Synthesis Of Acrylic Acid Research Articles

Synthesis of acrylic acid and acrylates from CO<sub>2</sub> and ethylene — the thorny path from dream to reality

The development of atom-economical and efficient processes for obtaining a variety of chemical products using CO<sub>2</sub> as C<sub>1</sub>-synthon plays an increasingly important role in modern scientific and technological research. Due to the inertness of CO2 many extremely attractive routes to valuable chemical products turn out to be impossible to implement, particularly for thermodynamic reasons, leaving one only dreaming about them as something unattainable. This review demonstrates how the catalytic coupling of ethylene and CO<sub>2</sub> into acrylic acid, once considered a "dream reaction" has not only become a reality, but has also evolved into the category of technological processes. The key stages of the long-term development of this unique reaction from the discovery of metal activation of CO<sub>2</sub> and stoichiometric preparation of metallalactones to catalytic synthesis using a variety of metal-catalysts (Ni, Pd, Ru, Rh) showcase the ingenuity and skill of researchers as well as an example of consistent development in this field of chemistry. We believe that this remarkably successful example will inspire scientists to tackle any "impossible" problems.<br> The bibliography includes 117 references.

Direct synthesis of acrylic acid from methanol and acetic acid over a constructed TiO2-coated NASICON catalyst

Direct conversion of methanol and acetic acid (HAc) into acrylic acid (AA) and methyl acrylate (MA) is remarkably significant for the high-value utilization of coal-based chemicals. However, the previous catalysts, due to their single function or poor synergy between multiple active sites, remain large challenges in direct synthesis of acrylic acid. Herein, we designed a novel catalyst system through coating TiO2 to sodium superionic conductor (NASICON) substrate for direct synthesis of acrylic acid from methanol and acetic acid. It was revealed that the catalyst with TiO2 coating showed obviously improved performance. The selectivity of AA+MA highly reached 56.1 % at 380 °C, corresponding to the spatiotemporal yield of 46.5 μmol·g−1·min−1. It was demonstrated that TiO2 coating catalyzes the oxidative dehydrogenation of methanol to formaldehyde, while NASICON substrate exerts important effects on the aldol condensation of formaldehyde and acetic acid, and their effective synergy promotes the direct synthesis of acrylic acid.

Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis

Transformation of methyl lactate to acrylic acid was investigated over Ca3(PO4)2, Ca2(P2O7) and their mixture in the temperature range of 250-425 °C. The initial concentration of methyl lactate in water was varied from 2 wt% to neat methyl lactate. The results showed that these phosphate catalysts did not contain any measurable amounts of either acid sites or basic sites. The best catalyst was Ca3(PO4)2 giving 62% selectivity to acrylic acid at 75% conversion at 400 °C using GHSV of 95280 h−1 and 2 wt% methyl lactate in the initial feed. This catalyst exhibited larger surface area in comparison to Ca2(P2O7). Elemental analysis revealed that some Ca leaching occurred during reaction, while in case of Ca2(P2O7) the calcium leaching was 3.4 fold higher than observed for Ca3(PO4)2. Long-term results over Ca3(PO4)2 showed that extensive catalyst deactivation occurred during the first 11 h time-on-stream, after which the activity dropped only slightly. In addition to kinetic studies with different parameters, also, kinetic modeling was performed and the activation energies for formation of different products were determined over different catalysts.

Production, Purification and Characterization of Nitrilase from Bacillus subtilis-AGAB-2 and Chemoenzymatic Synthesis of Acrylic Acid from Acrylonitrile

Production, Purification and Characterization of Nitrilase from Bacillus subtilis-AGAB-2 and Chemoenzymatic Synthesis of Acrylic Acid from Acrylonitrile

One-pot synthesis of acrylic acid from glycerol over SBA-15 supported heteropoly acid catalysts: Influence of mesoporosity and acidity

Heteropoly acids (HPAs) of the Keggin type exhibit substantial Brønsted acidity and are commonly utilized as acid catalysts, particularly in acrylic acid synthesis via glycerol oxydehydration. The primary goal of this research is to comprehensively assess the morphological and physicochemical properties of SBA-15 supported HPAs (H4SiW12O40.xH2O, H3PW12O40.xH2O, and H3PMo12O40.xH2O). The synthesized catalysts were characterized via physisorption analysis, XRD, SEM, FT-IR, NH3-TPD, and H2-TPR. Furthermore, the catalyst's catalytic activity in acrylic acid synthesis via single-step liquid phase glycerol oxydehydration was evaluated by correlating its characteristics with glycerol conversion and acrylic acid yields. The PW/SBA-15 catalyst exhibited the best performance, with the highest acrylic acid yield reaching 17.5% at 87.8% glycerol conversion. Given that the partial oxidation of acrolein to acrylic acid necessitates an optimal level of redox properties, the superior performance of PW/SBA-15 was characterized by high acid sites and moderate oxidative capabilities.

Progress on Catalysts for the Synthesis of Acrylic Acid (Methyl Ester) by Aldol Condensation of Acetic Acid (Methyl Ester) with Formaldehyde

Progress on Catalysts for the Synthesis of Acrylic Acid (Methyl Ester) by Aldol Condensation of Acetic Acid (Methyl Ester) with Formaldehyde

Synthesis and fabrication of acrylic acid treated rattan fiber epoxy composite

Abstract The present work encompasses synthesis and fabrication of short rattan fiber (1–3 mm) reinforced epoxy composite with enhanced mechanical properties. Acrylic acid has been considered as surfactant for surface modification of rattan fiber to enhance adhesion with thermosetting polymer such as epoxy. Calculation of various mechanical properties has been performed and analysed with different weight percentage of fiber matrix composition. Micrographs were studied using scanning electron microscopy. The acrylic acid treated composite shows better tensile, flexural and impact strength at 45.5 MPa, 121.89 MPa and 39.45 J m−1, respectively. Regression analysis reveals that the composite with 18% fiber content (optimum weight percentage) exhibits better mechanical properties. The results suggest that rattan fibers provide a natural and sustainable choice for reinforcing composites in a wide range of technical applications where synthetic fibres are currently utilized.

Synthesis of vinyl trimethyl silane and acrylic acid modified silica nanoparticles as corrosion inhibition protocols in saline medium

Metal corrosion is one of the detrimental processes in many areas which can lead to induce tremendous economic losses and reduce industrial production. Therefore, metal protection is becoming a technical, economical, and environmentally important approach for delaying the corrosion process. Nanomaterials functionalization is gaining high interest due to its outstanding engineering performance of material for anti-corrosion. In an aggressive medium such as seawater and 3.5 wt% NaCl (stimulated seawater) environments, stainless steels are widely utilized where the polymeric inhibitor could easily be incorporated on the metal surface. In this report, the biodegradable polymeric inhibitor has been newly grafted on mesoporous silica nanoparticles (MSN). The silane agent was grafted with polyacrylic acid vinyltrimethoxysilane (Si-PAA-VTMS) by reacting MSN with polyacrylic acid (PAA) and vinyltrimethoxysilane (VTMS). Furthermore, FTIR, SEM/EDX, AFM, and WCA measurements were applied for material surface characterization, adsorbed polymeric film, and corrosion properties of the prepared inhibitor. FTIR spectra displayed the presence of the carboxylic groups on the prepared Si-PAA-VTMS inhibitor indicating the successful synthesis. From SEM/EDX and AFM results, low porosity and dense double-layer coating of the polymer inhibitor were found on the surface morphologies which could effectively delay the rust formation. Hydrophobicity behavior was also examined after inhibitor adsorption onto the steel surface producing a higher water contact angle that repels the aggressive water content. Additionally, by utilizing optimum inhibitor concentration at 100 ppm, low corrosion rate (∼4.0–9.0 × 10−3 mm/year) and high inhibition efficiency (>80 %) were achieved at higher temperatures up to 60 °C.

Hydrophilized Ultrafiltration Membranes Synthesized from Acrylic Acid Grafted Polyethersulfone for Downstream Processing of Therapeutic Insulin and Cobalamin

The present study focuses on synthesis of novel high-performance acrylic acid (AA) grafted polyethersulfone (PES) ultrafiltration (UF) membranes for purification of small therapeutic biomolecules such as urea, insulin, and cobalamin. The membranes were indigenously synthesized by adding polyethylene glycol (PEG) of 6 kDa M.Wt. as a pore former and subsequent grafting of AA using 2 to 6 wt.% concentrations under UV-induced photo grafting. Scanning electron microscopy reveals that the PEG additive profoundly influences the pore density on the membrane surface. FTIR spectra confirm the graft polymerization of AA with the PES substrate. Separation performance of the grafted membranes was evaluated to establish the trade-off between the degree of grafting and MWCO. From the experimental results, the pure water flux (PWF) of 6% grafted PES membrane was enhanced from 8.5 (PES [0] [6]) to 18.20 l m−2 h−1 (PES [6 +] [6]) in the presence of PEG pore former, respectively. The grafting concentration window of 2–6% resulted in selective membranes to altogether remove uremic toxins into the permeate with retention of high molecular size proteins. Hence, 5 and 6 wt.% AA grafted membranes exhibited > 90% rejection for insulin and cobalamin biomolecules along with 24.5 and 23.8 l m−2 h−1 bar−1 permeability towards urea, respectively. The process results correlate well with the MWCO values of membranes ranging from 1 to 10 kDa. This work provides the efficacy of these grafted membranes for potential application in the downstream processing of therapeutic biomolecules such as insulin and cobalamin.

Synthesis of acrylic acid through aldol condensation of acetic acid with formaldehyde catalyzed by Bi‐,W‐ and Cs‐doped B2O3/SiO2 nanocomposites

AbstractBACKGROUNDAcrylic acid commercially produced by the successively catalytic oxidation of propylene has a high cost. The synthesis of acrylic acid by aldol condensation between coal derivatives, acetic acid and formaldehyde, is an economic alternative to the propylene oxidation process. However, the development of an environmentally friendly and effective catalyst has remained a challenge.RESULTSDiboron trioxide [B2O3(6–20%)]/silica (SiO2) nanocomposites with B2O3 particle sizes of 1–2 nm prepared by the wetness impregnation of boric acid into silica aerogel and subsequent calcination at 500 °C effectively catalyzed the gas‐phase aldol condensation reaction between acetic acid and formaldehyde (trioxymethylene) to acrylic acid with a selectivity of ≈87% at 340–400 °C. Bismuth (Bi‐), tungsten (W‐) and caesium (Cs)‐doped B2O3/SiO2 nanocomposites had higher catalytic activities in the gas‐phase aldol condensation reaction to acrylic acid than the undoped B2O3/SiO2 nanocomposite.CONCLUSIONWeak‐strength Lewis acid and alkali sites of the B2O3(6–20%)/SiO2 nanocomposites co‐catalyzed the aldol condensation reaction to form acrylic acid. The doping of B2O3/SiO2 nanocomposites with Bi, W and Cs components results in the formation of BiBO3, WO3 and CsBO2 phases, which lead to an increase in acidity and basicity resulting in higher catalytic activity in the formation of acrylic acid. © 2022 Society of Chemical Industry (SCI).

Synthesis of acrylic acid and acrylic esters via oxidation and oxidative alkoxylation of acrolein under mild conditions with selenium-modified microgel catalysts

Systematic studies of the performance of Se-modified microgel catalysts in acrolein oxidation and oxidative alkoxylation under green reaction conditions were conducted to afford high yields and selectivity of the process.

Highly Efficient Biobased Synthesis of Acrylic Acid.

Petrochemical based polymers, paints and coatings are cornerstones of modern industry but our future sustainable society demands greener processes and renewable feedstock materials. A challenge is to access platform monomers from biomass resources while integrating the principles of green chemistry in their chemical synthesis. We present a synthesis route starting from biomass‐derived furfural towards the commonly used monomers maleic anhydride and acrylic acid, implementing environmentally benign photooxygenation, aerobic oxidation and ethenolysis reactions. Maleic anhydride and acrylic acid, transformed into sodium acrylate, were isolated in yields of 85 % (2 steps) and 81 % (4 steps), respectively. With minimal waste and high atom efficiency, this biobased route provides a viable alternative to access key monomers.

Highly Efficient Biobased Synthesis of Acrylic Acid

AbstractPetrochemical based polymers, paints and coatings are cornerstones of modern industry but our future sustainable society demands greener processes and renewable feedstock materials. A challenge is to access platform monomers from biomass resources while integrating the principles of green chemistry in their chemical synthesis. We present a synthesis route starting from biomass‐derived furfural towards the commonly used monomers maleic anhydride and acrylic acid, implementing environmentally benign photooxygenation, aerobic oxidation and ethenolysis reactions. Maleic anhydride and acrylic acid, transformed into sodium acrylate, were isolated in yields of 85 % (2 steps) and 81 % (4 steps), respectively. With minimal waste and high atom efficiency, this biobased route provides a viable alternative to access key monomers.

A review on one-pot synthesis of acrylic acid from glycerol on bi-functional catalysts

Oxydehydration is one of the possible reactions to valorize glycerol to acrylic acid that has high demand in industry. Glycerol oxydehydration is a two-step reaction that is an interesting, yet challenging approach to give high acrylic acid yield. The reaction consists of the dehydration to 3-hydroxypropanal and subsequently to acrolein catalyzed by mainly Brønsted acid sites. Selective oxidation catalyzed by metal sites should then be carried out to form acrylic acid. A single-step or one-pot conversion requires a multi-component catalyst addressing the requirements of both steps to selectively form the desired product. Strong acid sites will catalyze the undesired glycerol oxidation reactions while metals with high redox capability tend to cause oxidative decomposition of acrolein. This work reviews the recent works on glycerol catalytic oxydehydration to form acrylic acid in a one-pot approach. The complete reaction mechanism and specific requirements are elucidated. Main focus is given to the pros and cons of four groups of catalysts i.e. vanadium pyrophosphates, supported heteropoly acids, mixed metal oxides and molecular sieves. The roles of specific acid sites, type and composition of active components and redox strength of active components are critically reviewed.

Acrylic acid synthesis via condensation of acetic acid and formaldehyde catalyzed by silica aerogel‐supported SiW/PW/PMo oxides

AbstractBACKGROUNDThe demand for acrylic acid continues to increase rapidly due to its widespread application. The traditional production of acrylic acid originates from non‐sustainable propylene oxidation. Considering the environmental requirements and economic sustainable development, it is of great significance to exploit new routes to replace the petrochemical route.RESULTSComparison of silica aerogel‐supported SiW/PW/PMo catalysts shows that PW/SiO2 catalyst with 30 wt% loading and calcined at 450 °C provides the best performance for the condensation of acetic acid and formaldehyde. Increasing the reaction temperature from 340 to 400 °C leads to the best acrylic acid selectivities of 87.1–84.2% at formaldehyde conversions of 35.7–45.2%.CONCLUSIONSThe catalytic performance of PW/SiO2 catalyst increases with increasing PW loading. The acidic and basic sites of the catalyst, especially the weak ones, are of vital importance to the synthesis of acrylic acid via the aldol condensation of acetic acid and formaldehyde. © 2020 Society of Chemical Industry

Effect of Solid Bases Catalyst on Conversion of Acrylonitrile into Acrylic Acid by Hydrothermal Reaction

This study aims at the shortcomings of the current industrial application of acrylonitrile wastewater treatment, using alkali-catalyzed hydrothermal technology to convert acrylonitrile into acrylic acid for achieving resource utilization. In this study, alkali metal, alkaline earth metal hydroxide and composite solid base were used as catalysts to investigate catalytic effects of these solid based on the hydrothermal reaction. The results show when using the alkali and alkaline-earth metal hydroxides as catalysts, the best effect of treatment was KOH and the highest yield of acrylic acid reached 56.60%. It was also found that, among the three kinds of solid base catalysts (Ca-O-Mg, K-O-Al, K-O-Si) adopted with the same mass and various loading capacity, K-O-Si (15%) was the most effective catalyst for the conversion of acrylonitrile, and the highest yield of acrylic acid reached 57.78%. This process provides an environmentally friendly method toward the synthesis of useful acrylic acid from acrylonitrile within a very short time.

Anionic natural graft copolymer used in removal of hazardous dye water pollutants

The carboxymethyl cellulose (CMC), guar gum, sodium alginate and chitosan etc. are natural polysaccharides. This paper presents the synthesis and characterization of natural polymer carboxymethyl cellulose (CMC) and synthetic monomer acrylic acid (AA) based graft copolymer (CMC–g–AA) and its applications in removal of Methylene blue dye from industrial effluents. CMC–g–AA has been synthesized using free radical initiator and characterized by FTIR, TGA, and SEM analysis. The AA concentration has been varied from 5.5 x 10 -2 to 35.5 x 10 -2 mol dm -3 to get maximum grafting of AA monomer onto CMC. The FTIR spectral analysis proves the successful grafting. The synthesized graft copolymer (CMC–g–AA) has been applied in adsorption of a water soluble monovalent cationic dye such as Methylene Blue.

Investigations on Amphoteric Chitosan/TiO2 Bionanocomposites for Application in Visible Light Induced Photocatalytic Degradation

The present investigation reports the greener synthesis and characterization of novel acrylic acid grafted amphoteric chitosan/TiO2 (CAT) bionanocomposites using ultrasonic radiations. This was done by grafting of acrylic acid onto chitosan in the presence of potassium persulfate by free radical polymerization reaction. The uniform distribution of metal oxide in CA/TiO2 nanocomposites was achieved on grafted acrylic acid/chitosan which contains a weak anionic group (-COOH) using ultrasonication technique. Physiochemical techniques such as X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), Fourier Transform Infra-Red spectroscopy (FT-IR), Energy Dispersive X-ray spectroscopy (EDX), and Thermal Gravimetric Analysis (TGA) were employed to characterize synthesized CAT. Nanocomposite CAT was applied for degradation of industrial dye. Malachite green (MG) often presents in the waste waters. The degradation kinetics were studied by monitoring the photocatalytic reaction for degradation of MG under visible light, and the rate constant of the reaction was found to be 7.13x10−3min−1. The current research work opens vistas for the new dimensions in the area of water treatment by solving the issues related to degradation reaction efficiency in visible light and cost effectiveness.

Biocatalysts Based on Bacterial Cells with Amidase Activity for the Synthesis of Acrylic Acid from Acrylamide

The biocatalytic synthesis of acrylic acid from acrylamide by the Rhodococcus erythropolis 4-1 and Alcaligenes faecalis 2 strains with amidase activity is studied. The optimum pH values are 6–7 for R. erythropolis 4-1 and 7–7.5 for A. faecalis 2, while the optimum temperature is 20–50°С for both strains. The optimum acrylamide concentration is 150 mM for R. erythropolis 4-1 and 250 mM for A. faecalis 2. The synthesis of acrylic acid with fractional additions of a substrate catalyzed by the biomass of A. faecalis 2 is more effective than using R. erythropolis 4-1. The biocatalyst is best stored at −20°C. The amidase activity of A. faecalis 2 cells immobilized on chitosan activated with glutaraldehyde and non-activated chitosan did not decline during the storage of either wet or dried granules.

Acrylic acid synthesis by oxidative condensation of methanol and acetic acid on B–P–V–W–Ox/SiO2 catalyst

The process of oxidative condensation of methanol with acetic acid to acrylic acid on B–P–V–W–Ox/SiO 2 catalyst modified by hydrothermal method has been studied. Modification of the catalyst by hydrothermal treatment of the carrier changes its physical and chemical properties, and therefore its catalytic properties. The influence of the main technological parameters – temperature, contact time and ratio of reagents on the selectivity and yield of the reaction products and on the conversion of acetic acid has been studied when hydrothermally treated catalyst was used. The best time of contact was 8 sec. which allows to reach the highest selectivity and yield of acrylic acid and methyl acrylate. The highest catalytic activity of the designed catalyst is observed at the reaction temperature of 673 K, however, it is impossible to increase temperature over this value due to the limited thermal stability of the catalyst and the sharp increase in the formation of complete oxidation products. With an increase of methanol part in the ratio of reagents (methanol: acetic acid) to 1,2:1, the selectivity of acrylic acid and methyl acrylate increases, and the selectivity of by-products is significantly reduced. The highest yield of the target products in the reaction of oxidative condensation of methanol with acetic acid is observed at a ratio of oxygen: acetic acid 1,5:1. The growth of the oxygen: acetic acid ratio promotes reduce of acetone and methyl acetate selectivity but does not change the selectivity of methyl acrylate and significantly increases the selectivity and yield of acrylic acid. At the best conditions of the reaction it was possible to achieve 54.7 % total yield of acrylic acid and methyl acrylate. Due to the wide availability and relatively low cost of the initial reagents (methanol and acetic acid), the synthesis of acrylic acid by the oxidative condensation of methanol with acetic acid in the presence of the developed catalyst is very promising