107-02-8

Basic information

• Product Name: Acrolein
• Synonyms: ACROLEIN;ACROLEIN MONOMER;ACRYLALDEHYDE;ACRYLIC ALDEHYDE;ACRALDEHYDE;ALLYLALDEHYDE;2-propen-1-one;2-PROPENAL
• CAS NO: 107-02-8
• Molecular Formula: C3H4O
• Molecular Weight: 56.06
• EINECS: 203-453-4
• Product Categories: Pharmaceutical Intermediates;Miscellaneous;Biocide;AA to AL;A;Aldehydes;Alphabetic;Analytical Standards;Analytical/Chromatography;Building Blocks;C1 to C6;Carbonyl Compounds;Chemical Synthesis;Chromatography;Environmental Standards;Herbicides;Metabolites;Organic Building Blocks;Others;Pesticides &A to Z;Dyes;Hematology and Histology;Stains &Stains and Dyes;Aliphatics, Intermediates, MTS & Sulfhydryl Active Reagents
• Mol File: 107-02-8.mol
• Article Data: 709

Chemical Properties

• Melting Point: −87 °C(lit.)
• Boiling Point: 53 °C(lit.)
• Flash Point: −2 °F
• Appearance: /Liquid
• Density: 0.839 g/mL at 25 °C(lit.)
• Vapor Density: 1.94 (vs air)
• Vapor Pressure: 4.05 psi ( 20 °C)
• Refractive Index: n20/D 1.403(lit.)
• Storage Temp.: 2-8°C
• Solubility: H2O: soluble2 to 3 parts
• Explosive Limit: 31%
• Water Solubility: Soluble. 21.25 g/100 mL
• Sensitive: Air & Light Sensitive
• Stability: Stable, but very readily polymerizes. May have ca. 0.1% hydroquinone added as stabilizer. Flammable. Incompatible with oxidizing
• Merck: 14,128
• BRN: 741856
• CAS DataBase Reference: Acrolein(CAS DataBase Reference)
• NIST Chemistry Reference: Acrolein(107-02-8)
• EPA Substance Registry System: Acrolein(107-02-8)

Safety Data

• Hazard Codes: F,T+,N,T
• Statements: 11-24/25-26-34-50-26/28-24
• Safety Statements: 23-26-28-36/37/39-45-61-16
• RIDADR: UN 1092 6.1/PG 1
• WGK Germany: 3
• RTECS: AS1050000
• F: 8-9
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: I
• Hazardous Substances Data: 107-02-8(Hazardous Substances Data)

Usage

Chemical Description

Different sources of media describe the Chemical Description of 107-02-8 differently. You can refer to the following data:
1. Acrolein is a highly reactive and toxic compound used in the production of plastics and other chemicals.
2. Acrolein is a colorless or yellow liquid with a pungent odor, used in the production of acrylic acid and other chemicals.

Aldehyde compound

Acrolein is a kind of irritant aldehyde compound. It is colorless to yellowish transparent liquid at normal temperature. It has the similar odor of charred oil, soluble in water, ethanol, ether, paraffin (n-hexane, N-octane, cyclopentane), toluene, xylene, chloroform, methanol, ethylether, acetaldehyde, acetone, acetic acid, acrylic acid and ethyl acetate. Acrolein easily polymerized into two polyacrolein; turned into a translucent solid in the light irradiation and generated acrylic acid when in oxidation. 0.2% hydroquinone can be added as a stabilizer when in storage. It is used in the manufacture of resins, pharmaceuticals, glycerol, methionine-alike (auxiliary feed) and so on. It is the more common pollutants in the environment. Acute exposure will damage the respiratory tract, eye and skin, and cause lung and tracheal edema, but also lead to abnormal fat metabolism in the human body, resulting in a lot of fat accumulation in the subcutaneous tissue. Subchronic and chronic exposure has caused monkeys, dogs and other experimental animals, tracheal and nasal cytoplasmic hyperplasia, but no carcinogenic phenomenon. Acute and chronic poisoning concentrations in freshwater were 68 μg/L and 21 μg/L, respectively. The intolerant concentration was 10 mg/m3. During the First World War the French army has used it to make chemical grenades. Acrolein and nicotine, carbon monoxide in cigarettes are the three major harmful ingredients, which can lead to gene mutation, and reduce the ability of cell-repair damage, and they are major factors to the damage of the retina. In cigarettes, the content of acrolein is 10,000 times higher than the carcinogenic substances of polycyclic aromatic hydrocarbons. As a tar component, acrolein toxicity is also thousands of times higher than formaldehyde, and the boiling point is of only 50 degrees Celsius. Cigarettes will immediately gasify when be ignited, invading the retinal pigment epithelium, causing its oxidative damage and preventing the intracellular "energy plant" mitochondria from producing energy. This epithelium is responsible for a variety of nutrients on the retina and waste metabolism. If they "strike", a number of eye cells die.

Chemical properties

Acrolein is colorless, transparent, flammable volatile and volatile liquid, with a strong irritation and the steam has a penetrating, displeasing odor. It is soluble in 2 to 3 times of the water, soluble in alcohol, ether and acetone. The lower explosive limit is 2.8% and the upper explosive limit is 31%. Acrolein may be incompatible with oxidizers, acids, alkalis, ammonia, and amines. Acrolein has the ability to polymerize unless inhibited with hydroquinone. Shock-sensitive peroxides may be formed over time NIOSH (2010).

Uses

Different sources of media describe the Uses of 107-02-8 differently. You can refer to the following data:
1. Acrolein (acraldehyde, acrylaldehyde, acrylic aldehyde, allyl aldehyde, propenal, 2-propenal) is another important aldehyde. It is used as a chemical intermediate in many industrial synthetic processes, including in the production of acrylic acid and allyl alcohol. Acrolein may also be used as a biocide and in the production of perfumes and colloidal metals. Residue from industrial emissions and the burning of wood and other organic substrates will contain traces of acrolein. Acrolein is also a constituent of diesel exhaust and photochemical smog. It is also formed during the pyrolysis of cotton and polyethylene and found in cigarette smoke. Much of the human toxicity data is obtained from the formation of acrolein in vivo as a metabolite of the anticancer drug, cyclophosphamide.
2. Acrolein is used as an antimicrobial agentto prevent the growth of microbes againstplugging and corrosion, to control the aquaticweed and algae, in slime control in papermanufacturing, as a tissue fixative, and inleather tanning.Because of its widespread use it occursin the environment—in air and water. Afterformaldehyde it is the second most abundantaldehyde, constituting 5% of total aldehydesin air. Acrolein is one of the toxic gasesproduced in a wood or building fire or whenpolyethylene or other polymer substancesburn (Morikawa 1988; Morikawa and Yanai1986). Firefighters are at greater risk ofexposure to this gas.
3. Acrolein is used in the etherification of food starch up to 0.6% and for the esterification and etherification of food starch up to 0.3% with vinyl acetate up to 7.5%.
4. Acrolein is used in the synthesis of acrylic acid. manufacture of colloidal forms of metals; making plastics, perfumes; warning agent in methyl chloride refrigerant. Has been used in military poison gas mixtures. Used in organic syntheses. Aquatic herbicide.
5. Contact herbicide and algicide; injected in water for the control of submerged and floating weeds in irrigation ditches and canals

Preparation

1. Propylene catalytic air oxidation method: the bismuth molybdate and bismuth phosphomolybdate catalyst of propylene is directly oxidated in the presence of air at the reaction temperature of 310-470 ° C, atmospheric pressure. The product is acquired when the acid of the by-product is removed from the product in the reaction, and then distillation. 2. Glycerol dehydration method: Glycerol and potassium bisulfate or potassium sulfate, boric acid, aluminum chlorides are under heat at 215-235 ° C in the system. 3. Formaldehyde-acetaldehyde method: under the catalysis of silica gel which is impregnated in sodium silicate, it is produced by gas-phase condensation of formaldehyde and acetaldehyde in the system. Laboratory method: Heat glycerol and potassium bisulfate or magnesium sulfate, boric acid, aluminum oxide together at 215~235 ° C. Distil off and condensate acrolein gas in the reaction, thus generating the crude. 10% sodium hydrogen phosphate solution were added to the crude to adjust the pH value to 6. Through fractionation, collecting 50~75 ℃ distillate, pure acrolein was abtained. Feed ratio (mol): glycerol: potassium hydrogen sulfate: potassium sulfate = 1 ︰ 0.5: 0.026. Industrial production method: at present, the main industrial method is propylene catalytic air oxidation method. The mixture of propylene, air and steam in a certain proportion is mixed with catalyst and sent to a fixed bed reactor. The reaction is carried out at 0.1~0.2 MPa and 350~450 ℃ for 0.8 s. The heat released from the reaction is recovered by steam produce. The resulting gaseous mixture is quenched with water and the exhaust gas from the quench tower is washed before being vented. The organic liquid coming out of the bottom of the quench tower is stripped of the stripper to vaporize the acrolein and other light components and then to remove water and acetaldehyde from the crude acrolein by distillation. Feed ratio (mol) Propylene: Air: Water vapor = 1: 10: 2.

Extinguishing agent

Dry powder, dry sand, carbon dioxide, foam, 1211 extinguishing agent

Description

The first time that acrolein was produced as a commercial product was in the 1930s through the vapor-phase condensation of acetaldehyde and formaldehyde. Another method was developed in the 1940s, which involved the vapor-phase oxidation of propylene. In the 1960s, some advances were found in propylene oxidation process by the introduction of bismuth molybdate-based catalysis, and that became the primary method used for the commercial production of acrolein. Some bioproducts formed for this reaction are acrylic acid, carbon oxides, acetaldehyde, acetic acid, formaldehyde, and polyacrolein. In World War I, it was used as a chemical weapon (pulmonary irritant and lachrymatory agent). Commercial acrolein contains 95.5% or more of the compound, the main impurities being water (<3.0% by weight) and other carbonyl compounds (<1.5% by weight), mainly propanol and acetone. Hydroquinone is added as an inhibitor of polymerization (0.1–0.25% by weight).

Chemical Properties

Acrolein is a highly flammable, clear to yellowish liquid. It has a piercing, disagreeable odor and causes tears.

Physical properties

Colorless to yellow, clear, watery liquid imparting a very sharp, acrid, pungent, or irritating odor. Odor threshold concentrations reported were 0.11 mg/kg by Guadagni et al. (1963), 0.21 ppmv by Leonardos et al. (1969), and 36 ppbv by Nagata and Takeuchi (1990). In addition, Katz and Talbert (1930) reported an experimental detection odor threshold concentration of 4.1 mg/m3 (1.8 ppmv).

Definition

A colorless liquid unsaturated aldehyde with a pungent odor. It can be polymerized to make acrylate resins.

Synthesis Reference(s)

Journal of the American Chemical Society, 68, p. 2487, 1946 DOI: 10.1021/ja01216a013

Air & Water Reactions

Highly flammable. A dangerous fire risk [Hawley]. Water soluble. Reacts slowly and exothermically with water to give 3-hydroxypropionaldehyde. A hazard can develop from this reaction if acrolein is stored over a layer of water.

Reactivity Profile

ACROLEIN, [INHIBITED] can react violently with oxidizing agents. Polymerizes exothermically on contact with small amounts of acids (including sulfur dioxide), alkalis, volatile amines and pyridines, salts, thiourea, oxidizing agents (air) and on exposure to light and heat. Polymerization initiated by amines and pyridines occurs after a deceptive induction period. Water solutions of mineral acids and metal ions can initiate polymerization. The inhibitor (usually hydroquinone) greatly reduces tendency to polymerize. Undergoes Diels-Alder reaction with itself to give acrolein dimer. This can become a runaway reaction at 90°C [Kirk-Othmer, 4th Ed, Vol. 1]. Mixing in equal molar portions with any of the following substances in a closed container caused the temperature and pressure to increase: 2-aminoethanol, ammonium hydroxide, chlorosulfonic acid, ethylenediamine, ethyleneimine [NFPA 1991].

Health Hazard

Acrolein is a highly toxic compound thatcan severely damage the eyes and respiratorysystem and burn the skin. Ingestion can causeacute gastrointestinal pain with pulmonarycongestion.LD50 value, oral (mice): 40 mg/kgAcrolein is a strong lachrymator and anasal irritant. Direct contact of liquid in theeyes may result in permanent injury to thecornea. Inhalation can result in severe irritationof the eyes and nose. A concentration of0.5 ppm for 12 minutes can cause intolerableeye irritation in humans. In rats, exposure toa concentration of 16 ppm acrolein in air for4 hours was lethal.Acrolein can be absorbed through theskin; the spillage of liquid can cause severechemical burns. Skin contact may lead tochronic respiratory disease and producedelayed pulmonary edema. Subcutaneousadministration of acrolein produced degenerationof fatty liver and a general anestheticeffect.LD50 value, subcutaneous (mice): 30 mg/kgOn the basis of the available data, aconcentration of 68 and 55 ppb may betoxic to aquatic life in fresh and salt water,respectively (U.S. EPA 1980). A concentrationas low as 21 ppb may producechronic toxicity to freshwater aquatic life.Acrolein is reported to be more toxic toaquatic organisms than are phenol, chloroandnitrophenols, aniline, o-xylene, and othertoxic compounds (Holcombe et al. 1987).Rainbow trout, spinally transected, wereexposed to an acutely toxic aqueous concentrationof acrolein to monitor their respiratory–cardiovascular responses. A steadyincrease was recorded in their cough rate.The ventilation rate, oxygen utilization, andheart rate steadily fell throughout their periodof survival.In a study on inhalation toxicity in rats,Crane et al. (1986) observed that the exposureto 1 atm of acrolein vapors causedphysical incapacitation. The animals lost theability to walk and expired. In a study oncytotoxicity of tobacco-related aldehydes tocultured human bronchial epithelial cells,acrolein was found to be more toxic thanformaldehyde (Graftstrom et al. 1985). Bothcompounds induced DNA damage.Certain sulfur compounds, such as dithiothreitol and dimercaptopropanol, reacted with acrolein to reduce itstoxicity (Dore et al. 1986). Such protectionagainst its toxicity was observed in isolatedrat hepatocytes.

Fire Hazard

Under fire conditions, polymerization may occur. If inside a container, violent rupture of the container may take place. When heated to decomposition, Acrolein emits highly toxic fumes. Alkalis or strong acids act as catalysts, causing a condensation reaction and liberating energy. Reaction may be very rapid and violent. Readily converted by oxygen to hazardous peroxides and acids. Unstable, avoid exposure to alkalis, strong acids, oxygen, elevated temperatures, such as fire conditions. (Polymerization inside container could cause violent rupture of container under fire conditions.)

Flammability and Explosibility

Acrolein is a highly flammable liquid (NFPA rating = 3) and its vapor can travel a considerable distance and "flash back." Acrolein vapor forms explosive mixtures with air at concentrations of 2.8 to 31% (by volume). Carbon dioxide or dry chemical extinguishers should be used for acrolein fires.

Safety Profile

Human poison by inhalation and intradermal routes. Poison experimentally by most routes. Human systemic irritant and pulmonary system effects by inhalation include: lachrymation, delayed hypersensitivity with multiple organ involvement, and respiratory system damage. Severe eye and skin irritant. Experimental reproductive effects. Human mutation data reported. Questionable carcinogen. Dangerous fire hazard when exposed to heat, flame, or oxidizers. An explosion hazard. Incompatible with amines, SO2, metal salts, oxidants, (light + heat). Violent polymerization reaction on contact with strong acid, strong base, weak acid conditions (e.g., nitrous fumes, sulfur dioxide, carbon dioxide), thiourea, or dimethylamine. When heated to decomposition it emits highly toxic fumes; can react vigorously with oxidizing materials. To fight fire, use CO2, dry chemical, or alcohol foam,

Potential Exposure

Used as pharmaceutical; slimicide; and in production of cosmetics and food supplements; as an intermediate in the production of glycerine and in the production of methionine analogs (poultry feed protein supplements). It is also used in chemical synthesis (1,3,6-hexametriol and glutaraldehyde); as a liquid fuel; antimicrobial agent, in algae and aquatic weed control; and as a slimicide in paper manufacture; making plastics, drugs, and tear gas. Also, most allyl compounds may be metabolized to allyl alcohol which is metabolized to acrolein.

Carcinogenicity

Acrolein is a reactive intermediate of the commonly used chemotherapeutic drugs cyclophosphamide and ifosphamide. Acrolein-modified DNA was found in human peripheral blood lymphocytes from cancer patients previously treated with cyclophosphamide (a chemotherapeutic), but no association was found for cyclophosphamine. Acrolein has a classification of C, possible human carcinogen, based on limited animal carcinogenicity data and paucity of human evidence for this effect.

Source

Reported in cigarette smoke (150 ppm) and gasoline exhaust (0.2 to 5.3 ppm) (quoted, Verschueren, 1983). May be present as an impurity in 2-methoxy-3,4-dihydro-2H-pyran (Ballantyne et al., 1989a). Acrolein was detected in diesel fuel at a concentration of 3,400 μg/g (Schauer et al., 1999). Gas-phase tailpipe emission rates from California Phase II reformulated gasoline-powered automobiles with and without catalytic converters were 0.06 and 3.8 mg/km, respectively (Schauer et al., 2002). Schauer et al. (2001) measured organic compound emission rates for volatile organic compounds, gas-phase semi-volatile organic compounds, and particle phase organic compounds from the residential (fireplace) combustion of pine, oak, and eucalyptus. The gas-phase emission rates of acrolein were 63 mg/kg of pine burned, 44 mg/kg of oak burned, and 56 mg/kg of eucalyptus burned.

Environmental Fate

Biological. Microbes in site water degraded acrolein to β-hydroxypropionaldehyde (Kobayashi and Rittman, 1982). This product also forms when acrolein is hydrated in distilled water (Burczyk et al., 1968). When 5 and 10 mg/L of acrolein were statically incubated in the dark at 25°C with yeast extract and settled domestic wastewater inoculum, complete degradation was observed after 7 days (Tabak et al., 1981). Activated sludge was capable of degrading acrolein at concentrations of 2,300 ppm but no other information was provided (Wierzbicki and Wojcik, 1965)Photolytic. Photolysis products include carbon monoxide, ethylene, free radicals and a polymer (Calvert and Pitts, 1966). Anticipated products from the reaction of acrylonitrile with ozone or hydroxyl radicals in the atmosphere are glyoxal, formaGroundwater. The half-life for acrolein in groundwater was estimated to range from 14 days to 8 weeks (Howard et al., 1991)Chemical/Physical. Wet oxidation of acrolein at 320°C yielded formic and acetic acids (Randall and Knopp, 1980). May polymerize in the presence of light and explosively in the presence of concentrated acids (Worthing and Hance, 1991) forming disacryl, a white plastic solid (Windholz et al., 1983; Humburg et al., 1989). In distilled water, acroleinwas hydrolyzed to β-hydroxypropionaldehyde (Burczyk et al., 1968; Reinert and Rodgers, 1987; Kollig, 1993). The reported hydrolysis rate constant at pH 7 is 6.68 × 108/year (Kollig, 1993). The estimated hydrolysis half-life in water is 22 days (Burczyk et al., 1968)

Metabolic pathway

When fish are exposed to 14C-acrolein, the metabolites are identified from the edible tissues and there is very little similarity in the metabolism of acrolein among the test species. The most notable observation is that acrolein is never detected in any tissues sampled, and glycidol, glycerol, 1,3- propanediol, and glyceric acid are the major metabolites found in catfish, crayfish, bluegill, and clams, respectively.

storage

Work with acrolein should be conducted in a fume hood to prevent exposure by inhalation, and splash goggles and butyl rubber gloves should be worn at all times to prevent eye and skin contact. Acrolein should be used only in areas free of ignition sources. Containers of acrolein should be stored in secondary containers in areas separate from amines, oxidizers, acids, and bases.

Shipping

Acrolein, stabilized, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquids. Inhalation Hazard Zone A.

Purification Methods

Purify acrolein by fractional distillation, under nitrogen, drying with anhydrous CaSO4 and then distilling under vacuum. Blacet, Young and Roof [J Am Chem Soc 59 608 1937] distilled it under nitrogen through a 90cm column packed with glass rings. To avoid formation of diacryl, the vapour is passed through an ice-cooled condenser into a receiver cooled in an ice-salt mixture and containing 0.5g catechol. The acrolein is then distilled twice from anhydrous CuSO4 at low pressure, catechol being placed in the distilling flask and the receiver to avoid polymerization. [Alternatively, hydroquinone (1% of the final solution) can be used.] [Beilstein 1 IV 3435.]

Toxicity evaluation

The main acrolein route of exposure is through smoke. Acrolein is produced as a by-product of combustion of organic compounds, being present in a large spectrum of different smoke produced by, for example, cigarettes, petrochemical fuels (like gasoline or oil), synthetic polymers, paraffin wax, trees, plants, food, animals, vegetables fats, and building fires. Additional exposure can be linked to traffic accidents or to water treated with biocides that contain acrolein. Improperly handled hazardous waste sites can release acrolein into the nearby environment (air, water, or soil).

Incompatibilities

May form explosive mixture with air. Elevated temperatures or sunlight may cause explosive polymerization. A strong reducing agent; reacts violently with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Polymerizes exothermically on contact with small amounts of acids (including sulfur dioxide), alkalis, volatile amines and pyridines, salts, thiourea, oxidizing agents (air) and on exposure to light, and heat. Polymerization initiated by amines and pyridines occurs after a deceptive induction period. Water solutions of mineral acids and metal ions can initiate polymerization. The inhibitor (usually hydroquinone) greatly reduces tendency to polymerize. Reacts with acids, alkalis, ammonia, amines, oxygenperoxides. Shock-sensitive peroxides or acids may be formed over time. Attacks zinc and cadmium

Waste Disposal

Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration. Conditions are 816 C, 0.5 second minimum for primary combustion; 1093 C, 1.0 second for secondary combustion.

InChI:InChI=1/C3H4O/c1-2-3-4/h2-3H,1H2

Upstream product

• 5194-51-4 (2E,4E)-hexa-2,4-diene 
• 107-05-1 3-chloroprop-1-ene 
• 187737-37-7 propene 
• 97-99-4 Tetrahydrofurfuryl alcohol 
• 110-87-2 3,4-dihydro-2H-pyran 
• 693-03-8 n-butyl magnesium bromide 
• 60-29-7 diethyl ether 
• 557-40-4 Allyl ether 
• 556-56-9 allyl iodid 
• 5371-48-2 3,4,5-pentanetriol 
• 50-70-4 D-sorbitol 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 92574-56-6 L-arabo-3.4.5.6-tetrahydroxy-hexene-⁽¹⁾ 
• 546-67-8 lead(IV) tetraacetate 

Downstream Products

• 5473-11-0 2-(N-pyrrolidinyl)bicyclo<3.2.1>octan-8-one 
• 6335-43-9 2-(Pyrrolidin-1-yl)bicyclo[3.3.1]nonan-9-on 
• 626-99-3 1,3-butadiene-1-carboxylic acid 
• 99294-64-1 4-acetyl-5-oxo-hexanal 
• 19261-13-3 1-(2-furyl)but-3-ene-1,2-diol 
• 54674-18-9 3-phenyl-4,5-dihydro-isoxazole-5-carbaldehyde 
• 239-32-7 benzo[4,5]furo[2,3-f]quinoline 
• 872297-34-2 1,4-diphenyl-1,2,3,4-tetrahydro-1,4-epoxido-naphthalene-2-carbaldehyde 
• 2568-20-9 2-(3-oxopropyl)cyclohexanone 
• 869-29-4 1,1-diacetoxy-2-propene 
• 5453-80-5 5-Norbornene-2-carboxaldehyde 
• 63549-44-0 N-allylidene-p-toluidine 
• 1721-26-2 ethyl 2-methyl nicotinate 
• 408320-67-2 4-ethoxy-2-methyl-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid ethyl ester 

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The catalytic gas-phase oxidation of propylene on a multicomponent Mo-Co-Fe-Bi-K-O catalyst gives up to 85percent yield of acrolein and acrylic acid along with undesirable side products - formaldehyde and acetaldehyde.Effect of four factors have now been studied with the aim of suppressing of formation of the by-product viz. the effect of potassium content in the catalyst, that of final annelating temperature of the catalyst, and those of addition of other components (tungsten, nickel).It has been found that a charge in potassium content in catalyst affect distinctly its activity and also selectivity for products of total oxidation of propylene but does not practically affect the yields of formaldehyde and acetaldehyde.The yields of the said side products decreased with increasing annelating temperature, however, with concominant considerable decrease in the catalytic activity.Whereas a partial substitution of molybdenum atoms in the catalyst by tungsten atoms is accompanied by an increase in production of formaldehyde and acetaldehyde, some catalysts with nickel gave acrolein as the only aldehyde.

Highly dispersible and magnetically recyclable poly(1-vinyl imidazole) brush coated magnetic nanoparticles: An effective support for the immobilization of palladium nanoparticles

A heterogeneous recoverable catalyst was prepared via the complexation of palladium onto the surface of magnetic nanoparticles coated by a poly(1-vinyl imidazole) brush. The stable, active and reusable catalyst was proven to be highly active in aerobic oxidation of primary and secondary alcohols with excellent yields. Only 0.1 mol% of the catalyst was used to oxidize 1 mmol of primary and secondary alcohols. The catalyst was readily recovered and reused up to 10 times under the described reaction conditions without significant loss of activity.

Direct oxidative transformation of glycerol into acrylic acid over phosphoric acid-added WVNb complex metal oxide catalysts

The addition of phosphoric acid to WNbO catalyst active for glycerol transformation to acrolein and to WVNbO catalyst active for direct transformation of glycerol to acrylic acid appreciably improved their catalytic performance. The phosphoric acid-added WNbO catalyst gave acrolein yield of 81.8%, and the phosphoric acid-addedWVNbO catalyst gave acrylic acid yield of 59.2% in the direct glycerol transformation. The improvement of the catalytic performance seems due to the increases of the acid amount and the Bronsted acidity.

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Bismuth molybdates prepared by solution combustion synthesis for the partial oxidation of propene

The solution combustion method (SCS) is demonstrated as an easy and fast alternative method allowing the synthesis of mixed oxides with thermally sensitive metals, still keeping a good control on their stoichiometry and phase composition. Bismuth molybdates with different theoretical Bi/Mo atomic ratios, namely α-Bi2Mo3O12, β-Bi2Mo2O9, and γ-Bi2MoO6 were synthesized by the SCS, fully characterized by XRD, Raman, SEM/EDX, BET and XPS analyses, and tested in the partial oxidation of propene to acrolein. The SCS method allowed obtaining crystalline catalysts with Bi/Mo atomic ratios close to the theoretical values and very good catalytic properties namely high propene conversion (from 13.4 to 23.4%) and acrolein selectivity (from 71.5 to 80.0%) at 425°C. A high purity of the SCS prepared bismuth molybdates was obtained by means of a subsequent calcination treatment. Such treatment did not alter the high catalytic activity of the catalysts, which slightly increased (from 12.3 to 25.5%), but induced a marked loss of acrolein selectivity (from 66.2 to 48.4%) at 425°C. This effect is due to a strong increase of the oxidation states of Mo and Bi and reduction of the specific surface area during the calcination.

Sustainable production of acrolein: Effects of reaction variables, modifiers doping and ZrO2 origin on the performance of WO 3/ZrO2 catalyst for the gas-phase dehydration of glycerol

Zirconia-supported tungsten oxide (WO3/ZrO2 or WZ) is known as an efficient catalyst for selective acrolein (AC) production from gas-phase dehydration of glycerol (GL). Two catalysts (WZ-CP and WZ-AN) were prepared herein using, respectively, a ZrO(OH)2 hydrogel (ZrO(OH)2-CP) and its derived alcogel (ZrO(OH)2-AN) for a precursor of ZrO2. To optimize the reaction variables and improve the catalyst performance, the WZ-CP catalyst was employed to show the effects of (A) reaction variables (temperature, partial pressures of GL and H2O, and co-feeding H2 or O2); (B) catalyst modification with alkali and alkali earth metal ions (Na+, K+ and Mg 2+), or transition metals (Pt, Pd, Rh and Ni). The reaction at 315 °C always produced the highest AC selectivity, and this temperature was then used to investigate the effects of the other variables and catalyst modifications. Increasing the molar GL/H2O ratio led to lower AC selectivity and accelerated the catalyst deactivation. Introducing 4-8 kPa O2 to the reaction feed significantly reduced the catalyst deactivation rate but the AC selectivity was only slightly lowered. However, an addition of 4 kPa H2 produced almost no effect on the reaction. The modified catalysts performed no better during the reaction unless the modifier was Pt or Pd, whose catalytic stabilities in the O2-containing (4 kPa) feed were significantly higher and their selectivity for AC production slightly lowered. Working under the conditions optimized with WZ-CP, the WZ-AN catalyst offered a high AC yield (62-68%) for longer than 30 h, during which the GL conversion remained higher than 93%.

Selectivity Control in the Reaction of Allyl Alcohol Over Zeolite Y

Allyl alcohol can be converted into hydrocarbons, acrolein and diallyl ether and control of product selectivity can be achieved by selection of the cation exchanged form of zeolite Y used as catalyst.

Effect of potassium addition to the TiO2 support on the structure of V2O5/TiO2 and its catalytic properties in the oxidative dehydrogenation of propane

Vanadium oxide has been deposited by a grafting technique onto TiO2 anatase, both pure and doped with potassium [(1.2 and 2.5) atoms nm-2]. The V content varied between 0.1 and 20 atoms nm-2 [0.01-2 V2O5 monolayers (ML)]. The prepared samples were characterized by X-ray photoelectron spectroscopy (XPS), 51V magic-angle spinning (MAS) NMR and a surface potential (SP) technique and tested as catalysts in the oxidative dehydrogenation (ODH) of propane and propan-2-ol decomposition, a probe reaction for acid-base properties. From the XPS and SP data it has been inferred that VOx are located beside the K centres on the bare surface of TiO2 with the lower K content sample, whereas they cover the K-doped fraction of the surface for the sample with higher K content. Monomeric and polymeric VOx species and V2O5 were detected by 51V NMR on pure and K-doped catalysts. For the K-doped samples the polymeric species were observed only at high V content and new tetrahedral VOx species and traces of KVO3 appeared. It has been found that the presence of K on the TiO2 surface leads to (a) a decrease in the reducibility of the vanadia phase at low V content; (b) a decrease in the surface potential (electronic work function); (c) a decrease in acidity and increase in basicity and (d) a decrease in the total activity for ODH of propane. The pattern of the activity and selectivity changes with the total V content depends on the amount of K on the support surface: with K 2O5 ML. At higher K content, higher amounts of vanadium (> 1 ML) are required to obtain the same catalytic performance. Polymeric [VOx] species seem to be more active and selective in the ODH of propane than monomeric species or bulk V2O5.

High catalytic performance of MoO3-Bi2SiO 5/SiO2 for the gas-phase epoxidation of propylene by molecular oxygen

MoO3-Bi2SiO5/SiO2 catalysts with a Mo/Bi molar ratio of 5, prepared by a two-step hydrothermal and simple impregnation method, were investigated for the epoxidation of propylene by O2 and characterized by XRD, N2 absorption-desorption isotherms, thermogravimetric analysis (TGA), temperature-programmed reduction, NH3 temperature-programmed desorption (TPD), and IR, Raman, and X-ray photoelectron spectroscopy (XPS). On MoO3-Bi2SiO 5/SiO2 with Mo/Bi=5 calcined at 723K, a propylene conversion of 21.99 % and a propylene oxide selectivity of 55.14 % were obtained at 0.15MPa, 673K, and flow rates of C3H6/O 2/N2=1/4/20cm3 min-1. XRD, IR spectroscopy, and XPS results show that Bi2SiO5 and MoO3 are crystalline nanoparticles. NH3-TPD results indicate that the surface acid sites are necessary for the high catalytic activity. The results of TGA and N2 absorption-desorption isotherms reveal that a reasonable calcination temperature is 723K. The reaction mechanism of propylene epoxidation on MoO3-Bi2SiO 5/SiO2 catalysis is hypothesized to involve an allylic radical generated at the molybdenum oxide species and the activation of O 2 at the bismuth oxide cations. A new sensation in epoxidation: We describe the probable synergistic effects of MoO3 and Bi 2SiO5 in propylene epoxidation. The reactive centers consist of nanoparticulate species of crystalline MoO3 to activate the propylene and bismuth oxide cluster cations to activate O2.

Silylation enhances the performance of Au/Ti-SiO2 catalysts in direct epoxidation of propene using H2 and O2

The effect of silylation on a series of Au/Ti-SiO2 catalysts for the direct epoxidation of propylene in the presence of H2 and O2 was studied. It was found that silylation significantly improved catalyst performance: propylene conversion, propylene oxide (PO) selectivity, and H2 efficiency increased. The extent of improvement depended on the Au and Ti content of the catalysts. The catalyst showing the best activity (Au(0.1)/Ti(1)-SiO2) exhibited an average PO formation rate of 121 gPO kgcat?1 h?1 and a PO selectivity of 92% at 473 K, while the catalyst having the maximum Au and Ti loading (Au(1)/Ti(5)-SiO2) showed the most significant improvement in performance with a 78% increase in the rate of PO formation upon silylation. The catalysts were characterized by contact angle measurements, FTIR, TGA, TEM, ICP-OES and these observations were used to elucidate the key factors governing the enhanced catalytic performance upon silylation. It was found that the silylated catalyst exhibited superior performance due to increased hydrophobicity, which aids product desorption, a decrease in acidic sites that are responsible for side-product formation, and a possible redistribution of the Au particles.

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Oxidation of Propene in the Gas Phase

A series of laboratory and modelling experiments on the oxidation of propene in the gas phase has been undertaken to determine conditions which give high yields of propene oxide.The conditions under which the experiments were conducted were 505 - 549 K and up to 4 bar pressure.It is proposed that propene oxide is formed from propene by reaction with several peroxy radicals including HO2 and CH3CO3.However, one of the more important radicals is hydroxypropylperoxy.Its reaction with propene, under these conditions (107) HOCH2CHO2CH3 + C3H6 -> HOCH2CHOCH3 + C3H6O is more important than concerted decomposition to formaldehyde and acetaldehyde.

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HETEROARYL DERIVATIVE, METHOD FOR PRODUCING SAME, AND PHARMACEUTICAL COMPOSITION COMPRISING SAME AS EFFECTIVE COMPONENT

The present invention relates to a 6-(isooxazolidin-2-yl)-N-phenylpyrimidin-4-amine derivative, and a pharmaceutical composition for preventing or treating cancer comprising the compound as an effective component. The compound exhibits high inhibitory activity against an epidermal growth factor receptor (EGFR) variant, or wild-type or variants of one or more of ERBB2 and ERBB4, and thus may be usefully used in the treatment of cancers in which same are expressed. In particular, the compound exhibits excellent inhibitory activity on proliferation of lung cancer cell lines, and can thus be usefully used in the treatment of lung cancer.

Novel Mo-V Oxide Catalysts with Nanospheres as Templates for the Selective Oxidation of Acrolein to Acrylic Acid

Abstract: Novel Mo-V-PMMA and Mo-V-PS catalysts are prepared by addition of hard polymethyl methacrylate (PMMA) and polystyrene (PS) nanospheres into Mo/V compounds in the preparation process, respectively. The catalytic tests in selective oxidation of acrolein reveal that Mo-V-PMMA catalyst shows very high acrolein conversion (99.1%) and the yield of acrylic acid (90.7%). The BET, DLS, SAXS, XRD, XPS, H2-TPR and NH3-TPD measurements reveal that the addition of PMMA and PS nanospheres causes the obvious changes of porous structure, crystal phases composition and chemical properties of catalysts. These differences between Mo-V-PMMA and Mo-V-PS catalysts are attributed to the totally different “real” nano–environment during heat treatment in the high–concentration component mixture. PS nanospheres are in a state of adhesion or agglomeration or not uniformly distributed in the active component solution, while PMMA nanospheres with much better hydrophilicity and monodispersed state promote Mo and V ions more easily and uniformly dispersed in the mixture. Graphic abstract: Novel Mo-V catalysts are prepared by addition of hard polymethyl methacrylate (PMMA) and polystyrene (PS) nanospheres into Mo/V mixture. Obvious changes of porous structure, crystal phases and chemical properties of catalysts are caused by the nanospheres introduction, showing very high acrolein conversion (99.1%) and the yield of acrylic acid (90.7%) in selective oxidation of acrolein.[Figure not available: see fulltext.].

Chemical Imaging of Mixed Metal Oxide Catalysts for Propylene Oxidation: From Model Binary Systems to Complex Multicomponent Systems

Industrially-applied mixed metal oxide catalysts often possess an ensemble of structural components with complementary functions. Characterisation of these hierarchical systems is challenging, particularly moving from binary to quaternary systems. Here a quaternary Bi?Mo?Co?Fe oxide catalyst showing significantly greater activity than binary Bi?Mo oxides for selective propylene oxidation to acrolein was studied with chemical imaging techniques from the microscale to nanoscale. Conventional techniques like XRD and Raman spectroscopy could only distinguish a small number of components. Spatially-resolved characterisation provided a clearer picture of metal oxide phase composition, starting from elemental distribution by SEM-EDX and spatially-resolved mapping of metal oxide components by 2D Raman spectroscopy. This was extended to 3D using multiscale hard X-ray tomography with fluorescence, phase, and diffraction contrast. The identification and co-localisation of phases in 2D and 3D can assist in rationalising catalytic performance during propylene oxidation, based on studies of model, binary, or ternary catalyst systems in literature. This approach is generally applicable and attractive for characterisation of complex mixed metal oxide systems.