PL210882B1 - Method of manufacturing of allyl alcohol - Google Patents

Description

REPUBLIC

POLAND

Patent Office of the Republic of Poland (12) PATENT DESCRIPTION (19) PL (11) 210882 (13) B1 (21) Application number: 386104 ^{(51) Int.Cl.}

C07C 33/03 (2006.01) C07C 29/14 (2006.01) (22) Date of notification: 17/09/2008 (54) Method for producing allyl alcohol

(73) The right holder of the patent: WARSAW UNIVERSITY OF TECHNOLOGY, (43) Application was announced: Warsaw, PL March 29, 2010 BUP 07/10 (72) Inventor (s): MAREK GLIŃSKI, Warsaw, PL (45) The grant of the patent was announced: URSZULA ULKOWSKA, Warsaw, PL 30.03.2012 WUP 03/12 (74) Representative: item. stalemate. Joanna Bocheńska

PL 210 882 B1

Description of the invention

The subject of the invention is a method of producing allyl alcohol which is a raw material for many chemical syntheses, incl. for the production of esters, in the pharmaceutical and perfume industry and plastics.

Allyl alcohol is derived from glycerin, allyl chloride, allyl acetate, propylene oxide or acrolein as the main substrates.

The conversion of glycerin to allylic alcohol as a result of its heating with technical formic acid or oxalic acid as substrates, described and developed in the first half of the 20th century, due to the costs associated with the loss of acid, formation of significant amounts of tar products and the long duration of the process, has only historical significance today.

Allyl alcohol is obtained on an industrial scale by hydrolysis of allyl chloride with 10% aqueous sodium hydroxide solution at a temperature of 423 K and a pressure of 1.3 - 1.4 MPa. When 100% conversion is achieved, the allylic alcohol yield is 85-95%, diallyl ether, propionaldehyde and heavy condensation products are also formed. The disadvantage of the method, apart from the loss of chlorine in the form of sodium chloride, is the additional cost associated with the need to produce a corrosion-resistant installation.

Allyl acetate, obtained from propylene, acetic acid and oxygen in the presence of a palladium catalyst in the acetoxylation reaction, is hydrolyzed to allylic alcohol by the action of acid catalysts (mineral acids or acidic ion exchange resins) or in the absence of a catalyst at a temperature of 503 K and a pressure of 30 MPa. The acetic acid obtained is recycled to the synthesis of allyl acetate. The process selectivity to allyl alcohol is about 90% based on the propylene used for ester synthesis.

Another process used to synthesize allyl alcohol is the catalytic isomerization of propylene oxide, which can be carried out in the liquid or gas phase. In this first variant, propylene oxide is introduced into a suspension of ground lithium phosphate Li3PO4 in an organic high-boiling solvent, kept at a temperature of 548-553 K. The propylene oxide conversion is 65% and the allylic alcohol yield is 60%.

The process can also be carried out in the gas phase, using a Li3PO4 catalyst deposited on an inorganic support, in the temperature range of 523-623 K. In this case, a higher substrate conversion of 70-75% and a selectivity to alcohol of 97% are obtained. By-products are propionaldehyde and acetone.

The method of hydrogen transfer between isopropyl alcohol and acrolein in the gas phase using a MgO-ZnO catalyst kept at a temperature of 673 K is also known. Allyl alcohol is obtained with a selectivity of up to 80%. 2-butanol was also used as a hydrogen donor in this reaction. The observed not too high conversions of acrolein are the main disadvantage of this method.

Recently, methods of direct hydrogenation under hydrogen gas pressure of acrolein in the liquid phase in the presence of metal catalysts, mainly gold, with a designed metallic active phase dispersion, deposited on selected supports in the form of metal oxides, are being developed. The reduction selectivity and the allylic alcohol yield depend primarily on the type of catalyst, as well as the reaction temperature and hydrogen pressure, the rate of mixing the catalyst with the reactants, and the type of solvent. The disadvantage of the latter method is the high cost of the active catalyst phase (gold) and the relatively quick loss of its activity.

The method according to the invention avoids the above-mentioned difficulties.

The method of producing allyl alcohol consists in passing a mixture of acrolein and ethanol, preferably anhydrous, wherein the molar ratio of acrolein to ethanol is from 1-3 to 1-12, respectively, through a catalyst bed containing magnesium oxide with a grain size of 0.15-2.5 mm. The catalyst bed is previously calcined at a temperature of 573 - 1073 K in a stream of air or inert gas for 1-10 hours and then modified with iodine, hydroiodic acid or anhydrous iodides of alkali or alkaline earth metals, preferably magnesium iodide, dissolved in alcohol, preferably methanol and the bed thus obtained is heated to a temperature of 423 - 673K before passing through the mixture of acrolein and ethanol.

The method according to the invention is presented in more detail in the examples of use.

Example 1 Magnesium oxide with grain size 0.16 - 0.40 mm was calcined at the temperature of 873 K in a stream of air for 1 hour and then for 5 hours in a stream of dry nitrogen. 0.25 g of the so prepared oxide is poured into a dry, nitrogen-rich vessel, poured over it with 5 cm ³ anhydrous methanol and 0.0064 g (0.025 mmol) of iodine is poured. The closed vessel is left to stand for 24 hours, then the methanol is distilled off under reduced pressure in a vacuum evaporator and the dry residue is poured into a tubular reactor located in an electrically heated oven. After heating the catalyst bed to a temperature of 573 K, dry nitrogen was passed through at a space velocity of 50 cm ³ / min. A solution of acrolein in anhydrous ethanol, mixed in a molar ratio of 1 to 3, is dosed to the top of the reactor using a dosing pump. The loading of the catalyst bed is 3 cm ³ / (gh). The gaseous reaction products are pre-cooled in a water cooler and then in a cooling bath containing a mixture of dry ice-2-propanol. Acrolein conversion 56%, allyl alcohol yield 51%.

Example II. The process was carried out in the same way as in Example 1, using the catalyst obtained by reacting 0.25 g of magnesium oxide with 0.0064 g (0.025 mmol) of iodine in 5 cm ^{3 of} methanol. Dry nitrogen is passed through the catalyst thus obtained, heated to a temperature of 523 K, at a space velocity of 50 cm ³ / min, and simultaneously the acrolein solution in anhydrous ethanol is dosed in a molar ratio of 1 to 6, with a bed loading of 3 cm ³ / (gh). There was an acrolein conversion of 78% and an allylic alcohol yield of 73%.

Example III. The process was carried out in the same way as in Example 1, using the catalyst obtained by reacting 0.25 g of magnesium oxide with 0.0064 g (0.025 mmol) of iodine in 10 cm ^{3 of} 2-propanol. Dry nitrogen is passed through the thus obtained catalyst, heated to a temperature of 473 K, at a space velocity of 50 cm ³ / min, and simultaneously the acrolein solution in anhydrous ethanol is dosed in a molar ratio of 1 to 6, with a bed loading of 3 cm ³ / (gh). There was an acrolein conversion of 66% and an allylic alcohol yield of 65%.

Example IV. The process used a catalyst obtained by reacting 0.25 g of magnesium oxide with a solution of hydroiodic acid 0.0116 g (0.05 mmol) 55% by weight of HI in 10 cm ^{3 of} methanol and proceeding analogously to example I. to a temperature of 523 K, dry nitrogen is flushed at a volumetric velocity of 50 cm ³ / min and simultaneously the acrolein solution in anhydrous ethanol is dosed in a molar ratio of 1 to 6, with a bed loading of 3 cm ³ / (gh). The acrolein conversion was 72% and the allylic alcohol yield was 70%.

Example 5 The process used a catalyst obtained by reacting 0.25 g of magnesium oxide with a solution of anhydrous ammonium iodide 0.0072 g (0.05 mmol) of NH4I in 10 cm ^{3 of} methanol and proceeding analogously to example I. the obtained catalyst, heated to a temperature of 473 K, is passed dry nitrogen at a space velocity of 50 cm ³ / min, and at the same time the acrolein solution in anhydrous ethanol is dosed in a molar ratio of 1 to 6, with a bed loading of 3 cm ³ / (gh). The acrolein conversion was 69% and the allylic alcohol yield was 67%.

Example VI. The process used a catalyst obtained by reacting 0.25 g of magnesium oxide with a solution of anhydrous magnesium iodide 0.0070 g (0.025 mmol) Mgl2 in 10 cm ^{3 of} methanol and proceeding analogously to example I. The catalyst thus obtained was heated to a temperature of 523 K dry nitrogen is passed at a space velocity of 50 cm ³ / min, while solution of acrolein dispensed in anhydrous ethanol in a molar ratio of 1 to 6, wherein the load bed of 3 cm ³ / (gh). The acrolein conversion was 71% and the allylic alcohol yield 68%.

Example VII. The process used a catalyst obtained by reacting 0.25 g of magnesium oxide with a solution of anhydrous cesium iodide 0.0065 g (0.025 mmol) of Csl in 10 cm ^{3 of} methanol and proceeding analogously to example 1. The catalyst thus obtained was heated to a temperature of 623 K dry nitrogen is passed at a space velocity of 50 cm ³ / min, while solution of acrolein dispensed in anhydrous ethanol in a molar ratio of 1 to 6, wherein the load bed of 3 cm ³ / (gh). There was an acrolein conversion of 76% and an allylic alcohol yield of 69%.

Claims (1)

Patent claim Process for the production of allyl alcohol, characterized by passing a mixture of acrolein and ethanol, preferably anhydrous, in which the molar ratio of acrolein to ethanol is from 1-3 to 1-12, respectively, through a catalyst bed containing magnesium oxide with a grain size of 0.15-2 , 5 mm previously calcined at a temperature of 573 - 1073 K in a stream of air or inert gas for 1-10 hours and then modified with iodine, hydroiodic acid or anhydrous iodides of alkali or alkaline earth metals, preferably magnesium iodide, dissolved in alcohol, preferably methanol and the bed thus obtained is heated to the temperature of 423 - 673K before passing through the mixture of acrolein and ethanol.