive, with an emphasis on the historical and future context. This paper also summarized the effect of acidity, reactor models, kinetics and reactor kinetics, and the daily procedure to use glycerol to solketal.
Many scenarios were conducted for the conversion of glycerol to different value-added chemicals, such as propane-acrolein, 1, 3-diol, propane-1,2-diol, acetal or ketal, polyols and polyurethane foams, glycerol carbonate, etc. [10,11,18]. Table 1 shows that among these glycerol conversions, the conversion of glycerol to solketal by acetalization is an interesting route. Solketal is one of the glycerol acetalization products together with glycerol acetal and glycerol formal (GlyF). Similar to other acetalization products, solketal can be used directly as a fuel additive for the reduction of soot and gum formation [19]. Solketal addition to a gasoline blend showed better fuel properties with a higher octane number [19]. Other applications of solketal are in solvents, inks, pharmaceuticals, and paints [20].
Table 1. Different conversion routes from glycerol to value-added products.
Table
As shown in Table 2 and Figure 1, different types of catalyst materials were reported for the solketal production consisting of zeolites, clays, resins, heteropolyacids, and others. Each catalyst has both advantages and drawbacks. A homogeneous catalyst, such as H2SO4, offers high activity, however, these homogenous catalysts are corrosive, not recyclable, difficult to separate, and considerably more expensive. Similarly, chloride, such as tin chloride (SnCl2), is also unwanted due to its corrosion tendency [30]. Reusability is also an important part of studies. Reusability is a factor which is studied as a typical sustainable principle. The basic mechanism of the metal salt catalysis is a nucleophilic attack by the hydroxyl group of glycerol to the carbocation obtained from the protonation step, resulting in the formation of the intermediate, followed by a water elimination step. The carbocation is produced from the Lewis or Brønsted acid sites, which activates the ketone carbonyl group through a protonation step (i.e., Brønsted acids) or polarization.
Energies 12 02872 g001 550Figure 1. Popularity of different types of catalytic materials for solketal production from 2014 to 2018. (Source: Web of Knowledge, https://www.webofknowledge.com, November 2018).
Table 2. Classification of heterogeneous catalysts for solketal production.
Table
However, homogeneous catalysts are not considered as environmental-friendly for the reaction system. Another challenge in the utilization of heterogeneous catalysts in solketal production is the byproduct (water) formed during the reaction, which induces a reversible reaction. Heterogeneous catalysts are regenerated easily and are more easily handled. Many resin catalysts exhibited excellent conversion of glycerol to solketal and selectivity, where the best catalytic performance was obtained by amberlyst. However, it is not feasible for a higher scale of production due to the limitation of thermal stability, so it is not easy to regenerate. The higher thermal stability can be found in hierarchical zeolite. The highest conversion of glycerol to solketal of 72% and the selectivity of 72% are reached by using H-Beta (BEA framework) under the condition of 60 °C, stirring at 700 rpm, 5% of catalyst, and molar ratio of glycerol:acetone of 1:4 for H-BEA. Within the zeolite materials, MFI zeolite showed 80%, which is a lower catalytic activity in comparison with amberlyst, but with almost 100% selectivity. The lower conversion is due to the relatively narrow channel size that affects the transport of the reactant carried out and the shape selectivity.
2. Glycerol-to-Solketal Over Resin Catalysts
Overall, the most important properties of solid acid catalysts for the conversion glycerol to solketal production was the Brønsted acidity of solid acids [31]. The conversion of glycerol to solketal with resin catalysts has been carried out [32,33,34,35,36]. Table 3 summarizes the conversion of glycerol to solketal over resin catalysts. A typical resin catalyst (i.e., amberlyst) catalyzed the reaction of glycerol with acetone to produce above 80% of the glycerol conversion. Guidi et al. [36] reported that a resin, amberlyst-36, which was applied at different reaction temperatures from 25 to 70 °C, was an excellent catalyst to convert glycerol with a conversion of 85% to 97% to solketal with a selectivity of 99%. The catalyst is also active at lower pressures with similar reaction parameters either in pure glycerol or in an equimolar reactant. According to some references, the high conversion was influenced not only by the surface acidity but also by the resin structure. Moreover, the surface acidity was an important parameter that played a crucial role in improving the selectivity and the conversion in the production of solketal. Although amberlyst-46 and amberlyst-36 is a similar material, both types of resins have a different acid capacity and structure morphology. Furthermore, all resins showed good selectivity to solketal (>80%), and the important catalytic parameter of the resin to conversion glycerol is the acid capacity (oversulfonated resin). With the highest acid capacity (sulfonic acid), these catalyst materials can improve not only the selectivity to solketal production but also the conversion of raw glycerol to above 90%. Another important thing to be highlighted as a limitation of the catalyst activity is the presence of NaCl as a poison for the surface acidity, which is possibly due to the impurities in glycerol.
Table 3. Glycerol-to-solketal over resin catalysts.
Table
3. Glycerol-to-Solketal over Mesoporous Silica
Koranyi et al. [37] reported the superiority of hafnium and zirconium modified TUD-1 as superior catalysts for the conversion of glycerol to solketal. These two catalysts (Hf-TUD-1 and Zr-TUD-1) were more active than Sn-MCM-41 and Al-TUD-1. The Zr and Hf-TUD-1 are examples of active metal-modified mesoporous silica in which Hf and Zr are in the framework. Their activity was higher than FAU(USY) and Al(TUD-1). The highest conversion of glycerol to solketal was more than 50%. The catalytic activity was a function of (i) the number of acid sites, (ii) the presence of mesopores, (iii) the existence of a large surface area, and (iv) the hydrophobicity of the catalyst [38]. The later, the hydrophobicity of the catalyst, was crucial to prevent the hydrolysis of solketal [37,38,39,40,41]. According to Table 4, Cs 2.5/KIT-6 catalyst was one of the best catalysts for the conversion of glycero-to-solketal [42]. KIT-6 was selected because of its large surface area (600-1000 m2/g), active sites, and accessible pores [42].
Table 4. Glycerol-to-solketal over mesoporous silica.
Table
Numerous references reported that mesoporous silica catalysts have the advantage of high stability in the conversion of glycerol to solketal, resulting in products with a relatively large percentage of conversion (95%) and selectivity to solketal (98%) [37,42,43,44,45,46]. The mesoporous structure with an activated surface by sulfonic acid might be applied efficiently for the conversion of glycerol to fuel additive [37,43,47]. A sulfonic acid-functionalized mesoporous polymer (MP-SO3H) contains a high acidity surface (1.88 mmol/g). The surface acidity of catalytic materials can accelerate the formation products of solketal via ketalization reactions as shown in Figure 2.
Energies 12 02872 g002 550Figure 2. Scheme of mechanism for the ketalization reaction of glycerol and acetone.
4. Ketalization of Glycerol over Clay Minerals
Malaya et al. [17,48] studied different clay-based catalysts with different acid strengths ranging from 0.12 to 5.7 meq/g [17]. The results show that a stronger acidity improved the conversion of glycerol up to ca. 80%. As shown in Table 5, solketal production from glycerol used two different sources, namely acetone or formaldehyde over solid acid catalysts [49,50,51,52]. Based on the conversion of glycerol and selectivity to solketal, the clay catalyst which showed the optimum results was reported by Timofeeva et al. in a batch reactor with activated catalyst by nitric acid of 0.5 M [53]. In the activated K10 montmorillonite by acid solution, this impact causes an increasing rate of reaction with the acid site of the material. It is well-known that the acid activation of natural montmorillonite with nitric acid can change the structure of montmorillonite (leaching of Al3+ cations from the octahedral to increase the surface area and microporosity of catalyst materials) [54,55,56]. The reaction of solketal production is shown in Figure 3. The use of formaldehyde as the major source of solketal production has a lower conversion value (only 83% glycerol conversion), with the K10 montmorillonite used as a catalyst. It may be due to the formation of the hemiacetal or hemicetal via two different pathways. The reaction between glycerol and acetone is preferred as it produces a more stable intermediate, hemicetal compound, with a tertiary carbenium ion [37]. While, in the reaction between glycerol with formaldehyde, the produced hemiacetal formation is not a stable carbenium ion. Thus, the conversion value for the glycerol-formaldehyde system is relatively small as compared to the reaction where acetone is used as a co-reactant [57,58,59].
Energies 12 02872 g003 550Figure 3. Synthesis scheme of glycerol to solketal.
Table 5. Glycerol-to-solketal over clay minerals.
Table
Koranyi et al. (2012) [37] reported the effect of water as an impurity in the acetalization of glycerol. The presence of water reduced the activity ca. 50% lower than the one with the model compound (pure glycerol). A high number of Brønsted and Lewis sites does not correspond directly to a high activity. Dealumination FAU and Al-TUD-1 with a high Brønsted and Lewis acidity were poor in the acetalization of glycerol [37]. Hydrophobic catalysts, such as hafnium and TUD-1 zirconium on TUD-1, are very prospective for glycerol to solketal. Ammaji et al. (2017) [62] also reported a similar observation, as the Zr-SBA-15 was the most active and selective catalyst.
5. Perspective on Ketalization of Glycerol over Hierarchical Zeolites
Dmitriev et al. (2016) [63] reported that zeolite beta was the most active solid acid catalyst as compared to amberlist-35 and cation-exchange resin (KU-2-8) [62]. The zeolite beta applied was a commercial one from zeolyst with SiO2/Al2O3 of 25 and a zeolite beta made by Angarsk. Kowalska et al. [64,65] studied the effect of (i) different zeolite topologies (MFI, BEA, and MOR), (ii) Si/Al ratio from 9.2 to 25.8, and (iii) mesoporosity. Two parent MFI zeolites with different Si/Al were applied (Si/Al = 12 and Si/Al = 27) [64]. The hierarchical zeolites were obtained by desilication using 0.2 M NaOH and dealumination using citric acid (0.5 M) and nitric acid (0.5 M). The diffusion limitation of the parent zeolites was considered as the highest activity of the parent MFI was significantly lower than the one from the hierarchical MFI. A high selectivity (up to 100%) to solketal was obtained with an acetone:glycerol ratio of 1. A higher acetone to glycerol ratio was obtained over a higher acetone to glycerol ratio. Both desilication and dealumination are very effective in improving the catalyst stability of zeolite based catalyst [66,67,68].
Rossa et al. [69] conducted the kinetics study of acetalization of glycerol with acetone to produce solketal with optimization of the kinetics parameters. Zeolite beta with an Si/Al of 19 was applied to find the best parameters: (i) External mass transfer (stirring rate), (ii) temperature, (iii) catalyst amount, and (iv) glycerol to acetone ratio. The targeted goals were glycerol conversion and solketal selectivity. The experimental design for beta zeolite showed that the suggested reaction parameters are: Temperature at 60 °C, stirring rate of 700 rpm, catalyst loading of 5%, and glycerol to acetone ratio of 1:3. A higher acetone content will increase the conversion of glycerol [24,70]. However, an increase of the acetone to glycerol ratio will increase the exergy destruction rate due to a reduction in the rate of formation toward the product and a higher consumption of electrical exergy to the acetalization reactor [20,71,72,73,74,75,76,77,78,79,80].
Hierarchical zeolite shows excellent glycerol conversion and selectivity to solketal through acetalization reactions. The catalytic materials show a higher glycerol conversion (until more than an 80% glycerol conversion) as compared to other porous and non-porous catalysts due to a large pore size and easy molecular diffusivity. The enhancement of the catalytic activity of zeolites in glycerol acetalization, through the generation of a hierarchical porosity, has been applied by different authors as shown in Table 6. Based on the literature, the crystallite size was one of the most determining factors in the activity of hierarchical zeolite as a catalyst [64,81,82,83,84,85]. The smaller the crystal size of zeolite, the easier the diffusion of the reactant and products though the zeolite pores [73,86,87]. The pore structure of the zeolite can be changed through the dealumination and desilication processes. The process not only can change the mesopore materials but also can increase the catalytic activity (improving the accessibility and mass transfer on the surface) [88]. Hierarchical zeolites with different topologies, such as ZSM-5 (MFI) [67,89,90], beta (BEA) [81,91,92], and Y (FAU) [64], have also been used in the acetalization of glycerol, and the results show that smaller pores can produce high glycerol conversion and selectivity to selectivity (almost 100% selective for solketal formation). However, overall, all materials displayed very good catalytic performance when reacting equimolar mixtures of glycerol and acetone [37,39]. From the experiments on H-beta zeolite, it was found that dealumination resulted in a decrease of strong acid sites, thus decreasing the catalytic activity.
Table 6. Glycerol-to-solketal over hierarchical zeolite catalysts.
Table
6. Solketal Synthesis over Carbon/Activated Carbon-Based Catalyst
Considering the abundant source of biomass as carbon and activated-carbon precursor, activated carbons were functionalized with acid groups for solketal synthesis [93,94]. Some papers showed the excellent performance of activated carbon for catalyzing the conversion of glycerol to solketal (Table 7) and some of these exhibited a high activity and selectivity under green conditions (solvent-free conditions at a mild temperature). The high surface area of activated carbon preserves the higher surface acid sites by some modification, including acid, metal, and composite modifications [24,95,96,97]. Therefore, they are promising candidates as heterogeneous catalysts for the acetalization of acetone with glycerol. From the utilization of acid functionalized activated carbon, the superior catalytic activity of the four acid-treated carbons was underlined as compared to the untreated activated carbon, confirming the importance of the higher number and strength of acid sites generated by the acid treatments. The catalysts were prepared by HNO3 and H2SO4 treatment to activated carbon. The catalytic activity of the catalyst showed excellent performance due to the high conversion and selectivity at room temperature.
Table 7. Glycerol-to-solketal over carbon/activated carbon-based catalyst.
Table
From the acid-modified carbon catalyst, it was found that the presence of acid groups, mainly sulfonic groups, was the key factor for the improved catalytic performance. A similar pattern also appeared from the Ni-Zr support on the activated carbon [100], in which the active metal contributes by enhancing the catalyst acidity. Another factor affecting the catalytic activity was the higher total acid density, the large mesopore of the carbon structure, and the activity of the metals.
7. Perspective and Conclusions
This mini review highlighted the recent development on solid catalysts for the conversion of glycerol-to-solketal. The product is an additive for fuels, which are very useful to reduce GHGs and to improve the economic viability of biodiesel business [6,8,16,20,34,101,102,103,104,105]. Tailor-made heterogeneous catalyst for an optimal conversion of glycerol is developed and required. Five major heterogeneous catalysts were emphasized in this study: Resins, mesoporous silica, zeolites, clays, and activated carbons. The stability of catalysts is one of the main hurdles for the commercialization of glycerol to solketal. Even though the reaction temperature was considered as mild, the stability of most of the solid catalysts decayed in the presence of water as a byproduct and other impurities (NaCl, methanol) from the glycerol source. The deactivation rate is even higher when the raw glycerol (contaminated with water) was fed to the reactor [106,107,108,109]. Therefore, the viability of the commercial plant depends on (i) the source of feeds [110], (ii) availability of glycerol and other feeds, and (iii) cost of glycerol as the feed. In general, at least three main challenges were identified:
The presence of water and impurities in the feed.
The shift from the batch reactor to the fixed bed reactor.
The presence of equilibrium offers other difficulties as higher acetone demand is expected. However, higher acetone to glycerol will lead to destructive instruments.
Acidity is agreed as an important properties of zeolite catalysts for glycerol to solketal. Strong acidity and medium hydrophobicity were expected in the design of the reactor. Based on some limitations of the catalyst performance, the utilization of raw glycerol directly will reduce the stability of the catalyst. This review described how a better material should be designed for the optimum conversion of glycerol (and generally polyol) to solketal. Hydrophobic catalysts, such as hafnium/TUD-1 and zirconium/TUD-1, are very prospective for glycerol to solketal. Extended works on low aluminum mesoporous silica materials are expected in the coming years.
Author Contributions
I.F. and O.M. contribute to design and conception, drafting the article, and final approval of the article. I.S., M.M.M., and G.F. contribute to collect the references, drafting the article, preparing all figures and all tables, and discussion. T.M.I.M. contributes to help data analysis and discussion.
Funding
This research was funded by Ministry of Research, Technology and Higher Education (KEMENRISTEKDIKTI) Republic of Indonesia through World Class Professor program in 2018, grant number: 123.6/D2.3/KP/2018. The APC was funded by the University of Technology Sydney seed fund (Org Unit 321740) with Account number (2232397).
Acknowledgments
Authors would like to express appreciation for the support from Ministry of Research, Technology and Higher Education (KEMENRISTEKDIKTI) Republic of Indonesia through World Class Professor program in 2018, grant number: 123.6/D2.3/KP/2018. The authors are thankful to Professor Paolo Pescarmona from University of Groningen for his rich suggestions on prospective catalytic materials in glycerol to solketal.
Conflicts of Interest
The authors declare no conflict of interest.

 

 

 

SOLKETAL

 

İsimler
IUPAC adı
(2,2-Dimetil-1,3-dioksolan-4-il) metanol
Diğer isimler
İzopropiliden gliserol
SOLKETAL
Tanımlayıcılar
CAS numarası
100-79-8 Rasemik ☑
14347-78-5 R enantiyomeri ☒
22323-82-6 S enantiyomeri ☒
3D model ( JSmol )
Etkileşimli görüntü
ChemSpider 
7247 ☑
ECHA Bilgi Kartı 100.002.626
PubChem CID
7528
UNII 
3XK098O8ZW ☒
CompTox Kontrol Paneli ( EPA )
DTXSID9021845 Bunu Wikidata'da düzenle
InChI[göster]
SMILES[göster]
Özellikleri
Kimyasal formül
Cı 6 H 12 O 3
Molar kütle 132.159 g · mol -1
Görünüm berrak renksiz sıvı
Yoğunluk 25 ° C'de 1.063 g / mL
Kaynama noktası 188-189 ° C (461 ila 462 K)
sudaki çözünürlük
karıştırılabilir
Çözünürlük solketal Çoğu organik çözücüde karışabilir (alkoller, eterler, hidrokarbonlar)
Tehlikeler
Alevlenme noktası 80 ° C (176 ° F; 353 K)

 

Solketal , iki komşu hidroksil grubunu birleştiren bir izopropiliden asetal grubuyla korunan bir gliserol formudur . Solketal, gliserol omurgasının merkez karbonu üzerinde kiral bir merkez içerir ve bu nedenle rasemat veya iki enantiyomerden biri olarak satın alınabilir . Solketal, ester bağı oluşumu ile mono-, di- ve trigliseritlerin sentezinde yaygın olarak kullanılmaktadır . Solketalin serbest hidroksil grupları , korumalı monogliserit oluşturmak için bir karboksilik asit ile esterleştirilebilir ; burada izopropilen grubu daha sonra sulu veya alkollü ortamdaki bir asit katalizörü kullanılarak çıkarılabilir. Solketal ,Korunmasız diol daha sonra di- veya trigliserit oluşturmak üzere ayrıca esterlenebilir.

 

Solketal MTBE'in yerine kullanılabilecek
potansiyele sahip bir oksijenli bileşiktir. Aseton petrol
esaslı bir madde olduğu için solketal tamamen
yenilenebilir değildir. Ancak aseton biyokütleden de
üretilebilir. Bu durumda solketal tamamen yenilenebilir
bir oksijenli yakıt katkısı olacaktır. Solketalın hacimsel
olarak %5 oranında benzine katılması durumunda
karışımın oktan sayısı 2,5 artar

 

solketal Pazar raporu 2020-2026, piyasaya genel bakıı, en iyi satıcılar, önemli pazar özellikleri, ürün türleri, pazar sürücüleri, zorluklar, eğilimler, Pazar manzarası, Pazar büyüklüıü ve tahmini, beı kuvvet analizi, Anahtar liderliıi ile Farmasötik Sınıf solketal Pazarı hakkında derinlemesine bilgi saılar. ülkeler / bölge. Rapor, öngörülen 2020-2026 yılındaki gelir, talep ve veri arzı, fütüristik maliyet ve geliıtirme analizine genel bir bakıı sunuyor. Farmasötik Sınıf solketal pazar raporu, kilit tedarikçilerin SWOT analizine ek olarak kapsamlı bir pazar ve satıcı ortamı içeriyor. .

 


Küresel Farmasötik Sınıf solketal pazar büyüklüıünün önümüzdeki yıllarda kabaca% X.X CAGR'de büyüyeceıi ve 2026'da X.X milyon USD'den 2020'de X.X milyon USD'ye ulaıacaıı tahmin edilmektedir.

 

Farmasötik Sınıf solketal Pazar Raporu Hakkında:

Küresel Farmasötik Sınıf solketal Pazar büyümesi, endüstri zinciri yapısı, tanımlar, uygulamalar ve sınıflandırmaları içeren pazarın ayrıntılı kapsamını saılar. Rapor, Farmasötik Sınıf solketal pazar segmentleri için SWOT analizi sunmaktadır. Rapor, Farmasötik Sınıf solketal pazarının önde gelen tüm trendleri hakkında faydalı bilgiler sunuyor. Tüm segmentler hakkında kapsamlı bir çalııma sunar ve pazarın önde gelen bölgeleriyle ilgili bilgileri paylaşır. Ayrıca, piyasadaki son geliımeler hakkında istatistiksel veriler saılar. Ayrıca şirket profili bölümü altında temel bir genel bakış, gelir ve stratejik analiz içerir. Farmasötik Sınıf solketal pazar analizi, kalkınma trendleri, rekabetçi peyzaj analizi, yatırım planı, iı stratejisi, fırsat ve kilit bölge kalkınma durumunu içeren uluslararası pazarlara sunulmaktadır. Bu rapor aynı zamanda ithalat / ihracat tüketimini, arz ve talebi Rakamlar, maliyet, sektör payı, politika, fiyat, gelir ve brüt marjları da belirtmektedir.

Küresel Farmasötik Sınıf solketal Pazarı için en çok listelenen üreticiler:

 

Solvay
Loba Feinchemie AG
Yuancheng Gongyuan Technology
Suzhou ChonTech BioPharma
Wuhan Hezhong Shenghua
Hangzhou ICH Biofarm
Beyond Industries
CM Fine Chemical
Chemos GmbH

 

Farmasötik Sınıf solketal Piyasa raporu aynı zamanda itici faktörler, sınırlayıcı faktörler ve birleıme, devralmalar ve yatırımlar gibi sektör haberleri gibi en son piyasa dinamiklerini takip etmektedir. Pazar büyüklüıü (deıer ve hacim), pazar payı, türlere göre büyüme oranı, uygulamalar saılar ve farklı bölge veya ülkelerde mikro ve makro tahminler yapmak için hem nitel hem de nicel yöntemleri birleıtirir. Rapor, dünyanın farklı bölgelerinde ve ülkelerinde farklı Pıhtılaıma Faktörü, mansap tüketim alanları ve rekabetçi peyzajın en segmentlere ayrılmıı tüketim ve satıı verilerini saılamayı amaçlamaktadır, bu rapor birincil ve ikincil yetkili kaynaktan en son piyasa verilerini analiz eder. Rapor, pazarı anlamaya ve buna baılı olarak iı geniılemesi için strateji oluıturmaya yardımcı olabilir. Strateji analizinde, pazarlama kanalından ve pazar konumlandırmasından potansiyel büyüme stratejilerine iliıkin bilgiler verir ve yeni girenler için derinlemesine analizler saılar veya Farmasötik Sınıf solketal endüstrisinde rakipler bulunur.

Farmasötik Sınıf solketal Pazar Analiz Raporu, Farmasötik Sınıf solketal Endüstri kompozit dünyasında güçlü genel bakıı ve çözüm ile Pazara Genel Bakıı, Büyüme, Talep ve Tahmin Araıtırması ile ilgili tüm Analitik ve ıstatistiksel bilgileri içermektedir. Farmasötik Sınıf solketal Pazar tahmini 2026 Araıtırma Raporu Öne çıkan hususlar sektörün temel Pazar Dinamikleri'ni içermektedir. Yukarı yönlü hammadde, tedarik stratejisi ve aıaıı yönlü alıcılar ile endüstrinin uygulamalarının ve zincir yapısının çeıitli tanımları ve sınıflandırılması verilmiıtir. Bu Farmasötik Sınıf solketal Pazar raporu, Pazar Payının Taneli Analizi, Üretim Teknolojisi, Pazara Giriı Stratejileri, Gelir Tahminleri ve Pazarın Bölgesel Analizi ile Kilit Üreticiler Profillerine detaylı olarak odaklanmaktadır. Ayrıca, pazarda ürün geliıtirme, birleıme ve devralma, ortaklıklar içeren baılıca stratejik faaliyetler tartııılmaktadır.

Türüne Göre Pazar:

 

Purityı98%
% 96 ıPurityı98%
Purityı% 96

 

Uygulamaya Göre Pazar:

 

çözücü
ılaç Ara
Diıerleri

 

Bölgesel Analiz:

Coırafi olarak, bu rapor üretim, tüketim, gelir (milyon ABD doları), pazar payı ve büyüme ile Kuzey Amerika, Avrupa, Asya Pasifik, Orta ve Güney Amerika, Orta Doıu ve Afrika ve Diıer Bölgeler gibi birçok önemli Bölgeye bölünmüıtür. Bu bölgelerde Küresel Farmasötik Sınıf solketal oranı.

Farmasötik Sınıf solketal pazarının 2020 yılında X.X milyon USD'den 2026'ya kadar X.X milyon USD'ye, tahmin dönemi boyunca% X.X CAGR'ye yükselmesi bekleniyor. Küresel Farmasötik Sınıf solketal pazar raporu, genel tüketim yapısı, kalkınma eıilimleri, satıı modelleri ve küresel Farmasötik Sınıf solketal pazarındaki en iyi ülkelerin satıılarına odaklanan kapsamlı bir araıtırmadır. Rapor, küresel Farmasötik Sınıf solketal endüstrisindeki tanınmıı saılayıcılara, pazar segmentlerine, rekabete ve makro ortama odaklanmaktadır. Belirli bir ülkedeki demografik koıullar ve iı çevrimlerinden pazara özgü mikroekonomik etkilere kadar çeıitli faktörler göz önünde bulundurularak pazarın bütüncül bir çalııması yapılır. Çalııma, bölgesel rekabet avantajı ve büyük oyuncuların rekabet ortamı açısından pazar paradigmalarındaki deıiıimi buldu.

Bu raporu satın almadan önce bilgi - www.precisionreports.co/enquiry/pre-order-enquiry/14105430

Raporun temel bilgileri:

 

Rapor, tanımı, uygulamaları ve üretim teknolojisi de dahil olmak üzere endüstrinin temel bir deıerlendirmesini sunar.
Rapor, endüstrinin 2020-2026 pazar geliıtirme eıilimlerini tahmin ediyor.
Rakip segmenti için rapor, Farmasötik Sınıf solketal'nın küresel kilit oyuncularının yanı sıra bazı küçük oyuncuları da içeriyor.
Rapor, kilit satıcılar için ıirket profilini, ürün özelliklerini, kapasitesini, üretim deıerini ve pazar paylarını sunar.
Toplam pazar, ıirkete, ülkeye ve rekabetçi peyzaj analizi için uygulamaya / türe göre bölünür.
Rapor, üreticilerin pazar durumu hakkında önemli istatistikler saılar ve sektörle ilgilenen ıirketler ve bireyler için deıerli bir rehberlik ve yönlendirme kaynaııdır.
Yukarı akıı hammaddelerinin, aıaıı akıı talebinin ve mevcut pazar dinamiklerinin analizi de yapılmaktadır.
Rapor, fizibilitesini deıerlendirmeden önce yeni bir Sanayi projesi için bazı önemli önerilerde bulunuyor.

 

Farmasötik Sınıf solketal Market 2020 global endüstri araıtırma raporu, pazar büyüklüıü, büyüme, pay, trendler ve endüstri analizi üzerine profesyonel ve derinlemesine bir çalıımadır. Rapor, endüstriyel zincir yapısına genel bir bakııla baılar ve yukarı havayı açıklar. Ayrıca rapor, farklı coırafyalar, tip ve son kullanım segmentindeki pazar büyüklüıünü ve tahminlerini analiz etmekte, ayrıca rapor, büyük ıirketler ve ıirket profilleri arasında pazar rekabetine genel bakıı sunmanın yanı sıra, raporda piyasa fiyatı ve kanal özellikleri de yer almaktadır. Ayrıca, pazar büyüklüıü, her bir bölümün ve alt bölümlerinin gelir payı ile tahmin rakamları da bu raporda yer almaktadır.

Raporda cevaplanan kilit sorular:

 

2026 yılında Farmasötik Sınıf solketal pazarının pazar büyüme oranı ne olacakı
Küresel Farmasötik Sınıf solketal pazarını yönlendiren temel faktörler nelerdirı
Farmasötik Sınıf solketal pazarındaki kilit üreticiler kimlerdirı
Farmasötik Sınıf solketal piyasasının piyasa fırsatları, piyasa riski ve piyasaya bakışları nelerdir?
Farmasötik Sınıf solketal pazarının en iyi üreticilerinin satııları, gelirleri ve fiyat analizleri nelerdir?
Farmasötik Sınıf solketal pazarının distribütörleri, tüccarları ve bayileri kimlerdir?
Küresel Farmasötik Sınıf solketal endüstrisindeki satıcıların karıılaıtııı Farmasötik Sınıf solketal pazar fırsatları ve tehditleri nelerdir?
Farmasötik Sınıf solketal pazarının türlerine ve uygulamalarına göre satış, gelir ve fiyat analizi nedir?
Farmasötik Sınıf solketal endüstrisinin bölgelerine göre satış, gelir ve fiyat analizi nedir?

 

 

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