KR20160074287A - Catalyst for dehydration of glycerin, and preparing method of acrolein - Google Patents
Catalyst for dehydration of glycerin, and preparing method of acrolein Download PDFInfo
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- KR20160074287A KR20160074287A KR1020140183429A KR20140183429A KR20160074287A KR 20160074287 A KR20160074287 A KR 20160074287A KR 1020140183429 A KR1020140183429 A KR 1020140183429A KR 20140183429 A KR20140183429 A KR 20140183429A KR 20160074287 A KR20160074287 A KR 20160074287A
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- metal oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to a catalyst for dehydration reaction of glycerin and a process for producing acrolein. More specifically, the catalyst for the dehydration reaction of glycerin minimizes the formation of by-products in the glycerin dehydration reaction, thereby improving the selectivity of acrolein and maintaining the catalytic activity during the reaction.
Description
The present invention relates to a catalyst for dehydration reaction of glycerol and a process for producing acrolein, which can improve the selectivity of acrolein by minimizing the formation of by-products and can maintain a high catalytic activity during the reaction, And a method for producing the same.
Acrolein is a simple unsaturated aldehyde compound, has high reactivity, including incomplete reactors, and is used as a key 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 supplements, or food supplements.
These acrolein were prepared from propylene synthesized mainly from petroleum process through atmospheric oxygen and selective gas phase oxidation reaction. However, as environmental problems such as the reduction of fossil fuels and the greenhouse effect have been increasing, many studies have been conducted on the synthesis of acrolein using renewable raw materials that are not based on fossil fuels.
Accordingly, glycerin, which can be obtained as a by-product of the step of synthesizing biodiesel as a natural product, has attracted much attention as a raw material for producing acrolein. In particular, the market size of glycerin is increasing with the production of biodiesel, and due to the decrease in the price of glycerin, a method of industrial application thereof has been studied.
As an example, it is known to obtain glycerine in the form of a mixture of acrolein and acrylic acid by dehydration in the presence of a catalyst. The dehydration reaction of the glycerin proceeds in a gas phase oxidation reaction in the presence of a catalyst, and the use of a catalyst is essential. However, previous catalysts used to prepare acrolein have been found to produce byproducts such as hydroxpropane, propanaldehyde, acetaldehyde, acetone, polycondensation product of glycerin, and cyclic glycerin ether to produce high purity acrolein There has been a limit to use, and there is a limit to generate phenol or polyaromatic compound as a by-product to form a coke on the catalyst, thereby causing inactivation of the catalyst.
Accordingly, development of a catalyst system capable of increasing the selectivity and purity of acrolein, improving conversion of glycerin and reaction yield, and maintaining the activity of the catalyst during the reaction by minimizing the formation of by-products causing the above problems Is required.
The present invention is to provide a catalyst for glycerin dehydration reaction which can minimize the formation of by-products and thereby improve the selectivity of acrolein and maintain high catalytic activity during the reaction.
The present invention also relates to a process for producing acrolein using the catalyst for the dehydration reaction of glycerin.
The present invention provides a catalyst for dehydration reaction of glycerin comprising a composite metal oxide containing cerium (Ce), boron (B), tungsten (W) and phosphorus (P)
The present invention also provides a process for producing acrolein comprising the step of reacting glycerin in the presence of the catalyst for dehydration of glycerol.
Hereinafter, a catalyst for dehydration reaction of glycerol and a method for producing acrolein according to a specific embodiment of the present invention will be described in detail.
As used herein, the term " glycerin dehydration reaction "means a whole process in which water is separated in the molecule of glycerin or between molecules of glycerin.
According to an embodiment of the present invention, there can be provided a catalyst for a glycerin dehydration reaction, which comprises a composite metal oxide containing cerium (Ce), boron (B), tungsten (W) and phosphorus (P).
The present inventors have recognized that the method of producing acrolein through the gas phase oxidation reaction using the existing propylene as a starting material has a limitation due to the environmental problems such as reduction of fossil fuel storage amount and greenhouse effect, A study was made on a method for producing acrolein using renewable raw materials. Thus, in the case of dehydration of glycerin in the presence of a catalyst comprising a composite metal oxide containing cerium (Ce), boron (B), tungsten (W) and phosphorus (P), acrolein It was verified through experiments that a high yield and a high conversion were produced, and the invention was completed.
Particularly, the composite metal oxide is formed in the form of an oxide further containing cerium in addition to boron, phosphorus and tungsten, and is remarkably produced as compared with a conventional catalyst for the dehydration reaction of glycerin or the production of acrolein such as zeolite, sulfate, The yield of acrolein can be increased. Particularly, when the composite metal oxide is used, the production of hydroxypropanone, which is a main by-product of the glycerin dehydration reaction, can be remarkably reduced.
In addition, in the case of conventional catalysts, there is a limitation in generating phenol or polyaromatic compound as a by-product to form a coke on the catalyst to cause inactivation of the catalyst. However, the catalyst for dehydration reaction of glycerin is not limited to the above- To keep the activity of the catalyst high during the reaction.
The catalyst for dehydration reaction of glycerin having such characteristics includes a composite metal oxide including cerium (Ce), boron (B), tungsten (W) and phosphorus (P). In the composite metal oxide, each of the components is strongly bonded to each other to serve as an acid site to receive a proton or a non-covalent electron pair. Thus, acrolein can be produced by dehydration reaction of glycerin with higher selectivity, conversion and yield.
In the composite metal oxide, phosphorus and tungsten may be combined with oxygen in the form of an oxide such as phosphoric acid (PO 4 ) or tungstic acid (WO 4 ), respectively. In particular, the composite metal oxide can bind the elements in an oxide form to increase the acid sites such as the Bronsted acid point or the Lewis acid point, thereby enabling the dehydration reaction of glycerin more efficiently.
The composite metal oxide may be at least one selected from the group consisting of Ni, Co, Cu, Zn, Mn, Ca, Mg, K, Li, Na, Cs, Sr , And at least one second metal selected from the group consisting of Ba, Nb, Mo, Fe, V, and La. The expression "second" is a term for distinguishing the metals from cerium (Ce), boron (B), tungsten (W) and phosphorus (P).
The second metal may be bonded to the composite metal oxide in such a manner that cerium (Ce), boron (B), tungsten (W), and phosphorus (P) share oxygen. The composite metal oxide can further improve the selectivity of acrolein by further including the second metal and can inhibit the production of byproduct hydroxypropanone.
In particular, the second metal may be a composite metal of Ni, Ni and Co, a composite metal of Ni and Cu, a composite metal of Ni and Zn, or a composite metal of Ni and Mn. It is possible to perform the action of the acid point which can cause the dehydration reaction of glycerin together with the suppression of the formation of the glycerin, and thus the acrolein can be produced more efficiently by dehydration reaction of glycerin.
In addition, the molar ratio between cerium (Ce) and tungsten (W) may be 1:15 to 1: 1. When the amount of cerium (Ce) is too small, the effect of improving the selectivity of acrolein may be insignificant. If the amount of cerium (Ce) is too large, the catalytic activity or selectivity may not be improved.
Meanwhile, the composite metal oxide may include a composite metal oxide represented by the following Formula 1:
[Chemical Formula 1]
(M) x (Ce) y BWPO z
In Formula 1,
M is at least one second metal selected from the group consisting of Ni, Co, Cu, Zn, Mn, Ca, Mg, K, Li, Na, Cs, Sr, Ba, Nb, Mo, Fe,
x is a real number from 0 to 3,
y is a real number greater than 0 and less than or equal to 3,
and z is a real number from 1 to 20. [
More specifically, in the above formula (1), M may be a composite metal of Ni, Ni and Co, a composite metal of Ni and Cu, a composite metal of Ni and Zn, or a composite metal of Ni and Mn, 1, and y can be a real number greater than 0 and less than or equal to 1.
The content of oxygen in the composite metal oxide, that is, the z value in the formula (1), can be appropriately controlled depending on the content and composition ratio of cerium, boron, tungsten, phosphorus and further components, Lt; / RTI >
And, specific examples of the composite metal oxide is Ce 0 .1 BWPO 8, Ni 0.05 Ce 0.1 BWPO 8, (NiCo) 0.05 Ce 0 .1 BWPO 8, (NiCu) 0.05 Ce 0 .1 BWPO 8, (NiZn) 0.05 Ce 0 .1 BWPO 8 , (NiMn) 0.05 Ce 0.1 BWP 1.2 O 8.8, or mixtures thereof.
The catalyst for dehydration reaction of glycerin may further include a carrier to which the composite metal oxide is fixed. The carrier can be used without any limitations as long as it is known to be usable 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 mixtures thereof, Can be used.
The support serves to fix the composite metal oxide of one embodiment, and the composite metal oxide may be fixed in a form sharing oxygen to a support having a large surface area. As described above, when the composite metal oxide is prepared in a form fixed to a carrier, it can be more easily stored and transported, and a large amount of glycerin can be efficiently reacted due to its large surface area.
The carrier may have a specific surface area of 10 to 500 m 2 / g, and preferably 50 to 200 m 2 / g. Particularly, since the catalyst for dehydration reaction of glycerin prepared by carrying the composite metal oxide on a carrier having a large specific surface area in the above range has a proper pore size, coke deposition phenomenon can be reduced and sufficient catalyst activity can be provided have.
The catalyst for dehydration reaction of glycerin may contain 1 to 50 parts by weight of a composite metal oxide containing at least one element selected from the group consisting of phosphorus and sulfur and tungsten, based on 100 parts by weight of the carrier.
Meanwhile, the catalyst for the dehydration reaction of glycerin may include a step of mixing a cerium precursor, a boron precursor, a tungsten precursor and a phosphorus precursor; And drying and firing the mixed solution.
As described above, the catalyst for the dehydration reaction of glycerin according to one embodiment of the present invention produced according to this method can minimize the formation of by-products in the dehydration reaction of glycerin, and can produce acrolein with high selectivity, The production of phenol or polyaromatic compound is inhibited and the activity of the catalyst can be kept high.
The cerium precursor, the boron precursor, the tungsten precursor and the phosphorus precursor collectively refer to materials for providing cerium, boron, tungsten, and phosphorus contained in the catalyst for dehydration reaction of glycerin, respectively, , Tungsten, and phosphorous. More specifically, the cerium precursor may be cerium nitrate, the tungsten precursor may be ammonium metatungstate, the phosphorus precursor may be triethylphosphate, and the boron precursor may be boronic acid.
In the step of mixing the cerium precursor, the boron precursor, the tungsten precursor and the phosphorus precursor, the cerium precursor, the boron precursor, the tungsten precursor and the phosphorus precursor as well as the Ni, Co, Cu, Zn, Mn, At least one second metal precursor selected from the group consisting of Li, Na, Cs, Sr, Ba, Nb, Mo, Fe, V and La may be further added.
As a specific example of the second metal, the content of M of the catalyst for dehydration reaction of glycerin can be applied without limitation, more preferably nitrate of the second metal can be used as a precursor of the second metal .
The method for preparing a catalyst for dehydration reaction of glycerin may include a step of drying and firing a mixed solution prepared by mixing the cerium precursor, the boron precursor, the tungsten precursor, and the phosphorus precursor.
More specifically, in the drying step, the mixed solution may be dried at a temperature of 100 ° C or more for 10 minutes to 24 hours to remove the solvent from the mixed solution. In this drying process, a drying method and a drying device known to be commonly used can be used. For example, drying can be performed using a heat source such as a hot air fan, an oven, or a hot plate.
The firing step is a series of steps of heating the reactants at a high temperature to produce a curable material. The firing step may be performed at a temperature ranging from 100 to 900 ° C, preferably 250 to 750 ° C. If the temperature is lower than the above range, the structure and crystallinity of the catalyst may change during the reaction, and if the temperature is higher than the above range, the interatomic interaction may be too strong to increase the particle size or cause unnecessary side reactions.
Further, the drying and calcining steps may be performed for 10 minutes to 10 hours, respectively. If the drying and calcining time is too short, the catalyst may not be completely dried and calcined, and if the drying and calcining time is too long, various side reactions such as carbonization of the catalyst may occur.
According to another embodiment of the present invention, there is provided a method of preparing a catalyst for dehydration reaction of glycerol, which comprises the step of supporting a mixture of cerium precursor, boron precursor, tungsten precursor and phosphorus precursor on a carrier. The step of supporting the mixed liquid on the carrier can be carried out by any method known in the art without limitation, and for example, an impregnation method or a powder mixing method can be used. The specific examples of the carrier and the mixing ratio can be applied without any limitations to the above.
The impregnation method is a step of preparing a carrier in the form of spheres or pellets, and then aging and firing the mixture together with the mixture solution in which the gel-state precipitates are formed, and the powder mixing method is a process of aging and / The powdery product obtained through the drying process is mixed with the powdery carrier, and the resultant mixture is calcined and supported.
That is, the catalyst for the dehydration reaction of glycerin of the above embodiment can be prepared by carrying the mixed solution on the carrier by the impregnation method or the powder mixing method, so that the mixed solution of the cerium precursor, the boron precursor, the tungsten precursor and the phosphorus precursor and the spherical or pellet form May be aged and fired together and may be carried. Alternatively, the mixed solution may be aged and dried to prepare a powder, and then mixed with a powdery carrier to be calcined.
According to another embodiment of the present invention, there is provided a process for producing acrolein comprising the step of reacting glycerin in the presence of the above-mentioned catalyst for dehydration reaction of glycerin.
As described above, the use of the catalyst for dehydration reaction of glycerin according to an embodiment of the present invention can perform the dehydration reaction of glycerin having a high selectivity of acrolein. In particular, Can be minimized.
The amount of the catalyst for the dehydration reaction of glycerin can be appropriately adjusted according to the amount and concentration of glycerin. For example, it may be used in an amount of 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of glycerin per hour.
In addition, the dehydration reaction may be performed at a temperature of 200 to 400 ° C. The dehydration reaction is an endothermic reaction. In order to produce acrolein with high conversion and selectivity, the reaction is preferably carried out at a temperature within the above range.
According to the present invention, there can be provided a catalyst for a glycerin dehydration reaction capable of minimizing the formation of by-products and improving the selectivity of acrolein and maintaining the catalytic activity during the reaction, and a process for producing acrolein using the same.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[ Example ]: Preparation of Catalyst for Glycerin Dehydration Reaction
[ Example One]
Ce 0 .1 BWPO catalyst 8 is fixed to 0.1, and a molar ratio of Ce, B, W, a molar ratio of P was prepared by fixing to 1. The To this end, 1.1 g of a cerium precursor (Cerium nitrate: Ce (NO 3 ) 3 6H 2 O), 1.56 g of a boric acid (H 3 BO 3 ), a tungsten precursor (H 26 N 6 O 40 W 12 ) and 4.6 g of phosphorus precursor (Triethyl phosphate: (C 2 H 5 O) 3 P (O)) were placed in a flask and stirred for 15 hours at room temperature using 15 ml of ethanol and 12 ml of distilled water as a solvent. Then, the catalyst was prepared by drying overnight in a 100 ° C oven and then calcining at 700 ° C for 6 hours.
[ Example 2]
Ni 0 .05 Ce 0 .1 BWPO 8 catalyst was prepared by fixing the molar ratio of Ni to 0.05, the molar ratio of Ce to 0.1, and the molar ratio of B, W and P to 1. To this end, 1.1 g of a cerium precursor (Cerium nitrate: Ce (NO 3 ) 3 6H 2 O), 1.56 g of a boric acid (H 3 BO 3 ), a tungsten precursor (H 26 N 6 O 40 W 12) 6.22g, precursor (Triethyl phosphate: (C 2 H 5 O) 3 P (O)) 4.6g, and the nickel precursor (Ni (NO 3) 2 6H 2 O) 0.37g placed in 15 ml flask ethanol And distilled water (12 ml) as a solvent were stirred at room temperature for 5 hours. Then, the catalyst was prepared by drying overnight in a 100 ° C oven and then calcining at 700 ° C for 6 hours.
[ Example 3]
(NiCo) 0.05 Ce 0 .1 BWPO 8 catalyst in a molar ratio of 0.05 NiCo composite metal, fixing the molar ratio of Ce to 0.1, and, B, W, a molar ratio of P was prepared by fixing to 1. The To this end, 1.1 g of a cerium precursor (Cerium nitrate: Ce (NO 3 ) 3 6H 2 O), 1.56 g of a boric acid (H 3 BO 3 ), a tungsten precursor (H 26 N 6 O 40 W 12) 6.22g, precursor (Triethyl phosphate: (C 2 H 5 O) 3 P (O)) 4.6g, nickel precursor (Ni (NO 3) 2 6H 2 O) 0.37g, and a cobalt precursor (Co (NO 3 ) 2 6H 2 O) were placed in a flask, and the mixture was stirred at room temperature for 5 hours using 15 ml of ethanol and 12 ml of distilled water as a solvent. Then, the catalyst was prepared by drying overnight in a 100 ° C oven and then calcining at 700 ° C for 6 hours.
[ Example 4]
(NiCu) 0.05 Ce 0 .1 BWPO 8 catalyst in a molar ratio of 0.05 NiCu composite metal, fixing the molar ratio of Ce to 0.1, and, B, W, a molar ratio of P was prepared by fixing to 1. The To this end, 1.1 g of a cerium precursor (Cerium nitrate: Ce (NO 3 ) 3 6H 2 O), 1.56 g of a boric acid (H 3 BO 3 ), a tungsten precursor (H 26 N 6 O 40 W 12) 6.22g, precursor (Triethyl phosphate: (C 2 H 5 O) 3 P (O)) 4.6g, nickel precursor (Ni (NO 3) 2 6H 2 O) 0.37g, and copper precursor (Cu (NO 3 ) 2 3H 2 O) were placed in a flask, and the mixture was stirred at room temperature for 5 hours using 15 ml of ethanol and 12 ml of distilled water as a solvent. Then, the catalyst was prepared by drying overnight in a 100 ° C oven and then calcining at 700 ° C for 6 hours.
[ Comparative Example One]
Zeolist Beta-Zeolite was calcined at 350 DEG C for 6 hours to prepare a catalyst.
[ Comparative Example 2]
H 3 PW 12 O 40 of Wako Co. was calcined at 500 ° C for 6 hours to prepare a catalyst.
[ Comparative Example 3]
The BPO 4 catalyst was prepared by fixing the molar ratio of B and P to 1. To this end, 1.56 g of boric acid (H 3 BO 3 ) and 4.6 g of phosphorus precursor (Triethyl phosphate: (C 2 H 5 O) 3 P (O)) were placed in a flask and 15 ml of ethanol and 12 ml of distilled water And the mixture was stirred at room temperature for 5 hours. Then, the catalyst was prepared by drying overnight in a 100 ° C oven and then calcining at 700 ° C for 6 hours.
[ Experimental Example ]: Conversion of glycerin, yield and selectivity of acrolein
Using the catalysts prepared according to the Examples and Comparative Examples, a high-throughput screening (HTS) apparatus was prepared so as to evaluate the performance with a small amount of catalyst in a short time under the conditions shown in Table 1 below. , And the conversion, selectivity and yield were calculated by analyzing the products in in-situ state by GC.
More specifically, the HTS apparatus has 16 reactors (9 mm in outer diameter, 25 cm in length) to perform a large amount of catalyst experiments in the shortest time. In order to inject the liquid reaction product at a constant rate, a pump Was sent to the evaporator heater, and the vaporized reactant was fed to the reactor at a constant rate along with the carrier gas, nitrogen. The sampling operation was performed in a chiller set at a temperature of 0 ° C for condensation and distilled water was added to the glass bottle to allow the reaction to condense. Reactions were analyzed using on-line gas chromatography (HP 6890N). Flame ionization detector (FID) was used and HP-FFAP (25m X 0.32mm X 0.52mm) was used for the column.
The conversion of glycerin, the yield of acrolein, and the selectivity of acrolein are shown in Tables 2 and 3 below.
Here, the conversion rate represents the rate at which glycerin is converted to another compound, and the selectivity represents the rate of conversion of glycerin to acrolein, and the selectivity represents the ratio of acrolein in the converted compounds.
Also, Comparative Example 1 shows a comparative value of production amounts of hydroxypropanone, propionic acid, and aromatics relative to the amount of acrolein produced. In the comparative selectivity 1, hydroxypropanone is a major by-product of the glycerin dehydration reaction, and propionic acid and aromatics are also by-products that can cause coke substances.
yield(%)
* Comparative selectivity 1 = amount of produced (hydroxypropanone + propionic acid + aromatic material) / amount of acrolein produced
As shown in Tables 2 and 3, in the case of reacting glycerin using the catalyst of the above example, the selectivity of acrolein was higher than that of the catalyst of Comparative Example. Also, the comparative selectivity 1, which is the ratio of the production amount of by-products to the production amount of acrolein, which is the target main product in the above reaction, is lower than that of the catalyst of the comparative example.
From the above results, it can be seen from the above results that the catalyst for the dehydration reaction of glycerin in the examples can produce acrolein with high selectivity and high purity from glycerol and can inhibit the formation of byproducts such as hydroxypropanone, propionic acid, Can be confirmed.
Claims (12)
And at least one second metal selected from the group consisting of Ni, Co, Cu, Zn, Mn, Ca, Mg, K, Li, Na, Cs, Sr, Ba, Nb, Mo, , Catalyst for dehydration reaction of glycerin.
Wherein the composite metal oxide has a molar ratio of cerium (Ce) to tungsten (W) of 1:15 to 1: 1.
Wherein the composite metal oxide comprises a composite metal oxide represented by Formula 1:
[Chemical Formula 1]
(M) x (Ce) y BWPO z
In Formula 1,
M is at least one second metal selected from the group consisting of Ni, Co, Cu, Zn, Mn, Ca, Mg, K, Li, Na, Cs, Sr, Ba, Nb, Mo, Fe,
x is a real number from 0 to 3,
y is a real number greater than 0 and less than or equal to 3,
and z is a real number from 1 to 20. [
Wherein M is a composite metal of Ni, Ni and Co, a composite metal of Ni and Cu, a composite metal of Ni and Zn, or a composite metal of Ni and Mn.
The composite metal oxide is Ce 0 .1 BWPO 8, Ni 0 .05 Ce 0 .1 BWPO 8, (NiCo) 0.05 Ce 0 .1 BWPO 8, (NiCu) 0.05 Ce 0.1 BWPO 8, (NiZn) 0.05 Ce 0.1 BWPO 8, and (NiMn) 0.05 Ce 0 .1 BWP 1 .2 O 8 .8, glycerin dehydration catalyst comprising at least one compound selected from the group consisting of.
And a carrier on which the composite metal oxide is fixed.
Wherein the carrier is selected from the group consisting of silica, alumina, silica-alumina, zirconia, magnesia, magnesium aluminate, calcium aluminate, silicon carbide, zirconium phosphate, zeolite and mixtures thereof.
Wherein the support has a specific surface area (BET) of 10 to 500 m < 2 > / g.
Wherein the composite metal oxide is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the carrier.
Wherein the dehydration reaction is carried out at a temperature of 200 to 400 캜.
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| KR1020140183429A KR20160074287A (en) | 2014-12-18 | 2014-12-18 | Catalyst for dehydration of glycerin, and preparing method of acrolein |
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