KR102253138B1 - Catalyst for dehydration of glycerin, preparing method thereof and production method of acrolein using the catalyst - Google Patents

Abstract

The present invention relates to a catalyst for a glycerin dehydration reaction, a method for producing the same, and a method for producing acrolein using the catalyst. The catalyst according to an embodiment of the present invention has a large specific surface area and a large pore volume, and by supporting cerium oxide in a predetermined content range on zirconium phosphate having high activity in dehydration reaction, through the effect of controlling metal oxide and acid properties. Breakthrough acrolein productivity can be secured in a long reaction. In addition, by using a gas phase-continuous flow reaction system having a relatively high productivity, it is possible to maximize the yield of acrolein and secure process stability.

Description

A catalyst for glycerin dehydration reaction, a method for preparing the same, and a method for producing acrolein using the catalyst {CATALYST FOR DEHYDRATION OF GLYCERIN, PREPARING METHOD THEREOF AND PRODUCTION METHOD OF ACROLEIN USING THE CATALYST}

The present invention relates to a catalyst for dehydration of glycerin for production of acrolein, and more particularly, a catalyst for dehydration of glycerin capable of securing breakthrough acrolein productivity in a long reaction by impregnating cerium oxide in a predetermined content range, and the like. It relates to a manufacturing method and a method of manufacturing acrolein using the catalyst.

Recently, as environmental problems such as depletion of fossil fuels and global warming have emerged, interest in alternative energy sources such as hydrogen energy, photovoltaic cells, and secondary batteries is increasing. Among them, biodiesel is considered as an alternative energy source that is more environmentally friendly than fossil resources and has a high possibility of realization because it is renewable. Already, some developed countries have legally stipulated that some of the biodiesel is included in the diesel fuel sold in their own country, or quality standards have been established to use it as a fuel. World biodiesel production has been steadily increasing year by year, and it is expected that the production will continue to increase in the future with the gradual strengthening of environmental regulations (Non-Patent Documents 1 and 2).

Biodiesel, called monoalkyl esters of vegetable oil or animal fat, is prepared by mixing vegetable oil (fatty triglyceride) and methanol and then decomposing alcohol. In the biodiesel production process, about 10% of glycerin is produced as a by-product, and as biodiesel production increases worldwide, the production of glycerin is also rapidly increasing. Accordingly, as the price of glycerin declines, the development of a new technology for utilizing glycerin is required, and among them, chemical conversion of glycerin is evaluated as a very important technology that can secure the competitiveness of biodiesel by increasing the value-added by-products of low cost. (Non-Patent Document 3).

Among the above studies, acrolein produced by dehydration of glycerin is an unsaturated aldehyde with the simplest structure, and has high reactivity, so it is used as a platform material for producing synthetic proteins such as acrylic acid, polyester resin, polyurethane, and methionine ( Non-Patent Document 4). Since acrolein is very toxic, most companies minimize storage and transport, and produce and convert acrolein directly at the production site for use as an intermediate for producing acrolein derivatives. Therefore, technology development for direct manufacturing of acrolein must be preceded in order to minimize storage and transport, and to secure competitiveness in terms of price and stability. The existing commercial process for producing acrolein is based on a partial propylene oxidation reaction, but due to the increase in accessibility to glycerin due to the rapid increase in biodiesel production, the development of acrolein manufacturing technology through the glycerin dehydration reaction is being re-examined (Non-Patent Document 5~ 7).

Preparation of acrolein through dehydration of glycerin is usually carried out on an acid catalyst, and acrolein is produced through 3-hydroxy propionaldehyde as an intermediate product. In general, when the reaction proceeds at a high temperature, which is a favorable condition for dehydration, it is reported that an acid catalyst having a certain level of acidity or higher is required. Among the previously reported catalysts, it is known that the yield of acrolein in the liquid phase reaction using sulfuric acid or hydrochloric acid is known to be the highest. This is limited. Therefore, the importance of a process for manufacturing acrolein through gas phase dehydration reaction of glycerin using a non-uniform catalyst has emerged (Patent Documents 1 to 3, Non-Patent Documents 8 to 9).

However, in the case of existing solid acid catalysts including zeolite and heteropolyacid having high acidity, there is a problem that deactivation proceeds rapidly due to rapid formation of coke on the catalyst surface when dehydration is performed. Even if the catalyst has an appropriate acid strength to suppress coke formation, when the specific surface area of the catalyst is small or the pore structure is not developed, the active sites are easily poisoned by the generated coke, and the catalyst may be rapidly deactivated.

Therefore, there is a need for a study on the development of a catalyst for producing acrolein through the dehydration reaction of glycerin, which has an appropriate acid strength and a large specific surface area, and has high resistance to deactivation, unlike conventional catalysts.

US 5,387,730 (D. AKTIENGESELLSCHAFT) 1993. 11.12. US 2006/087083 A3 (ARKEMA FRANCE DUBOIS) 2006.12.28. US 2012/005348 A1 (NIPPON KAYAKU) 2012.01.12.

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The present invention enhances acrolein productivity through a complementary effect between a phosphate catalyst having excellent acid properties and a skeletal structure and a metal oxide, and suppresses catalyst deactivation, thereby ensuring process stability, and glycerin dehydration showing high selectivity and yield for acrolein. It is intended to provide a catalyst for reaction.

In addition, the present invention is to provide a method for producing the catalyst with high reproducibility, which is advantageous for mass production.

In addition, the present invention is to provide a method for producing acrolein using the catalyst and a reaction system capable of maximizing productivity in the production process of acrolein through dehydration of glycerin.

According to one embodiment of the invention, as a catalyst in which cerium oxide is supported on zirconium phosphate (ZrP), a catalyst for a glycerin dehydration reaction supporting 6% to 18% by weight of cerium oxide based on the weight of the zirconium phosphate (ZrP) is Is provided.

For example, the cerium oxide may be at least one selected from the group consisting _{of CeO 2} and Ce ₂ O _3.

On the other hand, according to another embodiment of the present invention, (a) preparing a precursor solution by dissolving a zirconium precursor and a phosphate precursor in a first solvent; (b) aging the product obtained in step (a) to prepare a zirconium phosphate precipitate; (c) drying and heat treating the precipitate obtained in step (b) to produce a zirconium phosphate (ZrP) carrier; (d) dissolving a cerium precursor in a second solvent to prepare a cerium precursor solution; (e) impregnating the cerium precursor solution with the zirconium phosphate (ZrP) carrier produced in step (c), and then removing the second solvent to generate a precipitate; And (f) drying and heat-treating the precipitate obtained in step (e); including, and containing 6 to 18% by weight of cerium oxide based on the weight of the zirconium phosphate (ZrP) of a catalyst for a glycerin dehydration reaction to support A manufacturing method is provided.

Specifically, in step (c), the drying process may be performed at a temperature range of 70 to 150°C, and the heat treatment process may be performed at a temperature range of 300 to 500°C.

In addition, in step (f), the drying process may be performed at a temperature range of 70 to 150°C, and the heat treatment process may be performed at a temperature range of 300 to 500°C.

Meanwhile, according to another embodiment of the invention, in the presence of a catalyst supporting cerium oxide on zirconium phosphate (ZrP), glycerin or an aqueous glycerin solution is used as a reactant, and an inert gas or an inert gas and oxygen are mixed as a carrier gas. A catalyst for dehydration of glycerin comprising the step of dehydrating glycerin in a gas phase-continuous flow reaction system, and supporting 6% to 18% by weight of cerium oxide based on the weight of the zirconium phosphate (ZrP). A method for producing acrolein is provided.

Specifically, the glycerin dehydration reaction may be performed at a temperature of 250 to 400 °C.

In addition, in the glycerin dehydration reaction, the reaction amount (mmol) per unit time (h) and unit catalyst weight (g) of glycerin may range from 1.0 mmol/g _cat ㆍh to 200.0 mmol/g _cat ㆍh.

According to an embodiment of the present invention, the cerium oxide/phosphate catalyst in which the supported amount of cerium oxide is optimized to a predetermined content range is applied to the production process of acrolein through gas phase-dehydration reaction of glycerin. Compared to that, achlorine can be produced in a high yield, and a high-life catalyst can be stably obtained by reducing the deactivation of the catalyst.

In addition, the cerium oxide/phosphate catalyst of the present invention can be easily prepared through a simple catalyst preparation method, and has an excellent effect of securing excellent reproducibility in the preparation of the catalyst.

1 is a graph showing the results of X-ray diffraction analysis of a cerium oxide/zirconium phosphate supported catalyst according to Test Example 1 of the present invention.
Figure 2 is a graph showing the nitrogen adsorption and desorption analysis results of the cerium oxide / zirconium phosphate catalyst according to Test Example 2 of the present invention.
3 is a graph showing the yield of acrolein by the glycerin dehydration reaction of each catalyst while performing a glycerin dehydration reaction for 10 hours on zirconium phosphate, aluminum phosphate, titanium phosphate and boron phosphate catalysts according to Comparative Examples 1 to 4 of the present invention.
Figure 4 shows the yield of acrolein by the glycerin dehydration reaction of each catalyst while performing a glycerin dehydration reaction for 10 hours on the zirconium phosphate catalyst and the cerium oxide/zirconium phosphate catalyst according to Examples 1 to 2 and Comparative Examples 1 to 5 of the present invention. It is a graph shown (Example 1: 10CeO ₂ /ZrP, Example 2: 15CeO ₂ /ZrP, Comparative Example 1: ZrP, Comparative Example 2: 5CeO ₂ /ZrP, Comparative Example 3: 20CeO ₂ /ZrP, Comparative Example 4: 25CeO ₂ /ZrP, and Comparative Example 5: 30CeO ₂ /ZrP).
5 is a cerium oxide/zirconium phosphate, tungsten oxide/zirconium phosphate, cobalt oxide/zirconium phosphate, and a vanadium oxide/zirconium phosphate catalyst according to Examples 2 and 6 to 8 of the present invention. It is a graph showing the yield of acrolein by the glycerin dehydration reaction of each catalyst (Example 2: 15CeO ₂ /ZrP, Comparative Example 6: 15WO ₃ /ZrP, Comparative Example 7: 15CoO ₂ /ZrP, Comparative Example 8: 15V ₂ O ₆ /ZrP).

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

In addition, terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include", or "have" are intended to designate the existence of a feature, number, step, element, or combination of the implemented features, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

The present invention will be described in detail below and exemplify specific embodiments, as various modifications can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a catalyst for a glycerin dehydration reaction according to a preferred embodiment of the present invention, a method for preparing the same, and a method for preparing acrolein using the catalyst will be described in more detail.

According to an embodiment of the present invention, a catalyst for dehydration of glycerin is provided, in which 6 to 18% by weight of cerium oxide is supported based on the weight of the zirconium phosphate (ZrP) as a catalyst in which cerium oxide is supported on zirconium phosphate (ZrP). do.

In particular, the present invention relates to a catalyst for the production of acrolein through the dehydration reaction of glycerin, and more particularly, a zirconium phosphate catalyst having a large specific surface area and a large pore volume and having high activity in the dehydration reaction is prepared by a precipitation method and catalytic properties In order to improve the yield of acrolein through the change of, cerium oxide is impregnated in a predetermined content range to provide a catalyst for glycerin dehydration reaction capable of securing breakthrough acrolein productivity in a long-time reaction.

The catalyst for dehydration reaction increases acrolein productivity through a complementary effect between a phosphate catalyst having excellent acid properties and a skeleton structure and a metal oxide, and suppresses deactivation of the catalyst, thereby ensuring excellent process stability. In particular, the catalyst according to the present invention has a large specific surface area and a large pore volume, and by impregnating a cerium metal oxide in a predetermined range in a phosphate catalyst having high activity for dehydration reaction, it reacts for a long time through the effect of controlling metal oxide and acid properties. It is possible to secure breakthrough acrolein productivity. In addition, by using a gas phase-continuous flow reaction system having a relatively high productivity, it is possible to maximize the yield of acrolein and secure process stability.

The catalyst for dehydration reaction of the present invention uses zirconium phosphate (ZrP) having a high specific surface area as a carrier, and supports high activity in the dehydration reaction of glycerin by supporting cerium oxide in a predetermined content range, as well as for the selectivity and deactivation of acrolein. Stability can be secured. According to the high stability against deactivation of the catalyst of the present invention, it exhibits a characteristic of showing a stable yield compared to conventional catalysts even during a long reaction.

In this aspect, the catalyst for dehydration reaction of the present invention may exhibit a specific surface ^{area of 80 m 2} /g or more or 80 to 350 m ^{2 /g of zirconium phosphate (ZrP) serving as a carrier in the catalyst.} The specific surface area of the catalyst may be preferably 100 m ² /g or more or 100 to 250 m ² /g, more preferably 150 m ² /g or more or 150 to 250 m ² /g. For example, when the _{supported amount of CeO 2} in the catalyst is 15 wt% or less, the specific surface area of the supported catalyst may be 150 m ² /g or _{more, and when the supported amount of CeO 2} is 10 wt% or more, 190 m ² /g or less Can be.

In addition, the catalyst for dehydration reaction of the present invention supports a predetermined cerium oxide so as to secure breakthrough acrolein productivity in a long-term reaction through the effect of controlling acid properties with zirconium phosphate (ZrP).

For example, the cerium oxide may be at least one selected from the group consisting _{of CeO 2} and Ce ₂ O _3. Particularly, cerium oxide has a function of not only an acid catalyst but also an oxidation-reduction function, thereby suppressing the formation of coke on the surface of the catalyst.

The cerium oxide is supported in an amount of 6 to 18% by weight, preferably 8 to 16% by weight, more preferably 10 to 15% by weight based on the weight of zirconium phosphate (ZrP) used as a carrier. I can. In the case where less than 6% by weight of cerium oxide is supported in the catalyst, a sufficient cerium oxide active phase is not supported, so that the effect of improving the activity and inhibiting deactivation does not appear. In addition, when the amount of the cerium oxide supported exceeds 18% by weight, cerium oxide clusters are formed, thereby reducing physical properties and limiting mass transfer of reactants, which is not preferable. In particular, when the amount of cerium supported is too large, oxide clusters are formed, resulting in decreased dispersion of cerium oxide and a decrease in specific surface area.

Meanwhile, according to another embodiment of the present invention, there is provided a method of preparing a catalyst for a glycerin dehydration reaction as described above with high reproducibility, which is advantageous for mass production. The preparation method of the catalyst for glycerin dehydration reaction includes the steps of: (a) dissolving a zirconium precursor and a phosphate precursor in a first solvent to prepare a precursor solution; (b) aging the product obtained in step (a) to prepare a zirconium phosphate precipitate; (c) drying and heat treating the precipitate obtained in step (b) to produce a zirconium phosphate (ZrP) carrier; (d) dissolving a cerium precursor in a second solvent to prepare a cerium precursor solution; (e) impregnating the cerium precursor solution with the zirconium phosphate (ZrP) carrier produced in step (c), and then removing the second solvent to generate a precipitate; And (f) drying and heat treating the precipitate obtained in step (e).

The zirconium precursor used in the step (a) may be any conventionally used precursor including zirconium (Zr), and a precursor of chloride, nitrate, and alkoxide series It is preferable to use. For example, one or more of zirconium nitrate, zirconium chloride, zirconium butoxide, and the like may be used. In addition, the phosphate precursor used together with the zirconium precursor may be any precursor that is commonly used including a _{phosphoric acid group (PO 4) as a phosphate salt.} For example, one or more of phosphoric acid and ammonium phosphate may be used.

In addition, water or the like may be used as the first solvent used in step (a). In particular, the step (a) may be performed by mixing an appropriate amount of water such as phosphoric acid and the like and using it as a weak acid.

The amount of zirconium precursor, phosphate precursor, and solvent used in step (a) is used according to the ratio of the zirconium and phosphorus components to be prepared, and in general, an alkoxide-based zirconium precursor can be sufficiently hydrated in a solvent. It is preferable to stir for 1 to 2 hours so that.

Since the purpose of aging in step (b) is for chemical bonding of the zirconium precursor and phosphoric acid, which is a phosphate precursor, the aging temperature and time may be limited according to general aging conditions. For example, the aging temperature is 70 to 150°C, Preferably 80 to 120 ℃, drying time can be set to 3 to 24 hours, preferably 6 to 12 hours.

Since the purpose of thermal drying in step (c) is to remove moisture remaining in the generated zirconium phosphate precipitate, the drying temperature and drying time may be limited according to general moisture drying conditions. For example, the drying temperature is 70 to 150 °C, preferably 80 to 120 °C, drying time may be set to 3 to 24 hours, preferably 6 to 12 hours. If the drying temperature is less than 70° C., the solvent may not be sufficiently removed, and if it exceeds 150° C., constituents may be deformed during the drying process, which is not preferable.

In addition, the heat treatment in step (c) is performed for the purpose of synthesizing phosphate, and is performed for 2 to 5 hours, preferably 4 to 5 hours at a temperature range of 300 to 500°C, preferably 400 to 500°C. It is desirable to do it. This is not preferable because the heat treatment temperature is less than 300 °C or the heat treatment time is less than 2 hours because the precursor residue contained in phosphate is not completely removed, and the heat treatment temperature exceeds 500 °C or the heat treatment time exceeds 5 hours. In this case, it is not preferable because the phosphate phase may be denatured.

The metal oxide precursor used in step (d), that is, the cerium precursor contains cerium (Ce) element, and any precursor that is commonly used may be used, and a halide or nitrate , And it is preferable to use a precursor of the alkoxide series. For example, one or more of cerium nitrate, cerium chloride, cerium nitrate, cerium acetate, cerium sulfate, cerium alkoxide, etc. Can be used.

The content of the cerium precursor used in step (d) is impregnated so that the supported amount of cerium oxide is 6 to 18% by weight based on the weight of zirconium phosphate (ZrP), and preferably, the supported amount of cerium oxide is 8 to 16% by weight. , More preferably, it may be impregnated to be 10 to 15% by weight. That is, the amount of the cerium precursor impregnated can be determined by converting the theoretical amount of cerium oxide to be carried in moles when the catalyst is supported, and converting it to the amount of the precursor again, to determine the amount of the precursor. When the amount of the cerium precursor impregnated is not sufficient and the amount of cerium oxide supported is less than 6% by weight, the effect of increasing the acidity of ZrP is insignificant because a sufficient cerium oxide active phase is not supported. In addition, when the impregnation amount of the cerium precursor is added in an excessive amount and the supported amount of cerium oxide exceeds 18% by weight, cerium oxide clusters are formed, thereby reducing physical properties and limiting mass transfer of the reactants, which is not preferable. In particular, if the amount of impregnation of the cerium precursor is too large, oxide clusters are formed during the firing process, thereby inhibiting dispersion of the cerium oxide active phase, and a specific surface area may decrease, so that deactivation due to coke formation of the catalyst may occur rapidly.

The second solvent used in step (d) may be selected from water or alcohol, and water is preferable, but is not limited thereto.

The step (e) is a step for supporting the cerium oxide on a zirconium phosphate (ZrP) carrier, and after adding the zirconium phosphate (ZrP) prepared in step (c) to the cerium precursor solution prepared in step (d), vigorously Stirred and impregnated. Accordingly, a metal oxide/phosphate carrier evenly dispersed in zirconium phosphate (ZrP) can be prepared. For example, the stirring process of step (e) may be performed under conditions of about 300 rpm to 500 rpm.

Since the purpose of thermal drying in step (f) is to remove moisture remaining after impregnation with metal oxide, drying temperature and drying time may be limited according to general moisture drying conditions. For example, the drying temperature may be set at 70 to 150° C., preferably 80 to 120° C., and the drying time may be set at 3 to 24 hours, preferably 6 to 12 hours. The drying temperature is less than 70° C. and the solvent may not be sufficiently removed, and if it exceeds 150° C., deformation of constituents may occur during the drying process, which is not preferable.

In addition, the heat treatment in step (f) is performed for the purpose of synthesizing a metal oxide/phosphate, and at a temperature range of 300 to 500°C, preferably 400 to 500°C, for 2 to 5 hours, preferably 4 to 5 It is desirable to carry out for hours. This is not preferable because the synthesis of the metal oxide/phosphate catalyst is insufficient when the heat treatment temperature is less than 300 °C or the heat treatment time is less than 2 hours, and when the heat treatment temperature exceeds 500 °C or the heat treatment time exceeds 5 hours It is not preferable because the chemical structure may be modified and the phosphate phase may be denatured.

The method of preparing the catalyst for dehydration reaction may further include a step commonly employed in the technical field to which the present invention pertains, in addition to the steps described above.

Meanwhile, according to another embodiment of the present invention, a method of preparing acrolein through a dehydration reaction of glycerin on a catalyst prepared by the method as described above is provided. The manufacturing method of the acrolein is in the presence of a catalyst supporting 6 to 18% by weight of cerium oxide on zirconium phosphate (ZrP), using glycerin or an aqueous glycerin solution as a reactant, and an inert gas or a mixed gas of an inert gas and oxygen as a carrier gas. There is provided a method for producing acrolein comprising the step of dehydrating glycerin in a gas phase-continuous flow reaction system using.

In particular, according to the present invention, using a cerium oxide/zirconium phosphate catalyst having a complementary effect between a phosphate catalyst having excellent acid properties and a skeleton structure and a metal oxide, the productivity can be maximized in the production process of acrolein through the dehydration reaction of glycerin. It can provide a reaction system that can be used.

The production process of acrolein through the dehydration reaction of glycerin can be largely divided into a liquid phase dehydration reaction and a gas phase dehydration reaction. In previous studies, the liquid phase dehydration reaction of glycerin is mainly carried out in a batch reactor under liquid acid catalysts such as hydrochloric acid and sulfuric acid.By-products generated from the dehydration reaction of glycerin are deposited in the batch reactor, reducing the reaction activity and stability, and a liquid acid catalyst. It was confirmed that the reaction caused corrosion of the reactor and it was difficult to separate it from the product. That is, in the method for producing acrolein using a metal oxide/phosphate catalyst of the present invention, the dehydration reaction is in a temperature range of 250° C. to 400° C. in a gas phase dehydration reaction using a continuous flow reactor and 1.0 mmol/g _cat ·h of glycerin. It was carried out under conditions ranging from a unit time (h) of to 200.0 mmol/g _cat占h and a reaction amount per unit catalyst weight (g) (mmol). Preferably, the glycerin dehydration reaction may be carried out at a temperature of 280 °C to 320 °C, and the contact time of glycerin may be in the range of 20 mmol/g _cat ㆍh to 50 mmol/g _cat ㆍh. When the glycerin dehydration reaction is performed under a temperature condition of 250° C. or less, the selectivity of the polymerization reaction of glycerin increases, resulting in a slow reaction rate and a low conversion rate. When performed under a temperature condition of 400° C. or higher, the conversion rate of glycerin is high, whereas It is not preferable because the selectivity of 1-hydroxyacetone and allyl alcohol, which are by-products produced in the dehydration reaction, increases. In addition, if the reaction amount (mmol) per unit time (h) and unit catalyst weight (g) of glycerin is _{less than 1.0 mmol/g cat} ㆍh, the amount of acrolein production is too small, which is not preferable, and _{exceeds 200.0 mmol/g cat} ㆍh. In this case, it is not preferable because coking deposition due to reaction aquatic products of the catalyst occurs rapidly, thereby inhibiting the reaction.

The manufacturing method of the acrolein may further include a step commonly employed in the technical field to which the present invention pertains in addition to the above-described steps.

In addition, after performing the dehydration reaction, a partial oxidation reaction of acrolein from the product obtained from the dehydration reaction is performed, and a step of finally converting acrolein produced through the dehydration reaction of glycerin to acrylic acid may be further performed.

The manufacturing method of acrolein according to the present invention can maintain a glycerin conversion of 90% or more, measured at a time point 10 hours or more after the initiation of the reaction, and a selectivity to acrolein can be 35% or more, and the yield of acrolein is It can represent 35% or more. Preferably, the glycerin conversion may be maintained at 93% or more, selectivity to acrolein may be 44.5% or more, and the yield of acrolein may be 43% or more.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the contents of the present invention are not limited thereto.

[Production Example]

Preparation Example 1. Preparation of zirconium phosphate (ZrP) carrier

In the present invention, the phosphate to be impregnated with a metal oxide was prepared as zirconium phosphate through a precipitation method.

First, as a zirconium precursor and a solvent, zirconium butoxide and phosphoric acid were prepared in 4.57 mL and 60 mL (each 0.01 mol zirconium butoxide, 0.1 M phosphoric acid solution), and then the alkoxide was dissolved in a solvent. The phosphate precursor solution was stirred at room temperature for 1 to 2 hours. After the precursors of the solution were sufficiently hydrated, a phosphate precipitate could be obtained by aging in a convection oven at 120° C. for 10 hours to bind the chemical structure of zirconium phosphate. The zirconium phosphate precipitate obtained by the above process was filtered and washed with 2 L of distilled water. Then, after drying in a convection oven at 100°C for 10 hours, the catalyst is pulverized in powder form to remove water or organic molecules contained in the unrefined phosphate carrier at 400 at a heating rate of 2°C/min under an air atmosphere. After raising the temperature to °C, a sintering process was performed at 400 °C for 3 hours to finally obtain a zirconium phosphate (ZrP) carrier.

Manufacturing example 2 and 3. CE Oxide /zirconium Phosphate ( XCeO ₂ / ZrP , X=10, 15 wt%) catalyst preparation

A cerium oxide/zirconium phosphate supported catalyst was prepared, which was impregnated with cerium oxide in the zirconium phosphate carrier prepared by the method according to Preparation Example 1, and prepared and characterized, and a reaction experiment was performed. More specifically, a method for preparing a cerium oxide/zirconium phosphate (XCeO ₂ /ZrP, X=10, 15 wt%) catalyst by impregnating a zirconium phosphate carrier with cerium oxide is as follows.

First, in order to prepare a supported catalyst composed of various supported amounts, the amount of cerium nitrate/zirconium phosphate precursor as a cerium oxide precursor was determined according to the amount of cerium oxide supported in the final catalyst, 10CeO ₂ /ZrP (0.234 g, 0.9 g), Prepare 15CeO ₂ /ZrP (0.351 g, 0.9 g), 20CeO ₂ /ZrP (0.468 g, 0.9 g), and then dissolve each precursor and phosphate in water. The solution was stirred for about 1 to 2 hours so that the precursor and phosphate were sufficiently uniformly mixed. Thereafter, while heating at 80° C., a solid material was obtained by stirring until the distilled water was completely evaporated. Thereafter, the solid material was dried in an oven at 100° C. for about 12 hours, and the obtained sample was heated to 400° C. at a heating rate of 2° C./min in air, followed by a firing process at 400° C. for 3 hours to heat treatment. _{By doing so, a cerium oxide/zirconium phosphate (XCeO 2} /ZrP, X=10, 15 wt%) catalyst was prepared in which the supported amount of cerium oxide (CeO ₂ ) was 10 wt% and 15 wt%, respectively, based on the weight of ZrP.

compare Manufacturing example 1~4. cerium Oxide /zirconium Phosphate ( XCeO ₂ / ZrP , X=5, 20, 25, 30 wt%) catalyst preparation

In the same manner as in Preparation Examples 2 to 3, a supported catalyst having various impregnation amounts of cerium oxide was prepared and characterized and a reaction experiment was performed.

In particular, in order to prepare a supported catalyst composed of various supported amounts, the amount of cerium nitrate/phosphate precursor as a cerium oxide precursor was determined according to the amount of cerium oxide supported in the final catalyst. 5CeO ₂ /ZrP (0.117 g, 0.8 g), 20CeO ₂ /ZrP (0.468 g, 0.9 g), 25CeO ₂ /ZrP (0.584 g, 0.9 g), 30CeO ₂ /ZrP (0.701 g, 0.9 g), and then impregnated in the same manner as in Preparation Examples 2-3 processing and drying, a 5% by weight by loading a standard ZrP weight of the heat-treating step and cerium oxide (CeO ₂₎ performing, 20%, 25%, and 30% by weight of cerium oxide / zirconium phosphate (XCeO ₂ / ZrP , X=5, 20, 25, 30 wt%) catalyst was prepared.

[Test Example]

Test example 1. CE Oxide /zirconium Phosphate X-ray diffraction analysis evaluation of supported catalyst

Cerium oxide/zirconium phosphate prepared by the method of Preparation Examples 2 to 3 and Comparative Preparation Examples 1 to 4 (XCeO ₂ /ZrP, X=10, 15 wt% and X=5, 20, 25, 30 wt%) The catalyst was subjected to X-ray diffraction analysis (XRD), and the results of crystal phase analysis of the carrier obtained through the X-ray diffraction analysis (XRD) are shown in FIG. 1. The cerium oxide/zirconium phosphate supported catalysts prepared by the methods of Preparation Examples 2 and 3 were respectively expressed as 10CeO ₂ /ZrP and 15CeO ₂ /ZrP, and cerium oxide prepared by the method of Comparative Preparation Examples 1 to 4 / The zirconium phosphate supported catalyst was denoted as 5CeO ₂ /ZrP, 20CeO ₂ /ZrP, 25CeO ₂ /ZrP, and 30CeO ₂ /ZrP, respectively.

As shown in Figure 1, cerium oxide / zirconium phosphate prepared according to Preparation Examples 2 to 3 and Comparative Preparation Examples 1 to 4 (XCeO ₂ /ZrP, X=5, 10, 15, 20, 25, 30 wt%) According to the results of X-ray diffraction analysis of the catalyst, it can be seen that the peak appears large when the amount of cerium oxide supported in the catalyst is varied. In particular, in the cerium oxide supported catalyst having a low impregnation amount (X = 5 wt%), a peak indicating a cerium oxide crystal phase was hardly observed, and a modification similar to the result of X-ray diffraction analysis of an amorphous zirconium phosphate support having no crystallinity was observed. It could be confirmed that it was shown. In addition, at a very high loading amount (X=20, 25, 30 wt%), a cerium oxide peak was observed with a very large intensity, which indicates that an oxide-type crystal phase is well formed and oxide clusters are formed as the loading amount increases. . On the other hand, in the case of optimizing and impregnating the loading amount of cerium oxide to 10% by weight and 15% by weight according to Preparation Examples 2 to 3, the cerium oxide active phase was effectively generated and supported with excellent dispersibility without forming oxide clusters. Able to know.

Test example 2. CE Oxide /zirconium Phosphate Nitrogen in supported catalyst Adsorption and desorption Analysis evaluation

Cerium oxide/zirconium phosphate prepared by the method of Preparation Examples 2 to 3 and Comparative Preparation Examples 1 to 4 (XCeO ₂ /ZrP, X=10, 15 wt% and X=5, 20, 25, 30 wt%) The catalyst was subjected to nitrogen adsorption and desorption analysis, and the graph obtained through the nitrogen adsorption and desorption analysis is shown in FIG. 2. The cerium oxide/zirconium phosphate supported catalyst prepared by the method of Preparation Examples 2 to 3 was expressed as 10CeO ₂ /ZrP, 15CeO ₂ /ZrP, and cerium oxide/zirconium prepared by the method of Comparative Preparation Examples 1 to 4 The phosphate-supported catalyst was designated as 5CeO ₂ /ZrP, 20CeO ₂ /ZrP, 25CeO ₂ /ZrP, and 30CeO ₂ /ZrP.

From the nitrogen adsorption and desorption analysis results of the cerium oxide/zirconium phosphate supported catalyst shown in FIG. 2, all catalysts exhibited a Type IV type of H2 hysteresis, and through this, it was confirmed that all catalysts were mesoporous materials having mesoporous properties. Could. Through this, the zirconium phosphate (ZrP) prepared by Preparation Example 1 and Preparation Examples 2 to 3, cerium oxide / zirconium phosphate prepared by Comparative Preparation Examples 1 to 4 (XCeO ₂ /ZrP, X = 10, 15 wt. % And X=5, 20, 25, 30 wt%) successful synthesis of the catalyst was confirmed.

[Example]

Contrast 1~4. zirconium Phosphate ( ZrP ), aluminum Phosphate ( AlP ), titanium phosphate (TiP) and boron Phosphate (BP) Preparation of acrolein through dehydration of glycerin on a catalyst

In order to compare the activities of phosphate catalysts with different kinds of metals, among the phosphate catalysts, zirconium phosphate (ZrP), aluminum phosphate (AlP), titanium phosphate (TiP) and boron phosphate (BP) catalysts, which have typical acid properties. The glycerin dehydration reaction proceeded. The phosphate catalysts are zirconium butoxide (ZrP-related, Zirconium butoxide), aluminum chloride hexahydrate (AlP-related, aluminum chloride hexahydrate), titanium chloride (TiP-related, Titanium chloride), and sodium tetraborate decahydride (BP-related) as respective precursors. Related, sodium tetraborate decahydrate) was used, and it was directly synthesized by precipitation using phosphoric acid and used in the reaction experiment.

Preparation of acrolein through the dehydration reaction of glycerin was performed in a gas phase using a continuous flow U-tube fixed bed reactor. As a reactant, an aqueous glycerin solution in which distilled water and glycerin were mixed was used, and 1 and 4-dioxane were used as internal standards for analysis. For the catalytic reaction, a continuous flow U-tube fixed bed reactor was installed in an electric furnace, and 0.1 g of the catalyst was charged into the reactor, and nitrogen was flowed as a carrier gas at a flow rate of 30 mL/min, while the reaction temperature at a rate of 5 °C/min. After raising the temperature to 300° C., the reaction temperature was maintained for 1 hour in order to maintain a steady state of the reaction line. Thereafter, a glycerin aqueous solution was injected so that the reaction amount (mmol) per unit time (h) and unit catalyst weight (g) of _{glycerin became 45.9 mmol/g cat} ㆍh to perform a dehydration reaction of glycerin. The dehydration reaction of glycerin was carried out for 10 hours, and the product after the reaction contains unreacted glycerin with by-products such as 1-hydroxyacetone and allyl alcohol, in addition to acrolein, which is the main product of the reaction. The reaction product during the period was injected into gas chromatography through a sampling valve (six-port valve) and analyzed. The conversion rate of glycerin, selectivity and yield of acrolein by the dehydration reaction of glycerin were calculated by the following equations 1, 2, and 3.

[Equation 1]

Conversion rate of glycerin (%) = {(number of moles of glycerin supplied-number of moles of unreacted glycerin) / number of moles of supplied glycerin} × 100

[Equation 2]

Selectivity of acrolein (%) = {number of moles of acrolein produced/(number of moles of supplied glycerin-number of moles of unreacted glycerin)} × 100

[Equation 3]

Yield of acrolein (%) = (number of moles of acrolein produced/number of moles of glycerin supplied) × 100

According to Control Examples 1 to 4, the trend of acrolein yield change in the glycerin dehydration reaction for 10 hours under water over a zirconium phosphate, aluminum phosphate, titanium phosphate and boron phosphate catalyst is shown in Fig.3, and 10 hours after the reaction proceeds, glycerin The conversion rate, selectivity and yield of acrolein are shown in Table 1 below.

catalyst glycerin
Conversion rate (%) Acrolein
Selectivity (%) Acrolein
yield(%) Control Example 1 Zirconium phosphate (ZrP) 93.5 36.8 34.4 Control Example 2 Aluminum phosphate (AlP) 90.2 30.0 27.1 Control Example 3 Titanium phosphate (TiP) 85.3 25.9 22.1 Control Example 4 Boron phosphate (BP) 74.8 27.7 20.7

Referring to Figure 3, in the case of the glycerin dehydration reaction proceeded by zirconium phosphate, aluminum phosphate, titanium phosphate, and boron phosphate catalyst, the catalytic activity tends to be deactivated over time, which has been reported in various documents. It is judged that inactivation occurs due to coking deposition of the carbon material generated after the dehydration reaction. In particular, as shown in Table 1 and Figure 3, it can be seen that the zirconium phosphate catalyst exhibits excellent activity when compared with the activity of other phosphate catalysts, through which the preparation of a metal oxide/phosphate-supported catalyst for the glycerin dehydration reaction Thus, it has been shown that it is preferable to use zirconium phosphate as the active phase.

Example 1~2. cerium Oxide /zirconium Phosphate ( XCeO ₂ / ZrP , X=10, 15 wt% ) Preparation of acrolein through dehydration reaction of glycerin on a catalyst

_{Using the cerium oxide/zirconium phosphate (XCeO 2} /ZrP, X=10, 15 wt%) catalyst prepared by the methods of Preparation Examples 2 and 3, acrolein was prepared through dehydration of glycerin. For the catalytic reaction, a continuous flow U-tube fixed bed reactor was installed in an electric furnace, and 0.1 g of the catalyst was charged to the reactor, and nitrogen and oxygen as carrier gases were flowed at a flow rate of 30 mL/min and 1 mL/min, respectively. After raising the temperature to 275°C, which is the reaction temperature at a rate of °C/min, the reaction temperature was maintained for 1 hour in order to maintain a steady state of the reaction line. Thereafter, a glycerin aqueous solution was injected so that the reaction amount (mmol) per unit time (h) and unit catalyst weight (g) of _{glycerin became 45.8 mmol/g cat} ㆍh to perform a dehydration reaction of glycerin.

The change in the yield of acrolein in the glycerin dehydration reaction for 10 hours is shown in FIG. 4, and the conversion rate of glycerin, selectivity and yield of acrolein 10 hours after the reaction proceeds are shown in Table 2 below. The cerium oxide/zirconium phosphate supported catalyst prepared by the method of Preparation Examples 2 to 3 was expressed as 10CeO ₂ /ZrP, 15CeO ₂ /ZrP.

Comparative example 1. Zirconium Phosphate ( ZrP ) Preparation of acrolein through dehydration reaction of glycerin over catalyst

Using the zirconium phosphate (ZrP) catalyst prepared by the method of Preparation Example 1, acrolein was prepared through dehydration of glycerin in the same manner as in Examples 1 and 2. The change in the yield of acrolein in the glycerin dehydration reaction for 10 hours is shown in FIG. 4, and the conversion rate of glycerin, selectivity and yield of acrolein 10 hours after the reaction proceeds are shown in Table 2 below. By the method of Preparation Example 1, the zirconium phosphate catalyst was designated as ZrP.

Comparative example 2-5. cerium Oxide /zirconium Phosphate ( XCeO ₂ / ZrP , X=5, 20, 25, 30 wt%) Preparation of acrolein through dehydration of glycerin on a catalyst

_{Using the cerium oxide/zirconium phosphate (XCeO 2} /ZrP, X=5, 20, 25, 30 wt%) catalyst prepared by the method of Comparative Preparation Examples 1 to 4, glycerin in the same manner as in Examples 1 to 2 Acrolein preparation was performed through the dehydration reaction of. The change in the yield of acrolein in the glycerin dehydration reaction for 10 hours is shown in FIG. 4, and the conversion rate of glycerin, selectivity and yield of acrolein 10 hours after the reaction proceeds are shown in Table 2 below. _{The cerium oxide/zirconium phosphate (XCeO 2} /ZrP, X=5, 20, 25, 30 wt%) catalyst prepared by the method of Comparative Preparation Examples 1 to 4 _{was respectively 5CeO 2} /ZrP, 20CeO ₂ /ZrP, 25CeO ₂ /ZrP, and 30CeO ₂ /ZrP.

Comparative example 6. Tungsten Oxide /zirconium Phosphate (WO ₃ / ZrP ) Preparation of acrolein through dehydration reaction of glycerin over catalyst

For comparison with the results of dehydration activity of glycerin through a cerium oxide/zirconium phosphate catalyst according to the method according to Example 2, tungsten oxide/zirconium phosphate (WO ₃ /ZrP) prepared in the same manner as in Preparation Example 3 was used. And, using this, a process for producing acrolein through dehydration of glycerin on a catalyst was performed.

In particular, the tungsten oxide/zirconium phosphate (WO ₃ /ZrP) was prepared by impregnating tungsten oxide in a zirconium phosphate carrier in the same manner as in Preparation Example 2. At this time, the amount of tungsten oxide impregnated was 15 wt%. The glycerin dehydration reaction using the tungsten oxide/zirconium phosphate (WO ₃ /ZrP) was performed in the same manner as in Example 2. The trend of acrolein yield change in the glycerin dehydration reaction for 10 hours performed on the tungsten oxide/zirconium phosphate catalyst is shown in FIG. 5, and the conversion rate of glycerin, selectivity and yield of acrolein 10 hours after the reaction proceeded are shown in Table 2 below. Shown in. The prepared tungsten oxide/zirconium phosphate catalyst was designated as 15WO ₃ /ZrP.

Comparative example 7. Cobalt Oxide /zirconium Phosphate ( CoO ₂ / ZrP ) Preparation of acrolein through dehydration reaction of glycerin over catalyst

_{Using a cobalt oxide/zirconium phosphate (CoO 2} /ZrP) catalyst prepared in the same manner as in Preparation Example 3, a process for producing acrolein through dehydration of glycerin on the catalyst was performed in the same manner as in Example 2. At this time, the amount of cobalt oxide impregnated was 15 wt%. The trend of acrolein yield change in the glycerin dehydration reaction for 10 hours performed on a cobalt oxide/zirconium phosphate catalyst is shown in FIG. 5, and the conversion rate of glycerin, selectivity and yield of acrolein 10 hours after the reaction proceeded are shown in Table 2 below. Indicated. The prepared cobalt oxide/zirconium phosphate catalyst was designated as 15CoO ₂ /ZrP.

Comparative example 8. Vanadium Oxide /zirconium Phosphate ( V ₂ O ₆ / ZrP ) Preparation of acrolein through dehydration reaction of glycerin over catalyst

_{Using a vanadium oxide/zirconium phosphate (V 2} O ₆ /ZrP) catalyst prepared in the same manner as in Preparation Example 3, a process for producing acrolein through dehydration of glycerin on the catalyst was performed in the same manner as in Example 2. At this time, the amount of vanadium oxide impregnated was 15 wt%. The trend of acrolein yield change in the glycerin dehydration reaction for 10 hours performed on a vanadium oxide/zirconium phosphate catalyst is shown in FIG. 5, and the conversion rate of glycerin, selectivity and yield of acrolein after 10 hours after the reaction proceeded are shown in Table 2 below. Indicated. The prepared vanadium oxide/zirconium phosphate catalyst was designated as 15V ₂ O ₆ /ZrP.

According to Examples 1 to 2 and Comparative Examples 1 to 8, cerium oxide/zirconium phosphate (XCeO ₂ /ZrP, X=10, 15 wt%), zirconium phosphate (ZrP), cerium oxide/zirconium phosphate (XCeO ₂ /ZrP) , X=5, 20, 25, 30 wt%), tungsten oxide/zirconium phosphate (15WO ₃ /ZrP), cobalt oxide/zirconium phosphate (15CoO ₂ /ZrP), and vanadium oxide/zirconium phosphate (15V ₂ O ₆ / The glycerin conversion rate, selectivity of acrolein, and yield of acrolein after 10 hours reaction in the glycerin dehydration reaction of the ZrP) catalyst are as shown in Table 2 below.

catalyst glycerin
Conversion rate (%) Acrolein
Selectivity (%) Acrolein
yield(%) Example 1 10CeO ₂ /ZrP 96.6 45.0 43.4 Example 2 15CeO ₂ /ZrP 93.7 49.1 46.1 Comparative Example 1 ZrP 93.5 36.8 34.4 Comparative Example 2 5CeO ₂ /ZrP 96.1 43.1 41.4 Comparative Example 3 20CeO ₂ /ZrP 88.5 48.0 42.4 Comparative Example 4 25CeO ₂ /ZrP 83.4 44.5 38.1 Comparative Example 5 30CeO ₂ /ZrP 77.9 42.5 33.1 Comparative Example 6 15WO ₃ /ZrP 90.8 47.1 42.8 Comparative Example 7 15CoO ₂ /ZrP 92.4 44.6 41.2 Comparative Example 8 15V ₂ O ₆ /ZrP 91.3 39.6 36.2

Referring to FIG. 4, it was observed that the catalytic activity tends to become non-chemical over time on all catalysts, which is determined to be deactivated by coking deposition of the carbon material generated after the glycerin dehydration reaction. In particular, the cerium oxide/zirconium phosphate catalyst activity prepared by the method according to Preparation Examples 2 and 3 of the present invention (Examples 1 and 2) was the reaction activity of the conventional zirconium phosphate catalyst prepared by the method according to Preparation Example 1 (comparative Compared to Example 1), it can be seen that it is much higher, and through this, it is possible to maximize acrolein yield and secure process stability in a gas phase-continuous clouding reaction system for glycerin dehydration reaction.

On the other hand, as shown in Table 2 and 4, among the cerium oxide/zirconium phosphate catalysts, the 10CeO ₂ /ZrP and 15CeO ₂ /ZrP catalysts of Examples 1 and 2 have different amounts of impregnation. It can be seen that it exhibits superior activity than the zirconium phosphate catalyst, and as the impregnation amount increases, the glycerin conversion rate decreases and the selectivity increases and then decreases. Therefore, when applying the catalyst to the reaction system of the present invention, in order to obtain the maximum acrolein yield, it is recommended to use the 10CeO ₂ /ZrP and 15CeO ₂ /ZrP catalysts of Examples 1 and 2 having an appropriate impregnation amount of cerium oxide. desirable. _{In particular, by adding and supporting CeO 2} in the optimum range in the catalysts of Examples 1 and 2 according to the present invention, the yield of acrolein production can be increased by increasing the acidity of ZrP, and oxygen storage and storage of _{CeO 2} Due to the discharging ability, there is an effect of reducing deactivation by suppressing the formation of coke deposited on the catalyst surface.

In addition, the 15CeO _{2 /ZrP catalyst of Example 2 was superior to the 15WO 3} /ZrP, 15CoO ₂ /ZrP and 15V ₂ O ₆ /ZrP catalysts of Comparative Examples 6 to 8 impregnated with different metal oxides while having the same amount of impregnation. Shows activity. Therefore, it is preferable to use zirconium phosphate among the phosphate series as a method for obtaining the maximum acrolein yield in the metal oxide/phosphate catalyst system of the present invention, and to use a cerium oxide/zirconium phosphate catalyst impregnated with cerium oxide as the metal oxide. appear.

In particular, in _{the case of the 15WO 3} /ZrP catalyst _{in Comparative Example 6, WO 3} increases the acidity of the ZrP catalyst, so that the short-term activity of the catalyst can be increased, but the coke formation rate also increases due to the increase in acidity. There is a problem that the deactivation of is also rapidly progressing. However, in Example 2 according to the present invention, since _{the CeO 2 active phase of the 15CeO 2} /ZrP catalyst has its own acid property, it increases the reaction activity and has the ability to increase and discharge oxygen, which is the main cause of catalyst deactivation. It can be seen that it performs the function of suppressing the formation of coke.

Claims (8)

As a catalyst in which cerium oxide is supported on zirconium phosphate (ZrP),
6% to 18% by weight of cerium oxide is supported based on the weight of the zirconium phosphate (ZrP),
Catalyst for glycerin dehydration reaction.
The method of claim 1,
The cerium oxide is at least one selected from the group consisting _{of CeO 2} and Ce ₂ O _{3 glycerin dehydration catalyst.}
(a) dissolving a zirconium precursor and a phosphate precursor in a first solvent to prepare a precursor solution;
(b) aging the product obtained in step (a) to prepare a zirconium phosphate precipitate;
(c) drying and heat treating the precipitate obtained in step (b) to produce a zirconium phosphate (ZrP) carrier;
(d) dissolving a cerium precursor in a second solvent to prepare a cerium precursor solution;
(e) impregnating the cerium precursor solution with the zirconium phosphate (ZrP) carrier produced in step (c), and then removing the second solvent to generate a precipitate; And
(f) drying and heat treating the precipitate obtained in step (e);
Including,
A method for producing a catalyst for a glycerin dehydration reaction in which 6 to 18% by weight of cerium oxide is supported based on the weight of the zirconium phosphate (ZrP).
The method of claim 3,
In step (c), the drying process is performed at a temperature range of 70 to 150°C, and the heat treatment process is performed at a temperature range of 300 to 500°C.
The method of claim 3,
In the step (f), the drying process is performed at a temperature range of 70 to 150°C, and the heat treatment process is performed at a temperature range of 300 to 500°C.
In the presence of a catalyst in which cerium oxide is supported on zirconium phosphate (ZrP), glycerin or an aqueous glycerin solution is used as a reactant, and an inert gas or a mixture of inert gas and oxygen is used as a carrier gas in a gas phase-continuous flow reaction system. Including the step of dehydrating glycerin,
The catalyst is a method for producing acrolein, which supports 6% to 18% by weight of cerium oxide based on the weight of zirconium phosphate (ZrP).
The method of claim 6,
The glycerin dehydration reaction is a method for producing acrolein carried out at a temperature of 250 to 400 ℃.
The method of claim 6,
In the glycerin dehydration reaction, the reaction amount (mmol) per unit time (h) and unit catalyst weight (g) of glycerin is in the range of _{1.0 mmol/g cat} ㆍh to 200.0 mmol/g _{cat ㆍh.}

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