KR20120089918A - Preparing method of bio-diesel from bio-oils of high acid value using acid-base catalyst combinations - Google Patents

Abstract

PURPOSE: A producing method of bio-diesel from high acid-value bio-oil using an acid-base composite catalyst is provided to improve the selectivity and the reaction stability of the bio-diesel. CONSTITUTION: A producing method of bio-diesel from high acid-value bio-oil using an acid-base composite catalyst comprises a step of reacting the high acid-value bio-oil and methanol using a composite catalyst to obtain the bio-diesel. The composite catalyst contains 5-50wt% of solid acid catalyst, 5-50wt% of solid base catalyst, and 10-50wt% of alumina sol, silica sol, or their compound. The solid acid catalyst is selected from acidic zeolite, acidic clay, heteropoly acid, or acidic composite metal oxide. The solid base catalyst is selected from alkaline earth metal oxide, rare earth metal oxide, basic zeolite, or hydrotalcite.

Description

Preparing method of Bio-diesel from bio-oils of high acid value using Acid-base catalyst combinations}

The present invention constructs an acid-base composite catalyst system using a combination of at least one acidic catalyst and at least one basic catalyst from each of a solid catalyst group having an acidic and basic acid, and uses the same to obtain biodiesel from a high acidic biooil having an acid value of 5 or more. It relates to a method for producing efficiently.

Biodiesel, made from bio-oils isolated from animal and plant resources, is a renewable green fuel and is one of the important future energy sources. Currently, manufacturing costs are generally higher than those of petroleum-based diesel, but they have advantages in terms of biodegradability, nontoxicity, and significantly reduced emissions of fine dust and sulfur components during combustion. In addition, since carbon dioxide generated during combustion can be absorbed through the cultivation of raw material crops, it can be said to be a clean fuel that can cope with global warming in that it can drastically reduce the carbon dioxide emission. Accordingly, biodiesel is manufactured from bio oil and methanol at a commercial level, and innovative technologies are continuously being developed to improve productivity, economy, and product performance.

Refined bio-oil, which is commonly used as a raw material in the biodiesel industry, has a high raw material price due to refining costs. The manufacturing price is lowered and it is expected that various lower oils can be used as biodiesel raw materials. Therefore, there is increasing interest in the technical field that can convert high-acid bio-oil such as crude bio-oil and waste cooking oil having high acid value into bio-diesel, but the efficient technology of commercial level has not been presented. Acid value refers to the number of mg of KOH required to neutralize the free fatty acids contained in 1 g of fats and oils. Currently, biodiesel process technology using a conventional homogeneous catalyst is used to produce high-acid bio-oil. There is a problem that is difficult to convert to diesel. That is, when the homogeneous catalytic process technology, which is a conventional biodiesel manufacturing technology, is applied to the conversion of a high acid value bio oil having an acid value of 5 or more, free fatty acids in which KOH, NaOH, and alkali metal alkoxide materials applied as catalysts are acidic components of the high acid value bio oil It is known that it is difficult to secure commerciality due to the loss of bio-oil and complicated separation process due to saponification, as well as greatly lowering the function of the catalyst by reacting with.

Representative examples of the development and research of reaction technologies for converting high acid bio-oil to biodiesel include the results of Masato Gochu (J. of Japan Petroleum Institute, 50, (2) 79 (2007)) applying a CaO solid catalyst. have. In this study, a batch-reaction technique is proposed to convert a high acid spent cooking oil (acid value of about 5) to biodiesel using a CaO solid base catalyst material at 65 ° C. However, in the proposed technique, although a fast conversion rate was achieved, the basic material CaO used as a catalyst material was eluted largely during the reaction, and thus, the amount of the solid CaO catalyst recovered after the first reaction included more than 3,000 ppm of the Ca component in the biodiesel product. Approximately 20% of the initial input catalyst amount, there is a problem that a process for the continuous supply of CaO component and the removal of a large amount of Ca component in the biodiesel product must be secured.

In addition, a technique for converting a high acid value lower bio oil into biodiesel by applying a basic hydrotalcite material as a catalyst has been suggested by Papayacos (Bioresource Technology 99, 5037 (2008)). Although single conversion characteristics of high acid value bio-oil have been suggested in a batch reactor at 180-210 ° C. and 15-29 atmospheres, there is a need for improvements in recovery and reuse of hydrotalcite catalysts which are technically important and the dissolution of active ingredients.

Korean Patent Laid-Open Publication No. 10-2007-0104041 simplifies the process by presenting a catalyst technology using transition metal oxides such as ZnO, NiO, CoO, MoO ₃ , TiO ₂ as a solid catalyst for converting high acid value bio oil into biodiesel. However, the reaction temperature is a technology that can be applied in the high reaction temperature range of 220 ~ 260 ℃ range, a limited reaction condition range is required, there is a problem that the yield is low.

In addition, Korean Patent Laid-Open Publication No. 10-2009-0054769 discloses a process for preparing a biodiesel fuel useful for reforming a raw material having a high free fatty acid content using a zeolite in the form of a solid acid as a catalyst, Is not linked to the technology to convert biodiesel to biodiesel.

U.S. Patent No. 7,605,281 discloses biodiesel containing fats and bio oils containing fatty acids using a vanadium oxide-based specific substance such as TiVO ₄ , FeVO ₄ , SiO ₂ , CeVO ₄ , CO ₂ V ₂ O ₇ as a solid catalyst. A technique for converting at high temperatures to components has been proposed, but catalyst stability has not been secured and improvement is required.

The main technical contents presented in the prior art of converting high acid bio-oil into biodiesel can be summarized in two directions. Before the biodiesel manufacturing chemical reaction (ester exchange reaction) from the high acid oil, a pretreatment process is performed to remove fatty acids contained in the bio oil in advance, and the conventional biodiesel manufacturing technology is separated after separating the water generated in the pretreatment step. In addition to the direction of application, the other is generally applied to the metal oxide catalyst which is relatively stable to water or acidic components and relatively low catalytic activity, in order to increase the reaction activity, a high temperature of 250 ° C. or higher and an excessive amount of methanol It can be arranged in the direction of technology to apply excessive response variables such as reaction time. In the prior art, technical attempts have been made mainly to apply various solid metal oxides as catalyst materials, and technical progress and differentiation have appeared in partial areas. However, there is no technology for efficiently and stably converting high acid value bio oil under milder reaction conditions and applying a combination of characteristics of catalyst components.

Accordingly, the present inventors have tried to solve the above problems, and when applied to the process of converting high acid value bio-oil to biodiesel using a combined catalyst system combining a combination of acidic and base properties, and increased activity compared to the case of using a single catalyst system The present invention has been completed by knowing that biodiesel can improve the selectivity and secure the reaction stability.

That is, the present invention aims to improve the performance and stability of the catalyst system and to present an efficient biodiesel production technology by presenting the catalyst component composition, application method, reaction conditions, and the like.

The present invention is 5 to 50% by weight of at least one solid acid catalyst group selected from acidic zeolites, acidic clays, heteropolyacids and acidic composite metal oxides;

5 to 50% by weight of at least one solid base catalyst group selected from alkaline earth metal oxides, rare earth metal oxides, basic zeolites and hydrotalcites; And

10 to 50% by weight of alumina sol, silica sol or mixtures thereof;

It characterized by a method of producing a biodiesel by reacting high acid value bio-oil with methanol using a complex catalyst system comprising a.

According to the biodiesel manufacturing method of the present invention, it is possible to efficiently produce high value-added biodiesel from inexpensive high acid value bio-oil at 150 to 200 ° C., which is relatively lower than conventional biodiesel production technology using a solid catalyst. In addition, the conversion rate of the high acid value bio oil and the selectivity of the biodiesel are improved, and the reaction time can be shortened and the stability of the catalyst system can be improved as compared to the method of using only a metal oxide, a solid acid, or a solid base catalyst independently. .

1 is an acidic zeolite-hydrotalcite-alumina sol complex catalyst system (Example 2), an acidic zeolite monocatalyst system (Comparative Example 1), and hydrotalcite monocatalyst system (Comparative Example 7), respectively. It is a graph comparing the change of bio oil conversion rate by one continuous reaction result.
2 is an acidic zeolite-hydrotalcite-alumina sol complex catalyst system (Example 2), an acidic zeolite monocatalyst system (Comparative Example 1), and hydrotalcite monocatalyst system (Comparative Example 7), respectively. It is a graph comparing the change of biodiesel selectivity by the results of one continuous reaction.
Figure 3 is a batch 1 of the high acid value bio-oil applied to each of the acid zeolite-hydrotalcite-alumina sol composite catalyst system (Example 11), acid zeolite single catalyst system (Comparative Example 10), hydrotalcite single catalyst system (Comparative Example 16) It is a graph comparing the change of the bio-oil conversion rate in 4 hours after the reaction for three times.
Figure 4 is a batch 1 of the high acid value bio-oil applied to each of the acid zeolite-hydrotalcite-alumina sol composite catalyst system (Example 11), acid zeolite single catalyst system (Comparative Example 10), hydrotalcite single catalyst system (Comparative Example 16) It is a graph comparing the change of biodiesel selectivity in 4 hours after the reaction for three times.

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

The present invention relates to a method for producing biodiesel from a high acid value bio oil using a complex catalyst system in which at least one solid acid catalyst and at least one solid base catalyst are selected.

The composite catalyst system applied to the present invention may be combined in a weight ratio of a solid acid catalyst, a solid base catalyst, and a binder, and may constitute a catalyst system in which the solid acid and the solid base are separated into individual particles, and may be mixed in a single particle. It is also possible to configure a catalyst system. The solid acid catalyst participates in the esterification and transesterification reaction of the fatty acid, which is a high acid value constituent in the bio oil, and methanol, another reactant, to produce fatty acid methyl ester (component of biodiesel) and water, thereby reducing the acid value of the bio oil. Preferably serves to lower to an appropriate level of less than 1. In addition, the solid base catalyst acts simultaneously on the biodiesel conversion of the bio-oil containing the acid value is adjusted and water. When the catalyst system of the present invention which directly converts a high acid value bio oil into biodiesel is applied to the actual conversion reaction, biooil conversion and biodiesel selectivity are improved as compared to a catalyst system that applies the same amount of a solid acid catalyst or a solid base catalyst alone. It can be controlled to reach the desired result that the reaction rate is increased. In addition, the step of removing the water generated in the conversion reaction step of the high acid value bio-oil can be omitted, thereby contributing to the process simplification.

As the solid acid catalyst, an acidic property and stable material under bio oil conversion conditions may be included in the selection object, and one or more selected from acid zeolite, acid clay, heteropoly acid, and acid complex metal oxide may be used. Specifically, as the acid zeolite, SiO ₂ / Al ₂ O ₃ High silica beta, mordenite zeolites with ratios of 20 to 1,000 (ZEOcat ^® PB-H from Zeochem, ZEOcat ^® FM8 / 25H, ZEOcat ^® Z-700, H-BEA-300 from Sud-Chemie, H-MOR-90, Zeolyst CP811C-300, CBV90A), or a mixture thereof. As the acidic clay, activated clay (Donghae Chemical), Acid Clay (Yakuri Pure Chemicals) or ACTAL 20X (Advanced Clay Technology) can be used. As heteropolyacid, tungsten phosphate Cs _x H _{3 -x} PMo ₁₂ O ₄₀ (x = 2.0-2.7), Cs _x H _{3 - x} PW ₁₂ O ₄₀ (x = 2.0-2.7), and silicon tungsten-based Cs _x H _{3 -x} SiW ₁₂ O ₄₀ (x = 2.0-2.7) You can use one or more selected. Further, as the acidic composite metal oxide, WO ₃ -TiO ₂ , WO ₃ -TiO ₂ -Al ₂ O ₃ , WO ₃ -ZrO ₂ , WO ₃ -ZrO ₂ -Al ₂ O ₃ , WO ₃ -Nb ₂ O ₅ , WO ₃ -Nb ₂ O ₅ -Al ₂ O ₃ , WO ₃ -Ta ₂ O ₅ , WO ₃ -Ta ₂ O ₅ -Al ₂ O ₃ , WO ₃ -SnO ₂ , WO ₃ -Al ₂ O ₃ and WO ₃ One or more selected from -ZnO can be used.

In addition, the solid base catalyst may be one or more selected from alkaline earth metal oxides, rare earth metal oxides, basic zeolites and hydrotalcite exhibiting basic characteristics. Alkaline earth metal oxides include alkaline earth metal complex oxides, specifically MgO, CaO, SrO, BaO, MgO-SiO ₂ , CaO-SiO ₂ , SrO-SiO ₂ , BaO-SiO ₂ , MgO-Al ₂ O ₃ , CaO -Al ₂ O ₃ , SrO-Al ₂ O ₃ , BaO-Al ₂ O ₃ , MgO-TiO ₂ , CaO-TiO ₂ , SrO-TiO ₂ , BaO-TiO ₂ , MgO-ZnO, CaO-ZnO, SrO- At least one selected from ZnO and BaO-ZnO may be used, and at least one selected from La ₂ O ₃ , Ce ₂ O ₃ , Sm ₂ O _3, and ThO ₂ may be used as the rare earth metal oxide. The basic zeolite is preferably a zeolite in which hydrogen of a high silica beta or mordenite zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 20 to 1,000 is substituted with ions of Na, K, Rb, Cs, Mg, Ca, Sr or Ba. , Hydrotalcite, [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4 H ₂ O], [Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) 4 H ₂ O], [Mg ₄ Zng ₂ Al ₂ ( OH) ₁₆ (CO ₃ ) 4 H ₂ O], [Ca ₄ Al ₂ (OH) ₁₂ (NO ₃ ) ₂ x H ₂ O], [Ca ₆ Al ₂ (OH) ₁₆ (NO ₃ ) ₂ x H ₂ O ] And [Ca ₄ Zng ₂ Al ₂ (OH) ₁₆ (CO ₃ ) 4 H ₂ O] can be used.

In addition, alumina sol, silica sol or a mixture thereof may be used as the binder.

In the process of preparing a catalyst system in which a solid acid catalyst and a solid base catalyst are mixed in a single particle, the solid acid catalyst and the solid base catalyst may be directly mixed in a particulate state to be molded or a precursor compound solution may be prepared and then powdered. The mixture can be separated, mixed with an inorganic binder such as silica sol, alumina sol, or the like, and then molded and heat-treated at a high temperature to produce a catalyst having a suitable size, shape, and strength for catalytic reaction. There is no particular restriction on the method of mixing the solid acid catalyst and the solid base catalyst, and various solid binders are applied, and the general solid catalyst manufacturing technology is heat-treated at an appropriate temperature range so that the components exhibit acid or base properties. This can be used.

The composition ratio of the composite catalyst component of the present invention is controlled according to the characteristics of the solid acid and the solid base, the characteristics of the bio oil, and the reaction conditions. Specifically, the solid acid catalyst is 5 to 50% by weight, the solid base catalyst is 5 to 50% by weight and the binder. It is preferable to include 10 to 50% by weight, more preferably 25 to 40% by weight of the solid acid catalyst, 25 to 40% by weight of the solid base catalyst and 20 to 40% by weight of the binder. When the content of the solid acid catalyst or the solid base catalyst is less than 5% by weight or more than 50% by weight, there may be a problem in that the acidity and basicity are not balanced and the selectivity of the biodiesel and the lifetime of the catalyst are lowered. In addition, when the content of the binder is less than 10% by weight, the mechanical strength of the active material is low, so that it is difficult to use as a solid catalyst. When the content of the binder exceeds 50% by weight, the content of the active material may be lowered, thereby lowering activity and selectivity. If the acid value of the bio-oil is relatively high, the content of the solid acid catalyst can be increased. If the activity of the solid base is relatively low, the composition ratio of the solid base catalyst can be increased, so it is important to apply the optimum composition ratio according to the components. Do. The high acid value oil having an acid value of 5 or more is rapidly reacted with the solid catalyst material under the reaction conditions, thereby reducing the stability of the catalyst material and having a problem in separating and reusing the catalyst. In particular, in the case of the basic catalyst material, the basic catalyst component is eluted by the action of the high acid value raw material, and thus the usefulness as a solid catalyst for biodiesel production is lost. Therefore, the composition ratio of the solid acid catalyst to lower the high acid value must be maintained large, and the reaction conditions It should also be adjusted to suit this catalyst system configuration.

The composite catalyst system of the present invention can be used in a batch reactor or a continuous tubular reactor, and can control characteristics such as particle shape, size, and strength so as to be applied to the reactor shape or size. In particular, when the catalyst system in which the solid acid and the solid base are separated into individual particles is charged into the tubular continuous reactor, the mixed acid charge or the solid acid catalyst and the solid base catalyst may be charged in a spatially separated position. It is also possible to efficiently achieve the object of the present invention by first participating as a catalyst in the reaction of lowering the high acid value by first contacting the bio oil and converting the bio oil into biodiesel by contacting the bio oil with a solid base catalyst. .

In general, in the biooil conversion reaction using a solid catalyst, the activity of the solid catalyst is lower than that of the liquid catalyst system. Therefore, when a batch reactor is used, the weight ratio of the catalyst to the biooil should be increased to 0.05 to 0.5 level. The reaction conditions are selected in a range in which the molar ratio of the reacted methanol is greater than the equivalent. In the present invention, the volume ratio of methanol to the high acid value bio-oil may be applied in the range of 0.5 to 5.0, preferably 0.5 to 3.0, and when using a continuous reactor, the mass space velocity (WHSV) of the reactant containing the bio-oil and methanol Can be applied in the range 0.5 to 30 h ⁻¹ . At the catalyst input ratio and the reactant supply level as described above, suitable reaction conditions may be selected and applied to the reaction conditions in the reaction temperature range of 150 ~ 220 ℃, reaction pressure 15 ~ 40 atm.

According to the biodiesel manufacturing method according to the present invention, biodiesel can be prepared from a high acid value bio oil having an acid value of 5 to 50 with high bio oil conversion rate and bio diesel selectivity, and a solid acid or solid base catalyst can be prepared even under mild reaction conditions. It can increase the reaction rate compared to the single use method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

[ Example ]

Example 1 Continuous Reaction of Acidic Zeolite-Alkaline Metal Oxide-Alumina Sol Composite Catalyst System

(MgO: Al ₂ O ₃ = 4) prepared from 1.40 g of an acid zeolite as a solid acid catalyst (ZEOcat ^® Z-700, Zeochem), MgO as a solid base catalyst and an alumina (Al ₂ O ₃ ) sol as a binder : 6 weight ratio) 2.38 g of MgO-Al ₂ O ₃ is screened in 20-40 mesh size and charged into a 10 mm diameter stainless reactor with acidic zeolite material from the middle to the bottom of the catalytic reactor and MgO-Al ₂ O ₃ from the middle Charged at the top and reactant consisting of bio oil and methanol were continuously fed at the bottom of the reactor. MgO-Al ₂ O ₃ is composed of 29 g of Mg (OH) ₂ (Samjeon Pure Chemical Co., Ltd.) powder and 30 g of alumina sol (Al ₂ O ₃ , Cataloid AP-5, Shokubai Kasei Co., Ltd.) in 200 mL of distilled water. After drying, it is a basic solid material prepared by heat treatment at 700 ° C. for 4 hours.

The reactants were supplied with oil consisting of soybean oil and oleic acid (90% by weight soybean oil, 10% by weight oleic acid, acid value of about 20) and 99.5% pure methanol at a rate of 3 mL / h, respectively, at 200 ° C. and 40 atm. After stabilization for days, the product was analyzed every 1 day. In the product obtained by the esterification reaction, the sample obtained from the biodiesel layer was diluted with n-heptane solvent without any pretreatment and quantitatively analyzed by gas chromatography equipped with a DB-1 column. The analysis results are shown in Table 1 below.

Example 2 Continuous Reaction of Acidic Zeolite-Hytaltalcite-Alumina Sol Complex Catalyst System

2.38 g of hydrotalcite-Al ₂ O ₃ (hydrotalcite: Al ₂ O ₃ = 6: 4 weight ratio) prepared in the same manner as in Example 1, but using hydrotalcite instead of MgO Charged. The hydrotalcite was used as a hydrotalcite having a composition formula of [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4 H ₂ O], and hydrotalcite-Al ₂ O ₃ was hydrotalcite (CLC-120, two). Headquarters) 60 g of powder and 40 g of alumina sol are basic solid materials prepared by dispersing, mixing, filtering, drying with 500 mL of distilled water, and heat-treating at 700 ° C.

Example 3 Continuous Reaction of Acid Zeolite-Rare Earth Metal Oxide-Alumina Sol Composite Catalyst System

In the same manner as in Example 1, but 2.38 g of La ₂ O ₃ -Al ₂ O ₃ (La ₂ O ₃ : Al ₂ O ₃ = 6: 4 weight ratio) prepared using a rare earth metal oxide instead of MgO is charged It was. The rare earth metal oxide La ₂ O ₃ was used as a reagent of Samjeon Pure Pharmaceuticals, La ₂ O ₃ -Al ₂ O ₃ is 60 g La ₂ O ₃ powder and 40 g of alumina sol dispersed with 500 mL of distilled water, mixed, filtered After drying, it is a basic solid material prepared by heat treatment at 700 ° C.

Example 4 Continuous Reaction of Acidic Zeolite-Based Zeolite-Alumina Sol Hybrid Catalyst System

2.38 g of basic zeolite-Al ₂ O ₃ (basic zeolite: Al ₂ O ₃ = 6: 4 weight ratio) prepared by using a basic zeolite instead of MgO was charged. As the basic zeolite, Na-beta zeolite substituted with Na ions was used, and basic zeolite-Al ₂ O ₃ was dispersed, mixed, and filtered with 60 mL of basic zeolite (ZEOcat ^® PB) powder and 40 g of alumina sol with distilled water. After drying, it is a basic solid material prepared by heat treatment at 700 ° C.

Example 5 Acidic Zeolite-Hytaltalcite-Based Zeolite-Alumina Sol Complex Catalyst System Continuous Reaction

In the same manner as in Example 1, but using hydrotalcite and basic zeolite instead of MgO hydrotalcite-basic zeolite-Al ₂ O ₃ (hydrotalcite: basic zeolite: Al ₂ O ₃ = 3: 3: 4 weight ratio) 2.38 g were charged. The hydrotalcite was a hydrotalcite having a composition formula of [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4 H ₂ O], and the basic zeolite was Na-beta zeolite substituted with Na ions. Hydrotalcite-basic zeolite-Al ₂ O ₃ is dispersed and mixed with 30 g of hydrotalcite (CLC-120, Dubon), 30 g of basic zeolite (ZEOcat ^® PB) powder and 40 g of alumina sol with 500 mL of distilled water. It is a basic solid material manufactured by filtering, drying, and heat-processing at 700 degreeC.

Example 6 Continuous Reaction of Acidic Clay-Alkaline Metal Oxide-Alumina Sol Complex Catalyst System

In the same manner as in Example 1, but instead of acid zeolite acid clay (Acid Clay, Yakuri Chemical Co., Ltd.) 1.4 g was used, MgO-Al ₂ O ₃ (MgO: Al ₂ O ₃ = 6: 4 weight ratio) 2.38 g was used.

Example 7: Heteropolyacid-hydrotalcite-alumina sol complex catalyst system continuous reaction

The synthesis was carried out as in Example 1, an acidic zeolite, instead of cesium tungstophosphoric heteropoly acid _{Cs 2 .5 H 0 .5 PW 12} O 40 1.4 g use, and hydrotalcite -Al ₂ O ₃ (hydrotalcite : Al ₂ O ₃ = 6: 4 weight ratio) 2.38 g was used. The heteropoly acid Cs _2.5 H _0.5 PW ₁₂ O ₄₀ was synthesized as follows. A solution obtained by adding 21.99 g of cesium carbonate (Cs ₂ CO ₃ ) to 100 g of water was dissolved in tungsten phosphate [Samjeon Pure Chemical Co., Ltd. H ₃ PW ₁₂ O _40- nH ₂ O (85.9% content)] 181.06 g It was added to the B aqueous solution, which was added and dissolved with stirring. The slurry solution in which the white precipitate formed was heated to evaporate water to obtain a white solid powder, which was calcined in air at 300 ° C. for 3 hours to obtain 177.89 g of an off-white powder (Cs _2.5 H _0.5 PW ₁₂ O ₄₀ ). Hydrotalcite-Al ₂ O ₃ was synthesized in the same manner as in Example 2.

Example 8 Continuous Reaction of Acidic Composite Metal Oxide-Hytaltalcite-Alumina Sol Complex Catalyst System

In the same manner as in Example 1, except for using acidic zeolite acid composite metal oxide WO ₃ -ZrO ₂ 1.4 g, hydrotalcite-Al ₂ O ₃ (hydrotalcite: Al ₂ O ₃ = 6: 4 Weight ratio) 2.38 g was used. The acidic composite metal oxide WO ₃ -ZrO ₂ was synthesized as follows. In water, 100 g of ammonium paratungstate _{((NH 4) 10 (H} 2 W 12 O 42)? 4H 2 O) a A solution was dissolved was added to 11.26 g, zirconium oxo-chloride in water 500 g [ZrOCl _2? 8H ₂ O, Kanto Co.] was added with stirring to an aqueous solution obtained by dissolving B was added to 104.6 g, followed by an aqueous solution of 28% aqueous ammonia until a pH 8. Ammonia water was added, and the solution which produced the slurry was filtered, 500 g of water was added, stirred, and filtered. The filtered cake was dried at 100 ° C. for 5 hours, and then calcined at 600 ° C. for 5 hours to obtain WO ₃ -ZrO ₂ (20 wt% of WO ₃ ).

Example 9 Continuous Reaction of Acid Zeolite-Acid Composite Metal Oxide-Hytaltalcite-Alumina Sol Complex Catalyst System

In the same manner as in Example 1, using a mixture of 0.8 g of acidic zeolite and 0.6 g of acidic composite metal oxide WO ₃ -ZrO ₂ , hydrotalcite-Al ₂ O ₃ (hydrotalcite: Al ₂ O ₃ = 6: 4 weight ratio) 2.38 g was used. The mixture of acidic zeolite and acidic composite metal oxide WO ₃ -ZrO ₂ is ball milled with 0.8 g of acidic zeolite and 0.6 g of acidic composite metal oxide in a ball mill, 5 g of water is added thereto, and then filtered and filtered at 100 ° C. for 5 hours. Prepared by drying.

 Complex catalyst system continuity
Response period (days) Bio oil
Conversion Rate (%) Biodiesel
Selectivity (%) Example 1 37% by weight of acid zeolite;
25 wt% alkaline earth metal oxide; And
Alumina sol 38% by weight 2 66.6 52.4 3 65.0 57.9 4 65.5 55.9 5 66.1 55.1 Example 2 37% by weight of acid zeolite;
38% by weight of hydrotalcite; And
25% by weight of alumina sol 2 79.8 74.1 3 88.5 79.6 4 87.3 82.0 5 89.4 81.0 Example 3 37% by weight of acid zeolite;
38 wt% rare earth metal oxides; And
25% by weight of alumina sol 2 75.8 68.1 3 74.5 69.6 4 74.8 69.0 5 74.6 68.6 Example 4 37% by weight of acid zeolite;
38% by weight basic zeolite; And
25% by weight of alumina sol 2 81.8 73.1 3 83.5 73.6 4 83.3 74.0 5 83.4 75.0 Example 5 37% by weight of acid zeolite;
19% by weight of hydrotalcite;
19% by weight basic zeolite; And
25% by weight of alumina sol 2 88.8 80.1 3 89.5 81.6 4 90.3 82.0 5 89.9 82.0 Example 6 37 weight percent acidic clay;
38 wt% alkaline earth metal oxide; And
25% by weight of alumina sol 2 63.6 58.7 3 63.5 57.4 4 64.1 58.2 5 65.8 55.6 Example 7 37 weight percent heteropoly acid;
38% by weight of hydrotalcite; And
25% by weight of alumina sol 2 84.6 78.7 3 85.5 79.4 4 85.1 79.2 5 85.8 79.5 Example 8 37% by weight of the acidic composite metal oxide;
38% by weight of hydrotalcite; And
25% by weight of alumina sol 2 87.6 80.3 3 87.5 81.4 4 87.1 82.2 5 87.2 81.5 Example 9 21% by weight acidic zeolite;
16 wt% of acidic composite metal oxides;
38% by weight of hydrotalcite; And
25% by weight of alumina sol 2 88.6 82.3 3 89.3 82.2 4 89.1 83.0 5 89.2 82.6

Example 10 Batch Reaction of Acidic Zeolite-Alkaline Metal Oxide-Alumina Sol Complex Catalyst System

In a 300 mL high-pressure reactor, a rotary blade-type stainless solid catalyst packing network was installed on a rotating shaft, 3.0 g of 10-mesh acidic zeolite and MgO-Al ₂ O ₃ (MgO: Al ₂ O ₃ = 6: 4 weight ratio) 5.1 g Were charged respectively. The reactor was filled with nitrogen, and 120 mL of oil (acid value 40) consisting of 80% by weight of soybean oil and 20% by weight of oleic acid and 60 mL of 99.5% pure methanol were added, and the reaction pressure was 40 atm at 200 rpm. After the temperature was raised to 200 ° C., samples were analyzed every hour for 4 hours. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the reaction pressure was returned to normal pressure, the product was recovered, and bio oil and methanol were added again, and the reaction was carried out up to three times in the same manner. The analysis results are shown in Table 2 below.

Example 11 Batch Reaction of Acid Zeolite-Hytaltalcite-Alumina Sol Complex Catalyst System

In the same manner as in Example 10, but instead of MgO-Al ₂ O ₃ hydrotalcite-Al ₂ O ₃ (hydrotalcite: Al ₂ O ₃ = 6: 4 weight ratio) was used.

Example 12 Batch Reaction of Acid Zeolite-Rare Earth Metal Oxide-Alumina Sol Composite Catalyst System

In the same manner as in Example 10, La ₂ O ₃ -Al ₂ O ₃ (La ₂ O ₃ : Al ₂ O ₃ = 6: 4 weight ratio) was used instead of MgO-Al ₂ O ₃ .

Example 13: Batch Reaction of Acidic Zeolite-Based Zeolite-Alumina Sol Complex Catalyst System

In the same manner as in Example 10, using basic zeolite-Al ₂ O ₃ (basic zeolite: Al ₂ O ₃ = 6: 4 weight ratio) instead of MgO-Al ₂ O ₃ was used.

Example 14 Batch Reaction of Acidic Zeolite-Hytaltalcite-Based Zeolite-Alumina Sol Complex Catalyst System

In the same manner as in Example 10, but instead of MgO-Al ₂ O ₃ hydrotalcite-basic zeolite-Al ₂ O ₃ (hydrotalcite: basic zeolite: Al ₂ O ₃ = 3: 3: 4 weight ratio) Used.

Example 15 Batch Reaction of Acidic Clay-Alkaline Metal Oxide-Alumina Sol Complex Catalyst System

The same method as in Example 10, except that 3.0 g of acidic clay was used instead of acidic zeolite.

 Complex catalyst system reaction
time 2 hours 3 hours 4 hours reaction
Count oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) Example 10 37% by weight of acid zeolite; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 99.9 92.4 99.2 92.1 100 93.0 2 99.1 86.8 100 91.8 100 90.7 3 100 90.4 99.6 89.5 100 90.5 Example 11 37% by weight of acid zeolite; 38% by weight of hydrotalcite; And 25% by weight of alumina sol One 99.8 87.1 99.7 87.2 99.8 88.4 2 99.9 87.6 100 92.0 100 94.2 3 99.5 86.1 99.6 88.6 100 92.9 Example 12 37% by weight of acid zeolite; 38 wt% rare earth metal oxides; And 25% by weight of alumina sol One 99.8 89.1 100 90.2 100 91.4 2 99.9 89.6 100 91.0 100 92.2 3 99.5 90.1 100 91.6 100 93.0 Example 13 37% by weight of acid zeolite; 38% by weight basic zeolite; And 25% by weight of alumina sol One 99.9 91.1 100 92.2 100 92.4 2 99.9 90.6 100 92.0 100 93.2 3 99.5 90.1 99.6 91.6 100 91.9 Example 14 37% by weight of acid zeolite; 19% by weight of hydrotalcite; 19% by weight basic zeolite; And 25% by weight of alumina sol One 99.9 91.1 100 93.2 100 93.4 2 100 92.6 100 94.0 100 94.2 3 100 92.1 100 93.6 100 94.0 Example 15 37 weight percent acidic clay; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 100 92.9 100 91.6 100 93.2 2 99.7 84.1 100 88.7 100 90.9 3 94.8 73.4 97.2 73.7 100 92.0

Example 16 Batch Reaction of Acidic Zeolite-Alkalinetometal Oxide-Alumina Sol Single Particle Complex Catalyst System

In the same manner as in Example 10, 44.4 g of acidic zeolite, 29 g of Mg (OH) ₂ powder and 30 g of alumina sol were dispersed, mixed, filtered and dried in 200 mL of distilled water, and then heat-treated at 700 ° C. for 4 hours. To prepare a single particle composite catalyst system, which was used in 8.1 g. The analysis results are shown in Table 3 below.

Example 17 Batch Reaction of Heteropoly Acid-Alkaline Metal Oxide-Alumina Sol Single Particle Complex Catalyst System

The synthesis was carried out as in Example 10, the heteropoly acid _{Cs 2 .5 H 0 .5 PW 12} O 40 44.4 g, Mg (OH) 2 powder, 29 g of alumina sol and 30 g of distilled water and dispersed in a 200 mL, mixed, filtered After drying, heat treatment at 500 ℃ for 4 hours to prepare a single particle composite catalyst system, 8.1 g was used.

Example 18 Batch Reaction of Acidic Composite Metal Oxide-Alkaline Metal Oxide-Alumina Sol Single Particle Complex Catalyst System

In the same manner as in Example 10, 44.4 g of acidic composite metal oxide WO ₃ -ZrO ₂ , 29 g of Mg (OH) ₂ powder and 30 g of alumina sol were dispersed, mixed, filtered and dried in 200 mL of distilled water, and then dried. Heat treatment was performed at 500 ° C. for 4 hours to prepare a single particle composite catalyst system, and 8.1 g of the catalyst was used.

Example 19 Acidic Zeolite-Acid Composite Metal Oxide-Alkaline Metal Oxide-Alumina Sol Single Particle Complex Catalyst System Batch Reaction

In the same manner as in Example 10, 20.4 g of acid zeolite, 24.0 g of acidic composite metal oxide WO ₃ -ZrO ₂ , 29 g of Mg (OH) ₂ powder and 30 g of alumina sol were dispersed and mixed in 200 mL of distilled water, After filtration and drying, heat treatment was performed at 500 ° C. for 4 hours to prepare a single particle composite catalyst system, and 8.1 g of the catalyst was used.

 Single particle composite catalyst system reaction
time 2 hours 3 hours 4 hours reaction
Count oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) Example 16 37% by weight of acid zeolite; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 100 88.2 100 92.0 100 93.6 2 100 89.7 100 91.5 100 90.7 3 100 90.3 99.6 90.4 100 90.0 Example 17 37 weight percent heteropoly acid; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 100 90.2 100 92.0 100 93.0 2 100 91.7 100 91.5 100 93.7 3 100 91.3 100 92.4 100 93.0 Example 18 37% by weight of the acidic composite metal oxide; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 100 86.2 100 90.0 100 91.0 2 100 86.7 100 89.5 100 90.7 3 100 86.3 100 89.4 100 90.1 Example 19 17 wt% of acid zeolite; 20 wt% of acidic composite metal oxides; 38 wt% alkaline earth metal oxide; And 25% by weight of alumina sol One 100 91.2 100 92.0 100 93.0 2 100 91.7 100 92.3 100 93.7 3 100 91.3 100 92.4 100 93.1

Comparative Examples 1 to 9: Single catalyst continuous reaction

The same method as in Example 1, except that 3.8 g of acidic zeolite (Comparative Example 1), 4.7 g of acidic clay (Comparative Example 2), 7.5 g of heteropolyacid (Cs _2.5 H _0.5 PW ₁₂ O ₄₀ ) as a catalyst material (Comparative Example) 3), acidic composite metal oxide WO ₃ -ZrO ₂ (Comparative Example 4), Al ₂ O ₃ 4.8 g (Comparative Example 5), MgO 4.8 g (Comparative Example 6), Hydrotalcite 3.3 g (Comparative Example 7 ), 4.3 g of basic zeolite (Comparative Example 8) and 6.3 g of La ₂ O ₃ (Comparative Example 9) were respectively charged. The volumes of the catalyst beds all correspond to 6.0 mL. The activity and selectivity change of each catalyst material are shown in Table 4 below.

Single catalyst system continuity
Response period (days) Bio oil
Conversion Rate (%) Biodiesel
Selectivity (%) Comparative Example 1 Acid zeolite 2 65.4 60.8 3 61.8 50.8 4 62.3 48.2 5 57.5 44.6 Comparative Example 2 Acid clay 2 53.4 48.8 3 50.5 42.6 4 49.0 38.4 5 45.0 35.3 Comparative Example 3 Heteropolyacid
(Cs _2.5 H _0.5 PW ₁₂ O ₄₀ ) 2 73.4 65.8 3 66.8 53.2 4 64.3 51.2 5 63.5 50.6 Comparative Example 4 Acid Composite Metal Oxide
(WO ₃ -ZrO ₂ ) 2 67.4 61.5 3 63.8 56.8 4 61.3 53.2 5 59.5 51.6 Comparative Example 5 Al ₂ O ₃ 2 31.4 28.8 3 23.5 30.1 4 19.0 18.2 5 15.0 13.3 Comparative Example 6 MgO 2 72.8 64.8 3 51.3 29.2 4 48.2 32.6 5 35.5 31.1 Comparative Example 7 Hydrotalcite 2 96.7 80.5 3 87.9 78.8 4 86.4 73.5 5 75.8 55.0 Comparative Example 8 Basic zeolite 2 93.9 85.5 3 86.9 75.8 4 81.4 70.6 5 76.8 65.1 Comparative Example 9 Rare earth metal oxides
(La ₂ O ₃ ) 2 72.8 64.6 3 61.9 49.2 4 57.2 47.6 5 52.5 41.3

Comparative Examples 10 to 18: Single Catalytic Batch Reaction

The synthesis was carried out as in the Example 9, an acidic zeolite as catalyst material (Comparative Example 10), an acidic clay (Comparative Example 11), heteropolyacids _{(Cs 2 .5 H 0 .5 PW} 12 O 40) ( Comparative Example 12) , Acidic composite metal oxide (WO ₃ -ZrO ₂ ) (comparative example 13), Al ₂ O ₃ (comparative example 14), MgO (comparative example 15), hydrotalcite (comparative example 16), basic zeolite (comparative example 17 ) And rare earth metal oxides (La ₂ O ₃ ) (Comparative Example 18) were each charged by 9.0 g. The analysis results are shown in Table 5 below.

Single catalyst system reaction
time 2 hours 3 hours 4 hours reaction
Count oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) oil
Conversion rate
(%) diesel
Selectivity
(%) Comparative Example 10 Acid zeolite One 98.5 81.8 93.0 71.0 95.9 81.0 2 80.0 50.7 94.3 76.6 94.4 71.0 3 87.6 60.6 83.1 52.4 89.4 62.3 Comparative Example 11  Acid clay One 66.9 41.2 93.3 76.0 93.2 75.3 2 67.5 46.3 91.2 56.2 85.6 65.6 3 80.8 60.2 83.6 54.6 90.7 58.9 Comparative Example 12 Heteropolyacid
_{(Cs 2 .5 H 0 .5 PW} 12 O 40) One 98.9 86.3 96.0 81.0 97.9 86.0 2 90.1 80.4 94.8 76.6 96.4 81.0 3 89.6 70.6 93.1 72.4 86.4 68.5 Comparative Example 13 Acid Composite Metal Oxide
(WO ₃ -ZrO ₂ ) One 86.9 61.2 91.3 78.0 93.2 85.3 2 82.5 56.3 90.2 66.2 88.6 68.6 3 80.8 55.2 86.6 58.6 92.7 61.9 Comparative Example 14 Al ₂ O ₃ One 46.1 31.2 63.3 46.0 68.2 55.1 2 47.5 36.3 61.3 46.2 65.1 55.1 3 40.8 30.8 53.2 44.6 60.2 48.2 Comparative Example 15 MgO One 59.5 40.2 77.0 39.4 77.3 44.3 2 53.6 25.4 77.8 45.2 69.4 37.3 3 62.2 35.7 71.1 47.7 68.8 38.3 Comparative Example 16  Hydrotalcite One 99.0 89.9 99.3 91.4 100 90.4 2 97.6 89.2 98.0 88.2 99.4 87.3 3 93.l 82.4 95.8 88.4 96.5 84.3 Comparative Example 17 Basic zeolite One 97.2 89.1 99.0 91.8 100 92.4 2 95.6 86.2 99.3 88.6 99.4 87.3 3 91.2 79.4 94.8 84.6 95.5 86.8 Comparative Example 18 Rare earth metal oxides
(La ₂ O ₃ ) One 89.5 70.2 91.0 79.4 92.3 80.3 2 83.6 65.4 87.8 66.2 89.4 67.3 3 66.2 45.7 76.1 57.7 78.8 58.3

Looking at the results of Table 1 and Table 4, the analysis of the continuous reaction results, it can be seen that when using the composite catalyst system of the present invention, the conversion rate of the bio oil and the selectivity of the biodiesel are maintained even after the reaction time. On the other hand, when a solid acid catalyst or a solid base catalyst was used alone, the conversion rate of bio oil and the selectivity of bio diesel were shown to decrease rapidly over time. This result shows that the acid-base composite catalyst system is effective in maintaining stability as compared to the single catalyst system.

The results of Tables 2-3 and 5, which show the results of the batch reaction, clearly show the excellent catalytic activity of the composite catalyst system of the present invention. In the combined catalyst system, the bio oil was converted more than 99% even if the number of re-reactions increased, while the biodiesel selectivity was also maintained at 90% level. When applied, there is a rapid decrease in biooil conversion and biodiesel selectivity depending on the number of reactions.

The results of Example 10, in which the catalyst system was formed in the form of particles separated from each other, and Example 16, in which the catalyst system was formed in the form of a single particle, showed similar values, so that no specific effect on the particle shape of the catalyst system was found.

After all, according to the biodiesel manufacturing method of the present invention, by using the excellent catalyst stability and catalytic activity of the acid-base composite catalyst system, it is possible to produce biodiesel from bio-oil with high conversion and selectivity even under mild reaction conditions. I could confirm it.

Claims (13)

5 to 50% by weight of at least one solid acid catalyst group selected from acidic zeolites, acidic clays, heteropolyacids and acidic composite metal oxides;
5 to 50% by weight of at least one solid base catalyst group selected from alkaline earth metal oxides, rare earth metal oxides, basic zeolites and hydrotalcites; And
10 to 50% by weight of alumina sol, silica sol or mixtures thereof;
Method of producing a biodiesel by reacting high acid value bio-oil with methanol using a complex catalyst system comprising a.
The method of claim 1, wherein the acidic zeolite is SiO ₂ / Al ₂ O ₃ High silica beta having a ratio of 20 to 1,000, mordenite zeolite or a mixture thereof.
The method of claim 1, wherein the heteropoly acid is _{Cs x H 3 - x PMo 12} O 40 (x = 2.0 ~ 2.7), Cs x H 3 -x PW 12 O 40 (x = 2.0 ~ 2.7) , and Cs _x H _{3 - x} SiW ₁₂ O ₄₀ (x = 2.0 ~ 2.7) The method for producing a biodiesel characterized in that at least one selected from.
According to claim 1, wherein the acidic composite metal oxide is WO ₃ -TiO ₂ , WO ₃ -TiO ₂ -Al ₂ O ₃ , WO ₃ -ZrO ₂ , WO ₃ -ZrO ₂ -Al ₂ O ₃ , WO ₃ -Nb ₂ O ₅ , WO ₃ -Nb ₂ O ₅ -Al ₂ O ₃ , WO ₃ -Ta ₂ O ₅ , WO ₃ -Ta ₂ O ₅ -Al ₂ O ₃ , WO ₃ -SnO ₂ , WO ₃ -Al ₂ O ₃ And at least one selected from WO ₃ -ZnO.
The method of claim 1, wherein the alkaline earth metal oxide is MgO, CaO, SrO, BaO, MgO-SiO ₂ , CaO-SiO ₂ , SrO-SiO ₂ , BaO-SiO ₂ , MgO-Al ₂ O ₃ , CaO-Al ₂ O ₃ , SrO-Al ₂ O ₃ , BaO-Al ₂ O ₃ , MgO-TiO ₂ , CaO-TiO ₂ , SrO-TiO ₂ , BaO-TiO ₂ , MgO-ZnO, CaO-ZnO, SrO-ZnO and BaO -Method for producing a biodiesel, characterized in that at least one selected from ZnO.
The method of claim 1, wherein the rare earth metal oxide is La ₂ O ₃ , Ce ₂ O ₃ , Sm ₂ O ₃ And ThO ₂ Method for producing a biodiesel, characterized in that at least one selected from.
The method of claim 1, wherein the basic zeolite is SiO ₂ / Al ₂ O ₃ A method of producing a biodiesel, wherein the hydrogen of the high silica beta or mordenite acid zeolite having a ratio of 20 to 1,000 is zeolite substituted with ions of Na, K, Rb, Cs, Mg, Ca, Sr or Ba.
The method of claim 1, wherein the hydrotalcite is [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4 H ₂ O], [Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) 4 H ₂ O], [Mg ₄ Zng ₂ Al ₂ (OH) ₁₆ (CO ₃ ) 4 H ₂ O], [Ca ₄ Al ₂ (OH) ₁₂ (NO ₃ ) ₂ x H ₂ O], [Ca ₆ Al ₂ (OH) ₁₆ (NO ₃ ) ₂ x H ₂ O] and [Ca ₄ Zng ₂ Al ₂ (OH) ₁₆ (CO ₃ ) 4 H ₂ O] The method for producing a biodiesel characterized in that at least one.
The method of claim 1, wherein the high acid value bio-oil has a acid value of 5-50.
The biodiesel according to claim 1, wherein the reaction is a continuous or batch reaction under conditions of a volume ratio of methanol to a high acid value biooil 1: 0.5 to 5, a temperature of 150 to 220 ° C, and a pressure of 15 to 40 atmospheres. How to make.
The method of claim 10, wherein the continuous reaction is a method for producing a biodiesel, characterized in that the reaction mixture containing a high acid value bio-oil and the methanol at a mass space velocity of 0.5 ~ 30 h ^-1 .
The method of claim 10, wherein the continuous reaction is performed by charging the catalyst layer such that the solid acid catalyst is first contacted with a reactant composed of a high acid value bio oil and methanol.
The method of claim 10, wherein the batch reaction is a method for producing biodiesel, characterized in that the weight ratio of the complex catalyst system to the high acid value bio-oil.

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