Formation Of Acrylic Acid Research Articles

The formation of nickelalactone in CO2/C2H4 coupling reaction: A benchmark, dispersion correction, and energy decomposition analysis

The oxidative coupling of CO2 and ethylene for synthesizing acrylic acid and its derivatives is considered one of the “dream reactions” in catalysis. The formation of acrylic acid by CO2/C2H4 coupling is hardly possible due to the endothermic nature of the reaction. This work reports a comprehensive study of the nickelalactone formation from CO2/C2H4 coupling over Ni-catalysts. We have evaluated the accuracy of the DLPNO-CCSD(T) method in determining the barrier heights and the reaction energetics for the nickelalactone formation. Extrapolation to the complete basis set limit was performed using two-point extrapolation methods. It was found that the DLPNO-CCSD(T) method, in combination with the complete basis set cc-pVTZ/cc-pVQZ extrapolation, gives the error within 1.0 kcal/mol. To gain a molecular understanding of the formation of acrylic acid by CO2/C2H4 coupling, the distortion-interaction model was used as an energy decomposition method to analyze the inner- and outer-sphere reaction transition states, considering two competing pathways. It was found that i) the inner-sphere reaction is superior to the outer-sphere reaction owing to the lower distortion energy and stronger interactions, ii) three prominent pairs of orbital interactions exist between the Ni-C2H4 complex and the CO2 molecule, and iii) the dispersion correction is crucial to obtaining reliable non-covalent interaction energies.

Pd/C-catalyzed regiodivergent hydrocarboxylation and esterification of alkynes.

An unprecedented and highly reactive Pd/C catalytic system has been introduced for the regiodivergent hydrocarboxylation of terminal alkynes to selectively afford various acrylic and cinnamic acids employing oxalic acid as a CO source as well as a promoter for the formation of the active Pd-H complex. Herein, the formation of cinnamic acid is proposed to follow a unique anti-Markovnikov hydroiodination mechanism and the formation of acrylic acid might follow the traditional hydrocarboxylation pathway. Additionally, internal alkynes undergo hydrocarboxylation and carbonylative esterification with aliphatic alcohols to yield different α,β-unsaturated acids and esters respectively. The designed strategies were successfully leveraged for a diverse class of α,β-unsaturated acids and esters with excellent selectivity and yields under mild reaction conditions. Furthermore, the acid functionalization of complicated naturally derived alkynes, utilizing economical and bench-stable oxalic acid and a commercially accessible reusable catalyst with gram-scale applicability are the additional benefits of the established protocol.

Promotional effect of Cs modification to NASICON material on aldol condensation of acetic acid and formaldehyde to acrylic acid

The production of high value-added oxygenated chemicals from methanol and its derivatives is one of the important ways of coal conversion and clean and efficient utilization. Herein, a series of environmentally-friendly Cs-modified NASICON materials were applied to catalyze the aldol condensation of acetic acid (HAc) and formaldehyde (FA) to acrylic acid (AA) and methyl acrylate (MA). Encouragingly, the selectivity of target products (AA + MA) was highly up to 92.2%, corresponding to the space–time-yield more than 48.0 μmol·gcat-1·min-1 over the 2Cs/NSC catalyst, achieving the synchronization of good selectivity and productivity for the target products. Characterization results demonstrated that the acid-base modulation by Cs was responsible for catalyst supremacy. The weak basic sites on catalyst surface were efficient in adsorbing and activating HAc. Plenty of acidic sites especially the medium-strong and strong acidic sites were more favorable for the AA formation.

A novel and environmentally friendly NASICON-type material: Efficient catalyst for condensation of formaldehyde and acetic acid to acrylic acid and methyl acrylate

The development of environmentally friendly and efficient catalysts for the production of essential chemicals has always been a desirable goal for technology in the chemical industry. In this paper, we fabricated a kind of sodium (Na) super ionic conductor (NASICON)-type materials (H1-xTi2(PO4)3-x(SO4)x) with different Ti/P ratios through tuning titanium content in synthetic mother liquor, and applied them to the aldol condensation reaction of acetic acid (HAc) and formaldehyde (FA) to acrylic acid (AA) and methyl acrylate (MA), which has never been not reported in previous researches. More importantly, these novel catalysts have showed their tremendous potential at the efficiency of AA + MA production, and over an optimized catalyst of NSC-Ti/P-0.53, the AA + MA selectivity being 71% (HAc input-based) was achieved at 360 ℃ when the reactant with FA/HAc molar ratio of 5:1 was fed; whereas, a highest space–time-yield (STY) of target products (∼37.2 μmol·g−1·min−1) was obtained with the FA/HAc molar ratio of 1:2.5, which is comparable to the best result reported previously. The detailed analysis of characterizations demonstrated that the change in the Ti/P ratio in the series NASICON catalysts led to the variation in the phase composition, the textural properties, surface titanium oxidation state, etc. thereby tuning the surface acid-base property, which is quite important for the present condensation reaction. More amounts of acidic sites and basic sites as well as their moderate distribution were proved to exert the promotional effects on the formation of AA and MA.

Discovery of a novel acrylic acid formation pathway in Gluconobacter oxydans and its application in biosynthesis of acrylic acid from glycerol

This study revealed a novel metabolic pathway of acrylic acid in Gluconobacter oxydans. First, the intermediate metabolite acrolein was confirmed by HPLC and GC-MS analyses. Then, the enzymes involved were identified based on mRNA expression analysis and gene deletion studies. This novel pathway includes three successive reactions: i) an alcohol dehydrogenase catalyzes 1,3-propanediol to 3-hydroxypropionaldehyde; ii) two isozymes, 3-hydroxyacyl-(ACP) dehydratase and 3-hydroxydecanoyl-(ACP) dehydratase convert 3-hydroxypropionaldehyde to acrolein; iii) an aldehyde dehydrogenase oxidizes acrolein to acrylic acid. An engineered Escherichia coli strain, coexpressing the glycerol dehydratase of Klebsiella pneumoniae and the 3-hydroxyacyl-(ACP) dehydratase of G. oxydans was constructed for acrylic acid production from glycerol. The recombinant strain produced 144.0 ± 9.8 mg/L of acrylic acid in a shake-flask culture. This is the first report demonstrating the biosynthetic pathway of acrylic acid via acrolein, and it provides a new approach for acrylic acid biosynthesis.

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).

Simultaneous Grafting Polymerization of Acrylic Acid and Silver Aggregates Formation by Direct Reduction Using γ Radiation onto Silicone Surface and Their Antimicrobial Activity and Biocompatibility.

The modification of medical devices is an area that has attracted a lot of attention in recent years; particularly, those developments which search to modify existing devices to render them antimicrobial. Most of these modifications involve at least two stages (modification of the base material with a polymer graft and immobilization of an antimicrobial agent) which are both time-consuming and complicate synthetic procedures; therefore, as an improvement, this project sought to produce antimicrobial silicone (PDMS) in a single step. Using gamma radiation as both an energy source for polymerization initiation and as a source of reducing agents in solution, PDMS was simultaneously grafted with acrylic acid and ethylene glycol dimethacrylate (AAc:EGDMA) while producing antimicrobial silver nanoparticles (AgNPs) onto the surface of the material. To obtain reproducible materials, experimental variables such as the effect of the dose, the intensity of radiation, and the concentration of the silver salt were evaluated, finding the optimal reaction conditions to obtain materials with valuable properties. The characterization of the material was performed using electronic microscopy and spectroscopic techniques such as 13C-CPMAS-SS-NMR and FTIR. Finally, these materials demonstrated good antimicrobial activity against S. aureus while retaining good cell viabilities (above 90%) for fibroblasts BALB/3T3.

Nano-design of Zeolites Biomass Wastes Valorization: Dehydration of Lactic Acid into Acrylic Acid

The valorization of waste from biomass currently arouses great interest. In the present study we concentrate on the design of innovative BEA zeolite catalysts with applied metal nanoparticles - copper, vanadium and manganese for the dehydration of lactic acid to acrylic acid. Th e ab initio method based on density functional theory (DFT) was used to calculate the electron structure of the analyzed molecules. The non-local generalized gradient corrected functionals GGA-RPBE was used to in order to account for electron exchange and correlation. The cluster model was represented by a hierarchical zeolite M2Al2Si12O40H22 (M = Cu, V, Mn). Th e stabilization of the M-Ob-M dimer complex in the hierarchical structure of BEA, mechanism of adsorption of lactic acid on BEA zeolite with applied metal dimers and formation of acrylic acid on these zeolites were investigated. Th e examined metals form stable dimers interconnected by a bridge oxygen (Ob). Adsorption of lactic acid takes place in the vicinity of a dimer of M-Ob-M.The dehydration of lactic acid to acrylic acid in all cases consists in the separation of the hydroxyl group and creating a connection with a metal center of dimer and disconnection of a single hydrogen atom from the methyl group and its interaction with bridge oxygen of dimer.

Effect of Support Nature on Physicochemical Characteristics and Catalytic Properties of B-P-V-W-Ox Oxide Compositions in the Condensation Reaction by Acetic Acid with Formaldehyde

The influence of the support nature on physicochemical characteristics (surface acidity, porous structure) of complex oxide compositions B-P-V-W-Ox and their catalytic properties (activity, selectivity) in the reaction of gas-phase aldol condensation of acetic acid with formaldehyde to obtain acrylic acid was studied. It was found that the activity of catalysts varies symbolically with the size of the specific surface, and the selectivity of the formation of acrylic acid is determined by the presence of weak acid centers on the surface of the catalyst. In the presence of the catalyst B-P-V-W-Ox/TiO2 at a temperature of 375°C, acrylic acid was obtained with a yield of ~59% with a selectivity of formation of 92%.

Comparative study of gas-phase “dehydration” of alkyl lactates and lactic acid for acrylic acid production over hydroxyapatite catalysts

Gas-phase “dehydration” of methyl (ML) and ethyl lactates (EL) for acrylic acid (AA) production was studied and compared with the dehydration of lactic acid (LA) over serial hydroxyapatite catalysts of varying compositions (HAPm-360, molar Ca/P ratio m = 1.58–1.68, calcination temperature: 360 °C). The product distribution from both lactic esters was found very similar to that from LA; AA but not methyl (MA) or ethyl acrylate (EA) also appeared as the prevailing product (> 50 mol% by selectivity) from both ML and EL. Compared with the reaction of LA, both esters showed much lower reactivity but higher AA selectivity. Among the two esters EL was less reactive but produced a higher selectivity for AA formation. Correlating the AA selectivity or yield with the catalyst surface acid-base property uncovers that a suitable balance between the surface acidity and basicity (or acidity/basicity ratio) is the key to the lactic ester-to-AA reactions. However, the optimum surface acidity/basicity ratio for producing the highest AA selectivity from both esters was higher than that from LA. These results suggest that the lactic ester-to-AA reactions proceeded by catalytic tandem processes involving a formation of LA (or adsorbed lactate) as the key intermediate at the catalyst surface. Acid-base catalysis responsible for these observations is discussed.

The Influence of water and catalyst leach process toward propane oxidation on MoVTeNb catalyst

The effect of the water stream to the propane oxidation on diluted MoVTeNb catalyst has been investigated. The present work has elucidated that careful operation of high throughput instrumentation can be used in various beneficial ways to speed up the discovery process of improved catalysts in other forms than enabling efficient trial-and-error testing of compositional variations of a given catalyst system. The result shows that the addition of massive amounts of water to the feed should have a negative influence on the kinetics, as water will compete with all other polar molecules in the system for adsorption sites. This work also investigated the effect of catalyst leach process toward propane oxidation. From the result, it can be described that catalyst leach process tends to reduce the phase of the catalyst that responds to the total oxidation of propane. This work also proposed the reaction network and gave the comparison between the propane oxidation reaction kinetic using leached and un-leached catalyst. The result showed that the activation energy of the acrylic acid formation on the leached catalyst was slightly higher than that of on un-leached catalyst. On the other hand, the activation energy of the carbon dioxide formation on the leached catalyst was much higher than that of on un-leached catalyst. It can be described that the leaching process to the catalyst can reduce the phase of the catalyst responsible for the total oxidation of propane.

The Effect of Cofed Species on the Kinetics of Catalytic Methyl Lactate Dehydration on NaY

The catalytic dehydration of biomass-derived methyl lactate to acrylic acid is a renewable route to a high-value, high-volume monomer, but achieving high selectivity and production rates remains challenging. One roadblock is that the role of the species cofed with methyl lactate, typically water, in the dehydration mechanism over alkali-metal-exchanged zeolites remains unclear. In this study, we determined the effects of protic and aprotic cofed species, including water, methanol, and methyl acetate, on the rate and selectivity of methyl lactate dehydration over NaY via kinetic and spectroscopic investigations. We show that water plays multiple competing roles in the mechanism: (1) generating the unselective Brønsted acid sites on NaY leading to acetaldehyde and coke formation; (2) suppressing the activity of the Lewis acid sites responsible for lactate dehydration; and (3) facilitating the displacement of adsorbed sodium acrylate by lactate, leading to the formation of acrylic acid. The first process increases the rate of side product formation, while the second and third processes decrease and increase the dehydration rate, respectively. As a result of these competing roles, the rate-limiting step of methyl lactate dehydration shifts from acrylate product recovery to sodium lactate dehydration as the concentration of water increases.

Constructing A Rational Kinetic Model of the Selective Propane Oxidation Over A Mixed Metal Oxide Catalyst

This research presents a kinetic investigation of the selective oxidation of propane to acrylic acid over a MoVTeNb oxide (M1 phase) catalyst. The paper contains both an overview of the related literature, and original results with a focus on kinetic aspects. Two types of kinetic experiments were performed in a plug flow reactor, observing (i) steady-state conditions (partial pressure variations) and (ii) the catalyst evolution as a function of time-on-stream. For this, the catalyst was treated in reducing atmosphere, before re-oxidising it. These observations in long term behaviour were used to distinguish different catalytic routes, namely for the formation of propene, acetic acid, acrylic acid, carbon monoxide and carbon dioxide. A partial carbon balance was introduced, which is a ‘kinetic fingerprint’, that distinguishes one type of active site from another. Furthermore, an ‘active site’ was found to consist of one or more ‘active centres’. A rational mechanism was developed based on the theory of graphs and includes two time scales belonging to (i) the catalytic cycle and (ii) the catalyst evolution. Several different types of active sites exist, at least as many, as kinetically independent product molecules are formed over a catalyst surface.

Study of the gas-phase glycerol oxidehydration on systems based on transition metals (Co, Fe, V) and aluminium phosphate

The gas-phase glycerol (Gly) transformation in the presence of oxygen has been studied on cobalt oxide systems (10 and 20 wt% Co) supported on a synthetic mesoporous aluminium phosphate (AlPO4) calcined at 350 °C, as well as on a binary Co-Al phosphate with a Co content of 10 wt%. Synthetic binary phosphate of Al-M (M = Fe, V) have also been tested. The acidity (number and nature of acid sites) of the solids was determined by pyridine adsorption, whereas the reducibility was determined by H2 TPR. The propene oxidation was employed as a test reaction. The influence of the amount of oxidant agent and the reaction temperature on both the glycerol conversion and the yield to reaction products was studied. The formation of acrylic acid; acetic acid and carbon dioxide was favoured for values of O2/Gly ≥ 2 molar ratio and of temperatures beyond 250 °C. The Co oxide species in the supported systems that were the easiest to reduce (lower H2 desorption temperature) exhibited the highest activity to produce acrylic acid. The formation of acetic acid and carbon dioxide was also promoted, suggesting the participation of the acid sites in addition to redox sites. Among the metals investigated here, Co would form part of the required catalyst for the formation of acrylic acid from glycerol. Based on the identified products in this study, some possible reactions involved in the glycerol transformation into oxidized compounds, have been suggested.

Mechanistic Aspects of Acrylic Acid Formation from CO2–Ethylene Coupling over Palladium‐ and Nickel‐based Catalysts

AbstractThe detailed mechanism of catalytic conversion of CO2 and ethylene to acrylic acid has been investigated through DFT and DLPNO‐CCSD(T) calculations. Four bidentate ligands, dmpe (1,2‐bis(dimethylphosphino)ethane), dcpe (1,2‐bis(dicyclohexylphosphino)ethane), dtbpe (1,2‐bis(di‐tert‐butylphosphino)ethane), and tmeda (tetramethylethylenediamine) were systematically studied to understand the different catalytic behavior of the Pd‐based catalyst and the well‐known Ni‐based catalyst. The energy barrier of Pd‐/Ni‐catalyzed C−C coupling appears to increase with the larger steric hindrance of the ligand, whereas the barrier of the corresponding β‐H elimination shows an opposite tendency. The barrier for C−C coupling is likely higher than the associated barrier for β‐H elimination in both catalytic systems provided that the coordinated ligand is bulky enough. The palladium catalytic center is more effective than the nickel center for the C−C coupling and β‐H elimination steps in the presence of bulky ligands, whereas the nickel catalyst in turn performs better with small ligands. The palladium catalyst tends to be superior to the nickel catalyst during the following hydrogen transfer to the O atom. In general, the diamine ligand (tmeda) is less efficient than the diphosphine ligands for both systems. In the absence of the auxiliaries, a novel chelating carbene ligand was proposed to be quite efficient for Pd‐catalyzed C−C coupling. Two ligands (dcpm, dtbpm) showed relatively better performance towards the palladium‐catalyzed acrylic acid formation reaction among all the investigated ligands.

Isotope Studies in Oxidation of Propane over Vanadium Oxide

AbstractThe oxidation of propane has been studied over silica‐supported vanadium oxide and polycrystalline, bulk MoVTeNb oxide with M1 structure. Temperature‐programmed reaction experiments were performed, and the reactivity of propane molecules labeled with deuterium and 13C, respectively, was analyzed under steady‐state conditions. The measurement of kinetic isotope effects reveals fundamental differences in the activation of propane over the two catalysts. The reaction network of consecutive and parallel reactions of the formed propylene is comparable. However, oxygen insertion into the CHO group of acrolein under formation of acrylic acid is faster over M1 than oxidation at the CH2 group and decarbonylation to acetaldehyde. In contrast, the latter process is preferred over silica‐supported vanadium oxide resulting in lower selectivity to unsaturated oxygenates.

Thermal treatments of precursors of molybdenum and vanadium oxides and the formed MoxVyOz phases active in the oxydehydration of glycerol

This paper presents an in situ study of the crystallographic phases formed during the thermal treatment of precursors of vanadium and molybdenum oxides, measured under synchrotron X-ray diffraction. The interest in the speciation of MoxVyOz mixed oxides lies in the excellent catalytic performance of these materials for the selective conversion of glycerol to acrylic acid employing the oxydehydration reaction. The crystallographic structure of the active phases of MoxVyOz directly influences on the nearby metal valence and, therefore, on the dynamic changes in metal oxidation states during the catalytic reaction. In the present study, the thermal treatment of a mixture of the precursors of Mo and V under oxidizing or inert atmospheres revealed the major formation of 61% of MoV2O8 or 29% of Mo4V6O25, respectively, at a final temperature of 500°C. The most active phase for acrylic acid formation was MoV2O8 (3.5 times more active than the separate metal oxides), due to the instability of the phase with respect to framework oxygen at the reaction temperature. The cycle of reduction and oxidation of the vanadium in MoV2O8 during the reaction caused pronounced dynamic formation of oxygen vacancies, resulting in 97% conversion of glycerol and 32% selectivity towards acrylic acid.

Water-dispersible near-infrared luminescent silicon nanocrystals -immobilization on substrate

Abstract

Role of Crystalline Structure in Allyl Alcohol Selective Oxidation over Mo3VOx Complex Metal Oxide Catalysts

AbstractThe role of the crystalline phase of Mo3VOx in the catalytic oxidation of allyl alcohol over four kinds of crystalline (orthorhombic, trigonal, tetragonal, amorphous) Mo3VOx catalysts was investigated to determine the active sites for the reactions. Tetragonal Mo3VOx was found less active for the formation of acrylic acid from allyl alcohol, although acrolein was obtained selectively at higher temperature. For orthorhombic and trigonal Mo3VOx catalyst, allyl alcohol converted to acrolein and propanal competitively at the mouth of the heptagonal channel over the a–b plane of the rod‐type crystalline particles, and these aldehydes were oxidized consecutively to acrylic acid. Acrylic acid was formed effectively at increased reaction temperature over orthorhombic, trigonal and amorphous Mo3VOx catalysts, and the maximum yields of acrylic acid were 73 % for the orthorhombic Mo3VOx catalyst and 72 % for the trigonal Mo3VOx catalyst at 350 °C.

Oxidative Dehydration of Glycerol to Acrylic Acid over Vanadium-Substituted Cesium Salts of Keggin-Type Heteropolyacids

Acrylic acid is one of the most desired products from bioglycerol. In this work, we demonstrated that Keggin-type heteropoly compounds (HPCs) act as efficient bifunctional catalysts for the one-step conversion of glycerol to acrylic acid in gas phase. This is the first example of HPCs as catalysts for selective conversion of glycerol to acrylic acid. It was found that introduction of vanadium species into the secondary structure of the cesium salts of H3PMo12O40 and H3PW12O40 heteropolyacids is beneficial for acrylic acid formation. The combination of H0.1Cs2.5(VO)0.2PMo12O40 and H0.1Cs2.5(VO)0.2PW12O40 as solid solutions resulted in variations in the oxidization ability and surface acidity of the catalysts and, consequently, notably improved selectivity for acrylic acid. Up to 60% yield to acrylic acid was achieved over the catalyst with the formula of H0.1Cs2.5(VO)0.2(PMo12O40)0.25(PW12O40)0.75. The catalyst also showed good resistance to coke deposition and long-term stability due to the salt feature. ...