KR101897712B1 - Catalysts for converting reaction of high carbon compound using ABE fermentation products and preparation method of high carbon compound using the same - Google Patents

Abstract

The present invention relates to a catalyst for the conversion of a high carbon compound into an ABE fermentation product and a method for producing a high carbon compound using the same. More particularly, the present invention relates to a catalyst for the conversion of a high- in the absence from the ABE (acetone-butanol-ethanol) fermentation products can be provided a process for preparing hydrocarbon compounds of C ₅ -C ₁₉ range.

Description

TECHNICAL FIELD The present invention relates to a catalyst for the conversion of a high carbon compound of an ABE fermentation product and a method for producing a high carbon compound using the same.

The present invention relates to a catalyst for the conversion of a high-carbon compound into an ABE fermentation product and a method for producing a high-carbon compound using the catalyst. More particularly, the present invention relates to a catalyst for the conversion of acetone- ethanol from a fermentation product in the C ₅ -C ₁₉ range.

Research on the synthesis of alternative fuels from biomass has been going on for a long time due to the limit of petroleum resources on the earth. Typically, ethanol or 1-butanol obtained from biomass is commercialized, but it has limitations such as mixing with water, corrosiveness, and relatively low energy amount. Therefore, studies for synthesizing high-carbon alkane compounds having properties very similar to those of current fuel such as gasoline diesel have recently been actively researched.

When glucose is fermented using a strain of Clostridium acetobutylicum , acetone, 1-butanol and ethanol are produced in a weight ratio of 3: 6: 1. After separating the mixture of these three compounds from the fermentation tank, the aldol condensation reaction, the deoxygenation reaction and the hydrogenation reaction are successively carried out to synthesize C ₅ -C ₁₁ hydrocarbons. At this time, the aldol condensation reaction is a reaction between the aldehyde and acetone produced from the alcohol by the catalyst, thereby forming the CC bond. The resulting C ₅ -C ₇ ketone compounds again undergo aldol condensation with ethane al / butane, thereby synthesizing C ₇ -C ₁₁ ketone compounds. These are then converted to alcohols and hydrocarbons through a hydrogenation reaction (see Figure 1).

Such aldol condensation reaction and hydrogenation reaction are related to oxidation reaction, reduction reaction, dehydration reaction aldol reaction, and the like. Therefore, it is essential that a noble metal catalyst and a base catalyst exist.

According to the results of the study using Pd / C and K ₃ PO ₄ base catalyst, acetone / ethanol / butanol mixture was reacted at 145 ° C for 20 hours in a toluene solvent to obtain a mixture of C ₅ -C ₁₁ ketone and alcohol at a yield of 86% However, it has been reported that the reactivity is greatly reduced when the catalyst is reused (Non-Patent Document 1).

In addition, studies using Pd / C and KOH and K ₃ PO ₄ base catalysts have reported that C ₅ -C ₁₁ ketone compounds are synthesized at a yield of 70% from acetone / ethanol / butanol mixtures in water solvents ( Non-Patent Document 2). This study showed that after the fermentation, the acetone / ethanol / butanol mixture was present in the water, so it was possible to send the next reaction without separating the product from the reaction product. However, KOH and K ₃ PO ₄ were used in excess of 6 times the acetone, KOH and K ₃ PO ₄ are water-soluble bases, the separation of the base after the reaction is not easy, and the presence of water in the deoxidation and hydrogenation reaction steps after the reaction greatly slows down the reaction rate. In addition, although it is stated that the catalyst can be reused, the reaction rate is described only for the raw material reaction which is faster than the acetone / ethanol / butanol mixture, and it is not clear for the acetone / ethanol / butanol mixture actually.

In addition, studies using Cu-Hydrotalcite or Pd-Hydrotalcite catalysts have shown that the acetone / ethanol / butanol mixture is converted to a C ₅ -C ₁₁ high-carbon compound. In this paper, it is stated that the activity of the catalyst is not deteriorated due to reuse, but an excessive amount of butanol should be used and the reaction should proceed at a relatively high temperature of 240-300 ° C. Particularly, Cu-based catalysts have problems such as the generation of by-products such as ethyl acetate and the like.

Accordingly, the inventors of the present invention focused on the fact that a hydrocarbon compound having a C ₅ -C ₁₉ range can be prepared from ABE fermentation products under a solvent-free condition using a reusable palladium-based catalyst and a CaO base catalyst mixed catalyst, .

Non-Patent Document 1. Sreekumar, Sanil, et al. ChemSus Chem. 7.9 (2014): 2445-2448. Non-Patent Document 2. Xu, Guoqiang, et al. ChemSus Chem. 7.1 (2014): 105-109. Non-patent document 3. Onyesty ㅱ k, Gy, et al. RSC Advances. 5.120 (2015): 99502-99509.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a process for producing C ₅ -C ₁₉ from a fermentation product of ABE in the absence of a solvent using a reusable palladium- To provide a method for preparing hydrocarbon compounds in a range of < RTI ID = 0.0 >

In order to accomplish the above object, one aspect of the present invention relates to a catalyst for conversion of a high carbon compound of an ABE fermentation product, which comprises a palladium-based catalyst and CaO.

According to an embodiment of the present invention, the palladium-based catalyst may be selected from the group consisting of Pd, Pd (OAc) ₂ , Pd ₂ (dba) ₃ , Pd (OH) ₂ / C, Pd / C, Pd / CaCO ₃ , Polyethyleneimine / silica, and Pd-polyethyleneimine / silica.

According to another embodiment of the present invention, the high-carbon compound may be a carbon compound in the range of C ₅ -C ₁₉ .

Another aspect of the present invention relates to a process for the preparation of a high carbon (UC) fermentation product comprising: (a) mixing (i) a mixture of acetone, ethanol and butanol And a process for producing the compound.

According to one embodiment of the present invention, (i) the mixture of acetone, ethanol and butanol may be an ABE fermentation product.

According to another embodiment of the present invention, (b) adding hydrogen to the reactant of the step (a) to perform a second reaction.

According to another embodiment of the present invention, the palladium-based catalyst and CaO may be separated from the reactant in the step (a), hydrogenated, and then reused in the step (a).

According to another embodiment of the present invention, the hydrogenation treatment may be performed at 400-600 DEG C for 30-300 minutes.

According to another embodiment of the present invention, the step (a) may be carried out at 100-230 ° C for 3-60 hours.

According to another embodiment of the present invention, the molar ratio of acetone, ethanol, butanol, palladium and CaO may be 2.3: 3.7: 1: 0.1-1: 4-40.

According to another embodiment of the present invention, the step (b) may be performed at 250-300 ° C for 10-30 hours.

According to the present invention, it is possible to provide a method for producing a C ₅ -C ₁₉ hydrocarbon compound from an ABE fermentation product under a solvent-free condition using a reusable palladium-based catalyst and a CaO base catalyst mixed catalyst.

FIG. 1 is a schematic view showing a reaction for producing a high-carbon alkane using an ABE fermentation product.
FIG. 2 is a graph showing the relationship between the amount of X of the Pd / C-CaO catalyst prepared in Example 1 of the present invention (a), after one use (b), after two uses (c) Ray diffraction (XRD) characteristics.

In the following, various aspects and various embodiments of the present invention will be described in more detail.

One aspect of the present invention relates to a catalyst for the conversion of a high carbon compound of an ABE fermentation product comprising a palladium-based catalyst and CaO.

In the present invention, acetone-butanol-ethanol (ABE) fermentation is a process for producing acetone, butanol and ethanol by fermenting carbohydrates using a strain of clostridiaceae. The resulting mixture of acetone, butanol and ethanol may be continuously subjected to an aldol condensation reaction, a dehydrogenation reaction, and a hydrogenation reaction to synthesize C ₅ -C ₁₁ hydrocarbons. The aldol condensation reaction, dehydrogenation reaction, and hydrogenation reaction The presence of a noble metal catalyst and a base catalyst is essential.

According to an embodiment of the present invention, the palladium-based catalyst may be selected from the group consisting of Pd, Pd (OAc) ₂ , Pd ₂ (dba) ₃ , Pd (OH) ₂ / C, Pd / C, Pd / CaCO ₃ , Pd-polyethyleneimine / silica, but is not limited thereto. Preferably, Pd / C can be used.

According to another embodiment of the present invention, the high-carbon compound may be a carbon compound in the range of C ₅ -C ₁₉ .

Another aspect of the present invention relates to a process for the preparation of a high carbon (UC) fermentation product comprising: (a) mixing (i) a mixture of acetone, ethanol and butanol And a process for producing the compound. In particular, since no additional solvent is used, there is no need to separately separate the product from the solvent, which is effective for mass production.

According to one embodiment of the present invention, (i) the mixture of acetone, ethanol and butanol may be an ABE fermentation product.

According to another embodiment of the present invention, (b) adding hydrogen to the reactant of the step (a) to perform a second reaction. The ketone compound produced after the step (a) can be converted into a high-carbon alkane compound having very similar properties to fuels such as gasoline and diesel through hydrogenation.

According to another embodiment of the present invention, the palladium-based catalyst and CaO may be separated from the reactant in the step (a), hydrogenated, and then reused in the step (a). The separated palladium-based catalyst and CaO can be hydrogenated at 400-600 DEG C, preferably 450-550 DEG C, for 30-300 minutes, preferably 120-240 minutes. After the reaction of step (a), CaO is converted to CaCO ₃ . In the case of the conventional method of producing a high carbon compound using KOH and K ₃ PO ₄ , KOH and K ₃ PO ₄ are converted into K ₂ CO ₃ , KHCO ₃ and K ₂ HPO ₄ , , It is possible to switch back to CaO by a simple method of hydrogenating CaCO ₃ at a high temperature.

Therefore, unlike the conventional base catalyst, CaO can be easily reused in the process for preparing a high carbon compound using an ABE fermentation product using CaO as a base catalyst according to the present invention, .

According to another embodiment of the present invention, the step (a) may be carried out at 100-230 ° C for 3-60 hours. The reaction time and the reaction temperature may preferably be 150-210 ° C and 15-50 hours. It was confirmed that the yield of the carbon compound in the range of C ₅ -C ₁₉ was remarkably increased in the above-mentioned preferable range of values.

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According to another embodiment of the present invention, the step (b) may be performed at 250-300 ° C for 10-30 hours. The reaction time and the reaction temperature may preferably be 260-280 DEG C and 15-25 hours. It was confirmed that the yield of the carbon compound in the range of C ₅ -C ₁₉ was remarkably increased in the above-mentioned preferable range of values.

Hereinafter, production examples and embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

Example 1

1.33 g (23 mmol) of acetone, 2.74 g (37 mmol) of butanol and 0.46 g (10 mmol) of ethanol were placed in a 100 mL high-pressure reactor containing a glass liner, and 0.84 g of 5 wt% Pd / C mmol) and 0.52 g (9.2 mmol) CaO. Then, the reaction solution was reacted at 150 ° C for 20 hours, and the resulting solution was separated. The resultant solution was analyzed by GC. As a result, it was found that a product mixture having the yields shown in Table 1 was synthesized based on the acetone used.

product Yield (%) 2-pentanone (C ₅ ) 5.54 4-methyl-2-pentanone ( C 6) 0.22 _{2-heptanone (2-C 7} ) 20.20 _{4-heptanone (4-C 7} ) 0.65 4-nonanone (C ₉ ) 8.28 2-methyl-4-nonanone ( C 10) 0.42 6-undecanone (C ₁₁ ) 26.05 C ₁₃ - C ₁₉ 1.20 Alcohols 6.61 Alkanes - Total yield 69.17

Example  2 to 7

The procedure of Example 1 was repeated except that the amount of Pd / C and CaO was varied. The composition of the product and the yield of each material according to the amount of Pd / C and CaO are shown in Table 2 below.

Pd / C (mmol) Amount of CaO (mmol) Yield (%) Total yield (%) C ₅ C ₆ 2-C ₇ 4-C ₇ C ₉ C ₁₀ C ₁₁ C ₁₃ -C ₁₉ Alcohols Alkanes Example 2 0.1 4.6 6.07 0.37 17.33 0.15 1.30 0.10 2.36 - 0.36 - 28.04 Example 3 0.2 4.6 7.44 0.47 22.16 0.00 2.33 0.15 4.99 - 0.76 - 38.30 Example 4 0.4 4.6 8.09 0.60 24.93 0.34 3.16 0.23 6.63 0.41 0.95 - 45.34 Example 5 0.6 4.6 6.78 0.47 20.39 0.18 1.56 0.11 3.01 - 0.75 - 22.25 Example 1 0.4 9.2 5.54 0.22 20.20 0.65 8.28 0.42 26.05 1.20 6.61 - 69.17 Example 6 0.4 18.4 4.52 0.54 15.76 0.49 6.05 0.85 15.63 0.52 5.64 - 50.00 Example 7 0.4 36.8 2.59 0.58 7.57 0.54 5.12 1.39 16.04 0.33 6.20 - 40.36

Example  8 to 16

The reaction was carried out in the same manner as in Example 1 except that the reaction temperature and the reaction time were different. The composition of the product and the yield of each material according to reaction temperature and reaction time are shown in Table 3 below.

Reaction temperature () Reaction time (h) Yield (%) Total yield
(%) C ₅ C ₆ 2-C ₇ 4-C ₇ C ₉ C ₁₀ C ₁₁ C ₁₃ -C ₁₉ Alcohols Alkanes Example 8 150 5 5.25 0.39 22.39 0.20 2.58 0.23 7.36 - 0.71 - 39.11 Example 9 150 10 5.77 0.40 23.00 0.60 5.64 0.40 9.33 0.42 1.73 - 47.29 Example 10 150 15 6.98 0.46 22.44 0.70 6.74 0.49 16.40 0.93 2.91 - 58.05 Example 1 150 20 5.54 0.22 20.20 0.65 8.28 0.42 26.05 1.20 6.61 - 69.17 Example 11 150 25 6.25 0.32 19.91 0.94 9.64 0.58 25.72 1.48 9.00 - 73.84 Example 12 150 40 4.30 0.26 12.72 0.91 8.91 0.54 24.43 1.80 20.50 - 74.37 Example 13 150 50 4.26 0.26 12.50 0.92 8.40 0.50 21.57 1.95 24.80 - 75.16 Example 14 120 20 6.35 0.49 22.49 0.77 6.60 0.55 13.60 0.43 2.04 - 53.32 Example 15 180 20 3.84 0.13 9.17 1.18 11.63 0.58 33.79 2.38 17.49 0.27 80.46 Example 16 210 20 2.87 0.18 9.75 0.41 6.11 0.40 29.86 3.43 23.46 4.94 81.41

Example  17

After the reaction of Example 1, the temperature was increased to 270 DEG C, 200 psig of hydrogen was added, and the reaction was carried out for 20 hours. The composition of the product after the reaction and the yield of each material are shown in Table 4 below.

Yield (%) gun
yield
(%) Total ketone Total alcohol Hydrocarbon nC ₆ nC ₇ nC ₉ nC ₁₀ nC ₁₁ nC ₁₃ -C ₁₉ Reuse once 2.80 0.09 0.00 18.15 15.59 0.62 40.23 3.86 81.34

Example  18

After the reaction of Example 1, the solid catalyst was separated and reused, and the reaction was carried out in the same manner as Example 1. The yield of the resulting product is shown in Table 5 below.

Yield (%) Total yield (%) C ₅ C ₆ 2-C ₇ 4-C ₇ C ₉ C ₁₀ C ₁₁ C ₁₃ -C ₁₉ alcohols alkanes Example 1 5.54 0.22 20.20 0.65 8.28 0.42 26.05 1.20 6.61 - 69.17 Example 18
(One time reuse) 6.06 0.34 21.14 0.54 6.68 0.38 21.09 0.56 3.09 0.06 59.94

Example  19 to 20

After the reaction of Example 18, the solid catalyst was separated and reused, and the reaction was carried out in the same manner as in Example 1 (2 times of reuse / Example 19).

After the reaction of Example 19, the solid catalyst was separated and the separated solid catalyst was treated with hydrogen at 500 캜 for 3 hours, and then the reaction was carried out in the same manner as in Example 1 / Example 20). The yield of the resulting product is shown in Table 6 below.

Yield (%) Total yield (%) C ₅ C ₆ 2-C ₇ 4-C ₇ C ₉ C ₁₀ C ₁₁ C ₁₃ -C ₁₉ alcohols alkanes Example 19
(Reuse twice) 1.32 0.51 6.70 0.00 0.43 0.17 1.91 - 2.29 - 13.33 Example 20
(Activated after reuse twice) 4.42 0.16 15.12 0.70 9.56 0.38 29.42 0.40 7.70 0.14 68.00

Comparative Example  1 to 3

The reaction was carried out in the same manner as in Example 1 except that Pd / C and K ₃ PO ₄ were used as catalysts (Comparative Example 1), and the solid catalyst was separated and reacted for reaction (Comparative Example 2) Table 3 shows the results (Comparative Example 3) used in the reaction after re-use by treatment with hydrogen for 3 hours at 500 ° C.

Comparative Examples 4 to 6

The reaction was carried out in the same manner as in Example 1 except that Pd / C and K ₂ CO ₃ were used as catalysts (Comparative Example 4), and the solid catalyst was separated after the reaction and reused for the reaction (Comparative Example 5) The results of the re-use (Comparative Example 6) after the treatment with hydrogen for 3 hours at 500 ° C are shown in Table 7 below.

Yield (%) gun
yield
(%) C ₅ C ₆ 2-C ₇ 4-C ₇ C ₉ C ₁₀ C ₁₁ alcohols Pd / CK ₃ PO ₄ Comparative Example 1 4.24 0.56 17.01 0.36 3.24 0.30 8.00 11.43 45.24 Comparative Example 2 2.08 0.05 13.10 0.04 0.57 0.02 2.91 1.11 19.95 Comparative Example 3 1.48 0.24 2.99 0.00 0.51 0.07 0.83 1.60 7.76 Pd / CK ₂ CO ₃ Comparative Example 4 4.17 0.25 18.84 0.46 2.87 0.18 8.51 8.80 44.18 Comparative Example 5 3.00 0.17 13.20 0.21 0.80 0.16 1.50 0.70 19.79 Comparative Example 6 1.44 0.00 11.83 0.57 0.51 0.00 2.39 1.72 18.55

Referring to Table 2, it can be seen that the preferred yields are obtained at a preferred molar ratio of acetone, ethanol, butanol, palladium and CaO of 2.3: 3.7: 1: 0.4: 4.6-36.8.

Also, referring to Table 3, it can be confirmed that excellent yields are obtained at 150-210 ° C and 15-50 hours, which is the preferred reaction time and reaction temperature.

Also, referring to Table 4, it can be seen that the yield of the high-carbon compound having a high carbon content is remarkably increased through the process of reacting with hydrogen after the reaction of Example 1.

In addition, referring to Tables 5 to 6, the yield after the reuse of the solid catalyst obtained after the reaction of Example 1 was lowered compared to the case where the solid catalyst was reused once. However, the yield after re- , A high yield of carbon compound was obtained.

On the other hand, referring to Table 7, the catalysts Pd / CK ₃ PO ₄ and As a result of the reaction using Pd / CK ₂ CO ₃ as a catalyst, the yield was remarkably low as compared with the case of using the Pd / C-CaO catalyst according to the present invention, and the yield was lower when used (reused) twice . It can be seen that, when the catalyst is activated through the hydrogenation treatment at a high temperature, the catalyst is reused, the yield is lower.

FIG. 2 is a graph showing the relationship between the amount of the Pd / C-CaO catalyst prepared in Example 1 of the present invention before use (a), after one use (b), after two uses (c) Ray diffraction (XRD) characteristics. Referring to FIG. 2, the Pd / C-CaO catalyst is used in the reaction of producing the high carbon alkane using the ABE fermentation product. After the use of the Pd / C-CaO catalyst, the calcite and the vaterite and variations in the form of CaCO _3, we can see that twice using (re) after calcite (calcite), light bate (vaterite), transformed into three forms of CaCO ₃ in aragonite (aragonite). Further, it can be confirmed that it is converted into the crystal structure of CaO by hydrotreating for 30 minutes under a hydrogen atmosphere at 500 DEG C and activating.

Therefore, according to the present invention, it is possible to provide a method for producing a C ₅ -C ₁₉ hydrocarbon compound from an ABE fermentation product under a solvent-free condition using a reusable palladium-based catalyst and a CaO base catalyst mixed catalyst .

Claims (11)

A catalyst for the conversion of a high carbon compound of an ABE fermentation product comprising a palladium-based catalyst and CaO. The method according to claim 1,
The palladium catalyst is selected from Pd, Pd (OAc) ₂ , Pd ₂ (dba) ₃ , Pd (OH) ₂ / C, Pd / C, Pd / CaCO ₃ , Pd / alumina and Pd- A catalyst for the conversion of a high carbon compound of an ABE fermentation product. The method according to claim 1,
Wherein the high-carbon compound is a carbon compound in the range of C ₅ -C ₁₉ . (a) mixing a mixture of (i) acetone, ethanol and butanol, (ii) a palladium-based catalyst and (iii) CaO and performing a first reaction. 5. The method of claim 4,
Wherein the mixture of (i) acetone, ethanol and butanol is an ABE fermentation product. 5. The method of claim 4,
(b) adding hydrogen to the reactant of step (a) to perform a second reaction. 5. The method of claim 4,
Wherein the palladium-based catalyst and CaO are separated from the reactant in the step (a), hydrogenated, and then reused in the step (a). 8. The method of claim 7,
Wherein the hydrotreating is performed at 400-600 DEG C for 30-300 minutes. 5. The method of claim 4,
Wherein the step (a) is performed at 100-230 ° C for 3-60 hours. delete The method according to claim 6,
Wherein the step (b) is performed at 250-300 ° C for 10-30 hours.

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