Example 1
The following example is a reproduction of example 2 as published in WO2012/72697.
Glycerol was converted to acrolein over a catalyst bed with hydrogen used to lower the partial pressure of the reactants. A catalyst layer consisting of 56 g of a catalyst, 10 w % of W03 supported on ZrO2 in grains of the size 20-30 mesh, was used. The inlet liquid stream consisted of 20 wt % of glycerol in water fed to the preheater at 0.3 g/min. A gas stream of 100 ml/min of hydrogen was also fed to the preheater. The liquid stream was preheated and vaporized, to 280° C., prior entering the reactor. The inlet of reactor was held at 300° C. and a pressure of 5 bar gauge was applied over reactor. The outlet stream was cooled down in a condenser and the water was condensed. The liquid stream was collected in a sample vessel, while the gas stream 11 was collected in a Tedlar gas bag. The liquid sample was analyzed with a GC equipped with FID and a WAX-column for hydrocarbons (propanol, propanal, propionic acid etc.). The gas sample was analyzed with a two channel GC equipped with TCD for analyzing CO, CO2, ethene, ethane etc. Glycerol was converted to beyond the detection limit and acrolein was yielded in amounts above 80%. The production of hydroxyacetone was lowered to 5% while the yields of CO and CO2 essentially the same. Further, some 10% propionaldehyde was formed as a side product.
Example 2
The following example is a reproduction of example 1 as published in US 2011/112330.
A Cesium salt of tungstophosphoric acid (CsPW) was used for a 20 wt % aqueous solution of glycerol in a fixed catalyst bed together with air. The fixed catalyst bed was heated at a temperature of 260° C. to 350° C. whereas the Feed gas had following composition in mol percent:glycerin:oxygen:nitrogen:water=4.2:2.2:8.1:85.5. GHSV was 2445 h−1. Acrolein was obtained in 93.1% Yield
Example 3
The catalyst (Mo1Pd01.57e-4Bi0.09Co0.8Fe0.2Al0.123V4.69e-3K5.33e-3) was tested with a gas feed composition of nitrogen:oxygen:propylene:water in the ratio of 77:7.50:5.50:10 at 342° C., at a pressure of 15 psi, and a total flow of 130 cc/min. The reaction product showed a 99% conversion of propylene with a 98% selectivity for acrolein.
Example 4
The following synthesis was a reproduction of example 1 in EP 1460053
A ring-shaped catalyst having the following composition Mo:Bi:Co:Fe:Na:B:K:Si:O 12:1:0.6:7:0.1:0.2:0.1:18:X (wherein X is a value determined by oxidation degrees of the respective metal elements) was used. At 200° C. a mixed reaction raw gas composed of 8 mol % of propylene, 67 mol % of air and 25 mol % of steam was fed into the reaction tubes of a fixed bed multipipe type reactor from a top thereof such that the reaction raw gas was contacted with the catalyst for 3.5 seconds. In addition, the temperature of the niter was controlled so as to attain a propylene conversion rate of 98%. The Yield of acrolein was 92.5%.
Example 5
The following synthesis was a reproduction of example 1 in U.S. Pat. No. 6,388,129
Converting a gas mixture (modified air) consisting of 90% by volume of 02 and 10% by volume of N2 and 79.7 mol/h of recycled gas having the composition of 87.7% by volume of propane were converted to obtain propene via oxydehydrogenation of propane.
The by this process obtained propene can be furthermore converted to Acrolein by a process as described in example 3 or example 4.
Example 6
The following synthesis was a reproduction of example 1 in US 2016/23995
Synthesis of the Catalyst with an Sb/Fe ratio of 0.6:
A 0.05M solution was prepared by dissolving 2.21 g of oxalic acid in 500 ml of water at 80° C. with stirring. Once dissolution was complete, 140.97 g of iron nitrate nonahydrate were added to the oxalic acid solution while maintaining the temperature at 80° C. After complete dissolution of the iron nitrate nonahydrate, 30.51 g of antimony(III) oxide were added. The resulting solution was left to evaporate while maintaining the temperature at 80° C., with stirring, until a viscous solution was obtained, which was then dried in ail oven at 120° C. for 72 hours. After drying, the product obtained was pressed in the form of pellets which were subsequently ground in order to obtain a pulverulent product comprising particles having a size of between 250 and 630 μm. These particles were then calcined under static air from ambient temperature up to 500° C. while observing a temperature rise gradient of 1° C./min and then a phase of maintenance at 500° C. for 8 hours. The catalyst was subsequently left in the oven until the temperature had returned to 50° C. A catalyst exhibiting an Sb/Fe ratio of 0.6 (i.e., x=0.6) was obtained.
5 g of the catalyst prepared were placed in a fixed bed reactor. The reaction was carried out with a 7.2% by weight aqueous allyl alcohol solution. The reactor was heated to 400° C. and then fed with reactants (allyl alcohol/02/NH3) at atmospheric pressure. The contact time of the reactants with the catalyst was of the order of 0.1 sec. The reaction time was 5 hours. The products resulting from the reaction were analyzed after trapping at the reactor outlet in a bubbler maintained at low temperature (−4° C.). The liquid obtained was subsequently analyzed on a gas chromatograph equipped with a flame ionization detector. Allyl alcohol/O2/NH3 molar ratio: 1/1.6/0.4: Conversion of the allyl alcohol 87%, Yield: 17% Acrylonitrile, 52% acrolein, 5% acetaldehyde, 5% propionaldehyde, 1% acetonitrile.
Example 8
The following synthesis was a reproduction of example 1 in DE 755524
The experiments were run at an aldehyde-to-hydrogen ratio of 1:2 on a molar basis and at 5 bar operating pressure. An aqueous solution of 10 wt % acrolein and hydrogen was fed to a preheater, wherein the mixture was heated to about 150° C. The resulting mixed gaseous stream was then fed to a reactor comprising the catalyst (2 wt % Pd on Al2O3—and one where the Pd has been concentrated to the outermost surface of the catalyst (0.18 wt % Pd on Al2O3)). Full conversion of acrolein was observed. The selectivity to propionaldehyde was about 85%. Side products hydroxyacetone, CO and CO2.
Example 12
In this example a catalyst containing Pd and Pb was used. The synthesis is based on example 1 as disclosed in U.S. Pat. No. 6,680,405.
In a 4 L reactor equipped with a condenser and a stirrer, 350 g of a catalyst (a calcium carbonate catalyst containing 5 wt % palladium, 1 wt % lead and 1 wt % iron) and a reaction liquid of 700 g of methacrolein and 1280 g of methanol were charged. The reaction was continued for 4 hours at a bath temperature of 80° C. and under pressure of 400 kPa*abs, while blowing air and nitrogen at rates of 4.77 Nl/min and 5.0 Nl/min, respectively, thereby to synthesize methyl methacrylate. The reaction product was collected and analyzed, and as a result, a conversion of methacrolein and a selectivity of methyl methacrylate were found to be 75.1% and 85.2%, respectively.
Example 13
In this example a catalyst containing Pd and Pb was used. The synthesis is based on example 1 as disclosed in US 2014/206897.
50.1 g of methacrolein is added to the reactor, along with 25.2 g of methanol (for a molar ratio of methanol to methacrolein of about 1.1). Roughly 1 g of catalyst (e.g. comprising 3 wt % palladium and 2 wt % lead on silica) is added to the solution. A stirrer is turned on, and the solution is heated to about 50° C. Oxygen flow is begun at about 6 milliliters per minute (mL/min). The reactor is open to atmospheric pressure. The reaction is continued for about 4 hours. This results in methacrolein conversion of about 50 percent, with selectivity to methyl methacrylate of about 90 percent.
