WO2017111392A1 - Catalyst for glycerin dehydration reaction, preparation method therefor, and method for preparing acrolein by using catalyst - Google Patents

Abstract

The present invention relates to: a catalyst for a glycerin dehydration reaction; a preparation method therefor; and a method for preparing acrolein by using the catalyst. Particularly, according to one embodiment of the present invention, the catalyst is used in a glycerin dehydration reaction and exhibits a high catalytic activity, a high yield and a high acrolein and acrylic acid selectivity, and has a characteristic in which carbon is not readily deposited, thereby having a long lifespan compared with a conventional catalyst.

Description

 【Specification】

 [Name of invention]

 Glycerin dehydration reaction catalyst, preparation method thereof and preparation method of acrolein using the catalyst

Technical Field

 Cross Citation with Related Applications

 This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0184168 dated December 22, 2015 and Korean Patent Application No. 10-2016-0129986 dated October 7, 2016. All content disclosed in the literature is included as part of this specification.

 The present invention relates to a catalyst for glycerin dehydration, a method for preparing the same, and a method for preparing acrolein using the catalyst. [Background technology]

 Acrolein is a simple unsaturated aldehyde compound, has high reaction properties including incomplete reaction groups and is used as a major intermediate for the synthesis of various compounds. In particular, acrolein has been widely used as an intermediate for the synthesis of acrylic acid, acrylic esters, superabsorbent resins, animal feed complements, or food supplements.

 Such acrolein has been prepared by using propylene synthesized mainly in petroleum process as a starting material through atmospheric oxygen and selective gas phase oxidation reaction. However, as environmental problems such as the reduction of fossil fuels and the greenhouse effect are gradually raised, a lot of research has been conducted on the method of synthesizing acrolein using renewable raw materials that are not based on fossil fuels.

Accordingly, glycerin, which can be obtained as a by-product of the process of synthesizing biodiesel as a natural product, has received much attention as a raw material for the production of acrolein. In particular, the market size of glycerin is increasing according to the production of biodiesel, and the method of applying it industrially due to the price drop of glycerin is being studied. In one example, a method is known in which a glycerin is dehydrated in the presence of a catalyst to obtain a mixture of acrolein and acrylic acid. The dehydration reaction of the glycerin proceeds to gaseous oxidation reaction in the presence of the catalyst, so the use of a catalyst is essential.

 However, as the dehydration reaction of the glycerin proceeds, coke carbon is formed on the catalyst due to by-products such as hydroxypropanone, propanealdehyde, acetaldehyde, polycondensation products of glycerine, cyclic glycerin ether, phenol or polyaromatic compounds, etc. ) Is deposited and the catalyst is deactivated. Therefore, efforts have been made to develop catalysts that increase the lifespan that can suppress continuous deposition of coke carbon and enable continuous operation.

 Accordingly, there is a need to develop a catalytic reaction system capable of removing coke carbon to minimize the production of byproducts that produce coke carbon or to maintain the activity of the catalyst during reaction.

[Content of invention]

 [Problem to solve]

 The present invention is a catalyst for glycerin dehydration reaction reaction that has an increased lifespan by inhibiting the deposition of coke carbon in the dehydration reaction of glycerin or removing the generated coke carbon, and exhibits high selectivity and efficiency for acrolein and acrylic acid. It provides a manufacturing method.

 The present invention also provides a method for producing acrolein using the catalyst. [Measures of problem]

 According to one embodiment of the invention, there is provided a glycerin dehydration semi-aqueous catalyst represented by the following formula (1).

 [Formula 1]

In Chemical Formula 1, M ¹ and M ² may be the same as or different from each other, respectively, V, Fe, Nb, Zn, or a combination thereof, and a, b, c, d, and e represent the composition ratio of each atom, and a is 0.1 To 6, b / a is 0 to 1, c / a is 0 to 1, d / a is 0 to 1, e / a is 0 to 10, wherein at least one of b and c is 0 X and y are values 0 to 10 that are determined depending on the binding state of the crystallized water.

 For example, a may be 0.5 to 1, b may be 0.01 to 0.3, c may be 0.01 to 0.3, d may be 0.01 to 0.3, and e may be 1 to 5.

Specifically, the catalyst represented by Formula 1 is

Zr₀.9Nbo.o2Feo.iWo.iP2H_xO_y,Zro.9Feo.iWo.iP2HxO _y ,

Zr ₀ .9 Nbo.o2Feo.iWo.iP2H _x O _y ,

Zr ₀ . gZn ₀ .02Fe _0. iW ₀ . iP2¾0y, Zr ₀ . gZn ₀ .02 V ₀ .1Ψ0. iP2¾0y, Zr ₀ . gZn ₀ .02 V. iW ₀ . iP ₂ H _x 0 _y , Zro.8Zno.o2 (FeV) o.iWo.iP ₂ H _x O _y) Zro.8Zno.o2Feo.2Wo.iP ₂ H _x O _yi or

Zro.8Zno.o2Vo.2Wo.iP ₂ H _x O _y , Zro.gsZno ^ Vo.osW ^ HxOy, x may be 2 to 6, and y may be 1 to 3.

 On the other hand, according to another embodiment of the invention, the drying and baking process after mixing the aqueous solution of at least one precursor, zirconium precursor, phosphorus precursor, and tungsten precursor selected from the group consisting of precursors of V, Fe, Nb, and Zn Provided is a method for preparing a catalyst for glycerin dehydration comprising the step of producing a catalyst represented by Formula 1 through.

The drying process may be carried out at a temperature of 25 to 200 ^° C, it may be carried out for 3 to 48 hours. In addition, the firing process may be carried out at a temperature of 250 to 750 ^° C, it may be carried out for 3 to 48 hours. In addition, the precursor aqueous solution mixture may be stirred for 3 to 48 hours, and the precursor compound of the catalyst represented by Formula 1 is precipitated from the mixed aqueous solution, the precipitated catalyst precursor compound is filtered, washed with alcohol and dried and dried. The firing process can be performed.

On the other hand, according to another embodiment of the present invention, under the glycerin dehydration reaction reaction catalyst, there is provided a method for producing acrolein, including the step of dehydration reaction glycerin. 【Effects of the Invention】

 The catalyst according to one embodiment of the present invention is used in the glycerin dehydration reaction to exhibit high catalytic activity, high yield, and high selectivity for acrolein and acrylic acid, and is easily burned to the surface of the catalyst by burning off the coke carbon produced. It does not deposit and has a long life compared to the existing catalyst.

[Brief Description of Drawings]

 1 is a schematic diagram of an experimental reaction apparatus according to an embodiment of the present invention. 2 is a graph showing the performance of the reaction catalyst over time using a molding catalyst (5 mm in diameter, 5-15 mm in length) and an aqueous solution having a glycerin concentration of 50 wt% according to Example 16 of the present invention. .

 3 is a graph showing the performance of the reaction catalyst with time using a molding catalyst (5 mm in diameter, 5-15 mm in length) and 75 wt% aqueous solution of glycerin in accordance with Example 17 of the present invention.

[Specific contents to carry out invention]

 In the present invention, terms such as first and crab are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

 Also, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that the features, numbers, steps, components, or combinations thereof are present, one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, numbers, steps, components, or a combination thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

 Hereinafter will be described in more detail with respect to a glycerin dehydration semi-aqueous catalyst, a preparation method thereof and a method for producing acrolein using the catalyst according to an embodiment of the present invention.

 According to one embodiment of the invention, there is provided a catalyst for glycerin dehydration.

 [Formula 1]

cWdPeHxOy

cWdPeHxOy

In Formula 1, M ¹ and M ² may be the same or different from each other, and each of V, Fe, Nb, Zn, or a combination thereof, and a, b, c, d, and e represent the composition ratio of each atom. A is 0.1 to 6, b / a is 0 to 1, c / a is 0 to 1, d / a is 0 to 1, e / a is 0 to 10, At least one of b and c is not 0, and X and y are from 0 to 10 in a value determined by the binding state of the crystallized water.

 As described above, in the dehydration reaction of glycerin according to the conventional method, as the reaction proceeds, coke carbon is deposited on the catalyst, thereby deactivating the catalyst and shortening the catalyst life. In particular, acid catalysts having a high acid concentration of Brønsted among the known acid catalysts have good production efficiency of acrolein, but it is difficult to perform dehydration reaction for a long time because coke carbon is deposited on the acid catalyst during dehydration reaction. there is a problem.

 In particular, existing catalysts for the production of acrolein and acrylic acid from glycerin form by-products such as hydroxypropanone, propanealdehyde, acetaldehyde, acetone, polycondensation products of glycerin, cyclic glycerin ethers. In addition: Phenol and polyaromatic compounds are produced to form coke carbon on the catalyst causing inactivation. Deactivation of the catalyst makes it difficult to commercialize the Glycerin dehydration continuous operation is impossible.

In addition, one of the biggest causes of such deterioration of catalytic activity is Loss of catalytically active site due to deposition of coke carbon produced. In particular, factors affecting the formation of coke carbon in glycerin dehydration reaction are reaction conditions such as reaction temperature, space velocity, partial pressure of oxygen and water vapor in reaction water, mass transfer in catalyst by catalyst pore structure, and amount of acid point on catalyst surface. The scattered places are counting. The acid point of the catalyst is generally an active point that promotes dehydration reaction, but in the case where an excessive strong acid point is present on the surface of the catalyst, condensation between molecules caused by the side reaction causes excessive generation of coke carbon to cause deactivation of the catalyst. Results in.

 Therefore, in the present invention, in order to solve such a conventional problem, by applying a specific catalyst composition it is possible to suppress the generation of coke carbon in the reaction and thereby effectively extend the life of the catalyst. In particular, by using a catalyst capable of increasing the selectivity of acrolein and / or acrylic acid, it is possible to obtain acrolein and / or acrylic acid in high yield from glycerin. By using a catalyst that can remove the coke carbon generated by this, by operating a glycerol dehydration reaction process using a fixed bed reactor that is conventionally used commercially it can significantly improve the overall process efficiency.

 Acrelane can be obtained by dehydrating glycerin under an acid catalyst. At this time, it is known that the production efficiency of acrolein is good when a catalyst having a Bronsted acid point rather than a Lewis acid point is used as the acid catalyst. However, the acid catalyst having many Bronsted acid points has a problem in that carbon is deposited on the acid catalyst during dehydration reaction and is easily deactivated.

 The catalyst represented by Chemical Formula 1, which is designed to solve this problem, is a catalyst having a Bronsted acid point, but is not easily deactivated during glycerin dehydration reaction. In addition, the catalyst of Formula 1 may have better yield of acrolein and a catalytic activity than zirconium phosphate, which has a Bronsted acid point and is known to have excellent catalytic activity.

For example, in order to further improve acrolein yield and catalyst efficiency than conventional zirconium phosphate, the catalyst of Formula 1 is a 0.5 to 1, b is 0.01 to 0.3, c is 0.01 to 0.3, d is 0.01 To 0.3, and e may be 1 to 5. More specifically, the catalyst represented by Formula 1 is

Zro.gFeo.iWo. mQy, Zr ₀ .9Vo.iWo.iP ₂ H _x O _y , Zr ₀ .9Nbo.o ₂ Feo.iWo. iP2H _x O _y ,

Zr o. ₉ Zn ₀ . ₀ 2Fe ₀ . iW ₀ . ₁ P ₂ H _x 0 _y , Zr ₀ . gZn ₀ .02V0. iW ₀ . iP2H _x 0 _y , Zr ₀ . gZn ₀ .02 V ₀ . iW ₀ . _{iP2H x 0 y, Zr 0. sZn} 0 .02 (FeV) 0 .1W0. iP2H _x 0 _y , Zr ₀ . sn ₀ . _{0 2Fe 0 .2 0. iP2H x 0} y, or Zro. ₈ Zno.o2Vo.2Wo. iP2HxO _y , Zro.gsZno Vo.osW P ^ Oy, x may be 2 to 6, and y may be 1 to 3.

The mixed oxide may further include a metal represented by M ¹ and M ² in addition to the zirconium, tungsten, and phosphorus, wherein M ¹ and M ² together with the role of suppressing the formation of coke carbon and by-products, coke produced Through the role of converting carbon into oxygen and steam and converting it into C0 _X material, it is possible to suppress the deposition of coke carbon composed of phenol or polyaromatic compounds that cause catalyst deactivation. Can prolong the activity of.

 The catalyst for glycerin dehydration semi-flight of the present invention may further include a carrier on which the mixed oxide is fixed. The carrier can be used without any significant limitation as long as it is known that it can be used in conventional catalysts. Specific examples of such a carrier include silica, alumina, silica-alumina, zirconia, magnesia, magnesium aluminate, calcium aluminate, silicon carbide, zirconium phosphate, zeolite or a combination thereof. Preferably, a carrier having a pore size of 20 nm or more can be used.

The carrier serves to fix the mixed oxide of the embodiment, and the composite metal oxide may be fixed in a form of sharing oxygen to the carrier having a large surface area. As described above, when the complex metal oxide is manufactured in a form fixed to the carrier, storage and transport can be easily performed, and the glycerin can be efficiently reacted due to the large surface area. In addition, the carrier may have a specific surface area of 10 to 500 m ² / g, and preferably 50 to 200 m ² / g. In particular, the catalyst for glycerin dehydration reaction prepared by supporting the composite metal oxide on a carrier having a large specific surface area in the above range has a suitable pore size, so as to deposit coke. The phenomenon can be reduced and can also provide more catalytic activity.

 The catalyst for glycerin dehydration may include 1 to 50 parts by weight of the composite metal oxide represented by Formula 1 based on 100 parts by weight of the carrier.

 In addition, the glycerin dehydration reaction catalyst of the present invention may actually have a molded granulated form for use in a pilot process or a commercial process. When using a conventional powdered catalyst, normal operation may not be performed due to the internal pressure difference generated. Moreover, such a molding catalyst must maintain its physical strength for a long time by increasing its physical strength so as not to be broken or damaged even when stacking a large amount. Accordingly, in order to increase the physical strength of the catalyst during molding and granulation, an inorganic material such as silica, alumina, titania, zirconia, or the like is added to at least one filler, and can be prepared through a calcination process through heat treatment at a high temperature. The molded granulated catalyst has a fracture strength of 25 N or more, or 25 N to 100 N, measured at the time when cracks occur for specimens of 0.5 mm in length and 0.5 mm in diameter using a compressive strength machine such as BOSS 5500. Preferably at least 30N, more preferably at least 45N.

 On the other hand, according to another embodiment of the invention, there is provided a method for producing a catalyst represented by the formula (1) as described above. Specifically, the preparation method of the catalyst represented by the formula (1) is dried and mixed with an aqueous solution of at least one precursor, zirconium precursor, phosphorus precursor, and tungsten precursor selected from the group consisting of precursors of V, Fe, Nb, and Zn It includes the step of producing a catalyst represented by the following formula 1 through a calcination process.

The catalyst of the formula (1) is not particularly limited to a method of mixing the aqueous solution of the precursor of the M ¹ and M ² atoms, zirconium precursor, phosphorus precursor, and tungsten precursor. As a non-limiting example, the precursors may be mixed one by one in a sequential order, or may be mixed at one time. Among them, when a zirconium precursor is added to the reaction vessel, a precursor of M ¹ and M ² atoms, and a tungsten precursor are added thereto, and then a phosphorus precursor compound is added, a zirconium precursor and a precursor of M ¹ and M ² atoms, tungsten Precursor completely dissolved Since the phosphorus precursor compound is added, the precursors may be well dissolved to more easily form crystals having a stable structure, thereby improving catalyst yield.

 In the step of mixing the precursor compound of each component in the catalyst, before adding the precursor to the reactor, the solvent is added and the precursors are added while stirring the solvent, or some precursor is added to the black reaction vessel and the other precursor while stirring the precursor Or all the precursors are added to the reaction vessel and the mixture of the precursors is stirred to increase the amount of catalyst produced. For example, before the precursor is added to the reaction vessel, a solvent such as water may be added, and the precursor may be sequentially or simultaneously added while stirring the solvent such as water. In another example, some of the precursors may be added to the reaction vessel first, and the remaining precursors may be added sequentially or simultaneously with stirring. In another example, precursors may be sequentially or simultaneously introduced into the reactor to form a mixture and to stir the mixture.

In all the above cases, the mixture of precursors can be continuously stirred even after all the precursors have been added to the reactor. In particular, the agitation of the mixture may proceed under temperature conditions of about 25 to 200 ^° C. to facilitate the bonding between the metals.

 In addition, the agitation can be performed for a time period in which all the precursors added are well mixed so that a large amount of precipitation occurs. For example, the stirring may be performed for about 3 to 48 hours.

 Precipitating the precursor compound of the catalyst represented by the formula (1) from the aqueous solution in which the precursor compound of each of these components is mixed may be further included.

Precursors of each component used in the manufacturing method may utilize all the various precursors known in the art. Non-limiting examples of zirconium precursors include zirconyl chloride (Zi rconyl chloride), zirconyl bromide, zirconyl iodide and zirconyl nitrate (Zi rconyl ni trate) Can be used. And, M ¹ and M ² as a precursor of the atoms M ¹ and the oxides, M ¹ and M ² of a metal M ² metal Hydroxides, such as M ¹ and M ² a metal nitrate (ni trate), M ¹ and M ² a metal oxalate (oxal ate), M ¹ and M ² a metal phosphate or M ¹ and M halide of the ^second metal of the Can be used. For example, NH ₄ V0 ₃ , vanadium chloride (vanadium chloride), vanadium sulfate (vanadium sul fate) may be used as the vanadium precursor, and Fe (N0 ₃ ) ₃ may be used as the iron precursor, or chloride of iron (chlorine). ide) or a nitrate compound, and the like, and niobium precursors may include C ₄ H ₄ N b¾, and zinc precursors such as Zn (N0 ₃ ) ₂ . In addition, one kind or two or more kinds of precursors may be used as precursors of M ¹ and M ² atoms, respectively, and non-limiting examples may include zinc precursors and iron precursors, zinc precursors, iron precursors, and vanadium precursors. As the phosphorus precursor compound, phosphoric acid and phosphate in which one or more protons of phosphoric acid are substituted with a group 1, 2 or 13 cation, or an ammonium cation may be used. Examples of the tungsten precursors include ammonium meta-tungstate, ammonium para-tungstate, tungstic acid, tungsten blue oxide, and tungsten trioxide. The precursors may be anhydrous or hydrate. In addition, the precursors may be used in an appropriate amount depending on the ratio of atoms and atom groups of the formula (1). For example, the precursor compound for preparing a catalyst according to the present invention includes zirconium oxychloride (ZrOCl · 8¾0), zirconium oxynitrate (ZrO (N0 ₃ ) ₂ · ¾0), phosphoric acid (H ₃ P0 ₄ ), ammonium phosphate (( NH ₄ ) ₂ HP0 ₄ ), iron nitrate (Fe (N0 ₃ ) ₃ * 9H ₂ 0), zinc nitrate (Zn (N0 ₃ ) ₃ · 6¾0), ammonium meta-vanadate (a 隱 onium metavanadate, NH4VO3 ), Ammonium meta-tungstate may be used.

 In the step of mixing the precursors, a suitable solvent may be used for uniform mixing of the precursors. The solvent is not particularly limited, and water and the like are non-limiting examples.

The precursor compound of the catalyst represented by Formula 1 may be precipitated from the mixed aqueous solution of the precursors, and the catalyst precursor thus precipitated. Filtering the compound and washing with water or alcohol, or a combination thereof. In particular, when the precipitate of the metal compound is washed with alcohol, a wider surface area catalyst can be prepared. Such a large surface area catalyst may show better catalytic activity and acrolein selectivity in glycerin dehydration.

 Examples of the alcohol that may be used in the washing may include methanol, ethanol, propanol, butanol, pentane, alkyl alcohols having 1 to 10 carbon atoms such as nucleic acids, and the like.

In addition, after mixing the aqueous solution of the precursor may be carried out a drying and baking process to produce a catalyst represented by the formula (1). Here, the drying process may be carried out at a temperature of 25 to 200 ^° C, may be performed for 3 to 48 hours. In addition, the firing process may be carried out at a temperature of 250 to 750 ^° C, it may be carried out for 3 to 48 hours.

In the present invention, the method may further include forming and granulating the fired product after the dry firing process or before the drying process. The molding assembly process may be performed by mixing with a coagulant including an sol or slurry and an alcohol in a solution state containing an inorganic metal component to improve the mechanical strength of a mixed oxide having low mechanical strength. As such an inorganic metal component, 1 or more types of layering agents, such as a silica, an alumina, titania, a zirconia, are mentioned as an example. In the method for preparing a glycerin dehydration reaction catalyst of the embodiment, by extruding a mixture of a mixed oxide and a coagulant, the catalyst may be molded to have a superior mechanical strength. The catalyst formed in this manner may be a composite metal oxide. The strength of the catalyst is excellent as compared with the case where it is used as it is or is supported on a carrier. Accordingly, the shaped catalyst can maintain long-term reaction activity without generating an internal pressure even when applied to an actual pilot process or a commercial process. As such a compound, at least one inorganic metal sol consisting of silica sol, alumina sol, titania sol, zirconia sol and the like, and at least one alcohol consisting of glycerin, isopropyl alcohol, diacetone alcohol, methanol ethane and propanol It may include. The molded granulated catalyst may perform a drying and firing process. Here, the drying process may be performed for 3 to 48 hours at a temperature of 25 to 200 ^° C. In addition, the firing process may be performed for 3 to 48 hours at a temperature of 250 to 750 ^° C.

 The catalyst manufacturing method may further include a step generally employed in the art to which the present invention pertains, in addition to the above-described steps.

 On the other hand, according to another embodiment of the invention, there is provided a method for producing acrolein, including the step of dehydrating glycerine under the glycerine dehydration reaction reaction catalyst.

 The method for producing acrolein may be, for example, dehydration of glycerin under a continuous flow gas phase reaction system in which the catalyst is present to provide acrolein.

 Glycerin or an aqueous glycerin solution may be used as the semi-aquatic product of the preparation method. As a carrier gas of the reaction product, an inert gas or a mixed gas of inert gas and air or oxygen may be used. In particular, the dehydration reaction can be carried out under a glycerin concentration of 25 to 75% by weight. At this time, the content of the gaseous reaction product may include glycerin in an amount of 1 to 10 mol%, and may include oxygen in 1 to 20 mol%.

The catalyst amount of the formula I as described above in the manufacturing method of the acrolein, the reaction of glycidyl ^'can be properly adjusted according to the amount and concentration of serine, and, for example, 10 of the catalyst to 300 glycer in匪ol / h Can be filled at a weight space velocity of g _cat , preferably 10 to 100 glycer in 隱 ol / h. g _cat , more preferably, can be filled at a weight space velocity of 5 to 50 glycerol in ol / h · g _cat . If the amount of the catalyst is too small, a decrease in the yield of the final acrylic acid may occur due to a decrease in glycerin conversion,

In the present invention, the glycerin reaction process may be performed at a gas space velocity (GHSV) of 100 to 5000 h ^_1 , preferably 250 to 3000 h ^"1 , more preferably 500 to 1000 h- ¹ . In particular, glycerin Higher Gas Hourly Space Velocity (GHSV) in the reaction process means that more reaction water can be processed per unit time and catalyst. It means that the activity of the catalyst is very good. In addition, high activity at low reaction temperature means that the activity of the catalyst is good. In other words, the amount of catalyst used to obtain the same amount of product is reduced, so that the reactor can be made small, and the low temperature can be produced at low cost because less utility is used. It can be said to be excellent.

In addition, the step of reacting the glycerin may be carried out at a temperature of 250 to 350 ^° C, more preferably 280 to 320 ^° C. The step of reacting the glycerin is an endothermic reaction, acrolein with high conversion and selectivity In order to increase the yield of the final acrylic acid prepared it is preferable to perform a reaction in the silver range of the above range. If the reaction temperature is too low, the conversion of glycerin may be reduced, and if the reaction temperature is too high, the selectivity of acrolein may decrease due to excessive side reactions.

 In particular, when the dehydration reaction is carried out using the catalyst of the present invention, high catalyst activity, high yield, and high selectivity for acrolein and acrylic acid are shown, and the produced coke carbon is burned and removed to deposit on the catalyst surface. It does not have the advantage that the continuous process is possible because of the excellent properties. Regarding the dehydration reaction of glycerin, the preferred process condition is a process that can be operated continuously. If the reaction temperature is low and the reaction size is small, it may be a better process. This is because a decoking process is required to periodically remove it. Therefore, using the catalyst of the present invention, glycerin dehydration reaction can be carried out in a continuous process while maintaining high catalytic activity under operating conditions capable of effectively removing coke carbon.

 In addition, after performing the dehydration reaction, a partial oxidation reaction of acrolein from the product obtained from the dehydration reaction may be performed, and the final conversion of the resulting arcane to acrylic acid through the dehydration reaction of glycerin may be further performed. have.

In addition to the above-described steps, the method of manufacturing the aclein may further include a step commonly employed in the art to which the present invention pertains. On the other hand, the method for producing acrolein according to the present invention, after the reaction started

At least 300% of the glycerin conversion rate measured after 300 hours or more may be maintained, and the selectivity of at least one product selected from the group consisting of acrolein and acrylic acid may be at least 35%.

In addition, after performing glycerin dehydration reaction using the catalyst of the present invention, the C0 _X value measured by GC analysis in liquid and gaseous products is about 40% or less or 1% to 40%, preferably 36% or less. More preferably, it may be 35% or less. The value of C0 _X is a value indicating the degree to which the coke carbon or the reaction product is oxidized, and if it is too large, it can be seen that a adverse effect of oxidizing the reaction product other than the coke carbon occurs. In particular, it can be seen that the best effect appears if the reaction activity is maintained while maintaining a small value of C0 _X. Hereinafter, preferred embodiments of the present invention will be described in detail. However, these examples are only for illustrating the present invention, and the scope of the present invention is not to be construed as being limited by these examples.

<Example>

 Preparation Example 1: Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

An aqueous solution was prepared by adding 12.208 g of ZrOCl ₂ as a zirconium precursor to 150 mL of distilled water. Zn (N0 ₃ ) ₂ · 6¾0 was added to the aqueous solution as a zinc precursor. 225 g, ¾ ₆ 0 ₄₀ ¾ was added as 0.933 g as a tungsten precursor and stirred for about 30 minutes to 1 hour. Then, an aqueous solution was prepared by adding 8.714 g of NH ₄ ¾P0 ₄ as a phosphorus precursor compound to 150 mL of distilled water, and the aqueous solution prepared by adding an aqueous solution of phosphorus precursor to the aqueous solution of zirconium prepared above was stirred overnight at a temperature of about 95 ° C. It was.

Subsequently, the precipitate precipitated from the aqueous solution was washed with ethanol and dried at 100 ° C. for 12 hours, and then calcined at 700 ° C. for 6 hours to obtain a catalyst for glycerin dehydration reaction reaction ZrZno W ^ HxO _y . Preparation Example 2 Preparation of Catalyst for Glycerin Dehydration

An aqueous solution was prepared by adding 10.986 g of ZrOC as a zirconium precursor to 150 mL of distilled water. 1.54 g of Fe (N0 ₃ ) ₃ · 9¾0 as an iron precursor and 0.933 g of ¾ ₆ 0 ₄₀ ½ as a tungsten precursor were added to the aqueous solution and stirred for about 30 minutes to 1 hour. And, the addition of 8.714 g of匪 ₄ H ₂ P0 ₄ in the precursor compound in distilled water to 150 mL to prepare an aqueous solution, prepared by adding the precursor solution to the aqueous solution of zirconium prepared above aqueous solution at a temperature of about 95 ^° C Stir overnight.

 Subsequently, the catalyst Zro.sFe Wo.J ^ HxOy for glycerin dehydration reaction was obtained in the same manner as in Production Example 1. Preparation Example 3 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

NH ₄ V0 ₃ was used as the vanadium precursor instead of the iron precursor in Preparation Example 2.

A catalyst for glycerin dehydration reaction reaction Zro.gVo in the same manner as in Preparation Example 2, except that 0.448 g was used. iWo. iFyW y was obtained. Preparation Example 4 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

를 얻었다. 제조예 5: 글리세린 탈수 반웅용 촉매의 제조 Except for the addition of ammonium niobate (V) oxalate hydrate (C ₄ H ₄ NNb0 ₉ · x¾0, Ammonium niobate (V) oxalate hydrate) as the niobium precursor in Preparation Example 2, 0.230 g Catalyst for Glycerin Dehydration Semi-Fungction in the same manner as in Example 2

Got. Preparation Example 5 Preparation of Catalyst for Glycerin Dehydration

^HA를 얻었다. 제조예 6: 글리세린 탈수 반웅용촉매의 제조 Zn (N0 ₃ ) ₂ as a zinc precursor in Preparation Example ₂ . A catalyst for glycerin dehydration reaction in the same manner as in Preparation Example 2, except that 6¾0 was further added in a content of 0.225 g.

Got ^ HA. Preparation Example 6 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

Zn (N0 ₃ ) ₂ as a zinc precursor in Preparation Example 3. 6¾0 0.225 g The catalyst for the glycerin dehydration reaction reaction Zro.gZno. ^ Vo. I got .iP Oy. Preparation Example 7 Preparation of Catalyst for Glycerin Dehydration

The aqueous solution was added to Zr ^(Xl ₂ 9.766 g of zirconium precursor in distilled water to 150 mL was prepared as a zinc precursor with the aqueous solution of 0.225 g of _{Zn (N0 3) 2 · 6¾0} , an iron precursor Fe (N0 _{3) 3.} 9¾0 Was added 1.54 g, NH ₄ V0 ₃ as vanadium precursor 0.448 g, ¾ _{6 12} as 0.933 g as tungsten precursor and stirred for about 30 minutes to 1 hour, and NH ₄ H ₂ as a phosphorus precursor compound in 150 mL of distilled water. An aqueous solution was prepared by adding 8.714 g of P0 _4, and the aqueous solution prepared by adding an aqueous phosphorus precursor solution to the aqueous zirconium solution prepared above was stirred at a temperature of about 95 ^° C. overnight.

Subsequent processes were carried out in the same manner as in Preparation Example 1 for the catalyst for glycerine dehydration reaction. ₈ Zno.o2 (FeV) o.iWo.iP ₂ H _x O _y was obtained. Preparation Example 8 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst 、

An aqueous solution was prepared by adding 9.766 g of ZrOCl ₂ as a zirconium precursor to 150 mL of distilled water. 0.225 g of Zn (N0 ₃ ) ₂ · 6¾0 as a zinc precursor, 3.08 g of Fe (N0 ₃ ) ₃ · 9¾0 as an iron precursor, and 0.933 g of ¾ ₆ ^ 0 ₁₂ as a tungsten precursor were added to the aqueous solution for about 30 minutes to Stir for 1 hour. Then, an aqueous solution was prepared by adding 8.714 g of ΝΗ ₄ Η ₂ Ρ0 ₄ as a phosphorus precursor compound to 150 mL of distilled water, and the aqueous solution prepared by adding the phosphorus precursor solution to the aqueous solution of zirconium prepared above at a temperature of about 95 ° C. Stir overnight. Subsequent steps were obtained in the same manner as in Preparation Example 1 to obtain a catalyst for glycerin dehydration reaction reaction Zro.sZno ^ Feo.zWo. ^ H _x Oy. Preparation Example 9 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

NH ₄ V0 ₃ as vanadium precursor instead of iron precursor in Preparation Example 8

A catalyst for glycerin dehydration reaction reaction Ζι ^ Ζηο.ο ^. ^ Ο in the same manner as in Preparation Example 1, except that 0.896 g was used. Got ΗΑ. Preparation Example 10 Preparation of Glycerin Dehydration Semi-Ultramolding Granulation Catalyst

An aqueous solution was prepared by adding 12.208 g of ZrOCl ₂ as a zirconium precursor to 150 riiL of distilled water. 0.225 g of Zn (N0 ₃ ) ₂ · 6¾0 as a zinc precursor and 0.933 g of ¾ ₆ 0 ₄₀ ¥ ₁₂ as a tungsten precursor were stirred in the aqueous solution for about 30 minutes to 1 hour. And stirred overnight The an NH ₄ ¾P0 ₄ was added to 8.714 g The precursor compound in distilled water to 150 mL to prepare an aqueous solution, prepared by adding the precursor solution to the aqueous solution of zirconium prepared above aqueous solution at a temperature of about 95 ^° C It was.

 Thereafter, the precipitate precipitated from the aqueous solution was washed with ethane and dried at 100 ° C. for 12 hours, and then calcined at 700 ° C. for 6 hours.

 After the granulated product was molded and dried at 100 ° C. for 12 hours, the calcined product was calcined at 700 ° C. for 6 hours to obtain a glycerine dehydration semi-molded granulation catalyst ZrZno ^ WojP ^ A. At this time, the catalyst of the molded granulated and extruded form had a diameter of 0.5 cm in diameter and 0.5-1.5 cm in length. Preparation Example 11 Preparation of Glycerin Dehydration Semi-Umbilized Granulation Catalyst

iWo.i HxOy를 얻었다. 제조예 12: 글리세린 탈수 반웅용성형 조립 촉매의 제조 Fe (N0 ₃ ) which is an iron precursor in Preparation Example 10 ₃ . Molded granulation catalyst for glycerin dehydration reaction mixture in the same manner as in Preparation Example 10, except that 9 0 was further added in a content of 1.54 g.

iWo.i HxOy was obtained. Preparation Example 12 Preparation of Glycerin Dehydration Semi-Ultramolding Granulation Catalyst

NH ₄ V0 ₃ was used as the vanadium precursor instead of the iron precursor in Preparation Example 10.

A molding granulation catalyst Zro.gZno.t _K Ho. ^ HA for glycerin dehydration reaction was obtained in the same manner as in Production Example 10, except that 0.448 g was used. Preparation Example 13 Preparation of Glycerin Dehydration Semi-Umbilized Granulation Catalyst

NH ₄ V0 ₃ was used as the vanadium precursor instead of the iron precursor in Preparation Example 10. Except that an amount of 0.224 g, and in the same manner as in Production Example 10 glycerin dehydration catalyst half ungyong molding assembly Zr ₀ .95Zno.o2Vo.o5Wo.iP ₂ HxO _y # obtained. Comparative Production Example 1: Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

An aqueous solution was prepared by adding 12.208 g of ZrOCl ₂ as a zirconium precursor to 150 mL of distilled water. Then, an aqueous solution was prepared by adding 8.714 g of H ₄ H ₂ P0 ₄ as a phosphorus precursor compound to 150 mL of distilled water, and an aqueous solution prepared by adding an aqueous phosphorus precursor solution to the aqueous zirconium solution prepared above ^at a temperature of about 95 ^° C. Stir overnight.

 Thereafter, the precipitate precipitated from the aqueous solution was washed with ethanol and dried at 100 ° C. for 12 hours, and then calcined at 700 ° C. for 6 hours to obtain ZrP as a catalyst for glycerin dehydration. Comparative Production Example 2 Preparation of Glycerin Dehydration Semi-Aqueous Catalyst

Prepare an aqueous solution with a content of 12 g of boronic acid ¾B0 _{3 3} .

Maintain a temperature of 60 degrees or more, and is prepared by the content of 5.88 g of phosphorus precursor H ₃ P0 ₄ in 50 mL of distilled water, and the aqueous solution prepared by adding an aqueous solution of phosphorus precursor to the aqueous solution of boron was supported on Si0 ₂ using a carrier and the temperature was 100 degrees. After drying for 12 hours at, it was calcined at 500 degrees for 6 hours to obtain 11.08 wt% BPO ₄ / Si0 ₂ as a catalyst for glycerin dehydration. Examples 1-17 and Comparative Examples 1-2: Dehydration reaction of glycerin

 Glycerin dehydration reaction was performed using a catalyst prepared according to Preparation Examples 1 to 13 and Comparative Preparation Examples 1 and 2 using a reaction apparatus as shown in FIG. 1.

Preparation of acrolein through dehydration reaction of glycerin was carried out using a continuous flow fixed bed reactor. The continuous flow-fixed bed reactor was installed in an electric furnace, and the catalysts prepared by Production Examples 1 to 13 and Comparative Production Examples 1 and 2 were layered. Carrier gas and coke carbon when carrying out the reaction experiments with half-unggi 1 and half-unggi 2 as shown in Table 1 below The temperature of the reactor was raised to about 280-350 ^° C while nitrogen and air were blown at 10-1000 mL / min with oxidizing gas, respectively, and the temperature was maintained for a certain time to maintain the steady state of the reaction line. .

 Dehydration reaction of glycerine was then performed by injecting aqueous solution of glycerin (28.08-75.0 wt in ¾0; 7. 1 mol%) to the charged amount of catalyst at a constant rate. At this time, the detailed reaction conditions are as shown in Table 1 below.

TABLE 1

이렇게 글리세린 수용액을 기화 장치 (vapor i zer )에서 기화시키고 예열 (pre-heater ) 영역에서 가열 처리한 후， 반웅 온도에 도달되어 있는 실험 촉매가 층진되어 있는 ^'스테인레스 스틸 반응기 (stainless-steel reactor)로 주입하여 글리세린 탈수반응을 진행하였다. 이러한 반웅 결과로 생성되는 생성물은 웅축하여 각각 액상 생성물과 기상 생성물을 가스 크로마토그래피 (GC : Gas Chromatography)로 분석하였다.

The aqueous solution of glycerin was vaporized in a vapor i zer, heated in a pre-heater zone, and then deposited into a ^' stainless-steel reactor ^' in which the experimental catalyst, which had reached the reaction temperature, was layered. Glycerin dehydration was performed by injection. The resulting product was expanded and the liquid and gaseous products were analyzed by gas chromatography (GC: Gas Chromatography), respectively.

Specific analytical methods are divided into liquid product analysis and gas phase product analysis. The liquid product is the value of the liquid products by analyzing the gas phase liquid product with the GC-FID detector, the gaseous product is the value representing the value of the gas products by analyzing the gas product with the GC-TCD detector. The reason for the gas phase analysis together with the liquid phase is that the C components reacted with air (Ai r) This is to confirm the value converted to CO and co ₂ . For catalysts that analyze only liquid products, the co _x converted to gas should reflect the co _x value, depending on time, between about 1% and 34%.

 For the comparative comparison of catalysts that only analyzed liquid products and catalysts that analyzed both liquid and gaseous products, the activity values of the catalysts were analyzed separately from liquids and gaseous products, which were analyzed separately from Examples 13 and 14. Examples 11 and 12 are described respectively. Detailed process conditions for the glycerin dehydration reaction of Examples 1 to 12 and Comparative Example 1 performed using the catalysts prepared according to Preparation Examples 1 to 11 and Comparative Preparation Example 1 are shown in Table 2 below.

 TABLE 2

실시예 9 및 10은 성형 조립 촉매로 반응 실험을 실시함

Examples 9 and 10 carried out reaction experiments with shaped granulated catalysts

 Example 11 analyzed only the liquid product in Example 13

 * Example 12 is to analyze only the liquid product in Example 14 The analysis results for the product after glycerin dehydration reaction of Examples 1 to 12 and Comparative Example 1 are shown in Table 3 below.

 TABLE 3

^* 실시예 9 및 10은 성형 조립 촉매로 반응 실험을 실시함

^* Examples 9 and 10 are also subjected to the reaction test in the molding assembly Catalyst

 "Example 11 analyzed only liquid product in Example 13

 Example 12 analyzed only the liquid product in Example 14

Detailed process conditions for the glycerin dehydration reactions of Examples 13 to 17 and Comparative Example 2 performed using the catalysts prepared according to Preparation Examples 8, 9, 12, 13 and Comparative Preparation Example 2 are shown in Table 4 below. .

 TABLE 4

예 2의 글리세린 탈수 반웅후 액상 및 기상 생성물에 대한 분석결과는 하기 표 5에 나타낸 바와 같다.

Liquid and after the glycerin dehydration reaction of Example 2 The analytical results for the gaseous products are shown in Table 5 below.

 TABLE 5

상기 표 3 및 표 5에 나타낸 바와 같이， 본 발명에 따른 제조예 1 내지 13의 촉매를 사용하여 글리세린 탈수 반웅올 수행한 실시예 1 내지 17의 경우에， 기존에 상업적으로 사용되고 있는 고정층 반웅기를 이용한 글리세린 탈수반웅공정을 연속으로 운전할 수 있으며， 글리세린으로부터 아크를레인 및 /또는 아크릴산을 높은 수율로 수득할 수 있음을 확인할 수 있다.

As shown in Table 3 and Table 5, using the catalyst of Preparation Examples 1 to 13 according to the present invention Example 1 to Glycerin dehydration semiungol In the case of 17, it is possible to continuously operate a glycerin dehydration reaction process using a fixed bed reaction vessel that has been used commercially, and it can be seen that acrolein and / or acrylic acid can be obtained in high yield from glycerin.

On the other hand, Figures 2 and 3, according to Examples 16 and 17, respectively, the glycerin conversion rate, acrolein + acrylic acid selection when the glycerin was continuously reacted for a long time using the molded granulation catalyst of Preparation Examples 12 and 13 of the present invention Also, a graph showing the yield of C0 _X is shown. In particular, in the case of using an existing catalyst as in Comparative Example 2, even when using a 28.08 wt% solution of glycerin as a co-dump, it can be seen that the conversion was greatly reduced in 5 hours due to the formation of coke carbon on the catalyst. However, according to Examples 16 and 17 of the present invention, even when using a high concentration of 50 wt or 75 wt% glycerin aqueous solution, it is an excellent catalyst that can maintain the reaction performance for more than 200 hours by reducing the production of coke carbon as much as possible It can be seen that it has a performance of. Furthermore, it can be seen that the BPO ₄ catalyst of Comparative Example 2, like the previously known heteropolyacids, produced excessive coke carbon in a short time and cannot be used for commercialization.

In particular, it can be seen that the liquid phase result of Example 9-10, which was carried out with the molded granulation catalyst, and a fairly high level of acllein selectivity. In addition, as a result of analyzing the gas phase products from the liquid phase results (Table 3) and the liquid phase and the gas phase results (Table 5) from the results of Examples 11, 12, 13, 14 and 15, 16, a significant amount of C0 _X occurs over time. It can be seen that coke carbon removal occurs and continuous operation over 100 hours is possible. Accordingly, the present invention can be said to have an excellent feature capable of long time continuous operation at high space velocity conditions.

Claims

【Claims】 【Claim 1】 Catalyst for glycerin dehydration reaction represented by the following formula (1): [Formula 1]

In Formula 1, M ¹ and M ² may be the same or different from each other, and are each V, Fe, Nb, Zn, or a combination thereof, a, b, c, d, and e represent the composition ratio of each atom, a is 0.1 to 6, b/a is 0 to 1, c/a is 0 to 1, and d/a is 0 to 1. 1, and e/a is 0 to 10, where at least one of b and c is not 0, X and y are values determined depending on the bonding state of the crystal water and are 0 to 10. 【Claim 2】 In clause 1, a is 0.5 to 1, b is 0.01 to 0.3, c is 0.01 to 0.3, d is 0.01 to 3, and e is 1 to 5. A catalyst for glycerin dehydration reaction. 【Claim 3】 In clause 1, The catalyst is ZrZno.o2 o.iP ₂ H _x O _yi

Z r ₀ . gNb ₀ .02Fe ₀ . iW ₀ . iP2H _x 0 _y , Zr ₀ . gZn ₀ . ₀ 2Fe ₀ . iWo. ιΡ2¾0 _γ ， Zr ₀ . gZn _0.02V0 . iW ₀ . iP ₂ H _x 0 _y ， Zr ₀ . gZn _0.02V0 . . iP2¾0y, Zr ₀ . sZn _0.02 (FeV) (). iW ₀ . iP2¾0 _y , Zr ₀ . &Zn ₀ . ₀ 2Fe ₀ .2W0. iP2H _{x 0 y} , _{Zro.8Zno.o2Vo.2Wo.iP} 2 _H Catalyst for reaction. 【Claim 4】 After mixing an aqueous solution of at least one precursor selected from the group consisting of V, Fe, Nb, and Zn precursors, a zirconium precursor, a phosphorus precursor, and a tungsten precursor, a catalyst represented by the following formula 1 is produced through a drying and calcination process. Method for producing a glycerin dehydration reaction catalyst comprising the step of producing: [Formula 1]

cWdPeHA In Formula 1, M ¹ and M ² may be the same or different from each other, and are each V, Fe, Nb, Zn, or a combination thereof, a, b, c, d, and e represent the composition ratio of each atom, a is 0.1 to 6, b/a is 0 to 1, c/a is 0 to 1, and d/a is 0 to 1, e/a is 0 to 10, of which at least one of b and c is not 0, X and y are values determined depending on the bonding state of the crystal water and are 0 to 10. 【Claim 5】 According to clause 4, A method for producing a glycerin dehydration Banungyong catalyst, wherein the drying process is performed at a temperature of 25 to 200 ^° C. 【Claim 6】 In clause 4, A method for producing a glycerin dehydration banungyong catalyst, wherein the drying process is performed for 3 to 48 hours. 【Claim 7】 In paragraph 4, A method for producing a glycerin dehydration banungyong catalyst, wherein the calcination process is performed at a temperature of 250 to 750 ^° C. 【Claim 8】 In the above paragraph, A method for producing a glycerin dehydration banungyong catalyst, wherein the calcination process is performed for 3 to 48 hours. [Claim 9] According to clause 4, A method for producing a glycerin dehydration banungyong catalyst by stirring the mixture for 3 to 48 hours. 【Claim 10】 In paragraph 4, A method for producing a catalyst for glycerin dehydration banungyong, which involves precipitating the precursor compound of the catalyst represented by Formula 1 from the mixed aqueous solution, filtering the precipitated catalyst precursor compound, washing with water or alcohol, and then performing a drying and calcination process. [Claim 11] A method for producing arclaine comprising the step of carrying out a dehydration reaction of glycerin under the catalyst for the glycerin dehydration reaction of claim 1.