KR101536566B1 - Process For Preparing 1-Butanol Containing Higher Alcohols From Ethanol And Catalyst Therefor - Google Patents

Abstract

The present invention relates to a composite oxide M _a Cu _b Mg _c Al ₂ O _x wherein M is at least one metal selected from the group consisting of Cr, Sn, Zn, Fe, Co, Ni, Ru, Re, Pd and Pt, a = 0.0 ~ 2.0, b = 0.05 ~ 2.0, c = 3 ~ 8, x is a number matching the overall oxidation state of the compound] composite oxide M _a Cu _b Mg _c Al ₂ O _x [formula, M a is Cr, A = 0.0 to 2.0, b = 0.05 to 2.0, c = 3 to 8, x is at least one metal selected from the group consisting of Sn, Zn, Fe, Co, Ni, Ru, Re, Pd and Pt. represents the number of matching the overall oxidation state; and / or a composite oxide N _a Cu _b Mg _c Al ₂ O _x [equation, N denotes a metal selected from the group consisting of Co, Ni, Ru, Pd and Pt, a 1-butanol-containing higher alcohol production catalyst composition by catalytic condensation reaction of ethanol, wherein x = 0.01 to 2.0, b = 0.0 to 0.2, c = 3 to 8, .
The catalyst composition according to the present invention has a high conversion and a high selectivity, and not only has high long-term reaction stability, but also excellent activity recovery and durability after regeneration.

Description

Process for Preparing 1-Butanol Containing High Alcohols from Ethanol and Catalyst Therefor,

The present invention relates to a process for producing a 1-butanol-containing higher alcohol from ethanol and a catalyst therefor, and more particularly to a process for producing a 1-butanol-containing higher alcohol from ethanol by reacting ethanol in the presence of a complex oxide catalyst modified with selected metals, And a high-performance catalyst for use in the process.

Biofuels are attracting attention as measures against global warming. Particularly, ethanol is synthesized by converting sugar obtained from sugarcane or beet (sugar beet) by fermentation method. Recently, however, technology for synthesizing bioethanol from various biomass such as waste of agriculture and forestry products, green algae, Bar, and bioethanol production have been rapidly increasing, they have become a new eco-friendly raw material.

Currently, biofuels to replace petroleum transportation fuels are spreading around bioethanol. However, bioethanol is not the optimal fuel for existing petroleum based infrastructure. Bioethanol has a low energy density, low fuel efficiency, high hydrophilicity, and high causticity. Therefore, there is a problem that a new storage infrastructure should be built, such as a separate storage and mixing facility at a gas station and a water inflow prevention facility installed at a gas station have. In addition, there is a problem that a specially manufactured vehicle called FFV (Flexible fuel vehicle) must be used in order to use the fuel at a high concentration.

Butanol has a higher energy density than ethanol, so it has less fuel consumption loss when mixed with gasoline. It also has better properties such as vapor pressure, solubility in water and corrosiveness compared to ethanol, so it can be used without changing the distribution infrastructure of gasoline , Can be mixed and stored at refineries, and can be used directly in a gasoline engine, eliminating the need for retrofitting the vehicle.

In addition, 1-butanol is used in a variety of applications such as paints, solvents, and plasticizers, and butylaldehyde is used as a raw material for the production of 2-ethylhexanol for plasticizers. Butylaldehyde and 1-butanol are produced by hydroformylation of propylene obtained from petroleum as a raw material to produce butylaldehyde, which is hydrogenated to synthesize 1-butanol.

1-butanol can be produced biologically like bioethanol, but it can also be produced from (bio) ethanol by catalytic condensation reaction. The following documents are known for the production of 1-butanol by the catalytic condensation reaction of ethanol.

WO 1999/38822 discloses a technique for converting ethanol into acetaldehyde, diethyl ether, 1-butanol, 1,3-butadiene and the like using a calcium phosphate-based catalyst whose Ca / P molar ratio is controlled, And the selectivity to butanol is low.

In the present invention, hydroxyapatite having a different Ca / P molar ratio is used as a catalyst and ethanol is used as a catalyst. Although it has been disclosed to obtain a mixture containing ethylene, 1-butanol and 1,3-butadiene, the conversion and the selectivity to 1-butanol are unsatisfactory.

Korean Patent Registration No. 1113050 discloses the production of high molecular weight alcohols such as 1-butanol, hexanol, octanol, decanol and mixtures thereof from ethanol in the presence of a calcium phosphate compound catalyst. However, there is a problem in that the molar ratio of phosphorus and calcium is required to be finely controlled at the time of preparing the calcium phosphate-based catalyst, and the conversion and the selectivity to 1-butanol are not high.

DuPont, on the other hand, is a process for producing a hydrotalcite compound, which is obtained by arbitrarily adding an additional metal component to a hydrotalcite compound composed of Al and Mg components and then calcining the hydrotalcite structure under the conditions of partially decomposing or completely decomposing the hydrotalcite structure, (PCT / US2008 / 07443, PCT / US2008 / 074026, PCT / US2009 / 032197, PCT / US2009 / 032199 and U.S. Published Patent Application 2009/0054672A1). DuPont has proposed at least one additional metal component selected from Zn, Ni, Pd, Pt, Co, Fe, Cu, Cr, Rh, Ru, Au and Ir, but actually contains Cu, And the maximum yield of butanol was only 19.7% in the resultant case, illustrating the results of a drastic decrease in catalyst lifetime.

In addition, although a method of synthesizing butanol using a Cu-Mg-Al mixed oxide catalyst (Catalysis Today 147 (2009) 231-238) has already been disclosed, the catalyst prepared by the simple co- There is a problem that the production method is different from the catalyst system of the complex oxide type produced by calcination through hydrotalcite in the prior art and the selectivity of butylaldehyde and 1-butanol is remarkably low.

In addition, a technique (J. Org. Chem., 1957 (11), 540-542) for obtaining 47% of 1-butanol at an ethanol conversion of 13% under MgO-K ₂ CO ₃ -CuCrOx catalyst and an alkali metal- A technique (USP 5300695) for obtaining a higher alcohol by condensing a lower alcohol under L-type zeolite is known.

However, the catalysts disclosed so far have insufficient performance to be utilized as industrial catalysts. In order to have industrially useful properties, the conversion of ethanol and the selectivity of main products are improved while suppressing the formation of by-products, There is a need to solve the reaction stability problem.

The present inventors have conducted studies on a technique for producing 1-butanol-containing higher alcohols from ethanol by catalytic condensation reaction, and have found that they are excellent in ethanol conversion and selectivity of 1-butanol-containing higher alcohols, Which is superior in activity recovery and durability according to the present invention.

The present inventors have found that by reacting a catalyst comprising a complex oxide of the following formula (1) with a complex oxide of the formula (2) and / or a complex oxide of the formula (3) in the presence of the obtained catalyst composition, And selectivity, and have completed the present invention.

[Chemical Formula 1]

M _a Cu _b Mg _c Al ₂ O _x

M is at least one metal selected from the group consisting of Cr, Sn, Zn, Fe, Co, Ni, Ru, Re, Pd and Pt, a = 0.0 to 2.0 (preferably 0.0 to 1.0) b = 0.05 to 2.0 (preferably 0.1 to 1.0), c = 3 to 8 (preferably 4 to 6), and x denotes the number of times the total oxidation number of the compound is adjusted;

(2)

N _a Cu _b Mg _c Al ₂ O _x

Wherein N represents two or more metals selected from the group consisting of Co, Ni, Ru, Re, Pd and Pt, a = 0.01 to 2.0 (preferably 0.02 to 1.0) c = 3 to 8 (preferably 4 to 6), and x represents the number of times the total oxidation number of the compound is adjusted;

(3)

N _a Cu _b Mg _c Al ₂ O _x

Wherein n represents one metal selected from the group consisting of Co, Ni, Ru, Pd and Pt, a = 0.01 to 2.0 (preferably 0.02 to 1.0), b = 0.0 to 0.2, c = 3 To 8 (preferably 4 to 6), and x represents the number of times the total oxidation number of the compound is adjusted.

According to the present invention, ethanol is catalytically condensed in the presence of a catalyst composition prepared by suitably combining and mixing the complex oxide represented by the general formula (1) and the complex oxide represented by the general formula (2) and / or the complex oxide represented by the general formula (3) Can be obtained with high conversion and high selectivity. The catalyst composition according to the present invention not only has a high long-term reaction stability, but also has excellent activity recovery and durability after regeneration.

A first object of the present invention is to provide a catalyst composition comprising a complex oxide of the following formula (1), a complex oxide of the formula (2) and / or a complex oxide of the formula (3) To provide a catalyst composition comprising:

[Chemical Formula 1]

M _a Cu _b Mg _c Al ₂ O _x

M is at least one metal selected from the group consisting of Cr, Sn, Zn, Fe, Co, Ni, Ru, Re, Pd and Pt, a = 0.0 to 2.0 (preferably 0.0 to 1.0) b = 0.05 to 2.0 (preferably 0.1 to 1.0), c = 3 to 8 (preferably 4 to 6), and x denotes the number of times the total oxidation number of the compound is adjusted;

(2)

N _a Cu _b Mg _c Al ₂ O _x

Wherein N represents two or more metals selected from the group consisting of Co, Ni, Ru, Re, Pd and Pt, a = 0.01 to 2.0 (preferably 0.02 to 1.0) c = 3 to 8 (preferably 4 to 6), and x represents the number of times the total oxidation number of the compound is adjusted;

(3)

N _a Cu _b Mg _c Al ₂ O _x

Wherein n represents one metal selected from the group consisting of Co, Ni, Ru, Pd and Pt, a = 0.01 to 2.0 (preferably 0.02 to 1.0), b = 0 to 0.2, c = 3 To 8 (preferably 4 to 6), and x represents the number of times the total oxidation number of the compound is adjusted.

In this case, the complex oxide represented by the general formula (3) is specifically Co _a Cu _b Mg _c Al ₂ O _x , Ni _a Cu _b Mg _c Al ₂ O _x , Ru _a Cu _b Mg _c Al ₂ O _x , Pd _a Cu _b Mg _c Al ₂ O _x or Pt _a Cu _b Mg _c Al ₂ O _x wherein a = 0.01 to 2.0 (preferably 0.02 to 1.0), b = 0 to 0.2, c = 3 to 8 (preferably 4 To 6), and x represents the number of times the total oxidation number of the compound is matched. More preferably, Co _a Mg _c Al ₂ O _x , Ni _a Mg _c Al ₂ O _x , Ru _a Mg _c Al ₂ O _x , Pd _a Mg _c Al ₂ O _x or Pt _a Mg _c Al ₂ O _x wherein a, c and x are as defined above. ≪ / RTI >

A second object of the present invention is to provide a process for the production of a catalyst for catalytic condensation reaction of ethanol in the presence of a catalyst composition prepared by adding or mixing a complex oxide represented by the general formula (1) and / or a complex oxide represented by the general formula (2) Containing alcohol from ethanol to produce a higher alcohol containing 1-butanol.

Hereinafter, the present invention will be described in more detail.

The oxide catalyst made of Mg-Al as described above in the state of the art has a function of condensing ethanol whether it is derived from a Mg-Al hydrotalcite compound through calcination or coprecipitated in the form of oxide (water) . However, the Mg-Al oxide catalysts have low activity and are easily inactivated, resulting in a drastic decrease in catalyst performance. Up to now, most of the patents and literature have reported that, in order to improve the performance of a catalyst composed of Mg-Al, a catalyst having a Cu-Mg-Al composition in which a Cu component excellent in dehydrogenation ability to a hydroxyl group is added to Mg- . This is because, in order to produce higher alcohols containing 1-butanol from ethanol, ethanol is first dehydrogenated to produce acetaldehyde, which is subjected to aldol condensation.

In addition, when a Cu component is added to Mg-Al, there is also a positive effect of suppressing the by-product of an ether compound by an alcohol-alcohol dehydration reaction.

On the other hand, the doubling of the dehydrogenation capacity of the catalyst has a problem in that the selectivity of 1-butanol deteriorates as a result of promoting various side reactions that can be induced from alcohol and aldehyde compounds. For example, the by-products of acetal compounds and ester compounds (such as ethyl acetate, ethyl butyrate, butyl butyrate) are increased. In order to alleviate this problem, the catalyst performance is improved by adding components such as Co and Ni.

The inventors of the present invention have found that when the content of the above-mentioned components and the like is higher than that of the copper component when the hydrogenation ability is improved by adding components such as Co and Ni, which have a hydrogenation ability relatively higher than that of the Cu component, It was found that the effect of improving the selectivity was insignificant at the low temperature and the rate of decrease of the catalyst performance with the elapse of the operation time was large and the stability of the long term reaction of the catalyst was remarkably lowered.

In the catalyst of the present invention, the catalyst of formula (1) has a catalyst composition in consideration of the above-mentioned point. In the oxide of Al: Mg having an atomic ratio of 2: 3 to 8, the atomic ratio of Cu is used in the range of 0.05 to 2.0, preferably 0.1 to 1.0 , The conversion efficiency was not improved at lower temperatures, and the byproducts of aldehydes and esters were high at high temperatures.

A composition catalyst composed of the Cu-Mg-Al component described above in Formula 1 may be used alone or in combination with one or more components selected from Cr, Sn, Zn, Fe, Co, Ni, Ru, Re, Lt; / RTI > may be used. At this time, Cr in the M component is well known as a component that helps to double the dehydrogenation capacity of alcohol together with copper, and the same amount of copper can be used as much as the atomic ratio of copper. It is preferable that the component other than Cr in M is used at 50% or less of copper. This is because, as described above, it shows the characteristic of decreasing the conversion rate of ethanol and stability of long-term reaction during the excessive use.

On the other hand, the inventors of the present invention have found that when the Mg-Al oxide is improved to have a relatively larger hydrogenating ability than the dehydrogenating ability such as Co, Ni, Ru, Re, Pd and Pt, the conversion of ethanol is much lower than that of the Mg- , And the byproducts of ethers such as diethyl ether tended to increase, but the byproducts of aldehydes and ester compounds were remarkably reduced, and the selectivity of 1-butanol was increased.

In the present invention, the composite oxide of the general formulas (2) and (3) is a composition catalyst considering the above-mentioned points, and the complex oxide of the general formula (3) is Co _a Cu _b Mg _c Al ₂ O _x , Ni _a Cu _b Mg _c Al ₂ O _x , Ru _a Cu _b Mg _c Al ₂ O _x , Pd _a Cu _b Mg _c Al ₂ O _x, or Pt _a Cu _b Mg _c Al ₂ O _x wherein a = 0.01 to 2.0 (preferably 0.02 to 1.0) , b represents 0 to 0.2, c represents 3 to 8 (preferably 4 to 6), and x represents the number of times the total oxidation number of the compound is matched), more preferably at least one compound selected from the group consisting of , Co _a Mg _c Al ₂ O _x , Ni _a Mg _c Al ₂ O _x , Ru _a Mg _c Al ₂ O _x , Pd _a Mg _c Al ₂ O _x, or Pt _a Mg _c Al ₂ O _x , a, c and x are the same as defined above]. That is, the composite oxide catalyst of the formula (3) means a composition catalyst in which each of the N components independently forms a composite oxide with Mg-Al oxide, and at least two of the N components are Mg- And a composite catalyst constituting a composite oxide.

The content of the N component in the complex oxide of the general formulas (2) and (3) can be generally within the range of 0.05 to 2.0, preferably 0.1 to 1.0 in the composition of Mg: Al atomic ratio of 2: 3 to 8. When it is lower than the above range, the effect of improving the selectivity is lowered, and when it is higher than the above range, the lowering of the conversion rate is increased.

In the catalysts having the compositions of formulas (2) and (3), a small amount of copper component may be added in order to control the conversion of ethanol, and the content thereof (that is, the value of b) may be preferably used in the range of 0.0 to 0.2. When it is higher than the above range, the selectivity improving effect of the 1-butanol-containing higher alcohol is decreased.

In one preferred embodiment of the present invention, in the step of condensing ethanol to produce a 1-butanol-containing higher alcohol, complex oxides having the composition of the formulas (1), (2) and (3) In the case of using a catalyst prepared by physically mixing, it is possible to provide a catalyst which simultaneously enhances the conversion of ethanol as a reactant and the selectivity of 1-butanol-containing higher alcohol as a product, and has excellent long-term reaction stability.

For example, a mixture of complex oxides prepared by physically mixing the composite oxide of Formula 1 and the composite oxide of Formula 2 at a ratio of 5 to 50 wt%: 95 to 50 wt% can be exemplified. Likewise, a mixture of complex oxides prepared by physically mixing the complex oxide of the general formula (1) and the complex oxide of the general formula (3) in a proportion of 5 to 50 wt%: 95 to 50 wt% can be exemplified. At this time, when the content of the complex oxide represented by the general formula (1) is higher than the above range, it is advantageous in terms of the conversion of ethanol and the selectivity is low. When the content is less than the above range, the conversion of ethanol and the long term reaction stability are deteriorated.

According to one preferred embodiment of the present invention, the above-mentioned catalyst composition can be prepared by adding a mixture of the composite oxide of the formula (2) and the composite oxide of the formula (3) to the composite oxide of the formula (1). In this case, the mixture of the complex oxide represented by the general formula (2) and the complex oxide represented by the general formula (3) is contained in a proportion of 5 to 50 wt%: 95 to 50 wt%, particularly 10 to 50 wt%: 90 to 50 wt% . In the mixture of the composite oxide of the formula (2) and the composite oxide of the formula (3), the complex oxide of the formula (3) is used in an amount of 5 to 95: 95 to 5 wt%, particularly 10 to 90: 90 to 10 wt% .

In the present invention, the complex oxide represented by the general formula (1), the complex oxide represented by the general formula (2) and the complex oxide represented by the general formula (3) have different compositions. Particularly, the complex oxide represented by the general formula (1) and the complex oxide represented by the general formula Is preferably selected.

In the present invention, the complex oxides of formulas (1) to (3) can be prepared by first preparing a hydrotalcite compound from precursors of respective metals, and then subjecting to a complete calcination process. Alternatively, the complex oxides of formulas (1) to (3) can be prepared by first preparing oxides from precursors of respective metals by coprecipitation followed by calcination. When preparing the (water) oxide form by the co-precipitation method, a cleaning process for removing unnecessary cations and / or anions from the slurry, which is provided from the co-precipitant and the catalyst component precursor, is very difficult. Thus, judging from a process aspect of the catalyst preparation process, it may be more efficient to go through the process of first preparing the hydrotalcite form.

Methods for preparing hydrotalcite compounds containing +2 and +3 metal cations are well known in the literature and patents (Ref. Catalysis today 11 (2) 173-301 (1991), Journal of catalysis 173, 115-121 ), US7705192). These documents are incorporated into the present invention by reference.

However, even if the metal-containing complex oxide having the composition represented by the general formulas (1), (2) and (3) is prepared by the hydrotalcite route or the (ox) oxide route, the calcination process for producing the oxide can be carried out in the same manner. The calcination is carried out at a temperature of, for example, 300 to 800 DEG C, preferably 450 to 700 DEG C, particularly 550 to 650 DEG C for 1 to 20 hours, preferably 3 to 10 hours, to be. In particular, when prepared by the hydrotalcite route, it may be necessary to completely decompose the carbonate anion.

The metal-containing complex oxide represented by the general formula (1), the general formula (2) and the general formula (3) prepared under the above conditions can be subjected to a physical mixing process for use as an ethanol condensation catalyst according to the present invention. It is necessary to crush it to 50 mesh or less, preferably 70 mesh or less, particularly 100 mesh.

The form of the catalyst composition according to the present invention is not particularly limited and may be used in the form of a powder itself or in the case of a gas phase reaction in a fixed phase, any shaping assistant may be used to form a shaped body such as a sphere, pellet, cylinder, Can be used.

In a preferred embodiment of the present invention, the composite oxides may have a particle or powder form, and they are preferably mixed and / or kneaded in the form of a homogeneous mixture, and then molded into a desired shape.

Below, the reaction of catalytically condensing ethanol with a catalyst composition according to the present invention to produce 1-butanol-containing higher alcohols is described.

The catalytic condensation reaction of ethanol can be carried out by a process comprising the steps of:

(1) charging the catalyst composition into the reactor,

(2) feeding ethanol to the reactor while maintaining a specific reaction temperature and reaction pressure to perform a catalytic condensation reaction of ethanol,

(3) supplying an additional gas to the reactor simultaneously with the ethanol,

(4) Separation or purification of the obtained butanol.

The catalytic condensation reaction of ethanol can be carried out in a gas phase or a liquid phase, preferably in a gas phase.

Although the reaction temperature and the reaction pressure of the catalytic condensation reaction of ethanol are not particularly limited, the reaction temperature can be generally selected from the range of 150 to 500 ° C, preferably 200 to 350 ° C, At a pressure of from atmospheric pressure to 300 psi, preferably atmospheric pressure to 200 psi, especially atmospheric pressure to 10 to 100 psi. When the reaction temperature is lower than the above range, the conversion of ethanol is lowered and the yield of the product is lowered. When the reaction temperature is higher than the above range, the selectivity may be lowered due to formation of saturated and unsaturated hydrocarbons of methane, C2, C3 and C4 . Further, if the reaction pressure is higher than the above range, the conversion rate can be reduced.

The above catalytic condensation reaction of ethanol can be carried out in the presence of a gas selected from the group consisting of hydrogen, nitrogen or a mixture thereof for maintaining the activity of the catalyst. Optionally, the gas may further comprise one or more gases selected from the group consisting of oxygen, carbon dioxide and inert gas.

The reactor capable of carrying out the catalytic condensation reaction of ethanol using the catalyst composition according to the present invention is not particularly limited, but it may be preferable to use a fixed bed continuous reactor in terms of the industrial aspect.

Purification or separation of the obtained butanol and hexanol and the like can be carried out by a method commonly known in the art, for example, distillation, extraction and the like.

In the present specification, the reaction temperature and the reaction pressure mentioned above may mean the temperature and the pressure in the reactor.

The present invention will be described in more detail by way of examples. The following examples are given to illustrate the invention and are not to be construed as limiting the invention in any manner, and all such modifications and variations are intended to be included within the scope of the present invention.

Production Example 1 : Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _x Manufacturing

A solution A was prepared by dissolving 4.65 g of Cu (NO ₃ ) ₂ .3H ₂ O, 143.24 g of Mg (NO ₃ ) ₂ .6H ₂ O and 72.27 g of Al (NO ₃ ) ₃ .9H ₂ O in deionized water . 91.87 g of Na ₂ CO ₃ is dissolved in deionized water to prepare solution B. Prepare 2M NaOH solution (solution C).

200 ml of deionized water is poured into the beaker, and the solution A and the solution B are added dropwise at the same time to carry out the coprecipitation process, and the pH 9.5 is maintained using the mobile solution C. When both Solution A and Solution B are dropped, the pH is adjusted to 10.0 to 10.2, and the pH is confirmed after stirring for about 30 minutes.

The resulting reaction mixture was aged at 60 DEG C for 12 hours or more, filtered and washed, dried at 100 DEG C for 5 hours or more, and calcined at 600 DEG C for 6 hours to obtain a composite oxide having the above composition formula.

Production Example 2 : Preparation of Cr _0.2 Cu _0.2 Mg _5.8 Al _2.0 O _x

2.21 g of Cu (NO ₃ ) ₂ .3H ₂ O, 68.08 g of Mg (NO ₃ ) ₂ .6H ₂ O and 34.34 g of Al (NO ₃ ) ₃ .9H ₂ O in deionized water to prepare Solution A do. 44.63 g of Na ₂ CO ₃ is dissolved in deionized water to prepare solution B. A 2M NaOH solution (solution C) is prepared, and 3.67 g of Cr (NO ₃ ) ₃ .9H ₂ O is dissolved in deionized water to prepare solution D.

100 ml of deionized water was poured into the beaker, and the solution A and the solution B were added dropwise at the same time to carry out the coprecipitation process, and the pH 9.5 was maintained using the mobile solution C. When both solution A and solution B are dropped, the pH is adjusted to 10 to 10.2, and the pH is confirmed after stirring for about 30 minutes. The resultant reaction mixture was hydrothermally aged at 60 ° C. for 12 hours or more, the temperature was raised to drop the solution D at room temperature, and the pH of the solution was kept at 9.5 using the mobile solution C.

The resultant reaction mixture was warmed, aged at 80 DEG C for 5 hours, filtered and washed, dried at 100 DEG C for 5 hours or more, and calcined at 600 DEG C for 6 hours to obtain a composite oxide having the above composition formula.

Production Example 3 : Preparation of Co _0.2 Ni _0.2 Mg _5.8 Al _2.0 O _x

A composite oxide having the above composition formula was obtained by proceeding in the same manner as in Production Example 1, except that cobalt nitrate (Co) and nickel nitrate (Ni) were used instead of copper nitrate (Cu) in Solution A.

Production Example 4 : Preparation of Ru _0.2 Mg _5.8 Al _2.0 O _x

Solution A is prepared by dissolving 69.12 g of Mg (NO ₃ ) ₂ .6H ₂ O and 34.87 g of Al (NO ₃ ) ₃ .9H ₂ O in deionized water. 45.22 g of Na ₂ CO ₃ is dissolved in deionized water to prepare solution B. A 2M NaOH solution (solution C) is prepared, and 2.26 g of RuCl ₃ .2H ₂ O is dissolved in deionized water to prepare solution D.

100 ml of deionized water was poured into the beaker, and the solution A and the solution B were added dropwise at the same time to carry out the coprecipitation process, and the pH 9.5 was maintained using the mobile solution C. When both solution A and solution B are dropped, the pH is adjusted to 10 to 10.2, and the pH is confirmed after stirring for about 30 minutes. The resulting reaction mixture is aged at 60 DEG C for at least 12 hours, the temperature is raised, the solution D is dropped at room temperature, and the pH of the solution is maintained at 9.5 using the mobile solution C.

The resultant reaction mixture was heated again, aged at 80 DEG C for 5 hours, filtered and washed, dried at 100 DEG C for 5 hours or more, and calcined at 600 DEG C for 6 hours to obtain a composite oxide having the above composition formula.

Production Examples 5 to 10

Using the same method as in Preparation Example 1, to prepare a complex oxide having the following formula, respectively: Co _{0 .8 .2} Mg ₅ Al ₂ O _{x .0} (Preparation Example _{5), Co 0 .4 Mg 5} . ₈ Al _{2 .0} O _x (Production example _{6), Ni 0.2 Mg 5.8 Al} 2.0 O x ( Preparation example _{7), Ni 0 .4 Mg 5} .8 Al 2 .0 O x ( Preparation 8), Cu _{0. 2 Co 0 .2 Mg 5 .6 Al} 2 .0 O x (Preparation Example 9) and _{Cu 0 .02 Co 0 .18 Mg 5} .8 Al 2 .0 O x (Preparation Example 10)

Production Example 11 : Preparation of Co _0.4 Mg _5.8 Al _2.0 O _x (prepared by a hydroxide route)

5.38 g of Co (NO ₃ ) ₂揃 6H ₂ O, 69.45 g of Mg (NO ₃ ) ₂揃 6H ₂ O and 35.0 g of Al (NO ₃ ) ₃揃 9H ₂ O were dissolved in deionized water to prepare Solution A . 5 M NaOH solution (solution B) is prepared.

100 ml of deionized water is poured into the beaker, and the solution A and the solution B are simultaneously added dropwise to perform the coprecipitation process. At this time, the pH was maintained in the range of 9-10. After completing the coprecipitation process, set the pH to 10.0 ~ 10.2 and check the pH after stirring for about 30 minutes. Thereafter, the aging process is performed at 80 DEG C for 12 hours or more. Filtered and washed, dried at 100 ° C for 5 hours or more, and then calcined at 600 ° C for 6 hours to prepare a catalyst.

100 ml of deionized water is poured into the beaker, and the solution A and the solution B are simultaneously added dropwise to conduct coprecipitation, and the pH of the mobile phase is maintained in the range of 9 to 10. When the coprecipitation process is completed, the pH is adjusted to 10 to 10.2, and the pH is re-confirmed after approximately 30 minutes of stirring.

The resulting reaction mixture was aged at 80 DEG C for 12 hours or more, filtered and washed, dried at 100 DEG C for 5 hours or more, and calcined at 600 DEG C for 6 hours to obtain a composite oxide catalyst having the above composition formula.

The composite oxides obtained in the above Preparation Examples were used in the following examples by pulverizing the particle size uniformly to 100 mesh or less.

Example 1 20 wt% Cu _0.2 Mg _5.8 Al _2.0 O _x + 80 wt% Co _0.2 Ni _0.2 Mg _5.8 Al _2.0 O _x

20% by weight of Cu _0.2 Mg _5.8 Al _2.0 O _x (Preparation Example 1) and 80% by weight of Co _0.2 Ni _0.2 Mg _5.8 Al _2.0 O _x (Preparation Example 3) were uniformly mixed, To 40 mesh size to prepare a catalyst powder.

2 g of the catalyst powder was charged in a 1/2 inch tubular reactor and activated at 270 캜 in a 5% hydrogen atmosphere.

The continuous reaction was performed while supplying ethanol with a mixed gas of hydrogen and nitrogen (50%: 50% v / v) at an introduction rate of WHSV = 0.6 hr ^-1 . The reaction temperature was controlled in the range of 270 ~ 280 ℃ and the reaction pressure was in the range of 15 ~ 60 psi.

The products were quantitatively analyzed by measuring by gas chromatography, and the results of the obtained reaction experiments are shown in Table 2 below.

The conversion (%) of the reactant (ethanol) and the selectivity of the product (1-butanol) were calculated by the following equations (1) and (2), respectively.

[Equation 1]

Reactant conversion ratio (%) = (number of moles of carbon in the reacted ethanol / number of moles of total carbon in the reactant) 100

&Quot; (2) "

Product selectivity (%) = (moles of carbon in the product / moles of carbon in the reacted ethanol) 100

Example 2 : 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _x + 80 wt% Co _{0 .2} Mg _{5 .8} Al _{2 .0} O _x

Except that 20 wt% of Cu _0.2 Mg _5.8 Al _2.0 O _x (Preparation Example 1) and 80 wt% of Co _0.2 Mg _5.8 Al _2.0 O _x (Production Example 5) were used in the same procedure as in Example 1 Followed by an ethanol conversion reaction. The results of the reactivity test are shown in Table 2.

Example 3 : 20 wt% Cr _0.2 Cu _0.2 Mg _5.8 Al _2.0 O _x + 80 wt% Co _0.2 Mg _5.8 Al _2.0 O _x

Of 20% by weight _{Cr 0 .2 Cu 0 .2 Mg 5} .8 Al 2 .0 O x (Preparation Example 2) and 80 wt% _{Co 0 .2 Mg 5 .8 Al 2} .0 O x (Production Example 5) was used instead of the ethanol conversion reaction of Example 1. The results of the reactivity test are shown in Table 2.

Example  4 to 6

Substantially the same procedures and process conditions as in Example 1 were used, except that the catalysts containing the complex oxides obtained in Production Example 1, Production Example 4 and Production Examples 7 to 8 in the kind and content shown in Table 1 were used Followed by ethanol conversion reaction. The results of the reactivity test are shown in Tables 2 and 3.

Example No. Complex oxide
Manufacturing Example No. Catalyst composition and content Example 1 Production Example 1
Production Example 3 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x
80wt% Co 0 .2 Ni 0 .2} Mg 5 .8 Al 2 .0 O x Example 2 Production Example 1
Production Example 5 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x
80wt% Co 0 .2 Mg 5 .8} Al 2 .0 O x Example 3 Production Example 2
Production Example 5 _{20wt% Cr 0 .2 Cu 0 .2} Mg 5 .8 Al 2 .0 O x
_{80wt% Co 0 .2 Mg 5 .8} Al 2 .0 O x Example 4 Production Example 1
Production Example 4 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _x
80 wt% Ru _{0 .2} Mg _{5 .8} Al _{2 .0} O _x Example 5 Production Example 1
Production Example 7 10 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _x
90 wt% Ni _{0. 2} Mg _{5 .8} Al _{2 .0} O _x Example 6 Production Example 1
Production Example 8 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x
80wt% Ni 0 .4 Mg 5 .8} Al 2 .0 O x Example 7 Production Example 1
Production Example 5
Production Example 7 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x
40wt% Co 0 .2 Mg 5 .8} Al 2 .0 O x
_{40wt% Ni 0 .2 Mg 5 .8} Al 2 .0 O x

Example 7 : 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x +} 40 wt% Co _{0 .2} Mg _{5 .8} Al _{2 .0} O _x + 40 wt% Ni _{0 .2} Mg _{5 .8} Al _{2 .0} O _x

20% by weight of Cu _0.2 Mg _5.8 Al _2.0 O _x (Preparation Example 1), 40% by weight of Co _0.2 Mg _5.8 Al _2.0 O _x (Preparation Example 5) and 40% by weight of Ni _0.2 Mg _5.8 Al _2.0 O _x The catalyst was prepared according to the same procedure as in Example 1, except that Example 7 was used.

The ethanol conversion reaction using the catalyst 280 ℃, 60psi and WHSV = 0.6hr ^- was carried out continuously for one month under the process conditions ¹ and the flow of the hydrogen / nitrogen = 25/25 v / v of the gas.

The decarboxylation process was then performed at 420 < 0 > C and under air flow to reactivate the catalyst. The reactivated catalyst was used in the same process conditions and under the same hydrogen / nitrogen atmosphere as above.

The reaction results are shown in Table 4 below. Table 4 shows that the catalyst of Example 7 is excellent in long-term reaction stability, and has excellent activity recovery and durability upon regeneration.

Examples 8 and 9 : 20 wt% Cu _{0 .2} Mg _{5 .8} Al _{2 .0} O _{x +} 80 wt% Co _{0 .4} Mg _{5 .8} Al _{2 .0} O _x

20 wt% Cu_{0 .2}Mg_{5 .8}Al_{2 .0}O_x (Production Example 1) and 80% by weight of Co_{0 .4}Mg_{5 .8}Al_{2 .0}O_x (Example 8) was prepared according to the same procedure as in Example 1, except that the catalyst (Preparation Example 6, prepared by the hydrotalcite route) was used. 20 wt% Cu_{0 .2}Mg_{5 .8}Al_{2 .0}O_x (Production Example 1) and 80% by weight of Co_{0 .4}Mg_{5 .8}Al_{2 .0}O_x (Example 9) was prepared according to the same procedure as in Example 1, except that the catalyst (Preparation Example 11, prepared by the hydroxide route) was used.

Using the above catalysts, an ethanol conversion reaction was carried out in the same manner as in Example 1 except for the process conditions shown in Table 5 below. The reaction results are shown in Table 5 below.

compare Example  1 to 6

The ethanol conversion reaction was carried out in the same manner as in Example 1, except that only complex oxides having the composition shown in Table 6 were used as catalysts.

The results of the reactivity test are shown in Table 7.

Example No. Complex oxide
Manufacturing Example No. Catalyst composition and content Comparative Example 1 Production Example 1 _{100wt% Cu 0 .2 Mg 5 .8} Al 2 .0 O x Comparative Example 2 Production Example 4 100 wt% Ru _{0 .2} Mg _{5 .8} Al _{2 .0} O _x Comparative Example 3 Production Example 5 _{100wt% Co 0 .2 Mg 5 .8} Al 2 .0 O x Comparative Example 4 Production Example 7 100 wt% Ni _{0 .2} Mg _{5 .8} Al _{2 .0} O _x Comparative Example 5 Production Example 9 _{100wt% Co 0 .2 Cu 0 .2} Mg 5 .8 Al 2 .0 O x Comparative Example 6 Production Example 10 100 wt% Co _{0 .02} Cu _{0 .18} Mg _{5 .8} Al _{2 .0} O _x

Claims (9)

A catalyst composition for producing a 1-butanol-containing high-alcohol by catalytic condensation reaction of ethanol, comprising a mixture of the following (i) to (iii):
(i) a mixture of a composite oxide of the following formula (1) and a composite oxide of the following formula (2)
(ii) a mixture of a composite oxide represented by the following formula (1) and a composite oxide represented by the following formula (3)
(iii) a mixture of a composite oxide represented by the following formula (1), a composite oxide represented by the following formula (2) and a composite oxide represented by the following formula (3)
[Chemical Formula 1]
M _a Cu _b Mg _c Al ₂ O _x
Wherein M is one or more metals selected from the group consisting of Cr, Sn, Zn, Fe, Co, Ni, Ru, Re, Pd and Pt, a = 0.0-2.0, b = 0.05-2.0, 3 to 8, x represents the number of times the total oxidation number of the compound is adjusted;
(2)
N _a Cu _b Mg _c Al ₂ O _x
Wherein n represents two or more metals selected from the group consisting of Co, Ni, Ru, Re, Pd and Pt, a = 0.01 to 2.0, b = 0 to 0.2, c = Indicates the number of times the total oxidation number of the compound is adjusted];
(3)
N _a Cu _b Mg _c Al ₂ O _x
Wherein n represents one metal selected from the group consisting of Co, Ni, Ru, Pd and Pt, a = 0.01 to 2.0, b = 0, c = 3 to 8, x represents the total oxidation number of the compound Indicating the number of matches]. The catalyst composition according to claim 1, wherein the catalyst composition is a mixture of (i) the composite oxide of the formula (1) and the composite oxide of the formula (2) The catalyst composition for producing a 1-butanol-containing alcohol according to the catalytic condensation reaction of ethanol, wherein the complex oxide of the formula (1) and the complex oxide of the formula (2) are contained in a proportion of 5 to 50 wt%: 95 to 50 wt%. The catalyst composition according to claim 1, wherein the catalyst composition is a mixture of (ii) the complex oxide of the formula (1) and the complex oxide of the formula (3) The catalyst composition for producing a 1-butanol-containing alcohol according to the catalytic condensation reaction of ethanol characterized in that the complex oxide of the formula (1) and the complex oxide of the formula (3) are contained in a proportion of 5 to 50 wt%: 95 to 50 wt%. The catalyst composition according to claim 1, wherein the catalyst composition is a mixture of (iii) the composite oxide of the formula (1), the composite oxide of the formula (2) and the composite oxide of the formula (3) The composite oxide of the formula (2) and the composite oxide of the formula (3) are contained in a proportion of 5 to 50 wt%: 95 to 50 wt% with respect to the composite oxide of the formula (1) 95 to 5 wt%, based on the total weight of the catalyst component. delete The complex oxides of Chemical Formulas 1 to 3 described above are prepared by firing a hydrotalcite structure prepared by adding a metal precursor used for a mixture of an Al precursor and a Mg precursor respectively at a temperature of 400 to 800 ° C By weight based on the total weight of the catalyst. The catalyst composition for the production of 1-butanol containing higher alcohols by the catalytic condensation reaction of ethanol. A process for preparing a 1-butanol-containing higher alcohol from ethanol, comprising subjecting 1-butanol to a catalytic condensation reaction in the presence of the catalyst composition according to claim 1. The process of claim 7, wherein the catalyst composition is a mixture of (i) a complex oxide of formula (1) and a complex oxide of formula (2); A process for producing a 1-butanol-containing higher alcohol from ethanol, wherein the complex oxide of the formula (1) and the complex oxide of the formula (2) are contained in a proportion of 5 to 50 wt%: 95 to 50 wt%. 8. The catalyst composition of claim 7, wherein said catalyst composition is a mixture of (ii) a complex oxide of Formula (I) and a complex oxide of Formula (III); A method for producing a 1-butanol-containing higher alcohol from ethanol, wherein the complex oxide of the formula (1) and the complex oxide of the formula (3) are contained in a proportion of 5 to 50 wt%: 95 to 50 wt%.