JP2015054819A - Method for producing 3-butene-2-ol and 1,3-butadiene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 3-butene-2-ol and 1,3-butadiene from 2, 3-butanediol at a high selectivity without using radioactive substances.SOLUTION: Provided is a method for producing 3-butene-2-ol in which 2, 3-butanediol is dewatered using at least one kind selected from a group consisting of zirconium oxide, a zirconium oxide-alkali metal compound complex and zirconium-alkaline-earth metallic compound complex as a catalyst.

Description

  The present invention relates to a method for producing 3-buten-2-ol and 1,3-butadiene using a biomass resource-derived material as a raw material.

  3-Buten-2-ol is a useful substance that can be used as a raw material for chemical products and pharmaceuticals. Moreover, 3-buten-2-ol can be easily converted to 1,3-butadiene by dehydration, and thus is useful as an intermediate raw material for 1,3-butadiene. Examples of a method for converting 3-buten-2-ol to 1,3-butadiene include a method of dehydrating 3-buten-2-ol in the presence of a silica-alumina catalyst. Examples of the method for producing 3-buten-2-ol include a method of producing acrolein by allowing methylmagnesium iodide to act, a method of producing 2-butanol by partial oxidation, a method of producing by reducing methyl vinyl ketone, and the like. Are known.

  1,3-butadiene is an extremely important basic material in the chemical industry used as a raw material for various chemical products. Using 1,3-butadiene as a raw material, for example, synthetic products such as styrene-butadiene rubber, polybutadiene rubber, chloroprene rubber, and other chemical products such as ABS resin, adiponitrile, 1,4-butanediol are manufactured. As an industrial production method of 1,3-butadiene, a method of separating and producing 1,3-butadiene from a BB fraction (mixture mainly composed of olefins having 4 carbon atoms) produced by naphtha cracking, Alternatively, a method for producing by dehydrogenation of butane or butene is known.

  On the other hand, in recent years, the problem of global warming due to greenhouse gases such as carbon dioxide generated from fossil resources and the problem of depletion of fossil resources have become serious. For this reason, there is an increasing need to prevent global warming and transform into a sustainable recycling society. In the chemical industry, there is an urgent need to establish technology for producing various chemical products from substances derived from biomass resources, which are renewable resources. The above-mentioned 3-buten-2-ol and 1,3-butadiene are both produced from fossil resources, and the conversion of the raw materials to biomass resources is from the viewpoint of global environmental protection and fossil resource saving. Very important.

  Since 2,3-butanediol can be produced by microbial fermentation using sugar as a raw material, it is a substance that can be derived from biomass resources (Non-Patent Document 1). Therefore, if 2,3-butanediol can be converted into 3-buten-2-ol and 1,3-butadiene, the raw materials of 3-buten-2-ol and 1,3-butadiene are converted into biomass resources. It becomes possible.

  The reaction for converting 2,3-butanediol to 3-buten-2-ol is a dehydration reaction in which one molecule of water molecule is eliminated from 2,3-butanediol. The reaction for converting to butadiene is a dehydration reaction in which two water molecules are desorbed from 2,3-butanediol. Although it is known that the dehydration reaction of 2,3-butanediol proceeds by an acid catalyst, in many cases, the main product is methyl ethyl ketone rather than 3-buten-2-ol or 1,3-butadiene. . For example, it has been reported that when 2,3-butanediol is dehydrated using alumina which is widely used for dehydration of alcohols, methyl ethyl ketone is selectively produced (Patent Document 1). In addition, methods for dehydrating 2,3-butanediol using white diatomaceous earth or zeolite have been reported, but the main product in these methods is also methyl ethyl ketone (Non-patent Documents 2 and 3).

  As a method for selectively producing 3-buten-2-ol from 2,3-butanediol, a method for producing it by a dehydration reaction using thorium oxide as a catalyst has been reported (Non-patent Document 4). In addition, it has been reported that 3-buten-2-ol is produced by dehydrating 2,3-butanediol using a catalyst containing hydroxyapatite (Patent Document 1).

  In addition, as a method for selectively producing 1,3-butadiene from 2,3-butanediol, a method for producing by dehydration reaction using thorium oxide as a catalyst (Non-patent Document 4), cesium oxide-silica A method of producing a composite by a dehydration reaction using a catalyst (Patent Document 2) has been reported.

  The reaction of dehydrating 2,3-butanediol to produce 3-buten-2-ol belongs to the reaction of dehydrating diol to produce unsaturated alcohol. As an example of a reaction for dehydrating a diol to produce an unsaturated alcohol, a reaction for dehydrating 1,4-butanediol to selectively produce 3-buten-1-ol has been reported. As a catalyst for proceeding with this reaction, Patent Document 3 reports zirconium oxide, Patent Document 4 reports zirconium oxide treated with a basic substance, and Non-Patent Document 5 reports cerium oxide, neodymium oxide, samarium oxide, and the like. Has been.

Republic of Korea Published Patent No. 2012-0107353 Republic of Korea Published Patent No. 2012-099818 JP 2006-212495 A JP 2006-212696 A

Biotechnology Advances, 27, p. 715-725 (2009). Japanese Journal of Agricultural Chemistry, Vol. 18, p. 143-150 (1942). Industrial & Engineering Chemistry Research, Vol. 52, p. 56-60 (2013). Journal of the Council of Industrial Research, 18, p. 412-423 (1945). Applied Catalysis A: General, 356, p. 64-71 (2009).

  As mentioned above, 2,3-butanediol can be derived from biomass resources and can be converted to 3-buten-2-ol and 1,3-butadiene by chemical conversion. However, as described above, when 2,3-butanediol is dehydrated using an acid catalyst, in many cases, the main product is methyl ethyl ketone, and 3-buten-2-ol and 1,3-butadiene are hardly formed. . In the method using alumina disclosed in Patent Document 1, white diatomaceous earth disclosed in Non-Patent Document 2, and zeolite disclosed in Non-Patent Document 3, methyl ethyl ketone is 65 mol%, 66 mol%, It is produced with a selectivity of 90 mol%.

  Further, as described above, a method for selectively producing 3-buten-2-ol from 2,3-butanediol is disclosed, and thorium oxide disclosed in Non-Patent Document 4 is used as a catalyst. In the method, the selectivity for 3-buten-2-ol is 70.3%. However, since thorium oxide is a radioactive substance, it is very difficult to apply it to industrial production. In addition, the method of converting 2,3-butanediol to 3-buten-2-ol using a catalyst containing hydroxyapatite disclosed in Patent Document 1 has a selectivity of 3-buten-2-ol. It is 25.0 mol%, and the selectivity is very low.

  As described above, a method for selectively producing 1,3-butadiene from 2,3-butanediol is also disclosed, and a method using thorium oxide as a catalyst disclosed in Non-Patent Document 4 is also disclosed. Then, the selectivity for 1,3-butadiene is 62.1%. However, since thorium oxide is a radioactive substance, it is very difficult to apply it to industrial production. Patent Document 2 reports that the selectivity of 1,3-butadiene is 62 mol% when a cesium oxide-silica composite is used as a catalyst. However, as shown in Comparative Example 1 of the present application, as a result of the inventors additionally trying this method, the selectivity of 1,3-butadiene was only 18.4 mol%, and the selectivity was very low in this method. .

  As described above, several methods for producing 3-buten-2-ol and 1,3-butadiene from 2,3-butanediol are known, but they are produced with high selectivity without using radioactive substances. The method is anxious.

  As described above, in Patent Document 3, Patent Document 4 and Non-Patent Document 5, as a reaction for dehydrating diol to produce unsaturated alcohol, 1,4-butanediol is dehydrated and 3-butene- A method for selectively producing 1-ol has been reported. However, Non-Patent Document 5 reports a method using many kinds of rare earth oxides such as cerium oxide, neodymium oxide, and samarium oxide, and when these are used to dehydrate 1,4-butanediol. The selectivity of 3-buten-1-ol is 40.4 mol% to 87.4 mol%, but as shown in Comparative Example 3-14, the inventors have developed 12 types of rare earth oxides of this method. Was applied to the formation reaction of 3-buten-2-ol by dehydration of 2,3-butanediol, and the selectivity for 3-buten-2-ol was 0.00 mol% to 33.5 mol%. It was. That is, although 1,4-butanediol and 2,3-butanediol have similar chemical structures, the reactivity to dehydration is greatly different. In this method, 2,3-butanediol is converted from 3-butene-2. It was clearly shown that the oar cannot be selectively produced.

  Therefore, even if a method for selectively producing 3-buten-1-ol by dehydration of 1,4-butanediol has been reported, the same method is directly applied to the dehydration of 2,3-butanediol. It is clear that 3-buten-2-ol cannot always be selectively produced.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that 3-buten-2-ol and 1,3-butadiene are converted from 2,3-butanediol with high selectivity without using a radioactive substance. The inventors have found a manufacturing method and have completed the present invention.

  That is, the present invention uses 2,3-butanediol as a catalyst using at least one selected from the group consisting of zirconium oxide, zirconium oxide-alkali metal compound complex and zirconium oxide-alkaline earth metal compound complex. A method for producing 3-buten-2-ol is provided which comprises dehydration.

  In one embodiment of the present invention, the reaction temperature of 2,3-butanediol dehydration is 250 ° C. or higher and 400 ° C. or lower.

  In one embodiment of the present invention, zirconium oxide used as a catalyst is zirconium oxide prepared by firing in the range of 500 ° C. or higher and 1000 ° C. or lower.

  In one embodiment of the present invention, an oxidized oxide prepared by calcining a zirconium oxide-alkali metal compound complex or a zirconium oxide-alkali earth metal compound complex used as a catalyst in a range of 500 ° C. to 1000 ° C. It was prepared using zirconium.

  The present invention also provides a method for producing 1,3-butadiene by dehydrating 3-buten-2-ol produced by dehydrating 2,3-butanediol in the presence of an acid catalyst. .

  By dehydrating 2,3-butanediol in the presence of zirconium oxide, zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex, which is one embodiment of the present invention, The reaction for producing -2-ol can be described by the following reaction formula.

  Reaction for producing 1,3-butadiene by dehydrating 3-buten-2-ol produced by dehydrating 2,3-butanediol, which is one embodiment of the present invention, in the presence of an acid catalyst Can be described by the following reaction formula.

  According to the present invention, 3-buten-2-ol and 1,3-butadiene can be produced from 2,3-butanediol with high selectivity without using a radioactive substance.

It is a schematic diagram which shows an example of the continuous reactor which can be used in the manufacturing method of this invention.

  In the present invention, the biomass resource means an organic resource derived from a reproducible organism, and refers to a resource originating from an organic material generated by a plant immobilizing carbon dioxide using solar energy. Specifically, corn, sugarcane, potatoes, wheat, rice, soybeans, pulp, kenaf, rice straw, wheat straw, bagasse, corn stover, switchgrass, weeds, wood, waste paper, charcoal, natural rubber, cotton, etc. And animal and vegetable oils such as safflower oil, sunflower oil, soybean oil, corn oil, rapeseed oil, olive oil, palm oil, castor oil, beef tallow, lard, fish oil, and whale oil.

  In the present invention, a substance derived from biomass resources (biomass resource-derived substance) means a substance derived from the above biomass resources by fermentation, chemical conversion or the like, a substance that can be induced, or a derived substance.

  As described in Non-Patent Document 3, 2,3-butanediol, which is a raw material of the present invention, can be obtained from biomass resources by microbial fermentation. In microorganisms that ferment sugars as a carbon source, Klebsiella pneumoniae, Klebsiella oxymora, Paenibacillus polymyxa naturally exist, (2R, 3R) -2,3-butanediol, (2S, 3R) -2,3-butanediol (Meso-2,3-butanediol) can be produced. In addition, it is known that (2S, 3S) -2,3-butanediol is selectively produced in the genus Ocribactrum as shown in International Publication No. 2007/094178. In addition, Clostridium autoethanogenum is also known as a microorganism that ferments carbon monoxide as a carbon source as described in International Publication No. 2009/151342, and 2,3-butanediol produced from such a microorganism is also present. Can be the subject of the invention.

  In addition to these, a method using a microorganism imparted with 2,3-butanediol-producing ability by gene recombination may be used, and specific examples thereof include “Applied Microbiology and Biotechnology, Vol. 87, No. 6, p. 2001-2009”. (2010) ”.

  Sugars used for fermentation of 2,3-butanediol by microorganisms are sugars that can be used by microorganisms, such as starch-derived glucose, cellulose-derived glucose, sucrose, molasses, glucose, galactose, xylose, fructose, arabinose, mannose, etc. Good. Glycerol may be used for fermentation of 2,3-butanediol. 2,3-butanediol in the fermentation broth can be purified by combining one or more separation operations such as membrane separation, ion exchange, and distillation. For example, high-purity 2,3-butanediol can be isolated from the fermentation broth by the methods disclosed in JP2010-150248A and International Publication No.2013-054874.

  As described above, 2,3-butanediol produced by microbial fermentation includes (2R, 3R) -2,3-butanediol, (2S, 3S) -2,3-butanediol, (2S, 3R). There are three isomers of -2,3-butanediol (meso-2,3-butanediol). The raw material of the present invention may be any isomer or a mixture of a plurality of isomers. 2,3-butanediol may be a purified product or an unpurified product. The present invention is characterized in that 2,3-butanediol, which can be procured as a biomass resource-derived material, can be used as a raw material. However, 2,3-butanediol derived from fossil resources such as petroleum is used as a raw material. It does not exclude use.

  The present invention includes a step of dehydrating 2,3-butanediol, and in one embodiment of the present invention, includes a step of dehydrating 3-buten-2-ol. These dehydration steps can proceed using a continuous reactor. The continuous reactor is a reactor in which a tubular reactor is filled with a solid catalyst, and a raw material is passed through a catalyst layer to advance the reaction. Examples of the form of filling the catalyst layer include a fixed bed in which the catalyst is stationary, a moving bed in which the catalyst is moved, a fluidized bed in which the catalyst is fluidized, etc., but 2,3-butanediol or 3-buten-2-ol Any of these formats can be applied in the step of dehydrating the water.

  The reaction apparatus used in the step of dehydrating 2,3-butanediol or 3-buten-2-ol is not particularly limited. For example, the apparatus illustrated in FIG. 1 can be used. The apparatus shown in FIG. 1 includes a reaction tube 4, a vaporizer 3 having a raw material inlet 1 and a carrier gas inlet 2, a reaction liquid collection container (cooler) 7, and a tubular furnace 5. Can be fixed inside the reaction tube 4. The reaction tube 4 can be heated to a desired temperature by the tubular furnace 5. The gas phase flow reaction using the apparatus of FIG. 1 can be performed by supplying a raw material from the raw material inlet 1 to the vaporizer 3 and introducing the vaporized raw material into the reaction tube 4. The raw material can be introduced into the reaction tube 4 together with the carrier gas. The product can be collected as a liquid in the reaction liquid collection container 7 or can be collected as a gas from the gas opening 8.

  In the step of dehydrating 2,3-butanediol or 3-buten-2-ol, the pressure in the reactor is not particularly limited, but is preferably 0.001 MPa or more and 0.5 MPa or less. It can be carried out easily under atmospheric pressure where no operation is required.

  In the step of dehydrating 2,3-butanediol or 3-buten-2-ol, a carrier gas can be circulated together with the reaction raw material in the reactor. As the carrier gas, hydrogen is preferably used in addition to an inert gas such as argon, helium, and nitrogen, and these gases can be used alone, but a mixture of a plurality of gases at an arbitrary ratio is also used. Can do. In order to suppress the activity deterioration of the catalyst used for the dehydration reaction, it is preferable that the carrier gas contains hydrogen. The carrier gas may be mixed with water vapor, air, oxygen or the like. The mixing ratio of the reaction raw material and the carrier gas can be appropriately selected. For example, the flow rate of the carrier gas per 1 g / hour of 2,3-butanediol or 3-buten-2-ol can be 20 mL / min to 120 mL / min, but is not limited thereto.

  In the step of dehydrating 2,3-butanediol or 3-buten-2-ol, W / F (hours) when the feed rate of the reaction raw material is F (g / hours) and the catalyst weight is W (g) The contact time, which is a physical quantity given by, is not particularly limited, but is preferably 0.01 hours or longer and 10 hours or shorter, more preferably 0.05 hours or longer and 5 hours or shorter.

In the present invention, in the step of dehydrating 2,3-butanediol, at least one selected from the group consisting of zirconium oxide, zirconium oxide-alkali metal compound complex, and zirconium oxide-alkali earth metal compound complex is used as a catalyst. It is characterized by use. Each catalyst contains zirconium oxide (ZrO ₂ ), and is used as a raw material for a commercially available zirconium oxide or a zirconium oxide-alkali metal compound composite catalyst or a zirconium oxide-alkali earth metal compound composite catalyst. be able to. In addition, zirconium oxide can be prepared from zirconium hydroxide, nitrate, carbonate, acetate, etc., and can be used as a catalyst or as a raw material of the catalyst.

  The zirconium oxide-alkali metal compound composite of the present invention refers to a state in which an alkali metal hydroxide and / or an alkali metal oxide is attached to zirconium oxide. Further, the zirconium oxide-alkaline earth metal compound composite of the present invention refers to a state in which an alkaline earth metal hydroxide and / or an alkaline earth metal oxide is attached to zirconium oxide.

  The zirconium oxide-alkali metal compound composite and the zirconium oxide-alkaline earth metal compound composite can be prepared, for example, by an impregnation method. In the impregnation method, for example, powdered zirconium oxide is impregnated with an alkali metal hydroxide or alkali metal salt solution, or an alkaline earth metal hydroxide or alkaline earth metal salt solution, and dried and fired. Thus, a zirconium oxide-alkali metal compound composite or a zirconium oxide-alkali earth metal compound composite is prepared. The impregnation method is “Edited by“ Encyclopedia of Catalyst Utilization ”Editorial Committee, Encyclopedia of Utilization of Catalysts, Industrial Research Committee, issued on December 20, 2004, p. As shown in "17-18", it is classified into an evaporation to dryness method, an equilibrium adsorption method, an incipient-wetness method, a spray drying method, a CVD method, etc., but any method can be used in the present invention. it can.

  The content ratio of zirconium oxide and alkali metal compound or alkaline earth metal compound in the zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex is the same as that of zirconium oxide used as a raw material in the preparation of each complex. It can be appropriately adjusted by changing the addition amount of alkali metal hydroxide, alkali metal salt, alkaline earth metal hydroxide or alkaline earth metal salt.

  The zirconium oxide-lithium compound composite used in the present invention is, for example, “Journal of Molecular Catalysis, 243, p. 52-59 (2006)” or “Supervised by Masakazu Iwamoto, Catalyst Preparation Handbook, NT Corporation. -As reported in "S, April 25, 2011, p. 162-163", it is prepared by impregnating zirconium oxide with an aqueous lithium hydroxide solution by an incipient-wetness method, followed by drying and firing. be able to.

  A complex of zirconium oxide and another alkali metal compound or alkaline earth metal compound can be prepared basically in the same manner as the zirconium oxide-lithium compound complex. When preparing a zirconium oxide-sodium compound complex, a zirconium oxide-sodium compound complex can be prepared by using, for example, an aqueous sodium hydroxide solution instead of an aqueous lithium hydroxide solution. Similarly, a zirconium oxide-magnesium compound composite can be prepared by using, for example, a magnesium nitrate aqueous solution instead of a lithium hydroxide aqueous solution. Similarly, a zirconium oxide-calcium compound composite can be prepared by using, for example, an aqueous calcium nitrate solution instead of an aqueous lithium hydroxide solution. The same applies to other alkali metals and alkaline earth metals.

  In the zirconium oxide-alkali metal compound complex and the zirconium oxide-alkaline earth metal compound complex used in the method of the present invention, the abundance ratio of zirconium oxide and the alkali metal compound or alkaline earth metal compound is not particularly limited, The molar ratio with respect to the zirconium atom 1 is preferably 0.0001 or more and 1 or less, and more preferably 0.001 or more and 0.5 or less for alkali metal atoms or alkaline earth metal atoms.

  In the zirconium oxide-alkali metal compound composite used in the method of the present invention, the alkali metal is not particularly limited, but lithium, sodium and potassium are preferably used.

  In the zirconium oxide-alkaline earth metal compound composite used in the method of the present invention, the alkaline earth metal is not particularly limited, but beryllium, magnesium, calcium, and strontium are preferably used.

  The above-described zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex can be used alone, or two or more kinds of zirconium oxide-alkali metal compound complex or zirconium oxide-alkali. A combination of earth metal compound composites can also be used. Moreover, the zirconium oxide, zirconium oxide-alkali metal compound composite, and zirconium oxide-alkaline earth metal compound composite used as the catalyst can be used alone or in combination of two or more thereof. it can.

  The reaction temperature in the step of dehydrating 2,3-butanediol of the present invention is preferably 250 ° C. or higher in order to keep the conversion rate good, and in order to keep the selectivity of 3-buten-2-ol good. 400 degrees C or less is preferable.

  The zirconium oxide used as a catalyst in the present invention is preferably prepared by firing. As a calcination temperature, 500 degreeC or more and 1000 degrees C or less are preferable, and 600 degreeC or more and 900 degrees C or less are more preferable. The firing of zirconium oxide can be performed by using an electric furnace or the like and heating while circulating a gas containing oxygen in the furnace. The amount of gas containing oxygen and the firing time can be adjusted as appropriate. For example, when using an electric furnace with a content volume of 2 L, it can be fired for about 1 to 12 hours while circulating air at a flow rate of about 10 to 60 mL / min, but the firing conditions are not limited to this. Absent.

  As the zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex used as a catalyst in the present invention, those prepared using calcined zirconium oxide are preferably used. The firing temperature of zirconium oxide is preferably 500 ° C. or higher and 1000 ° C. or lower, and more preferably 600 ° C. or higher and 900 ° C. or lower. The firing of zirconium oxide can be performed by using an electric furnace or the like and heating while circulating a gas containing oxygen in the furnace. The amount of gas containing oxygen and the firing time can be adjusted as appropriate. For example, in the case of using an electric furnace having an internal capacity of 2 L, it can be fired for about 1 to 12 hours while circulating air at a flow rate of about 10 to 60 mL / min, but the firing conditions are not limited to this. . Using the zirconium oxide thus calcined, adding an alkali metal hydroxide or alkali metal salt solution, or an alkaline earth metal hydroxide or alkaline earth metal salt solution as described above, drying, etc. By performing this, a zirconium oxide-alkali metal compound composite or a zirconium oxide-alkaline earth metal compound composite can be prepared.

  The present invention can include a step of producing 1,3-butadiene by dehydrating 3-buten-2-ol produced in the step of dehydrating 2,3-butanediol in the presence of an acid catalyst. The dehydration step of 3-buten-2-ol can proceed in the same reaction tube as the dehydration step of 2,3-butanediol. In this case, by filling the catalyst used for dehydration of 2,3-butanediol on the upstream side of the flow path of the raw material and the catalyst used for dehydration of 3-buten-2-ol on the downstream side, The dehydration of the diol and the dehydration of 3-buten-2-ol proceed sequentially to produce 1,3-butadiene. Therefore, in this case, the reaction temperature in the dehydration step of 3-buten-2-ol is preferably performed at a temperature of 250 ° C. or more and 400 ° C. or less as in the above-described dehydration step of 2,3-butanediol.

  Further, the dehydration step of 2,3-butanediol and the dehydration step of 3-buten-2-ol can be carried out by separate reactors. In this case, 3-buten-2-ol produced in the 2,3-butanediol dehydration step may or may not be purified.

  It does not specifically limit as an acid catalyst used for the dehydration process of 3-buten-2-ol, The acid catalyst generally used by vapor phase dehydration reaction can be used. Examples of the acid catalyst include alumina, silica, silica-alumina, titania, zeolite, diatomaceous earth, clay, phosphoric acid, and alkali metal phosphate.

  3-Buten-2-ol obtained by dehydration of 2,3-butanediol exists as a liquid at room temperature and normal pressure, and can be recovered as a liquid component in the product of the dehydration reaction. The recovered 3-buten-2-ol can be separated from other components by, for example, distillation. When obtained as a mixture with water by distillation, 3-buten-2-ol and water are separated by azeotropic distillation, a separation membrane such as a zeolite membrane, and the like to obtain high-purity 3-buten-2-ol be able to.

  1,3-butadiene produced by the dehydration of 2,3-butanediol or the dehydration of 3-buten-2-ol can be purified by distillation, extractive distillation or the like.

  In the dehydration of 2,3-butanediol, when the conversion is less than 100%, unreacted 2,3-butanediol can be recovered as a liquid component. The recovered 2,3-butanediol can be separated from other components by, for example, distillation. By reusing the separated 2,3-butanediol, the yield of 3-buten-2-ol and 1,3-butadiene can be increased.

  Hereinafter, the present invention will be described using examples, but the present invention is not limited to the following examples.

  The conversion and selectivity shown in the following examples were calculated by the following formulas (Formula 1) and (Formula 2), respectively.

(Formula 1) Conversion (%) = ((Substance amount of feedstock−Substance quantity of raw material after reaction) / Substance quantity of feedstock)) × 100
(Formula 2) Selectivity (%) = (Product quantity) / Feed substance quantity) × 100

  In the examples and comparative examples, the fixed bed flow type reactor shown in FIG. 1 was used. A quartz reaction tube 4 having an inner diameter of 20 mm and a total length of 400 mm is provided. A vaporizer 3 having a carrier gas introduction port 2 and a raw material introduction port 1 is provided at the upper portion of the reaction tube, and a gas release port 8 is provided at the lower end. The thing which has the reaction liquid collection container (cooler) 7 which has is used. The catalyst was fixed and filled in the center of the reaction tube, and the catalyst layer 6 was heated to the reaction temperature in a ceramic electric tubular furnace 5 (Asahi Rika Seisakusho, ARF-30KC, furnace length 300 mm) and held at that temperature. During the reaction, the reaction liquid collection container 7 was cooled in an ice bath.

  The reaction was continued for 3 hours or 5 hours. The collected reaction solution and the gas leaked from the gas opening were used for gas chromatography analysis every 1 hour. The content of each compound was calculated from the calibration curve prepared using the reference sample of each compound and the peak area value of each compound, and the conversion rate of the raw material and the selectivity of the product were determined. As the conversion rate and selectivity over the entire reaction time, the average value of the conversion rate and selectivity obtained every other hour was calculated.

Reference Example 1 Calcination of Zirconium Oxide Zirconium oxide (ZrO ₂ , Daiichi Rare Element Chemical Co., Ltd.) was allowed to stand in an electric furnace (internal volume 2 L) in which air (flow rate 30 mL / min) was circulated, and 100 ° C. / The temperature was raised to a firing temperature (700 ° C., 750 ° C., 800 ° C., 850 ° C., 900 ° C., or 1000 ° C.) at a rate of h, and firing was performed by holding at the firing temperature for 3 hours.

Examples 1-4 Dehydration reaction of 2,3-butanediol A reaction tube was filled with zirconium oxide (1.0 g) calcined at 900 ° C., and hydrogen was circulated at a flow rate of 45 mL / min from the carrier gas inlet. The reaction temperature was the temperature shown in Table 1. 2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture) was supplied to the vaporizer from the raw material inlet at a flow rate of 1.06 g / hour by a syringe pump and introduced into the reaction tube together with the carrier gas. The reaction was continued for 5 hours. Table 1 shows the average values of conversion rate and selectivity for 5 hours.

Example 5 Dehydration reaction of 2,3-butanediol Using nitrogen as the carrier gas, the reaction temperature was set to the temperature shown in Table 2, and the dehydration reaction was performed in the same manner as in Example 1 except for the other conditions. Table 2 shows the average values of conversion rate and selectivity for 5 hours.

Examples 6 to 11 Dehydration reaction of 2,3-butanediol Dehydration was performed in the same manner as in Example 1 except that zirconium oxide calcined at the temperature shown in Table 3 was used and the reaction temperature was the temperature shown in Table 3. Reaction was performed. Table 3 shows the average values of conversion rate and selectivity for 5 hours.

Reference Example 2 Preparation of Zirconium Oxide-Lithium Compound Complex (Catalyst 1) A magnetic dish to which zirconium oxide calcined at 900 ° C. was added was placed on a hot plate (hot plate temperature was 65 to 80 ° C.), and an incandescent lamp was applied from the top. The water was removed by evaporation while adding a lithium hydroxide aqueous solution dropwise. The lithium hydroxide aqueous solution was added in such a ratio that the molar ratio of lithium atom: zirconium atom was 0.26: 1. The obtained mixture was put in an electric furnace and fired at 600 ° C. for 3 hours to obtain a zirconium oxide-lithium compound composite (catalyst 1).

Reference Example 3 Preparation of Zirconium Oxide-Lithium Compound Complex (Catalyst 2) The same conditions as in Reference Example 2 except that the molar ratio of lithium atom: zirconium atom was 0.041: 1 were the same as in Reference Example 2. A lithium compound composite (catalyst 2) was obtained.

Reference Example 4 Preparation of Zirconium Oxide-Lithium Compound Complex (Catalyst 3) The same conditions as in Reference Example 2 were followed except that the molar ratio of lithium atom: zirconium atom was 0.016: 1. A lithium compound composite (catalyst 3) was obtained.

Reference Example 5 Preparation of Zirconium Oxide-Sodium Compound Complex (Catalyst 4) A sodium hydroxide aqueous solution was used instead of the lithium hydroxide aqueous solution, and the molar ratio of sodium atom: zirconium atom was 0.12: 1. Other conditions were the same as in Reference Example 2 to obtain a zirconium oxide-sodium compound complex (catalyst 4).

Reference Example 6 Preparation of Zirconium Oxide-Magnesium Compound Complex (Catalyst 5) A magnetic dish to which zirconium oxide calcined at 800 ° C. was added was placed on a hot plate (hot plate temperature was 65 to 80 ° C.), and an incandescent lamp was applied from the top. Then, the water was removed by evaporation while adding a magnesium nitrate aqueous solution dropwise. The magnesium nitrate aqueous solution was added in such a ratio that the molar ratio of magnesium atom: zirconium atom was 0.095: 1. The obtained mixture was put in an electric furnace and calcined at 800 ° C. for 3 hours to obtain a zirconium oxide-magnesium compound composite (catalyst 5).

Reference Example 7 Preparation of Zirconium Oxide-Calcium Compound Complex (Catalyst 6) Using an aqueous calcium nitrate solution instead of an aqueous magnesium nitrate solution, the molar ratio of calcium atom: zirconium atom was 0.068: 1. The conditions were the same as in Reference Example 6 to obtain a zirconium oxide-calcium compound composite (catalyst 6).

Examples 11 to 17 Dehydration reaction of 2,3-butanediol Using one of the catalysts 1 to 6 instead of zirconium oxide, the reaction temperature was 350 ° C., the hydrogen flow rate was 80 mL / min, and other conditions The dehydration reaction was carried out in the same manner as in Example 1. The average values of conversion rate and selectivity for 5 hours are as shown in Tables 4 and 5.

Comparative Example 1 Dehydration Reaction of 2,3-Butanediol According to Patent Document 2, a cesium oxide-silica composite was prepared by the following procedure. Cesium carbonate (Wako Pure Chemical Industries, Ltd., 4.65 g) was dissolved in ultrapure (50 mL), and silica gel (Sigma-Aldrich, Davisil (registered trademark), 35-60 mesh, 10 g) was added. The resulting mixture was stirred at 80 ° C. for 24 hours to evaporate water. The obtained powder was fired at 600 ° C. under air flow to prepare a cesium oxide-silica composite (13.1 g).

  The reaction tube was filled with a cesium oxide-silica composite (5.0 g), and nitrogen was circulated at a flow rate of 45 mL / min from the carrier gas inlet. The reaction temperature was 400 ° C. 2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture) was supplied to the vaporizer from the raw material inlet at a flow rate of 2 mL / hour with a syringe pump, and introduced into the reaction tube together with the carrier gas. The reaction was continued for 5 hours. Table 6 shows the average values of conversion rate and selectivity for 5 hours.

Comparative Example 2 Dehydration reaction of 2,3-butanediol Alumina (Catalysis Society of Japan, Reference Catalyst of Catalysis Society, JRC-ALO-6) was used in place of zirconium oxide as a catalyst, and the reaction temperature was set to 325 ° C. The dehydration reaction was performed in the same manner as in Example 1. Table 6 shows the average values of conversion rate and selectivity for 5 hours.

Comparative Examples 3-14 Dehydration reaction of 2,3-butanediol Instead of zirconium oxide as a catalyst, the metal oxide shown in Table 6 was used, the reaction temperature was the temperature shown in Table 6, and other conditions were as in Example 1. The dehydration reaction was performed in the same manner as described above. Each metal oxide used was fired at 800 ° C. by the method shown in Reference Example 1. Table 6 shows the average values of conversion rate and selectivity for 5 hours.

Example 18 Dehydration reaction of 3-buten-2-ol Using 3-buten-2-ol (Sigma-Aldrich) as a raw material and alumina as a catalyst (Catalysis Society of Japan, Reference Catalyst of Catalysis Society, JRC-ALO-6) The reaction temperature was 350 ° C., and the dehydration reaction was performed in the same manner as in Example 1 except for the other conditions. The average values of conversion rate and selectivity for 5 hours were as follows.
Conversion rate (mol%): 100
1,3-butadiene selectivity (mol%): 94.9

Example 19 Dehydration reaction of 3-buten-2-ol Methyl ethyl ketone (Kanto Chemical Co., Ltd.) was used in accordance with the composition of the crude purified solution of 3-buten-2-ol obtained by recovering 2,3-butanediol from the reaction solution of Example 16. Company, 14 mg), isobutyraldehyde (Tokyo Chemical Industry Co., Ltd., 278 mg), isobutanol (Kanto Chemical Co., Ltd., 38 mg), 3-buten-2-ol (Sigma-Aldrich, 6.71 g), acetoin (Tokyo Chemical Industry Co., Ltd.) Ltd., 994 mg) and distilled water (1.97 g) were mixed to prepare the crude product.

The reaction tube was filled with alumina (Catalysis Society of Japan, Catalysis Society Reference Catalyst, JRC-ALO-6, 1.0 g), and nitrogen was circulated from the carrier gas inlet at a flow rate of 30 mL / min. The reaction temperature was 280 ° C. The crude purified solution prepared as described above was supplied from the raw material inlet to the vaporizer with a syringe pump at a flow rate of 1.0 mL / hour, and introduced into the reaction tube together with the carrier gas. The reaction was continued for 1 hour. The conversion of 3-buten-2-ol and the yield of 1,3-butadiene relative to 3-buten-2-ol were as follows.
Conversion rate (mol%): 100
1,3-butadiene yield (mol%): 94.8

Reference Example 8 Recovery of 2,3-butanediol A simulated reaction solution was prepared in accordance with the composition of the reaction solution produced in Example 2. That is, 2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture, 97%, 32.5 g), methyl ethyl ketone (Kanto Chemical Co., Ltd., 99%, 5.88 mg), isobutyraldehyde (Tokyo Chemical Industry Co., Ltd.) Company, 97%, 451 mg), isobutanol (Kanto Chemical Co., Inc., 99%, 2.32 mg), 3-buten-2-ol (Sigma-Aldrich, 97%, 22.7 g), acetoin (Tokyo Chemical Industry Co., Ltd.) Company, 98%, 2.36 g) and distilled water (9.17 g) were mixed to prepare a simulated reaction solution. The obtained simulated reaction solution was distilled under reduced pressure to isolate 2,3-butanediol (31.3 g). The purity of the isolated 2,3-butanediol was measured by gas chromatography and found to be 96.9%. The recovery rate of 2,3-butanediol was 96%.

  From Examples 1 to 17, 3-butene-2 was obtained by dehydrating 2,3-butanediol in the presence of zirconium oxide, zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex. -All have been shown to be manufacturable with high selectivity.

  From Example 3 and Examples 6 to 11, it was shown that the selectivity of 3-buten-2-ol tends to be improved by firing zirconium oxide.

  From Comparative Examples 3 to 14, the catalyst that is disclosed in Non-Patent Document 10 and dehydrates 1,4-butanediol to selectively produce 3-buten-1-ol is obtained from 2,3-butanediol. It was shown that it is not applicable to the production of 3-buten-2-ol by dehydration.

  Example 18 showed that 3-buten-2-ol can be quantitatively converted to 1,3-butadiene by dehydration in the presence of an acid catalyst.

  Example 19 showed that 3-buten-2-ol produced from 2,3-butanediol can be quantitatively converted to 1,3-butadiene even in a crudely purified state.

  By dehydrating 2,3-butanediol using zirconium oxide, zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex as a catalyst, as shown in Examples 1 to 17 3-Buten-2-ol can be produced with high selectivity. Also, as shown in Examples 18 and 19, 3-buten-2-ol can be quantitatively converted to 1,3-butadiene. Therefore, from Examples 1 to 19, by dehydrating 2,3-butanediol using zirconium oxide, zirconium oxide-alkali metal compound complex or zirconium oxide-alkaline earth metal compound complex as a catalyst, 3- By producing buten-2-ol and dehydrating the resulting 3-buten-2-ol in the presence of an acid catalyst, 1,3-butadiene can be produced from 2,3-butanediol with high selectivity. It was shown that.

  From the comparative example 1, it was shown that the method using the cesium oxide-silica composite which is the prior art has low selectivity for 3-buten-2-ol and 1,3-butadiene.

  From Comparative Example 2, alumina, which is a general acid catalyst, produces a large amount of methyl ethyl ketone by dehydration of 2,3-butanediol, and the selectivity of 3-buten-2-ol and 1,3-butadiene is low. Indicated.

  Reference Example 8 shows that unreacted 2,3-butanediol in the dehydration reaction of 2,3-butanediol can be recovered from the reaction solution by distillation with a high recovery rate and high purity.

  According to the present invention, 3-buten-2-ol and 1,3-butadiene can be produced with high selectivity without using a radioactive substance from 2,3-butanediol. Since 3-buten-2-ol is a raw material for pharmaceuticals and the like, it can be easily converted to 1,3-butadiene, and 1,3-butadiene is a basic chemical product that is a raw material for synthetic rubber and nylon. Is extremely useful in industry.

DESCRIPTION OF SYMBOLS 1 Raw material inlet 2 Carrier gas inlet 3 Vaporizer 4 Reaction tube 5 Tubular furnace 6 Catalyst layer 7 Reaction liquid collection container (cooler)
8 Gas opening

Claims (5)

  Dehydrating 2,3-butanediol using at least one selected from the group consisting of zirconium oxide, zirconium oxide-alkali metal compound complex and zirconium oxide-alkaline earth metal compound complex as a catalyst, A method for producing 3-buten-2-ol.   The method according to claim 1, wherein the dehydration reaction temperature is 250 ° C. or higher and 400 ° C. or lower.   The method according to claim 1 or 2, wherein the zirconium oxide used as the catalyst is zirconium oxide calcined in the range of 500 ° C or higher and 1000 ° C or lower.   The zirconium oxide-alkali metal compound composite or zirconium oxide-alkaline earth metal compound used as a catalyst is prepared using zirconium oxide baked in a range of 500 ° C or higher and 1000 ° C or lower. 2. The method according to 2.   The manufacturing method of 1, 3- butadiene including dehydrating 3-buten-2-ol manufactured by the method of any one of Claims 1-4 in presence of an acid catalyst.

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