Production Of Acrylic Acid Research Articles

One-Pot Synthesis of Mixed-Phase MoVTeNbOx Catalysts for Selective Oxidation of Propane to Acrylic Acid.

One-pot hydrothermal synthesis assisted by sodium citrate and citric acid is developed to fabricate mixed-phased MoVTeNbOx catalysts with different phase compositions for selective oxidation of propane to acrylic acid. Structures of various catalysts are comprehensively characterized. Interfacial interactions occur among the M1 and M2 phases of mixed-phase MoVTeNbOx catalysts to exert synergistic effects on the selective production of acrylic acid. Various mixed-phase MoVTeNbOx catalysts exhibit the same type of active site on the M1-phase component, with a significantly enhanced ability to adsorb and activate propane. The propane conversion increases linearly with the density of surface site for propane adsorption, while the propene selectivity increases linearly with the density of surface site for propene adsorption. Among the synthesized catalysts, a MoVTeNbOx catalyst composed of 35.3 wt % M1 phase, 19.2 wt % M2 phase, and 45.7 wt % amorphous phase exhibits the largest density of active site and consequently the best catalytic performance with 38.9% propane conversion and 71.2% acrylic acid selectivity at 380 °C.

Unravel the Active Sites and Intermediates for Selective Production of Acrylic Acid from Biomass

Unravel the Active Sites and Intermediates for Selective Production of Acrylic Acid from Biomass

Chemical plant optimization layout based on the domino hazard index considering the fixed hazard unit outside the available area

The layout of chemical plants is a significant step to promote the safe and efficient operation of a chemical factory. In the actual production process, the chemical process plant layout may be affected by immovable hazards outside the available layout area. In this paper, the external hazard unit is arranged as one of the chemical process plants. The domino effect potential of all chemical process plants is quantified by using the classical domino hazard index (DHI). A layout optimization model considering the effects of external hazard units has been proposed to obtain the optimal plant layout from economic and safety aspects. The feasible layout solutions are obtained under the orientation, boundary and non-overlapping constraints by the non-dominated sorting genetic algorithm II (NSGA-Ⅱ). The proposed model is further analyzed through a hypothetical case of three storage tanks outside the acrylic acid (AA) production plant layout area. The results show that the total cost range for the optimal solution is 650348–1365443 $, with corresponding DHI values ranging from 29 to 129. The plant with larger DHI value will be arranged to far away from the external hazard units to obtain a safer layout. This work can provide rational layout solutions for the layout designers to make different decisions according to the actual situation.

Evaluation of two acrylic acid production processes from renewable crude glycerol: Rigorous process design, techno-economic evaluation, and life cycle assessment

This study aims to propose and evaluate two acrylic acid (AA) production processes that utilize bio-based crude glycerol as a feedstock. Scheme 1 employs acrolein as an intermediate, while Scheme 2 utilizes allyl alcohol as an intermediate. For process intensification, Scheme 1 employs a one-pot reactor configuration that couples the glycerol dehydration and oxidation reactions and uses an additional reactor to suppress the formation of side products. Scheme 2 implements a membrane that helps prevent the multiple azeotropic distillation between water and other substances. Furthermore, both processes were systematically optimized based on varying levels of information available in the process (i.e., three objectives for Scheme 1, single objective for Scheme 2). From a techno-economic evaluation, Scheme 2 (2.136 USD/kg) slightly outperforms Scheme 1 (2.514 USD/kg) in terms of the minimum required selling price (MRSP). Both values are significantly higher than the market price (1.24–1.32 USD/kg) based on the conventional process that uses propene as a feedstock. Subsequently, a cradle-to-gate life cycle assessment was conducted to compare these processes across five impact categories (i.e., global warming potential, fossil source scarcity, human non-carcinogenic toxicity, water consumption, and terrestrial acidification). We have observed that Scheme 1 can be more sustainable than Scheme 2 and the conventional process if the issue associated with the acrolein left in the wastewater can be addressed. In contrast, Scheme 2 is far from environmentally friendly even compared to the conventional process, primarily because of the use of formic acid as a co-reactant.

Modeling of the Phase Behavior of Carboxylic Acid Systems Using the SAFT-VR Mie DBD Model: Application to the Simulation of the Acrylic Acid Production Process

Modeling of the Phase Behavior of Carboxylic Acid Systems Using the SAFT-VR Mie DBD Model: Application to the Simulation of the Acrylic Acid Production Process

A new concept of biocatalytic synthesis of acrylic monomers for obtaining water-soluble acrylic heteropolymers

Rhodococcus strains were designed as model biocatalysts (BCs) for the production of acrylic acid and mixtures of acrylic monomers consisting of acrylamide, acrylic acid, and N-alkylacrylamide (N-isopropylacrylamide). To obtain BC strains, we used, among other approaches, adaptive laboratory evolution (ALE), based on the use of the metabolic pathway of amide utilization. Whole genome sequencing of the strains obtained after ALE, as well as subsequent targeted gene disruption, identified candidate genes for three new amidases that are promising for the development of BCs for the production of acrylic acid from acrylamide. New BCs had two types of amidase activities, acrylamide-hydrolyzing and acrylamide-transferring, and by varying the ratio of these activities in BCs, it is possible to influence the ratio of monomers in the resulting mixtures. Based on these strains, a prototype of a new technological concept for the biocatalytic synthesis of acrylic monomers was developed for the production of water-soluble acrylic heteropolymers containing valuable N-alkylacrylamide units. In addition to the possibility of obtaining mixtures of different compositions, the advantages of the concept are a single starting reagent (acrylamide), more unification of processes (all processes are based on the same type of biocatalyst), and potentially greater safety for personnel and the environment compared to existing chemical technologies.

On the History of Developing Catalysis in Ukraine (1850s–1980s)

The article is dedicated to the history of developing highly effective catalysts in the leading scientific institutions of Ukraine and explores the prerequisites for developing theories in physical chemistry, in particular those related to kinetics and catalysis. It highlights the significance of scientific discoveries at the turn of the 19th and 20th century and their application by native scientists to advance theoretical development in the field of chemistry. Special attention is paid to the works of Lev Pisarzhevskii, focusing on his advancements in electronic chemistry and, in particular, the electronic theory of catalysis. The article also outlines current challenges in creating highly efficient catalysts for the chemical and light industry, emphasizing the importance of such indicators of catalysts as activity and selectivity. Drawing on historical, scientific and patent data, the study investigates the process of creating a highly efficient catalyst for obtaining acrylic acid from acrolein. This catalyst holds a great ractical importance for the production of various polymers in industrial conditions. It is shown that, as a result of research conducted by native scientists of the Institute of Physical Chemistry of the Academy of Sciences of the Ukrainian SSR and the Chemistry Department of Kyiv State University, the catalyst K-2-5 was developed. The catalyst has good indicators for the industrial production of acrylic acid from acrolein. The authors also highlight works studying the properties of the obtained catalyst, specifically its porous structure, which is an important factor in catalytic processes. They extensively focus on the kinetic indicators of catalytic reactions that occur when using this catalyst. The article also emphasizes the relevance of these developments for advancing research in catalysis and chemical industrial production.

Investigation on the flammability limit and limiting oxygen concentration of propane/propylene mixture at elevated temperature and pressure

With the development of industrial technology, a new process has emerged for the production of acrylic acid using propane as a feedstock. There are few studies on the combustion characteristics of propane/propylene mixtures at elevated temperature and pressure. In this study, a flammability limit test system was used to determine the flammability limit and limiting oxygen concentration of propane and propane/propylene mixture at different initial temperatures (30–120 °C) and pressures (0.1–2 MPa). The results showed that with the increase of initial temperature and pressure, the flammability limit range expanded, and the limiting oxygen concentration reduced. In addition, the flammability limit range of the propane/propylene mixture is greater than that of propane, indicating that the addition of propylene increases the explosion risk. The empirical formula of the experimental gas was fitted to predict the combustion and explosion parameters under different conditions. In addition, the chemical reaction simulation of propane/propylene mixture was also investigated. The results showed that with the propylene ratio increased, the adiabatic flame temperature and adiabatic overpressure increased, the proportion of H-abstraction reaction decreased and the proportion of pyrolysis reaction increased significantly, which promoted the explosive reaction and the increase of explosion temperature.

Enhanced surface synergistic effect of alkaline earth metal oxide modification on VPO/SiO2 catalysts for gas-aldol condensation of acetic acid and formaldehyde

Aldol condensation of the syngas-methanol derivatives is an important renewable route for acrylic acid production and coal clean-efficient utilization. In this work, a series of mesoporous alkaline earth metal (x) oxide-modified VPxO/SiO2 catalysts were designed and prepared for gas-aldol condensation of formaldehyde and acetic acid to acrylic acid. The doping of alkaline earth metal oxide into VPO/SiO2 effectively promoted the dispersion and exposure of the VPO species and adjusted the amount of surface (VO)2P2O7/γ-VOPO4 (V4+/V5+). Especially, the SrO and BaO obviously altered the surface chemical environment of VPO species and the strength of acid-base sites, exhibiting strong interaction with both (VO)2P2O7 and γ-VOPO4. The formaldehyde conversion and acrylic acid selectivity over the VPxO/SiO2 increased with about 5.0–10.0 % and 8.0–16.0 % comparing with the VPO/SiO2, respectively. By optimizing the doping amount of BaO and reaction temperature, the VPBaO/SiO2 catalyst achieved a formaldehyde conversion of 70.4 % and an acrylic acid yield of approximately 65.5 % (with formation rate of 12.5 mmol gcat−1 h−1). The VPxO/SiO2 catalysts also showed slightly improved catalytic stability than the VPO/SiO2.

Process assessment of renewable-based acrylic acid production from glycerol valorisation

The continuous growth of biodiesel production via transesterification is leading to an increase in the generation and availability of the by-product glycerol. In this study, a glycerol-based process for the production of acrylic acid has been designed and simulated. The valorisation of glycerol route includes a two-step conversion process where glycerol is first dehydrated to acrolein and acrolein is selectively oxidised to acrylic acid. This renewable-based process is then compared in terms of heat integration and techno-economic performance to the traditional petrochemical route from propylene from a techno-economic and environmental point of view. The study includes the detailed design of the separation train in which azeotropic distillation is also assessed along with the sensitivity analysis of the most relevant variables of the process. Using a production basis of approximately 10,250 kg h−1 of acrylic acid (purity>99.5 wt%), results show that the glycerol route generates 37.3% less CO2 emissions than the propylene-based. From the heat integration analysis, slightly lower heating (96.6%) but higher cooling (32.4%) energy savings can be attained in the glycerol route as opposed to heating (100%) and cooling (21.6%) energy savings available in the propylene-based route. In terms of economics, the glycerol-based route has a lower capital expenditure (£74.0 million) and operating expenditure (£171.4 million yr−1) compared to the propylene route (£91.3 million and £180.2 million yr−1, respectively). Nevertheless, considering the use of raw material and its cost, the glycerol route is more demanding (1.96 kg h−1 of pure glycerol per kg h−1 of acrylic acid amounting to £138.6 million yr−1) than the propylene route (0.92 kg h−1 of propylene per kg h−1 of acrylic acid at £117.2 million yr−1).

Multi-objective optimization of chemical process plant layout considering economy and inherent safety

Economy and safety are important factors for the layout design of chemical process plants. However, safety factors are often translated into economic indicators as a part of the objective function for layout optimization in previous studies. This may result in safety performance of chemical process plants does not meet the actual production requirements. In this paper, a multi-objective optimization method for chemical process plant layout is proposed to obtain series of solutions that can achieve the trade-off between economy and safety. The economic objective function is characterized by the total capital cost, including land cost, pipe cost, protection device cost and expected property loss from accidents. The safety objective function involves inherent safety which is evaluated by the Comprehensive Inherent Safety Index (CISI). The proposed multi-objective optimization model solved by non-dominated sorting genetic algorithm II (NSGA-II) is applied for layout optimization of an acrylic acid production plant. The results show a strong trade-off between competing economic and safety objectives according to the Pareto curve. The optimal solution ranges from 236,099 $ to 379,622 $ for total cost, corresponding to 87.7–132 for CISI. Safety will be improved significantly in the low-safety layout scheme when the capital investment increases slightly.

Selective Production of Acrylic Acid from Glycerol Through a Single-stage Gas Phase Catalytic Oxydehydration over Vanadium-incorporated Zeolite Beta Catalysts

Selective Production of Acrylic Acid from Glycerol Through a Single-stage Gas Phase Catalytic Oxydehydration over Vanadium-incorporated Zeolite Beta Catalysts

Production of acrylic acid from Bio-Derived lactic acid over a Defect-Rich molybdenum phosphosulfide catalyst

Introducing phosphorous and sulphur with molybdenum possess molybdenum phosphosulfate (MoP|S), and the material showed significant activity and stability for the vapour phase dehydration of bio-derived lactic acid to acrylic acid. Adding excessive thiourea-raptured layer spacing creates a defect-rich catalytic structure with more edges and kinks. This disordered atomic arrangement on the basal surface enhanced the dehydration performances of MoS2 catalysts. Considering the inverse trend of acetaldehyde and AA selectivity, we can assume that the decarboxylation of LA is favoured at low temperatures, whereas dehydration is favoured at high temperatures. Rate expression governed by the power law equation was found to be the best fit during the kinetic study, and the Ea of the dehydration was 11.39 KJ/mol. A conversion of 94% with a selectivity of 91% for acrylic acid at 450 °C was achieved over the defect-rich MoS2 catalyst.

Biobased acrylic acid production in a sugarcane biorefinery: A techno-economic assessment using lactic acid, 3-hydroxypropionic acid and glycerol as intermediates

Acrylic acid (AA) is a versatile platform chemical of immense global demand. Today, the biorefinery is among the most promising initiatives of sustainably producing this commodity from bio-derived precursors. This study evaluated the economic and environmental performance of three production pathways to biobased acrylic acid using sugarcane A-molasses as feedstock. The 3 intermediates were lactic acid (LA), 3-hydroxypropionic acid (3-HP) and glycerol. Production scenarios were simulated in Aspen Plus ® software and resultant mass and energy flows provided inputs for subsequent estimation of the minimum selling price (MSP) and greenhouse gas (GHG) emissions. The MSP in US$/kgAA and the net GHG in kgCO2/kgAA were the key metrics against which the performance of the developed scenarios were compared. Accordingly, the scenario using LA as intermediate emerged superior with an MSP that was 11 % higher than the actual market price for fossil-based AA. The same had an estimated net GHG emissions of 4.4 kgCO2/kgAA. 3-HP was the second best performing intermediate with an MSP of 2425 US t-1 and green premium of 30 %. The 3-HP pathway, however, had a fairly low yield at fermentation of about 0.51 g LA/g glucose compared to the 1 g LA/gram glucose recorded by the LA pathway. Ultimately, glycerol proved to be an unattractive intermediate owing to a dismal product yield (0.50 g GLY/g glucose) as well as the cost and complexity of glycol recovery from the fermentation soup.

Selective conversion of lactic acid to renewable acrylic acid over SDA-free Na-ZSM-5: The critical role of basic sites of sodium oxide

Dehydration of biomass-derived lactic acid (LA) is a promising, sustainable alternative to conventional acrylic acid (AA) production through the oxidation of petroleum-derived propylene. Although alkali-exchanged zeolites (e.g., K-ZSM-5) are known to be active for AA production, controlling the selectivity of competitive decarbonylation remains elusive. Herein, we report on a new, highly selective, and durable catalyst—NaxOy/Na-ZSM-5 catalyst for the high-yield production of AA (∼80%) up to 200 h. When Na-ZSM-5 was directly synthesized using Na cations as the structure-directing agent under strongly basic (NaOH) conditions, the inevitable excess sodium residue remained on the surface. Characterization performed by TPD and 23Na NMR analyses revealed the presence of sodium oxide (NaxOy) in addition to Na cations coordinated to Si–O–Al sites in the synthesized ZSM-5, providing the additional basicity and thereby leading to significant enhancement in the AA selectivity through the synergy between two active sites. The catalytic role of NaxOy in LA dehydration was systematically verified by the direct sodium impregnation experiments and in-situ IR spectroscopy.

Conceptual Process Design to Produce Bio-Acrylic Acid via Gas Phase Dehydration of Lactic Acid Produced from Carob Pod Extracts

This work discusses the conceptual process design for the integrated production of bio-based acrylic acid from carob pod aqueous extracts. CHEMCAD was used for the process simulation and cost estimation of the relevant equipment. The process was designed for a capacity of 68 kt of carob pod per year, operating 8000 h annually, and involving extraction, fermentation, catalytic dehydration, and distillation to achieve 99.98%w/w acrylic acid as the main product. The economic assessment for the base case suggests a fixed capital investment of EUR 62.7 MM with an internal rate of return of 15.8%. The results obtained show that carob pod is a promising biomass source for the production of bio-acrylic acid.

Continuous production of methyl acrylate and acrylic acid via co-activation reaction of aldehyde condensation and esterification catalyzed by siloxane-functionalized vanadium phosphorus oxide-TiO2 catalyst

Continuous production of methyl acrylate and acrylic acid via the co-activation reaction of aldehyde condensation and esterification.

Highly efficient acrylic acid production from formaldehyde and acetic acid over the NASICON-type catalyst.

The condensation of formaldehyde and acetic acid to acrylic acid (AA) is considered as one of the important routes for the clean and high value utilization of coal-based methanol derivatives. Herein, we successfully synthesized environment-friendly NASICON catalysts using Ti(SO4)2 as the titanium source. With guaranteed high selectivity (∼78%), the space time yield of AA + MA (methyl acrylate) can be up to 123.9 μmol g-1 min-1, far higher than the results reported previously. Based on the characterizations, it is demonstrated that the modulation of the acidic and basic properties (including distribution, ratio of B/L, etc.) led by the specific elemental and hybrid TiP2O7 phase plays crucial roles in catalyst supremacy.

Production of dimethylsulfoniopropionate, dimethylsulfide and acrylic acid from marine microalgae

Production of dimethylsulfoniopropionate (DMSP), dimethylsulfide (DMS), and acrylic acid (AA) from 22 marine microalgae representing six phyla were examined at different growth stages. The concentrations of DMSP, DMS, and AA per cell in the media showed significant changes during the whole growth period, and the highest concentrations were found at the stationary growth phase or the senescent phase. Different species had different concentration levels of DMSP, DMS, and AA, among which Pyrrhophyta, Bacillariophyte, and Chrysophyta had relatively large release. The highest concentrations of DMSP, DMS, and AA were 56.70, 0.86, and 44.60 fmol cell−1 in Scrippsiella trochoidea, Prymnesiacee, and Karenia mikimotoi, respectively. The ratios of DMS/DMSP and AA/(DMSP+AA) in the 22 marine microalgae differed dramatically over the growth cycle. The DMS/DMSP ratios were <25%, indicating that only a small fraction of DMSP was converted to DMS by enzymatic cleavage. Moreover, there was a higher ratio of enzymatic degradation of DMSP in the senescent growth stage. The AA/(DMSP+AA) ratio, representing the degradation ratio of DMSP, increased significantly at the beginning of growth period and then decreased. Hence, the changes in these ratios could approximately illustrate the degradation mechanism of DMSP among diverse species at different growth phases.

Fenton Process for Treating Acrylic Manufacturing Wastewater: Parameter Optimization, Performance Evaluation, Degradation Mechanism

Acrylic manufacturing wastewater is characterized by high toxicity, poor biodegradability, high chemical oxygen demand (COD) and ammonia nitrogen. Herein, we exploited traditional Fenton technology to treat acrylic fiber manufacturing wastewater. The impacts of key operating variables including the initial concentration of H2O2 (CH2O2), the initial concentration of Fe2+ (DFe2+), and solution pH (pH) on the COD removal rate (RCOD) were explored and the treatment process was optimized by Response Surface Methodology (RSM). The results indicated that the optimum parameters are determined as pH 3.0, 7.44 mmol/L of Fe2+ and 60.90 mmol/L of H2O2 during Fenton process. For the actual acrylic manufacturing wastewater treatment shows that the removal rates for COD, TOC, NH4+-N and TN are 61.45%~66.51%, 67.82%~70.99%, 55.67%~60.97% and 56.45%~61.03%, respectively. It can meet the textile dyeing and finishing industry water pollutant discharge standard (GB4287-2012). During the Fenton reaction, the effective degradation and removal of organic matter is mainly achieved by HO• oxidation, supplemented by flocculation and sedimentation of Fe3+ complexes. This study will provide useful implications in the process parameters for the practical application of Fenton method in acrylic acid production wastewater.