Patent Grant
9592496
This application is a National Stage Application of International Application No. PCT/KR2014/010955, filed Nov. 14, 2014, and claims the benefit of Korean Application No. 10-2013-0139783, filed Nov. 18, 2013, and Korean Application No. 10-2014-0158524, filed Nov. 14, 2014, all of which are hereby incorporated by reference in their entirety for all purposes as if fully set forth herein.
The present invention relates to a catalyst composition for oxidative dehydrogenation and a method of preparing the same. More particularly, the present invention relates to a catalyst composition for oxidative dehydrogenation to prevent loss occurring in a filling process due to superior mechanical durability and wear according to long-term use, to inhibit polymer formation and carbon deposition during reaction and to provide a superior conversion rate and superior selectivity, and a method of preparing the same.
Butene oxidative dehydrogenation as a representative method of preparing butadiene as a raw material of synthetic rubber is carried out at 300 to 450° C. In this regard, oxygen, water, etc. as an oxidizing agent are added thereto, but butadiene is prepared only using butane. However, a metal oxide catalyst such as molybdenum, bismuth or cobalt as a catalyst for oxidative dehydrogenation of butane is prepared into a pellet through preparation and molding processes, and, when a reactor is filled with these catalysts, some thereof is lost. In addition, due to use of the catalysts, wear occurs. In particular, during molding a metal oxide precursor and then firing the same, various problems such as fragmentation of a pellet occur.
Accordingly, there is an urgent need for a catalyst composition for oxidative dehydrogenation of butane in order to minimize catalyst loss occurring upon filling a reactor with a catalyst and catalyst wear according to use, and a method of preparing the same.
Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide a catalyst composition to prevent loss occurring in a filling process due to superior mechanical durability and wear according to long-term use, to inhibit polymer formation and carbon deposition during reaction and to provide a superior conversion rate and superior selectivity, a method of preparing the same, and a binder applied thereto.
The above and other objects can be accomplished by the present invention described below.
In accordance with one aspect of the present invention, provided is a catalyst composition comprising a multi-ingredient-based metal oxide catalyst and a mixed metal hydroxide.
In accordance with another aspect of the present invention, provided is a method of preparing a catalyst composition, the method comprising a) mixing a multi-ingredient-based metal oxide catalyst and a mixed metal hydroxide, b) molding the mixture, and c) firing the molded material.
In accordance with yet another aspect of the present invention, provided is a binder that is a mixed metal hydroxide and applied to a multi-ingredient-based metal oxide catalyst.
As apparent from the fore-going, the present invention advantageously provides a catalyst composition to prevent loss occurring in a filling process due to superior mechanical durability and wear according to long-term use, to inhibit polymer formation and carbon deposition during reaction and to provide a superior conversion rate and superior selectivity, and a method of preparing the same.
Hereinafter, the present invention is described in detail.
A catalyst composition according to the present disclosure comprises a multi-ingredient-based metal oxide catalyst and a mixed metal hydroxide.
In an embodiment, the multi-ingredient-based metal oxide catalyst may comprise bismuth and molybdenum. In this case, superior conversion rate and selectivity are exhibited.
In another embodiment, the multi-ingredient-based metal oxide catalyst may comprise bismuth, molybdenum and cobalt. In this case, superior conversion rate and selectivity are exhibited.
In an embodiment, the multi-ingredient-based metal oxide catalyst may be a catalyst for oxidative dehydration reaction.
In an embodiment, the multi-ingredient-based metal oxide catalyst may be a coprecipitation catalyst. In this case, strength of the metal oxide catalyst is enhanced, and a structure of the catalyst is maintained. Accordingly, in addition, superior activity and selectivity are exhibited.
In an embodiment, a specific surface area of the multi-ingredient-based metal oxide catalyst is 2 to 15 m2 g−1, 3 to 12 m2 g−1 or 5 to 10 m2 g−1. Within these ranges, the catalyst exhibits superior activity and selectivity.
In an embodiment, the multi-ingredient-based metal oxide catalyst has a pore volume of 0.01 to 0.1 ccg−1, 0.01 to 0.06 ccg−1 or 0.02 to 0.05 ccg−1. Within these ranges, the catalyst exhibits superior activity and selectivity.
In an embodiment, in the oxidative dehydration reaction, butadiene is generated from butane or butene.
In an embodiment, the mixed metal hydroxide is a plate structure or a layered structure. In this case, a wider specific surface area than conventional metal hydroxide is possible.
The plate structure or the layered structure according to the present disclosure is not specifically limited. In an embodiment, thickness may be larger than a side length. In another embodiment, a value of a side length to thickness (L/T) may be 1.5 to 5.
In an embodiment, the specific surface area of the mixed metal hydroxide may be 5 to 500 m2 g−1, 10 to 300 m2 g−1 or 50 to 200 m2 g−1. Within these ranges, binding of the metal hydroxide to the catalyst is increased.
In an embodiment, a pore volume of the mixed metal hydroxide may be 0.1 to 1.0 ccg−1, 0.1 to 0.5 ccg−1 or 0.2 to 0.5 ccg−1. Within these ranges, binding of the metal hydroxide to the catalyst is increased.
In an embodiment, the mixed metal hydroxide comprises aluminum and magnesium. In this case, the metal oxide catalyst exhibits enhanced strength.
In an embodiment, a molar ratio of aluminum to magnesium is 1:6 to 6:1, 1:1 to 6:1, or 2:1 to 4:1. Within these ranges, the metal oxide catalyst exhibits superior strength.
In another embodiment, the mixed metal hydroxide is hydrotalcite. In this case, the metal oxide catalyst exhibits superior strength.
In an embodiment, the amount of the mixed metal hydroxide is 0.01 to 20% by weight, 0.1 to 5% by weight, or 1 to 2.5% by weight based on 100% by weight of the catalyst composition. Within these ranges, superior crush strength, butene conversion rate and butadiene selectivity are exhibited.
The weight of the catalyst composition according to the present disclosure means the weight of a mixture of the multi-ingredient-based metal oxide and the mixed metal hydroxide, or the weight of the fired catalyst composition.
In an embodiment, the catalyst composition may be fired. In this case, an amorphous metal oxide catalyst exhibits enhanced strength.
In an embodiment, the catalyst composition is a coprecipitation catalyst. In this case, strength of the metal oxide catalyst is increased and a structure of the catalyst is maintained. Accordingly, superior activity and selectivity are exhibited.
In an embodiment, the catalyst composition is a pellet type. In this case, strength of the metal oxide catalyst is enhanced.
In an embodiment, the catalyst composition may have a crush strength (Newton) of 4.5 or more, 4.5 to 15 or 7 to 14. Within these ranges, molding may be carried out into a variety of morphologies, and superior activity and selectivity are exhibited.
In an embodiment, a specific surface area of the catalyst composition is 5 to 500 m2 g−1, 10 to 300 m2 g−1 or 50 to 250 m2 g−1. Within these ranges, strength of the metal oxide catalyst is enhanced.
In an embodiment, a pore volume of the catalyst composition may be 0.01 to 0.5 ccg−1, 0.01 to 0.3 ccg−1 or 0.02 to 0.3 ccg−1. Within these ranges, the strength of the metal oxide catalyst is enhanced.
A method of preparing a catalyst composition according to the present disclosure comprises a) mixing a multi-ingredient-based metal oxide catalyst and a mixed metal hydroxide, b) molding the mixture, and c) firing the molded material.
In an embodiment, the method of preparing the catalyst composition may comprise a) preparing a slurry by mixing the multi-ingredient-based metal oxide catalyst, the mixed metal hydroxide and water, b) preparing a molded material by molding the slurry and c) firing the molded material. In this case, strength of the metal oxide catalyst is enhanced, and, when compared with conventional metal oxide catalysts, superior conversion rate and selectivity are exhibited upon butadiene generation.
Since, in the method of preparing the catalyst composition according to the present disclosure, heat-treating among conventional processes of preparing, molding and heat-treating a multi-ingredient-based metal oxide is omitted, process simplication may be accomplished and production costs may be reduced.
The fired catalyst composition shows similar reactivity when compared with a multi-ingredient-based metal oxide catalyst powder in oxidative dehydration reactivity (conversion rate and selectivity) of butene.
In an embodiment, in the mixing (a), the multi-ingredient-based metal oxide catalyst may be prepared through i) coprecipitating, ii) drying and iii) firing. In this case, strength of the metal oxide catalyst is enhanced.
In an embodiment, in the mixing (a), the mixed metal hydroxide is fired at 500 to 600° C., 550 to 600° C. or 570 to 580° C. Within these ranges, self-adhesion is superior and thus strength of the catalyst is enhanced.
In an embodiment, in the mixing (a), water is mixed in an amount of 50 to 100 parts by weight, 10 to 20 parts by weight or 5 to 7 parts by weight based on 100 parts by weight of a mixture of the multi-ingredient-based metal oxide catalyst and the mixed metal hydroxide. Within these ranges, a pellet may be easily molded and strength of the metal oxide catalyst is enhanced.
In an embodiment, the water may be double-distilled water at 5° C. or less, 0° C. or less, or 5 to −10° C. In this case, time required in mixing and molding processes may be secured by decreasing a reaction rate.
In an embodiment, the amount of the mixed metal hydroxide may be 0.01 to 20% by weight, 0.1 to 5% by weight, or 1 to 2.5% by weight based on the total weight of a mixture of the multi-ingredient-based metal oxide and the mixed metal hydroxide. Within these ranges, excellent crush strength, butene conversion rate and butadiene selectivity are exhibited.
In an embodiment, the molded material of the molding (b) is a pellet type. In this case, the size of the catalyst composition may be easily controlled.
In an embodiment, the firing (c) may be carried out at 200 to 500° C., 300 to 400° C. or 300 to 350° C. Within these ranges, excellent crush strength, butene conversion rate and butadiene selectivity are exhibited.
In an embodiment, the firing (c) may be carried out for 1 to 8 hours, 2 to 6 hours, or 3 to 4 hours. Within these ranges, excellent crush strength is exhibited.
In an embodiment, the method of preparing the catalyst composition may further comprise aging the molded material before the firing (c). In this case, excellent crush strength is exhibited.
In an embodiment, the aging may be carried out at room temperature or at 20 to 30° C. for 12 to 96 hours or 20 to 30 hours. Within these ranges, excellent crush strength is exhibited.
A method of the aging is not specifically limited so long as the method is conventionally used in the art.
In an embodiment, the method of preparing the catalyst composition may further comprise drying the molded material before c) the firing.
In an embodiment, the drying may be carried out at room temperature or at 20 to 30° C. for 12 to 96 hours or 10 to 15 hours. Within these ranges, excellent crush strength is exhibited.
The binder according to the present disclosure is a mixed metal hydroxide and is applied to the multi-ingredient-based metal oxide catalyst.
In an embodiment, the mixed metal hydroxide comprises aluminum and magnesium. In this case, excellent crush strength, butene conversion rate and butadiene selectivity are exhibited.
In another embodiment, the mixed metal hydroxide is hydrotalcite. In this case, excellent crush strength, butene conversion rate and butadiene selectivity are exhibited.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
A coprecipitation-fired a molybdenum-bismuth-iron-cobalt (Mo12Bi1Fe1Co8) composite oxide catalyst having a specific surface area of 5 M2 g−1 and a pore volume of 0.03 ccg−1 was ground into a fine powder at room temperature using a ball mill, and then, hydrotalcite having a plate structure was added thereto in an amount of 1.25% by weight, followed by mixing. Thereto, double-distilled water maintained at 0° C. was added in an amount of 50 parts by weight based on 100 parts by weight of the mixed powder and mixed, thereby preparing a slurry. The slurry was injection-molded under a pressure of 80-100 kgcm−2, thereby preparing a globular pellet. The prepared pellet was aged at room temperature for 24 hours and then dried for 24 hours. In order to enhance strength, the dried pellet was fired (heat-treated) at 300° C. for two hours, thereby preparing a final catalyst composition.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 1.3% by weight based on 100% by weight of the mixed powder.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 1.3% by weight based on 100% by weight of the mixed powder and firing was carried out at 350° C.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 2.5% by weight based on 100% by weight of the mixed powder.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 2.5% by weight based on 100% by weight of the mixed powder and firing was carried at 350° C.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 3.0% by weight based on 100% by weight of the mixed powder.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was added in an amount of 3.0% by weight based on 100% by weight of the mixed powder and firing was carried out at 350° C.
A catalyst composition was prepared in the same manner as in Example 1, except that silica instead of the hydrotalcite was added in an amount of 2.0% by weight based on 100% by weight of the mixed powder.
A catalyst composition was prepared in the same manner as in Example 1, except that alumina instead of hydrotalcite was added in an amount of 1.25% by weight based on 100% by weight of the mixed powder.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was not added.
A catalyst composition was prepared in the same manner as in Example 1, except that the hydrotalcite was not added and the firing was carried out at 350° C.
A catalyst composition was prepared in the same manner as in Example 1, except that aluminum hydroxide instead of the hydrotalcite was added in an amount of 1.25% by weight based on 100% by weight of the mixed powder.
Each of the prepared catalyst compositions was reacted at a reaction temperature of 380° C. using a fixed-bed reactor such that a reaction product had a composition ratio of 1-butene:oxygen:helium of 5:12:84. Subsequently, a composition, etc. of generated butadiene was analyzed using gas chromatography (GC).
Properties of the catalyst compositions prepared according to Examples and Comparative Examples were measured according to methods below, and results are summarized in Tables 1 and 2 below.
As shown in Table 1, it can be confirmed that the catalyst composition according to the present disclosure exhibits excellent crush strength, conversion rate and selectivity, etc., when compared with the catalyst compositions (Comparative Examples 1 to 5) which do not comprise the mixed metal hydroxide.
In addition, it can be confirmed that a crystal structure of the catalyst is maintained since the catalyst composition according to the present disclosure binds to the multi-ingredient-based metal oxide catalyst in which the mixed metal hydroxide is fired, crush strength of the pellet may be easily controlled since a use amount of the mixed metal hydroxide is not specifically limited, catalyst activity reduction due to an increased addition amount of the mixed metal hydroxide may be controlled by changing the composition of the catalyst, crush strength is only increased without catalyst activity change up to 2.5% by weight of the mixed metal hydroxide, and subsidiary effects such as side-reaction decrease due to basic properties of the mixed metal hydroxide are exhibited.
However, in the case in which a binder is added to a multi-ingredient-based metal oxide catalyst before firing, deformation of a coprecipitated structure is caused, and it is difficult to mold a fired a multi-ingredient-based metal oxide catalyst with water or a silica sol-based binder. In addition, when, in order to minimize deformation of a coprecipitated structure, only water or a small amount of binder is added as a binder, crush strength of a prepared pellet is decreased.
Next, as illustrated in
In addition, as illustrated in
As shown in Table 2 and : butene conversion rate in catalyst composition not comprising mixed metal hydroxide, and
: 1,3-butadiene conversion rate in catalyst composition not comprising mixed metal hydroxide).
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2013-0139783 | Nov 2013 | KR | national |
| 10-2014-0158524 | Nov 2014 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2014/010955 | 11/14/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/072779 | 5/21/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4487850 | Li | Dec 1984 | A |
| 5104987 | King | Apr 1992 | A |
| 5449821 | Neumann et al. | Sep 1995 | A |
| 5507980 | Kelkar et al. | Apr 1996 | A |
| 5922925 | Akporiaye | Jul 1999 | A |
| 6586360 | Ingallina et al. | Jul 2003 | B1 |
| 7622623 | Fridman | Nov 2009 | B2 |
| 8188328 | Fridman | May 2012 | B2 |
| 20020025908 | Ingallina | Feb 2002 | A1 |
| 20030176275 | Fraaije | Sep 2003 | A1 |
| 20110172475 | Peters | Jul 2011 | A1 |
| 20130095323 | Grafov | Apr 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 10-3721735 | Apr 2014 | CN |
| 10-3785450 | May 2014 | CN |
| 1 057 530 | Dec 2000 | EP |
| 2842625 | Mar 2015 | EP |
| 51-105992 | Sep 1976 | JP |
| 57-123122 | Jul 1982 | JP |
| 09-511211 | Nov 1997 | JP |
| 2001-009276 | Jan 2001 | JP |
| 2011-512236 | Apr 2011 | JP |
| 2013-538679 | Oct 2013 | JP |
| 10-1996-0010530 | Apr 1996 | KR |
| 1020090103424 | Oct 2009 | KR |
| 1020110106181 | Sep 2011 | KR |
| 1020130046214 | May 2013 | KR |
| 2009044999 | Apr 2009 | WO |
| 2012030891 | Mar 2012 | WO |
| 2013161702 | Oct 2013 | WO |
| Entry |
|---|
| Maurizio Bellotto et al., “Hydrotalcite Decomposition Mechanism: A Clue to the Structure and Reactivity of Spinel-like Mixed Oxides”, Journal of Physical Chemistry, vol. 100, No. 20, 1996, pp. 8535-8542. |
| Nieto, J.M. Lopez et al.; Preparation, characterization and catalytic properties of vanadium oxides supported on calcined Mg/Al-hydrotalcite; Applied Catalysis A: General 132: 41-59 (1995). |
| Blasco, T. et al.; Influence of the Acid-Base Character of Supported Vanadium Catalysts on Their Catalytic Properties for the Oxidative Dehydrogenation of n-Butane; Journal of Catalysis 157: 271-282 (1995). |
| Nieto, J.M. Lopez et al.; Selective Oxidation of n-Butane and Butenes over Vanadium-Containing Catalysts; Journal of Catalysis 189: 147-157 (2000). |
| Number | Date | Country | |
|---|---|---|---|
| 20150352534 A1 | Dec 2015 | US |
