TWI612132B - Solid base catalyst for manufacturing biodiesel, fabricating method thereof and manufacturing method of biodiesel using thereof - Google Patents

Abstract

The invention provides a solid alkali catalyst for producing biodiesel, a preparation method thereof and a method for producing the biodiesel using the same, wherein the preparation method of the solid alkali catalyst comprises the following steps. First, a first solid reactant is provided as a sodium source or a potassium source. Next, the first solid reactant is mixed with the second solid reactant to obtain a mixture, wherein the second solid reactant comprises a source of titanium. Finally, the mixture is heat treated to obtain a solid base catalyst. Since the above second solid reactant can be natural soil or solid waste, the present invention can make the limited resources of the earth can be used as best as possible, and also meets the current environmental standards.

Description

Solid base catalyst for producing biodiesel, Preparation method and application method thereof

The present invention relates to a solid base catalyst for producing biodiesel, in particular to a solid base catalyst prepared by using a sodium salt or a potassium salt and capable of producing biodiesel, a preparation method thereof and application thereof Biomass diesel manufacturing method.

Petrochemical fuel is currently the most common source of power in the world, and it plays an important role in industrial development, transportation and agricultural development, and thus enhances the quality of human life and makes life more convenient. However, with the rapidly increasing population of the world, the use of fossil fuels has begun to increase substantially, but its limited production is a long-standing concern. Moreover, the long-standing problems of fossil fuels, such as the inability to reuse, air pollution, mining, and price instability, are difficult to solve.

In contrast, biodiesel in biomass has similar properties to fossil diesel, and this fuel has reduced pollutant emissions and health. Its impact, biodegradability, non-toxicity, sulfur-free, low gas pollution from combustion and safe storage are considered to be both economical and potential energy alternatives.

The production methods of biodiesel are mainly divided into chemical catalysis and biocatalysis. Among them, chemical base catalysis is a widely used technology due to its high transesterification rate and short reaction time. The catalyst used for chemical base catalysis includes liquids and solids. Among them, solid base catalysts are popular in the industry because of their easy separation and recyclability. At present, solid base catalysts commonly used in the manufacture of biodiesel have calcium oxide, lithium carbonate, etc. However, calcium oxide has poor air stability, easily absorbs moisture in the air and carbon dioxide, and has a larger surface area of calcium oxide particles. Small, the overall transesterification rate is low. The basic strength of lithium carbonate is weak, so the transesterification effect is not good.

On the other hand, with the development of global economic development, urbanization and public construction, wastes derived from various business developments, in addition to occupying a large amount of land, also cost huge amounts of transportation or disposal costs, which not only causes Environmental load also affects environmental quality relatively.

In view of this, the effective use of various commercial wastes to prepare solid alkali catalysts required for the production of biodiesel can not only reduce the burden of waste disposal, but also reduce the cost of purchasing solid alkali catalysts. It helps to provide a source of energy.

In view of the above, an aspect of the present invention provides a solid base catalyst for producing biodiesel, which comprises a compound represented by the following chemical formula (1) or chemical formula (2): Na _a X _b O _c (1) K _a XbO _c (2); wherein X is titanium, zirconium, hafnium, vanadium, niobium, iron, molybdenum, tungsten, boron, copper, nickel, zinc, cobalt, chromium or manganese, and a is 1 to 6 An integer, b is a positive integer from 1 to 4 and c is a positive integer from 1 to 7.

According to one embodiment of the foregoing aspect, the solid base catalyst comprises sodium titanate, potassium titanate, sodium zirconate, potassium zirconate, sodium citrate, potassium citrate, sodium citrate, potassium citrate, sodium metasilicate. , potassium metasilicate, sodium pyroantimonate, potassium pyroantimonate, sodium hypocitrate, potassium hypobromite, sodium orthovanadate, potassium orthovanadate, sodium metavanadate, potassium metavanadate, sodium hypovanadate , potassium hypovanadate, sodium ferrite, sodium peroxoferrate, potassium ferrite, potassium peroxate, sodium tungstate, potassium tungstate, sodium peroxytungstate, potassium peroxytungstate, sodium molybdate, Potassium molybdate, sodium peroxo molybdate, potassium peroxo molybdate, sodium tetraborate, potassium tetraborate, sodium metaborate, potassium metaborate, sodium cobaltate, potassium cobaltate, sodium nickelate, potassium nickelate, copper acid Sodium, potassium cuprate, sodium cuprous, potassium citrate, sodium zincate, potassium zincate, sodium chromate, potassium chromate, sodium manganate or potassium manganate.

Another aspect of the present invention provides a method for preparing a solid base catalyst for producing biodiesel, comprising the steps of (a) providing a first solid reactant as a sodium source or a potassium source, and step (b) mixing first. The solid reactant is reacted with a second solid reactant to obtain a mixture, wherein the second solid reactant comprises a source of titanium and the mixture is heat treated in step (c) to obtain a solid base catalyst.

According to another embodiment of the foregoing aspect, the second solid reactant may further comprise a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, a boron source, a germanium source, and a copper. Source, nickel source, iron source, zinc source, cobalt source, chromium source or manganese source. The second solid reactant may be titanium aluminum alloy, iron slag, high temperature furnace insulating brick, recycled battery, scrap metal, steel slag, titanium-containing sludge, waste brick, tile, porcelain, pottery, strontium, zirconium British stone, borate, borosilicate ore, vanadium-containing spent catalyst, antimony concentrate, tungsten steel, waste catalyst or natural clay and its products.

Thereby, the present invention can utilize the above-mentioned natural or solid waste as a second solid reactant to prepare a solid alkali catalyst, so that the limited resources of the earth can be utilized to the best and meet the current environmental standards.

According to still another embodiment of the foregoing aspect, step (b) further comprises the following steps. First, a solution containing the above mixture is provided, followed by drying the solution. Preferably, the molar ratio of the first solid reactant to the second solid reactant in step (b) is from 1:5 to 5:1.

According to still another embodiment of the foregoing aspect, the step (c) is to calcine the aforementioned mixture in an air environment. Preferably, the temperature of step (c) is from 700 ° C to 1000 ° C, and the time may last from 0.5 hours to 4 hours. Further, the step (c) further comprises the step of grinding the above mixture into a powder.

A further aspect of the present invention provides a method for producing a biodiesel comprising the step (I) of providing a solid base catalyst, and the step (I) comprising the step (a) of providing the first solid reactant as a sodium source or a potassium source. And step (b) mixing the first solid reactant with the second solid reactant to obtain a mixture, wherein the second solid reactant comprises a titanium source and the step (c) heat treating the mixture to obtain a solid base catalyst, and the step (II) The oil and fat are mixed with the alcohol and heated under reflux, and a solid base catalyst is added to carry out the transesterification reaction, and the step (III) is used to produce the transesterification reaction. The material is separated, and the ester liquid is taken out and the ester liquid is vacuum distilled in step (IV) to remove residual alcohol and residual water in the ester liquid to obtain biodiesel.

According to one embodiment of the foregoing aspect, the molar ratio of fat to alcohol in step (II) is from 1:6 to 1:36.

Thereby, the solid base catalyst prepared by the invention is applied to the manufacture of biodiesel, and in addition to the recycling of the waste, the effect of increasing the transesterification rate of the transesterification reaction is met, which meets the demand for mass production in the industry.

S100, S102, S104‧‧‧ steps

S200, S202, S204, S206‧‧‧ steps

The above and other objects, features and advantages of the present invention will become more apparent and understood. The description of the drawing is as follows. FIG. 1 is a flow chart showing the preparation method of the solid base catalyst for producing biodiesel according to the present invention. Figure 2 is a flow chart showing the manufacturing method of the biodiesel of the present invention; and Figure 3A is a diagram showing the X of the solid base catalyst prepared by different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention. The results of the ray diffraction analysis; FIG. 3B is an electron microscope image of the solid base catalyst prepared by using different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention; FIG. 3C is a view showing the experiment of the present invention Example 1 shows the relationship between the transesterification of the solid base catalyst prepared by different lithium carbonate to alumina molar ratio in the transesterification reaction; the 3D figure shows the fixation of the lithium carbonate to the oxidation in the 3A to 3C X-ray diffraction analysis results of solid base catalyst prepared by aluminum molar ratio and prepared at different calcination temperatures; Figure 3E is a diagram showing the relationship between the transesterification ratio of the solid base catalyst in the 3D diagram for the transesterification reaction; and the 3F diagram fixing the molar ratio of lithium carbonate to alumina in the 3A to 3C diagrams. The results of X-ray diffraction analysis of the solid base catalyst prepared by calcination time; the 3G diagram shows the relationship of the transesterification ratio of the solid base catalyst to the transesterification reaction of FIG. 3F; FIG. 4A is the experiment of the present invention In the case of using bauxite as the second solid reactant in Example 1, the transesterification ratio of the solid base catalyst prepared by different lithium carbonate to the bauxite molar ratio is shown in FIG. 4B. FIG. 4C is a diagram showing the relationship between the transesterification ratio of the solid base catalyst prepared by different calcination temperatures in the case of using bauxite as the second solid reactant in the experimental example 1; FIG. 4C is the experimental example 1 of the present invention. The relationship between the transesterification rate of the solid base catalyst prepared by different bake time of bauxite as the second solid reactant, and the transesterification rate of the transesterification reaction of the present invention; X-ray diffraction analysis results of the solid base catalyst prepared by the ear ratio; FIG. 5B is the experimental example 2 of the present invention The relationship between the transesterification rate of the solid base catalyst prepared by different lithium carbonate to titanium dioxide molar ratio in the transesterification reaction; the 5C figure is to fix the molar ratio of lithium carbonate to titanium dioxide in the 5A diagram and at different calcination temperatures X-ray diffraction analysis results of the prepared solid base catalyst; Figure 5D is a diagram showing the transesterification ratio of the solid base catalyst to the transesterification reaction in Figure 5C; Figure 5E shows the results of X-ray diffraction analysis of the solid base catalyst prepared by fixing the lithium carbonate to titanium dioxide molar ratio of Figure 5A and prepared by different calcination time; the 5F figure is the solid base catalyst of Figure 5E. The transesterification ratio diagram of the esterification reaction; and the 5G diagram is a graph showing the relationship between the number of times of repeated use of the solid base catalyst prepared by lithium carbonate and titanium dioxide in the experimental example 2 of the present invention on the transesterification ratio.

The present invention is directed to providing a solid base catalyst for the manufacture of biodiesel. The solid base catalyst comprises _a compound of any one of Li _a X _b O _c , Na _a X _b O _c , and K _a X _b O _c , wherein X is titanium, aluminum, zirconium, vanadium, niobium, iron, molybdenum, Tungsten, boron, lanthanum, cobalt, chromium, manganese, nickel, zinc or copper, a is a positive integer from 1 to 6, b is a positive integer from 1 to 4, and c is a positive integer from 1 to 7.

According to an embodiment of the present invention, the solid base catalyst may be composed of lithium aluminate (LiAlO ₂ ), lithium titanate (Li ₂ TiO ₃ ), lithium zirconate (Li ₂ ZrO ₃ ), lithium niobate (LiBiO _{3 ).} Lithium niobate (Li ₃ NbO ₄ ), lithium metasilicate (LiNbO ₃ ), lithium niobate (LiNbO ₂ ), lithium pyroantimonate (Li ₄ Nb ₂ O ₇ ), lithium orthovanadate (Li _{3 )} VO ₄ ), lithium metavanadate (LiVO ₃ ), lithium pentoxide (LiVO ₂ ), lithium tungstate (Li ₂ WO ₄ ), lithium peroxytungstate (Li ₆ WO ₆ ), lithium molybdate (Li _{2 )} MoO ₄ ), lithium peroxodimolybdate (Li ₆ MoO ₆ ), lithium tetraborate (Li ₂ B ₄ O ₇ ), lithium metaborate (LiBO ₂ ), lithium chromate (LiCrO ₂ or Li ₃ CrO ₄ ), manganese Lithium acid (Li ₂ MnO ₃ , LiMnO ₂ ), lithium cobaltate (LiCoO ₂ ), lithium cobaltite (Li ₆ CoO ₄ ), lithium nickelate (Li ₂ NiO ₂ or LiNiO ₂ ), lithium copperate (Li _{2 )} CuO ₂ ), lithium cuprousate (LiCuO), sodium titanate (Na ₂ TiO ₃ ), potassium titanate (K ₂ TiO ₃ ), sodium zirconate (Na ₂ ZrO ₃ ), potassium zirconate (K ₂ ZrO _{3 )} sodium), sodium bismuthate (NaBiO _3), bismuth potassium (KBiO _3), sodium niobate (Na _4), potassium niobate _{(K 3 NbO 4) 3 NbO} , metaniobate (NaNbO _3), metaniobate Potassium (KNbO ₃ ), sodium pyroantimonate (Na ₄ Nb ₂ O ₇ ), potassium pyroantimonate (K ₄ Nb ₂ O ₇ ), sodium orthovanadate (Na ₃ VO ₄ ), potassium orthovanadate (K ₃ VO ₄ ), sodium metavanadate (NaVO ₃ ), potassium metavanadate (KVO ₃ ), sodium hypovanadate (NaVO _{2 )} ), potassium hypovanadate (KVO ₂ ), sodium ferrite (Na ₂ FeO ₄ ), sodium peroxoferrate (Na ₂ FeO ₄ ), potassium ferrite (K ₂ FeO ₄ ), potassium peroxoferrate (KFeO) ₂ ), sodium tungstate (Na ₂ WO ₄ ), potassium tungstate (K ₂ WO ₄ ), sodium peroxytungstate (Na ₆ WO ₆ ), potassium peroxytungstate (K ₆ WO ₆ ), sodium molybdate (Na ₂ MoO ₄ ), potassium molybdate (K ₂ MoO ₄ ), sodium peroxymolybdate (Na ₆ MoO ₆ ), potassium peroxo molybdate (K ₆ MoO ₆ ), sodium tetraborate (Na ₂ B ₄ O ₇ ), potassium tetraborate (K ₂ B ₄ O ₇ ), sodium cobaltate (NaCoO ₂ ), sodium cobaltite (Na ₂ CoO ₂ ), potassium cobaltate (KCoO ₂ ), potassium cobaltite (K ₂ CoO) ₂ ), sodium nickelate (Na ₂ NiO ₂ ), potassium nickelate (K ₂ NiO ₂ ), sodium copper phosphate (Na ₂ CuO ₂ ), potassium copperate (K ₂ CuO ₂ ), sodium cuprous (NaCuO) , potassium citrate (KCuO), sodium zincate (Na ₂ ZnO ₂ ), potassium zincate (K ₂ ZnO ₂ ), sodium chromate (NaCrO ₂ or Na ₃ CrO ₃ ), potassium chromate (KCrO ₂ or K) ₃ CrO ₃ ), sodium manganate (Na ₂ MnO ₃ or NaMnO ₂ ) or potassium manganate (K ₂ MnO ₃ or KMnO ₂ ).

The present invention further provides a method for preparing the above solid base catalyst. Please refer to FIG. 1 . FIG. 1 is a flow chart showing a method for preparing a solid base catalyst for producing biodiesel according to an embodiment of the present invention. The method for preparing a solid base catalyst for producing biodiesel comprises the steps S100, S102 and S104.

First, as shown in step S100, a first solid reactant is provided. According to an embodiment of the invention, the first solid reactant system comprises an alkali gold group element, and is preferably a lithium source, a sodium source and a potassium source. Further, the lithium source may be pure lithium, lithium alloy, lithium nitrate (LiNO ₃ ), lithium carbonate (Li ₂ CO ₃ ), lithium hydroxide (LiOH), lithium oxide (Li ₂ O), spodumene, lithium mica. Or lithium feldspar, the sodium source may be sodium carbonate (Na ₂ CO ₃ ), sodium oxide (Na ₂ O), albite (NaAlSi ₃ O ₈ ), Chilean saltpeter (NaNO ₃ ) or caustic soda, and the potassium source may be Potassium carbonate (K ₂ CO ₃ ), lithium hydroxide (LiOH), potassium oxide (K ₂ O), potassium mica, potassium feldspar or potassium alum.

Next, the first solid reactant and the second solid reactant are mixed to obtain a mixture as shown in step S102. Specifically, in step S102, the first solid reactant and the second solid reactant may be separately ground and then mixed thoroughly, or mixed and then ground, and the invention is not limited thereto. In addition, the molar ratio of the first solid reactant to the second solid reactant in this step is 1:5 to 5:1, and the influence of the molar ratio between the two on the catalytic effect of the solid base catalyst will be It will be disclosed in the experimental examples described later, and will not be described here.

The second solid reactant comprises an aluminum source, a titanium source, a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, an iron source, a boron source, a germanium source, a cobalt source, a chromium source, a manganese source, and a nickel source. Or copper source. According to an embodiment of the present invention, the second solid reactant may be an oxide, a hydroxide, a nitrate or a carbonate of the foregoing element, such as alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconium dioxide. (ZrO ₂ ), bismuth nitrate (Bi(NO ₃ ) ₃ .5H ₂ O), bismuth oxide (Bi ₂ O ₃ ), niobium pentoxide (Nb ₂ O ₅ ), ammonium vanadate (NH ₄ VO ₃ ), Vanadium (III) oxide (V ₂ O ₃ ), vanadium (VI) oxide (V ₂ O ₅ ), iron oxide (Fe ₂ O ₃ ), ferrous oxide (FeO), tungsten oxide (WO ₃ ), molybdenum trioxide (MoO ₃ ), boron oxide (B ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), manganese dioxide (MnO ₂ ), manganese hydroxide (Mn(OH) ₂ ), cobalt oxide (Co ₂ O ₃ ) Cobalt oxide (CoO), nickel oxide (NiO), nickel hydroxide (Ni(OH) ₂ ), copper oxide (CuO), cuprous oxide (Cu ₂ O) or zinc oxide (ZnO).

In addition, the source of the aforementioned second solid reactant may be obtained from solid waste which is common in life or industry. Taking aluminum source as an example, aluminum is the third most abundant element on the earth, and it is also the most abundant metal. In addition to the easy acquisition of bauxite for natural clay, there are many articles applied to aluminum in life. However, when these aluminum-containing items need to be eliminated, a large amount of garbage is generated. Therefore, the method for preparing a solid alkali catalyst provided by the invention can also utilize an aluminum-magnesium alloy, a titanium-aluminum alloy, an bauxite or an aluminum-containing waste (such as an aluminum foil, an aluminum can, a high temperature furnace insulating brick, Waste metal, tantalum or waste catalysts are used as the second solid reactants to make the Earth's limited resources available to the best of its ability, while also meeting current environmental standards.

Taking titanium source as an example, "titanium iron sludge or slime" is a waste derived from the production or refining of titanium dioxide. Its characteristics are viscous colloids, the color of waste liquid is dark green, strong acid and iron chloride, most The national standard is a kind of hazardous business waste. In the present invention, in addition to the use of the titanium-containing waste as the second solid reactant, in addition to the preparation of a solid alkali catalyst for the production of biodiesel, the purpose of waste utilization can be further achieved. What's more, the second solid reactant can also be taken from iron slag, recycled batteries, steel slag, waste bricks, tiles, porcelain, pottery, zircon, borate, borosilicate ore, vanadium Waste catalyst, antimony concentrate, tungsten steel or natural clay and its products.

In addition, in accordance with an embodiment of the present invention, step S102 may further comprise first impregnation (not shown) of the first solid reactant and the second solid reactant. In detail, the above treatment first provides a solution containing the above mixture, that is, the first solid reactant and the second solid reactant are added to water and then thoroughly stirred to form the above solution. Finally, the above solution is dried, thereby achieving thorough mixing for subsequent sintering.

Finally, as shown in step S104, the above powder mixture is heat-treated to obtain a solid base catalyst. According to an embodiment of the present invention, step S104 is a calcination step, and preferably the calcination step has a temperature of 700 ° C to 1000 ° C, and the time may last from 0.5 to 4 hours, and the calcination temperature and calcination time are on the solid base. The influence of the catalytic effect of the catalyst will be disclosed in the experimental examples described later, and will not be described herein. In addition, the step S104 may further comprise the step of grinding the calcined mixture into a powder, so that the solid base catalyst can be uniformly dispersed in the oil during the subsequent transesterification reaction, and the specific surface area of the solid alkali catalyst is further increased. In order to increase its transesterification rate in the reaction.

The present invention further provides a method for producing biodiesel by transesterification reaction using the above solid base catalyst. As shown in FIG. 2, the method for producing a biodiesel by transesterification of a solid base catalyst comprises the step S200 and the step. S202, step S204 and step S206.

First, as step S200, a solid base catalyst prepared in steps S100 to S104 is provided. Next, the fats and oils are mixed and heated under reflux at 65 ° C while the above solid base catalyst is added to carry out the transesterification reaction as shown in step S202. Preferably, the above oil and fat refers to triglyceride in oil, and the oil may be vegetable oil, such as soybean oil, olive. Olive oil, Cron oil, Canola oil, Coconut oil, Castor oil or Cocoa ester, the present invention does not intend to use this Limited. Moreover, the oil can also be the used waste oil, thereby recycling the used oil as a fuel, which is quite environmentally friendly and hygienic. Further, the above alcohol is preferably methanol.

Subsequently, as shown in step S204, the fatty acid methyl ester, glycerin, and solid base catalyst produced by the transesterification reaction are separated. The specific method for the separation is, for example, firstly allowing the aforementioned product to be separated and then sequentially separated, and the layered upper ester liquid is a fatty acid methyl ester, which is a biodiesel which can be used as a fuel. Finally, in order to purify the biomass diesel, the residual methanol and water in the ester liquid may be removed by rapid evaporation or vacuum distillation, as shown in step S206.

Further, the upper ester liquid may be washed with water several times before evaporation or distillation to remove as much as possible of the residual solid base catalyst and glycerin in the upper ester liquid. The manner in which the oleyl alcohol is heated and refluxed is well known to those skilled in the art and can be carried out according to the prior art, and therefore will not be further described herein.

In addition, in order to explain the catalytic effect of the above solid base catalyst on the transesterification reaction, the synthesized biodiesel will be identified by the transesterification rate to determine the content of the fatty acid methyl ester. In this study, the Ministry of Economy The Standards Inspection Bureau, CNS15051, Oil Derivatives (ie fatty acid methyl esters) - Determination of total fatty acid methyl esters and methyl linoleic acid methyl esters" was used to calculate the transesterification rate of biodiesel. In this method, methyl heptadecanoate is used as an internal standard, n-heptane is used as a solvent, and it is set to a solution having a concentration of about 10 mg/ml, and then 250 mg of the purified diesel oil is purified by a fine scale, and then added. Configure 5 ml of the internal standard solution and mix it evenly, then analyze it by gas chromatography. At the time of analysis, a sample of 0.1 to 1.0 μL is sucked into the injection port of the gas chromatograph using a syringe, and then analyzed by a flame ion detector. The chromatogram obtained after the analysis is integrated to calculate the total fatty acid. The content of methyl ester.

The composition of the solid base catalyst provided by the present invention, the preparation method thereof and the method for producing the biodiesel using the same have been roughly described above. The respective steps of the present invention, experimental data thereof and the experimental data thereof will be further described below by using various experimental examples. The achievable effects are not intended to limit the scope of the invention to be protected, and are described first.

[Experimental Example 1]

In Experimental Example 1, a lithium source was used as the first solid reactant and an aluminum source was used as the second solid reactant, and the solid base catalyst prepared contained lithium aluminate.

Preferably, the first solid reactant is a commercially available reagent grade lithium carbonate (Li ₂ CO ₃ , purity > 98%, Katayama Chemical Co.), and the second solid reactant is a commercially available reagent grade. Alumina (Al ₂ O ₃ , purity >99%, Showa Chemical Co.), and the preparation method is as follows. First, 1 mole of lithium carbonate and 1 mole of alumina were placed in a beaker, and 100 mL of deionized water was added and stirred for 30 minutes to uniformly mix into a solution containing a mixture of lithium carbonate and alumina. Next, the above solution was placed in an oven and baked at 120 ° C for 24 hours, and the dried mixture was ground in a mortar and placed in a high temperature furnace (Dengyng instruments CO. LTD, DF-40) for calcination, wherein calcination was carried out. The temperature was 900 ° C and the calcination time was 1 hour. Finally, after the above mixture is calcined and cooled to room temperature, it can be ground using a mortar to obtain a solid base catalyst for subsequent transesterification.

Next, the present invention changes various synthesis conditions of the solid base catalyst such as the molar number of lithium carbonate, the calcination temperature of the solid base catalyst, and the calcination time to investigate the above-mentioned solid alkali catalyst containing lithium aluminate. Preferred synthetic parameters. Firstly, the effect of changing the amount of lithium carbonate added on the synthesis of solid base catalyst is discussed. The fixed conditions such as the amount of alumina used are 1 mole, the calcination temperature is 900 ° C, the calcination time is 1 hour, and the amount of lithium carbonate is 0.25 m. 0.5 mu, 1 m, 2 m, 3 m. The detailed synthesis steps are referred to in FIG. 1 and the foregoing, and are not described herein again.

The synthesized solid base catalyst was measured for its composition by X-ray Diffractometer (MAC Science, MXP18), and its surface topography and utilization ratio were observed by a field-scanning scanning electron microscope (JEOL, JSM-7401F). The Surface Area and Porosity Analyzer (BET) was used to measure the specific surface area and pore structure and to measure the transesterification rate.

Please refer to FIGS. 3A to 3C. FIG. 3A is an X-ray diffraction analysis result of the solid base catalyst prepared by using different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention, and FIG. 3B is a diagram An electron micrograph image of a solid base catalyst prepared by different lithium carbonate to alumina molar ratio in Experimental Example 1 and a 3C graph of different lithium carbonate to alumina molar ratio in Experimental Example 1 of the present invention Diagram of the transesterification rate of the prepared solid base catalyst for the transesterification reaction.

First, as shown in Fig. 3A, the data in the figure is from bottom to top, respectively, when the solid base catalyst is prepared, the molar ratio of lithium carbonate to alumina is 0.25:1, 0.5:1, 1:1, 2:1. And lithium carbonate, aluminum oxide, rhombohedral structure of lithium aluminate with 3:1 (ie lithium carbonate in an amount of 0.25 m, 0.5 m, 1 m, 2 m and 3 m) (r-LiAlO ₂ ) and lithium tetralithate (t-LiAlO ₂ ) in a tetragonal phase structure are indicated by hollow circles, filled circles, open triangles and solid triangles, respectively.

Wherein, when the molar ratio of lithium carbonate to alumina is 0.25:1, lithium aluminate of two different crystal phases of t-LiAlO ₂ and r-LiAlO ₂ are present in the solid base catalyst, and r-LiAlO The crystallinity of ₂ is good, but since there is too little lithium carbonate added, residual alumina remains. When the molar ratio of lithium carbonate to alumina is 0.5:1, it is understood from the diffraction peak that the crystallinity of t-LiAlO ₂ is better than that of r-LiAlO ₂ , but there is still residual alumina. When the molar ratio of lithium carbonate to alumina is 1:1, it can be seen from the figure that only lithium aluminate having a crystal phase of t-LiAlO ₂ is present, and a small amount of residual alumina can be presumed to be when the drug is taken. The error caused. When the molar ratio of lithium carbonate to alumina is 2:1, it can be seen from the figure that only lithium aluminate having a crystal phase of t-LiAlO ₂ is also present. Further, at this time, although there is no residual alumina, too much unreacted lithium carbonate exists. When the molar ratio of lithium carbonate to alumina is 3:1, lithium aluminate of two different crystal phases of t-LiAlO ₂ and r-LiAlO ₂ are present in the solid base catalyst, and the crystallinity of r-LiAlO ₂ is obtained. better. In addition, it can be seen from the figure that there is lithium carbonate remaining at this time.

The surface morphology of lithium aluminate is shown in Fig. 3B. The left to right and top to bottom of the graph show the molar ratio of lithium carbonate to alumina during synthesis. The surface morphology of lithium aluminate prepared by 0.25:1, 0.5:1, 1:1, 2:1 and 3:1. It can be seen from the figure that when the amount of lithium carbonate added is increased, the surface morphology of the solid base catalyst prepared by the preparation is gradually changed into an irregular block.

Next, the analysis results of the analysis of the specific surface area and the pore structure of the solid base catalyst by the specific surface area analyzer are as shown in Table 1. The specific surface areas of the solid base catalyst were 0.9578 (0.25 m), 0.9811 (0.5 m), and 1.0271, respectively. 1 mole), 1.0264 (2 moles) and 0.8947 (3 moles) m ² /g and the average pore diameters are 1024.65 (0.25 m), 973.64 (0.5 m), 747.29 (1 m), 549.25 (2 m) and 638.42 (3 m) Å. It can be seen that the solid base catalyst prepared by using different amounts of lithium carbonate in the present invention belongs to a macroporous structure, and the lithium aluminate prepared when the molar ratio of lithium carbonate to alumina is 1:1 has The largest surface area.

Subsequently, the transesterification ratio of the solid base catalyst prepared by using different amounts of lithium carbonate is shown in FIG. 3C, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid alkali catalyst is used in an amount of 6 wt%. The reaction time was 2 hours and the reaction temperature was 65 °C. It should be noted that when the transesterification reaction is carried out by the solid base catalyst containing lithium aluminate in Experimental Example 1, it can be fixed such as an oil to alcohol ratio (e.g., 1:24), and a solid base catalyst amount (e.g., 6 wt%). With the reaction temperature (such as 65 ° C) and so on The reaction conditions were changed, and the reaction time was changed to observe the optimum transesterification conditions of the solid base catalyst of Experimental Example 1. It can be seen from the following Table 2 that the solid base catalyst of Experimental Example 1 has the best transesterification effect at the reaction time of 2 hours, and therefore will be carried out under such conditions, but the present invention is not limited thereto.

As shown in Fig. 3C, when the molar ratio of lithium carbonate to alumina is 0.25:1, the transesterification ratio of the solid base catalyst is only 0.90%, and when the molar ratio of lithium carbonate to alumina is 3: At 1 o'clock, its transesterification rate was as high as 97.09%. However, it is known from Fig. 3A that lithium carbonate remains in the solid base catalyst synthesized when the molar ratio of lithium carbonate to alumina is 3:1.

Next, the effects of different calcination temperatures on the prepared solid base catalyst were further investigated. The molar ratio of fixed lithium carbonate to alumina was 1:1 and the calcination time was 1 hour, and the calcination temperature was 600 ° C and 700 ° C, respectively. It is carried out at 800 ° C, 900 ° C, and 1000 ° C. Please refer to FIG. 3D and FIG. 3E. FIG. 3D shows the X-ray diffraction of the solid base catalyst prepared by fixing the lithium carbonate to alumina molar ratio in FIGS. 3A to 3C and preparing at different calcination temperatures. As a result of the analysis, FIG. 3E is a graph showing the relationship between the transesterification rate of the transesterification reaction of the solid base catalyst in FIG. 3D.

First, in the 3D figure, the data from the bottom to the top are solid base catalysts prepared by calcination temperatures of 600 ° C, 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, and lithium carbonate, alumina, and different crystal phases of aluminum. Lithium acid r-LiAlO ₂ and t-LiAlO ₂ are indicated by hollow circles, filled circles, open triangles and solid triangles, respectively. When a solid base catalyst is prepared using a calcination temperature of 600 ° C, the detected diffraction peaks belong to the starting materials of alumina and lithium carbonate, so it can be judged that the alumina has not obtained sufficient energy at a calcination temperature of 600 ° C. To synthesize lithium aluminate. When using a calcination temperature of 700 ° C to prepare a solid base catalyst, most of the diffraction peaks belong to the starting materials of aluminum oxide and lithium carbonate, and only a few of the diffraction peaks belong to lithium aluminate, and at this time t-LiAlO ₂ Lithium aluminate with two different crystal phases of r-LiAlO ₂ is present in the solid base catalyst, but the lithium dilithate of these two crystal phases has no diffraction peaks, so the crystallinity is not good. From the above factors, it can be judged that when the calcination temperature is 700 ° C, although the production of lithium aluminate has begun, the energy provided by the reaction temperature is insufficient. When a solid base catalyst is prepared using a calcination temperature of 800 ° C, it can be seen that there is no lithium carbonate in the solid base catalyst, and the diffraction peak of lithium aluminate is also more obvious than the solid base catalyst prepared by using a calcination temperature of 700 ° C. . Further, lithium aluminate having two different crystal phases of t-LiAlO ₂ and r-LiAlO ₂ is present in the solid base catalyst, so the calcination temperature of 800 ° C is a preferred reaction temperature for preparing the solid base catalyst of the present invention. Furthermore, when a solid base catalyst is prepared using a calcination temperature of 900 ° C, only lithium aluminate which is a t-LiAlO ₂ crystal phase structure is present in the solid base catalyst, and no lithium carbonate remains, as for a little residual alumina. It can be presumed to be the error caused by the weighing of the medicine. When a solid base catalyst was prepared using a calcination temperature of 1000 ° C, the results were also similar to those at a calcination temperature of 900 °C.

Subsequently, the transesterification rate of the solid base catalyst prepared by different calcination temperatures is shown in FIG. 3E, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid base catalyst is used in an amount of 6 wt%. Time is 2 hours, anti The temperature should be 65 °C. As shown in the figure, when the solid base catalyst prepared by using the calcination temperature of 600 ° C and 700 ° C is in the transesterification reaction, the product is not formed or the lithium aluminate crystal in the solid base catalyst is not crystalline. Preferably, the transesterification rate obtained is only 29.25% and 29.54%. When the solid base catalyst prepared by calcination temperature of 800 ° C and 900 ° C is used, since the crystallinity of the produced lithium aluminate is good, the transesterification rate is increased to 60.89% and 66.59%. However, when a solid base catalyst prepared by calcination at a temperature of 1000 ° C is used, it may be because the temperature is too high, so that a sintering phenomenon occurs, resulting in a decrease in the active site of the solid base catalyst, so that the transesterification rate is lowered to 3.80%.

Finally, the effects of different calcination time on the solid base catalyst prepared were investigated. The molar ratio of fixed lithium carbonate to alumina was 1:1 and the calcination temperature was 900 °C. The calcination time was 0.5 hour, 1 hour, 2 respectively. Hour, 3 hours, 4 hours. Please refer to FIG. 3F and FIG. 3G. FIG. 3F is a result of X-ray diffraction analysis of the solid base catalyst prepared by fixing the molar ratio of lithium carbonate to alumina in the 3A to 3C and preparing at different calcination times. Fig. 3G is a graph showing the relationship between the transesterification rate of the transesterification reaction of the solid base catalyst in Fig. 3F.

First, the data of FIG. 3F, respectively, from bottom to top by the baking time is 0.5 hours, the solid base catalyst prepared in 1 hour, 2 hours, 3 hours, 4 hours, and aluminum oxide, respectively, and t-LiAlO ₂ solid circles Mark with a solid triangle. It can be seen from the figure that the spectra of solid base catalysts prepared using different calcination times are similar to each other and belong to the absorption peak of lithium aluminate having a tetragonal phase structure. However, the characteristic peak intensity of the solid base catalyst prepared using the calcination time of 0.5 hours is weaker than that of the solid base catalyst prepared by the remaining calcination time, while the weaker characteristic peak intensity indicates that the solid base catalyst has poor crystallinity, so it is presumed that A calcination time of 0.5 hours is still insufficient to complete the reaction.

Subsequently, the transesterification rate of the solid base catalyst prepared by different calcination time is shown in FIG. 3G, wherein the fixed oleyl alcohol molar ratio is 1:12, and the solid base catalyst is used in an amount of 6 wt%. The time was 2 hours and the reaction temperature was 65 °C. As shown, when the calcination time was increased from 0.5 hours to 1 hour, the transesterification rate increased from 37.34% to 66.59%. However, when the calcination time is increased to 2 hours or even 4 hours, the transesterification rate is greatly reduced. It is speculated that the reason may be that the calcination time is too long, resulting in a change in the morphology of the solid base catalyst, resulting in a decrease in the active site. The ester effect is less than ideal.

In addition, the second solid reactant can be carried out by using bauxite as the aluminum source in addition to the alumina of the commercially available reagent grade, and the preparation method thereof is referred to FIG. 1 and will not be described herein. Please refer to FIG. 4A to FIG. 4C. FIG. 4A is a solid base catalyst pair prepared by using lithium bauxite as a second solid reactant in the experimental example 1 of the present invention with different lithium carbonate to bauxite molar ratio. The transesterification ratio diagram of the transesterification reaction, and Fig. 4B shows the transesterification reaction of the solid base catalyst prepared by using different calcination temperatures when the bauxite is used as the second solid reactant in the experimental example 1 of the present invention. The ester rate relationship diagram, and FIG. 4C is a diagram showing the relationship between the transesterification ratio of the solid base catalyst prepared by the different calcination time when the bauxite is used as the second solid reactant in the experimental example 1 of the present invention. .

As shown in Fig. 4A, the fixed calcination temperature is 800 ° C and the calcination time is 4 hours, and the molar ratio of lithium carbonate to bauxite is changed to 1:0.5, 1:1, 1:2, 1:3, respectively. 1:4 Preparation of a solid base catalyst. When a solid base catalyst is prepared by using a molar ratio of lithium carbonate to bauxite of 1:4, the transesterification rate is Up to 99.49%. Next, as shown in FIG. 4B, the molar ratio of lithium carbonate to bauxite was 1:4, and the solid calcination temperature was changed to 600 ° C, 700 ° C, 800 ° C, 900 ° C, and 1000 ° C to prepare a solid alkali catalyst. When the solid base catalyst is prepared at a calcination temperature of 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, the transesterification rate is above 95%, wherein the transesterification rate of the solid base catalyst prepared at a calcination temperature of 800 ° C is used. Up to 99.49%. Finally, as shown in Fig. 4C, the molar ratio of lithium carbonate to bauxite was fixed at 1:4, and the calcination temperature was 800 ° C, and the calcination time was 1, 2, 3, 4, and 5 hours, respectively. Solid base catalyst. As can be seen from the figure, the calcination time in the preparation of the solid base catalyst prepared from lithium carbonate and bauxite is preferably 3 hours.

It can be seen from the description of Experimental Example 1 that the present invention can prepare not only a commercially available reagent grade lithium carbonate and alumina, but also a solid base catalyst containing lithium aluminate and having a good transesterification effect, and bauxite can be used as the second solid. The reactants prepare a solid base catalyst which also has a good transesterification effect, and achieves the best use thereof.

[Experimental Example 2]

In Experimental Example 2, a lithium source was used as the first solid reactant and a titanium source was used as the second solid reactant, and the solid base catalyst prepared contained lithium titanate.

In the present experimental example, the first solid reactant used was lithium carbonate, and the second solid reactant was titanium dioxide, and the solid base catalyst was lithium titanate. First, 0.1 mol of titanium dioxide and 0.1 mol of lithium carbonate were placed in a mortar and stirred well. Next, the mixed titanium dioxide and lithium carbonate are placed in a high-temperature furnace and calcined at 800 ° C for 4 hours, and then ground and ground. The powder can be used as a solid base catalyst for subsequent transesterification. Please refer to FIGS. 5A to 5F. FIGS. 5A and 5B are X-ray diffraction analysis results of the solid base catalyst prepared by using different lithium carbonate to titanium dioxide molar ratio in Experimental Example 2 of the present invention and the pair thereof. X-ray diffraction analysis results of the solid base catalyst prepared by different molar calcination temperatures of lithium carbonate to titanium dioxide molar ratio in Figure 5C and Figure 5D. And its transesterification rate diagram for the transesterification reaction, 5E and 5F are X-ray windings of the solid base catalyst prepared by fixing the lithium carbonate molar ratio of the lithium carbonate to the titanium dioxide molar ratio of FIG. 5A and different calcination times. The results of the analytical analysis and its relationship to the transesterification rate of the transesterification reaction.

First, as shown in Fig. 5A, the data in the figure are from bottom to top, respectively, when the solid base catalyst is prepared, the molar ratio of lithium carbonate to titanium dioxide is 1:1, 2:1 and 3:1, and lithium titanate. Lithium carbonate and titanium dioxide are indicated by solid circles, solid squares and solid triangles, respectively. Wherein, when the molar ratio of lithium carbonate to titanium dioxide is 1:1 and 2:1, lithium titanate is present in the solid base catalyst. However, when the molar ratio of lithium carbonate to titanium dioxide is 3:1, it is found that lithium carbonate remains in the solid base catalyst. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is as shown in Table 3 and Figure 5B. Shown. It can be seen that the solid base catalyst containing lithium titanate prepared by the lithium carbonate to titanium dioxide molar ratio of 2:1 and 3:1 has a good transesterification effect.

Next, the molar ratio of the fixed lithium carbonate to the titanium dioxide was 2:1 and the calcination time was 4 hours, and a solid base catalyst was prepared at a calcination temperature of 700 ° C, 800 ° C, 900 ° C, and 1000 ° C, respectively. As shown in Fig. 5C, when a solid base catalyst is prepared using a calcination temperature of 700 ° C, the detected diffraction peaks are almost all of the starting materials of lithium carbonate and titanium dioxide, so it can be judged that the calcination temperature is 700 ° C. Not enough energy is available to synthesize a solid base catalyst. The pattern of the solid base catalyst prepared at a calcination temperature of 800 ° C, 900 ° C, and 1000 ° C is similar, that is, lithium titanate is present in the solid base catalyst. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is as shown in Table 4 and Figure 5D. Shown. From this, it is understood that the solid base catalyst prepared at a calcination temperature of 800 ° C, 900 ° C, and 1000 ° C can have an average transesterification ratio of 95% or more.

Finally, as shown in Fig. 5E, the molar ratio of lithium carbonate to titanium dioxide is 2:1, and the calcination temperature is 800 ° C, and the solid base catalyst is prepared at 1, 2, 3, and 4 hours respectively. . As can be seen from the figure, the calcination time in the preparation of the solid base catalyst prepared by using lithium carbonate and titanium oxide is preferably 4 hours, and the residue of lithium carbonate is observed under other conditions. At this time, the prepared solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil-to-alcohol ratio of 1:24, a catalyst amount of 6 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification rate of the solid alkali catalyst is as shown in Table 5 and Figure 5F. Shown. From this, it is understood that the patterns of the solid base catalysts prepared using different calcination times are similar to each other, and the calcination time in the preparation of the solid base catalyst prepared from lithium carbonate and titanium oxide is preferably 4 hours.

As can be seen from the above description, in the second solid reactant of the present invention, in addition to the aluminum source, a solid base catalyst having a good transesterification effect can be prepared by using a titanium source as the second solid reactant. It is worth noting that in the current industry, in the preparation of titanium dioxide or related processes, many titanium-containing sludges which are unfavorable to the environment are often produced. The method of the present invention can further recycle the solid waste containing titanium to achieve environmental protection. .

Further, please refer to Fig. 5G, which is a graph showing the relationship between the number of times of repeated use of the solid base catalyst prepared by lithium carbonate and titanium dioxide in the experimental example 2 of the present invention, and the transesterification ratio. More specifically, if the solid base catalyst can be repeatedly used, the cost of producing the quality diesel can be reduced, and the practical value of the solid base catalyst can be improved. Accordingly, in this experimental example, the number of repeated use of the solid base catalyst containing lithium carbonate is further investigated, and the conditions of the fixed transesterification reaction are as follows: oil alcohol molar ratio 1:24, solid alkali catalyst addition amount 6 wt%, The reaction time was 4 hours and the reaction temperature was 65 °C.

As can be seen from the figure, the solid base catalyst of this experimental example can obtain a transesterification rate of more than 80% before repeated use for 10 times, and even 60% of the transesterification rate even when the 11th time of repeated use, that is, The solid base catalyst prepared by the invention has considerable economic benefits.

[Experimental Example 3]

In Experimental Example 3, a sodium source or a potassium source was used as the first solid reactant and a titanium source was used as the second solid reactant, and the solid base catalyst prepared contained sodium titanate or potassium titanate.

In this experimental example, the first solid reactant used sodium carbonate and potassium carbonate, and the second solid reactant used titanium dioxide. The solid base catalyst is prepared by first mixing 1 mol of sodium carbonate or potassium carbonate with 1 mol of titanium dioxide, calcining at 800 ° C for 4 hours, and then taking out and grinding into a powder to obtain a solid base catalyst. At this time, the above solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil to alcohol ratio of 1:36, a catalyst amount of 8 wt%, a reaction time of 2 hours, and a reaction temperature of 65 ° C are fixed in the reaction, and the transesterification ratio of the solid base catalyst is shown in Table 6.

It can be seen from Experimental Example 3 that in the present invention, in addition to the lithium source, a solid base catalyst having a good transesterification effect can be prepared by using a sodium source or a potassium source as the first solid reactant.

[Experimental Example 4]

In this experimental example, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a zirconium source. At this time, a solid base catalyst containing lithium zirconate can be obtained in accordance with the following procedure. First, 1 mol of lithium carbonate, sodium carbonate or potassium carbonate is mixed with 1 mol of zirconia, calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. At this time, the above solid base catalyst was subjected to a transesterification reaction. Preferably, other conditions such as an oil to alcohol ratio of 1:36, a catalyst amount of 8 wt%, a reaction time of 2 hours, and a reaction temperature are fixed in the reaction. The degree of transesterification of the solid base catalyst is shown in Table 7. It can be seen that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is a zirconium source.

[Experimental Example 5]

In this experimental example, the first solid reactant may be a lithium source and the second solid reactant is a rhodium source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is cerium nitrate. At this time, a solid base catalyst comprising lithium niobate is prepared according to the following procedure. First, 1 mol of lithium carbonate and 2 mol of lanthanum nitrate were mixed by an impregnation method, and then calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. However, in the present experimental example, the ruthenium source may also be ruthenium oxide, and the present invention is not intended to be limited thereto. When the cerium source is cerium oxide, 1 mole of lithium carbonate and 1 mole of cerium oxide are first mixed, and then calcined at 800 ° C for 4 hours, and then ground and ground into powder, that is, the preparation of the solid alkali catalyst is completed.

Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source, and the preparation procedure of the solid base catalyst is as follows. First, 1 mol of sodium carbonate or potassium carbonate and 1 mol of cerium oxide were mixed, and then calcined at 700 ° C for 4 hours, and then taken out and ground into a powder, which is a solid base catalyst containing sodium citrate or potassium citrate.

Next, the transesterification reaction was carried out by each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 8. It can be seen that, in the present invention, when the second solid reactant is a ruthenium source, a solid base catalyst having a transesterification effect can be prepared, and when the second solid reactant is ruthenium oxide, the solid base catalyst is transferred. The ester ratio is better than when it is cerium nitrate.

[Experimental Example 6]

In this experimental example, the first solid reactant may be a lithium source and the second solid reactant is a rhodium source. Preferably, the first solid reactant is carbonic acid Lithium, and the second solid reactant is antimony pentoxide. In more detail, when the molar ratio of lithium carbonate to antimony pentoxide is 1:1, 2:1 and 3:1, lithium bismuth niobate and lithium pyroantimonate may be separately prepared according to the following preparation methods. Solid base catalyst with lithium niobate. First, lithium carbonate and antimony pentoxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.

Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.

Next, the transesterification reaction was carried out by each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 9. Therefore, in the present invention, when the second solid reactant is a ruthenium source, a solid base catalyst having a transesterification effect can be prepared, that is, a ruthenium-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Biodiesel is used to achieve the best results.

[Experimental Example 7]

In this experimental example, the first solid reactant may be a lithium source or a sodium source, and the second solid reactant is a vanadium source. Wherein when the first solid reactant is sodium carbonate and the second solid reactant is ammonium vanadate, the molar ratio of sodium carbonate to ammonium vanadate is 3:1 or 1:1, and is separately prepared according to the following preparation method. A solid base catalyst containing sodium orthovanadate or sodium metavanadate. In more detail, sodium carbonate and ammonium vanadate are mixed with different molar ratios, and then calcined at 800 ° C for 4 hours, and then ground and ground into powder, which can be used as a solid containing sodium orthovanadate or sodium metavanadate. Alkali catalyst. The preparation method of lithium vanadate is substantially as described above, and will not be described herein.

Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 10. It can be seen that in the present invention, when the second solid reactant is a vanadium source, a solid alkali catalyst having a transesterification effect can be prepared, that is, a vanadium-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Produce biodiesel to achieve the best results.

[Experimental Example 8]

In this experimental example, the first solid reactant may be a sodium source or a potassium source, and the second solid reactant is an iron source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the second solid reactant is iron oxide, and the sodium ferrite-containing, potassium ferrite, and sodium peroxyferrate can be respectively prepared according to the following preparation methods. Or a solid base catalyst of potassium peroxate. First, 1 or 3 mol of sodium carbonate or potassium carbonate and 1 mol of iron oxide are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. Next, the transesterification reaction was carried out by the above solid base catalyst, and the transesterification ratio of the solid base catalyst was as shown in Table 11. From this, it is known that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is an iron source.

[Experimental Example 9]

In this experimental example, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a boron source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the second solid reactant is boron oxide, and the solid base containing sodium borate or potassium borate can be separately prepared according to the following preparation method. catalyst. First, 2 mol of lithium carbonate, sodium carbonate or potassium carbonate and 1 mol of boron oxide are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst. Next, the transesterification reaction was carried out by the above solid base catalyst, and the transesterification ratio of the solid base catalyst was as shown in Table 12. Therefore, in the present invention, when the second solid reactant is a boron source, a solid base catalyst having a transesterification effect can be prepared, that is, a boron-containing waste can be recovered in the future and recycled by a solid alkali catalyst. Produce biodiesel to achieve the best results.

[Experimental Example 10]

In this experimental example, the first solid reactant is a lithium source and the second solid reactant is a tungsten source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is tungsten oxide. In more detail, when the molar ratio of lithium carbonate to tungsten oxide is 3:1 and 1:1, a solid base catalyst containing lithium peroxytungstate and lithium tungstate can be separately prepared according to the following preparation method. First, lithium carbonate and tungsten oxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.

Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.

Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 13. It can be seen from the above that in the present invention, a solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant is a tungsten source.

[Experimental Example 11]

In this experimental example, the first solid reactant is a lithium source and the second solid reactant is a molybdenum source. Preferably, the first solid reactant is lithium carbonate and the second solid reactant is molybdenum trioxide. In more detail, when the molar ratio of lithium carbonate to molybdenum trioxide is 3:1 and 1:1, a solid base catalyst containing lithium peroxodimolybdate and lithium molybdate can be separately prepared according to the following preparation method. . First, lithium carbonate and tungsten oxide of different molar ratios are mixed, and calcined at 800 ° C for 4 hours, and then taken out and ground into a powder to obtain a solid base catalyst.

Further, in the present experimental example, the first solid reactant may also be a sodium source or a potassium source. Preferably, the first solid reactant is sodium carbonate or potassium carbonate, and the method for preparing the solid base catalyst is the same as the preparation of the solid base catalyst with lithium carbonate, and details are not described herein again.

Next, the transesterification reaction was carried out by using each of the above solid base catalysts, and the transesterification ratio of the solid base catalyst was as shown in Table 14. From this, it is known that the solid base catalyst having a good transesterification effect can also be prepared when the second solid reactant in the present invention is a molybdenum source.

[Experimental Examples 12 to 16]

In Experimental Examples 12 to 16, the first solid reactant may be a lithium source, a sodium source or a potassium source, and the second solid reactant is a cobalt source (Experimental Example 12), a chromium source (Experimental Example 13), and manganese. Source (Experimental Example 14), nickel source (Experimental Example 15), and copper source (Experimental Example 16). Specifically, the first solid reactant is lithium carbonate, and the second solid reactant may be, for example, chromium oxide, manganese dioxide, manganese hydroxide, cobalt oxide, cobalt oxide, nickel oxide, nickel hydroxide, copper oxide or Cuprous oxide. The method for preparing the solid base catalyst is substantially the same as that of Experimental Example 1 to Experimental Example 11, and will not be described herein.

Next, the transesterification ratio of the transesterification reaction by each of the above solid base catalysts is shown in Table 15, and it is understood that the second solid reactant in the present invention is also a cobalt source, a chromium source, a manganese source, a nickel source, and a copper source. A solid base catalyst having a transesterification effect can be prepared, that is, a scrap containing the above metal can be recovered in the future to be solid The method of the alkali-based catalyst is recycled to produce biodiesel to achieve the best use of the product.

[Comparative Example 1]

In Comparative Example 1, a conventional calcium oxide (purchased from Katayama Pharmaceutical Co., Ltd., Taiwan) was used as a solid base catalyst. As mentioned above, calcium oxide is a solid base catalyst commonly used in the manufacture of biodiesel, but calcium oxide has poor air stability and easily absorbs moisture and carbon dioxide in the air and fails. The calcium oxide of Comparative Example 1 and the three solid base catalysts of Experimental Example 1 and Experimental Example 2 of the present invention were exposed to a space at a constant temperature of 25 ° C and a relative humidity of 50%, and were allowed to stand for 0 hours, 24 hours, and 48 hours, respectively. After 72 hours, the transesterification reaction was carried out. Preferably, the conditions of the transesterification reaction are oleyl alcohol molar ratio 1:24, solid alkali contact The amount of the medium added was 6 wt%, the reaction time was 2 hours, and the reaction temperature was 65 ° C, and the transesterification rates of the three solid base catalysts for the oil were listed in Table 16. Specifically, the oil product used in the foregoing is soybean oil (purchased from Great Wall Enterprise Co., Ltd.), but the present invention is not intended to be limited thereto.

It can be seen from Table 16 that after exposure to air for 24 hours, the transesterification rate of lithium aluminate decreased from 98.06% to 74.97%, and the transesterification rate of lithium aluminate after 48 hours and 72 hours of exposure to air. It dropped to 57.65% and 51.92%. When the lithium titanate was exposed to air for 24 hours, 48 hours and 72 hours, the transesterification rate decreased only slightly from 99.28% to 90.17%. In contrast, calcium oxide has been greatly reduced from the original 96.66% to 3.00% after exposure to air for 24 hours, so it is known that although the solid base catalyst reduces its transesterification rate after exposure to air, the present invention provides The solid base catalysts, such as lithium aluminate and lithium titanate, are relatively stable compared to calcium oxide, except that the transesterification effect on the oil is better than that of calcium oxide.

[Comparative Example 2]

In Comparative Example 2, the solid base catalyst was prepared by first mixing 1 mol of calcium carbonate (CaCO ₃ ) with 1 mol of titanium dioxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 3]

In Comparative Example 3, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide (Mg(OH) ₂ ) with 1 mol of zirconium dioxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 4]

In Comparative Example 4, the solid base catalyst was first mixed with 1 mole of magnesium hydroxide, 1 mole of calcium carbonate, 1 mole of anhydrous cesium acetate (Sr(CH ₃ COO) ₂ ) or 1 mole of anhydrous cesium acetate. (Ba(CH ₃ COO) ₂ ) and 1 mole of cerium oxide are then calcined at 700 ° C to 800 ° C for 4 hours.

[Comparative Example 5]

In Comparative Example 5, the solid base catalyst was prepared by first mixing 3 mol of magnesium hydroxide or calcium carbonate with 1 mol of bismuth pentoxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 6]

In Comparative Example 6, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide, calcium carbonate or strontium carbonate (SrCO ₃ ) with 1 mol of tungsten oxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 7]

In Comparative Example 7, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide, calcium carbonate or cesium carbonate with 1 mol of molybdenum trioxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 8]

In Comparative Example 8, the solid base catalyst was prepared by first mixing 1 mol of calcium carbonate with 1 mol of boron oxide and then calcining at 800 ° C for 4 hours.

[Comparative Example 9]

In Comparative Example 9, the solid base catalyst was prepared by first mixing 1 mol of magnesium hydroxide with 1 mol of zirconium dioxide and then calcining at 800 ° C for 4 hours.

The solid base catalyst prepared in the above Experimental Example 2, Experimental Example 3, Experimental Example 4, Experimental Example 5, Experimental Example 6, Experimental Example 9, Experimental Example 10, Experimental Example 11 and Comparative Example 2 to Comparative Example 9 was used for the conversion. After the esterification reaction, the transesterification ratio was as shown in Table 17. It should be noted that the solid base catalyst is prepared under optimized conditions in each of the experimental examples, but the present invention is not intended to be limited thereto.

It can be seen from Table 17 that the solid base catalyst prepared by using the alkali gold group element such as lithium, sodium or potassium as the first solid reactant is in the transesterification reaction. The performance is superior to a solid base catalyst prepared by using an alkaline earth element such as magnesium, calcium, barium or strontium as the first solid reactant.

In summary, the solid base catalyst for producing biodiesel provided by the present invention has good transesterification effect on oil, and is stable and recyclable than conventional solid base catalyst, and can effectively reduce manufacturing. The cost of biodiesel. In addition, since the second solid reactant used in the preparation of the solid alkali catalyst in the present invention can be obtained from solid waste which is common in life or industry, further enables the limited resources of the earth to be utilized as much as possible, and is also in line with the current environmental protection. standard.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

S100, S102, S104‧‧‧ steps

Claims (14)

A solid base catalyst for producing biodiesel containing a compound represented by the following chemical formula (1) or chemical formula (2): Na _a X _b O _c (1); K _a X _b O _c (2); Wherein X is titanium, zirconium, hafnium, vanadium, niobium, iron, molybdenum, tungsten, boron, copper, nickel, zinc, cobalt, chromium or manganese, a is a positive integer from 1 to 6, and b is a positive integer from 1 to 4. And c is a positive integer from 1 to 7. The solid base catalyst according to claim 1, which comprises sodium titanate, potassium titanate, sodium zirconate, potassium zirconate, sodium citrate, potassium citrate, sodium citrate, potassium citrate, and partial Sodium citrate, potassium metasilicate, sodium pyroantimonate, potassium pyroantimonate, sodium orthovanadate, potassium orthovanadate, sodium metavanadate, potassium metavanadate, sodium hypovanadate, potassium hypovanadate, iron Sodium, sodium peroxoate, potassium ferrite, potassium peroxate, sodium tungstate, potassium tungstate, sodium peroxytungstate, potassium peroxytungstate, sodium molybdate, potassium molybdate, peroxymolybdenum Sodium, potassium peroxo molybdate, sodium tetraborate, potassium tetraborate, sodium cobaltate, potassium cobaltate, sodium nickelate, potassium nickelate, sodium copperate, potassium cuprate, sodium cuprous, potassium cuprous , sodium zincate, potassium zincate, sodium chromate, potassium chromate, sodium manganate or potassium manganate. A method for preparing a solid base catalyst for producing biodiesel according to claim 1, comprising the steps of: (a) providing a first solid reactant as a sodium source or a potassium source; (b) mixing the same a first solid reactant and a second solid reactant to obtain a mixture, wherein the second solid reactant comprises a titanium source; (c) heat treating the mixture to obtain the solid base catalyst. The preparation method according to claim 3, wherein the second solid reactant further comprises a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, a boron source, a germanium source, a copper source, a nickel source, and an iron. Source, zinc source, cobalt source, chromium source or manganese source. The preparation method according to claim 4, wherein the second solid reactant is titanium aluminum alloy, iron slag, high temperature furnace heat insulating brick, recycled battery, scrap metal, steel slag, titanium-containing sludge, Waste bricks, tiles, porcelain, pottery, strontium, zircon, borate, borosilicate, vanadium-containing spent catalyst, antimony concentrate, tungsten steel, waste catalyst or natural clay and its products. The preparation method according to claim 3, wherein the step (c) is to calcine the mixture in an air environment, and the temperature of the step (c) is 700 ° C to 1000 ° C, and the time system is 0.5. Hours to 4 hours. The preparation method of claim 3, wherein the step (c) comprises: grinding the mixture into a powder. The preparation method of claim 3, wherein the first solid reactant in the step (b) has a molar ratio of 1:5 to 5:1 to the second solid reactant. A method for producing biodiesel comprising the steps of: (I) providing a solid base catalyst prepared by the preparation method as described in claim 3; (II) The oil and fat are mixed with an alcohol and heated under reflux, and the solid base catalyst is added to carry out a transesterification reaction; (III) the product of the transesterification reaction is separated, and an ester liquid is taken out; and (IV) vacuum The ester liquid is distilled to remove the residual alcohol and residual moisture in the ester liquid to obtain the biodiesel. The manufacturing method according to claim 9, wherein the second solid reactant further comprises a zirconium source, a vanadium source, a germanium source, a molybdenum source, a tungsten source, a boron source, a germanium source, a copper source, a nickel source, and an iron. Source, zinc source, cobalt source, chromium source or manganese source. The manufacturing method according to claim 9, wherein the second solid reactant is titanium aluminum alloy, iron slag, high temperature furnace heat insulating brick, recycled battery, scrap metal, steel slag, titanium-containing sludge, Waste bricks, tiles, porcelain, pottery, strontium, zircon, borate, borosilicate, vanadium-containing spent catalyst, antimony concentrate, tungsten steel, waste catalyst or natural clay and its products. The manufacturing method according to claim 9, wherein the step (c) is to calcine the mixture in an air environment, and the temperature of the step (c) is 700 ° C to 1000 ° C, and the time system is 0.5. Hours to 4 hours. The manufacturing method according to claim 9, wherein the first solid reactant in the step (b) has a molar ratio of 1:5 to 5:1 to the second solid reactant. The manufacturing method according to claim 9, wherein the molar ratio of the oil to the alcohol in the step (II) is 1:6 to 1:36.