KR20090110958A - The Catalyst and The Making Method of Biodiesel - Google Patents

Abstract

PURPOSE: A biodiesel catalyst and a manufacturing method of biodiesel are provided to offer the biodiesel of high quality, and to increase yield efficiently using canola oil, waste cooking oil palm oil, corn oil and sunflower oil etc. CONSTITUTION: A biodiesel catalyst is a Ti-M-N complex catalyst. The M is a platinum based metal and one or more among Pt, Pd, Ir, and Ru. The n is a 2 group metal, and one or more among Be, Mg, Sr, and Ba. The weight ratio of Ti and M is 100 : 1 ~ 1 : 1. The ratio of the N in the sum total of the Ti and M is 10 : 1 ~ 1 : 10.

Description

Biodiesel catalyst and biodiesel manufacturing method {The Catalyst and The Making Method of Biodiesel}

The present invention cracks using soybean oil, rapeseed oil, palm oil, waste edible oil, jatropha oil, cassava oil, canola oil, corn oil and sunflower oil in a composite catalyst to make biodiesel used as a fuel for diesel internal combustion engines. It is about.

In the prior art, an esterification reaction using an acid catalyst or an alkali catalyst is used to make a methyl ester and used in a diesel internal combustion engine. However, if the acid catalyst and the alkali catalyst generated during the esterification reaction are contained in the final product, the engine is not removed. There is a problem such as a metal precipitates inside.

In the present invention, by removing the disadvantages shown in the prior art, by cracking on a solid catalyst, soybean oil, rapeseed oil, palm oil, waste edible oil to maintain the state of the product by-products such as glycerol and impurities of the acid catalyst or alkali catalyst in the final product biodiesel To provide a method for producing biodiesel using fish oil, bovine oil, chicken oil, pork oil, jatropha oil, cassava oil, canola oil, corn oil, sunflower oil.

In the present invention, in order to solve the above problems, using a cracking catalyst and using a Ti-MN composite metal catalyst to crack the raw material oil of animal and vegetable oil at a temperature between 250 ℃ to 380 ℃ to produce a biodiesel of excellent performance do. Here, M is a precious metal of at least one metal of Pt, Pd, Ir, Ru, N is a group 2 compound of at least one of Be, Mg, Sr, Ba.

The present invention thus obtained provides the effect of obtaining high quality and high quality biodiesel by the production method of the present invention using the catalyst for biodiesel production used in the present invention, using animal and vegetable fats and oils as raw materials.

The cracking catalyst used in the present invention is TiCl ₄ or titanium tetraisopropoxide as a Ti metal and platinum metal as a platinum group metal as M metal, chloroplatinic acid, platinum nitrate, or palladium metal as palladium chloride or palladium nitrate or iridium metal as iridium metal. Or a ruthenium metal with at least one metal compound of ruthenium chloride or ruthenium nitrate, and beryllium metal, a Group 2 metal as N metal, beryllium chloride or beryllium nitrate, or magnesium metal as magnesium chloride or magnesium nitrate or barium metal as nitrate. A barium, barium chloride or strontium metal is prepared by the sol-gel method by mixing at least one metal compound in strontium nitrate or strontium chloride and stirring at 60 rpm or more at 60 ° C. to 150 ° C. for at least 3 hours in an aqueous solution of nitric acid, sulfuric acid or hydrochloric acid. Woman makes Ti-MN complex catalyst. Wherein M represents a platinum group metal and is at least one metal of Pt, Pd, Ir, Ru, and N is a group 2 metal and is at least one of Be, Ma, Ba, Sr. The ratio of the materials used in the Ti-MN composite catalyst is mixed in a weight ratio of Ti: M = 100: 1 to 1: 1, and the ratio of N metal to the sum of Ti and M metal is 10: 1 to 1: Use by mixing in weight ratio of 10. When the weight ratio between the metals is exceeded, the conversion rate of the cracking reaction in the catalyst is remarkably decreased, and the yield of biodiesel is remarkably decreased.

The catalyst prepared above is coated on the surface of pellets or beads of ceramic material, plastic, glass, or metal, having a diameter of 0.1 mm to 15 mm, and placed in a reactor. Add one or two or more of animal and vegetable oils such as rapeseed oil, palm oil, waste cooking oil, fish oil, beef oil, chicken oil, pork oil, jatropha oil, cassava oil, canola oil, corn oil and sunflower oil. Cracking the raw material oil of animal and vegetable fats and oils for more than 5 minutes at 60 rpm or more at a temperature between ℃ produces biodiesel of excellent performance. The catalyst-coated beads or pellets are separated and recovered, and distilled at 190 ° C. to obtain more pure biodiesel to obtain high quality biodiesel. If the reaction temperature is lower than the above range, the cracking conversion rate is significantly lowered, and the yield of biodiesel is significantly lowered. If the reaction temperature is higher than the above range, excessive cracking occurs and the yield to biodiesel is significantly decreased or carbonization occurs. On the other hand, if the reaction time is less than 5 minutes, the cracking conversion rate is lowered, the biodiesel yield is significantly reduced. The weight ratio of beads or pellets coated with Ti-MN composite catalyst and animal and plant oil into the raw material in the reactor is used at a weight ratio of 1: 100 to 10: 1, and when the weight ratio is out of the above, the cracking reaction is significantly reduced or uniform. It is difficult to obtain biodiesel of composition. If the diameter of the pellet or beads coated with the catalyst is smaller than the diameter range, the diameter of the catalyst is difficult to recover. If the diameter is large, the specific surface area decreases, and the conversion rate of the cracking reaction is significantly reduced.

In addition, after filling the Ti-MN catalyst coated beads or pellets into a fixed bed reactor, the raw material oil of the above-mentioned animal and vegetable fat and oil passes through the catalyst layer in a space velocity of 1,000 to 100,000 per hour and passes at 250 ° C. at 380 ° C. at atmospheric pressure. After the cracking reaction at a temperature between ℃ and distillation at 190 ℃ to obtain a high quality biodiesel. If the space velocity exceeds 100,000 per hour, the cracking reaction is remarkably degraded. If the space velocity is less than 1,000 per hour, excessive cracking occurs, resulting in a nonuniform composition, resulting in a significant drop in yield of biodiesel.

The present invention is explained in more detail by the following examples, which are not intended to limit the present invention.

Example 1

Ti-MN composite catalyst component was prepared by the sol-gel method by stirring for 3 hours at 10 g of titanium tetraisopropoxide as Ti metal, 3 g of chloroplatinic acid as M metal and 1 g of magnesium chloride as N metal at 90 ° C. at 60 rpm in an aqueous nitric acid solution. A Ti-Pt-Mg composite catalyst was made, coated on a surface of TiO ₂ beads having a diameter of 2 mm, and then put into a reactor at the same weight as the mixture of soybean oil and jatropha oil in a 1: 1 weight ratio, and then heated at 60 rpm at 330 ° C. After stirring for a cracking reaction, the catalyst-coated beads were separated and recovered using a mesh, and then distilled at 190 ° C. to obtain a more pure biodiesel to obtain high quality biodiesel.

Example 2

The Ti-MN composite catalyst component was mixed with 10 g of titanium tetraisopropoxide as a Ti metal, 3 g of ruthenium nitrate as M metal, and 1 g of strontium nitrate with Sr metal used as N metal, and 3 at 90 rpm in a nitric acid solution at 60 rpm. After stirring for a time to prepare a Ti-Ru-Sr composite catalyst by sol-gel method, which was coated on a glass bead surface of 2mm in diameter, and put the palm oil and waste cooking oil in a weight ratio such as 1 to 1 weight ratio in the reactor After cracking by stirring at 60 rpm at 330 ° C. for 10 minutes, the catalyst-coated beads were separated and recovered using a mesh, and then distilled at 190 ° C. to obtain a pure biodiesel, thereby obtaining high quality biodiesel. .

Table 1 below shows a comparison of the performance of the biodiesel produced by Examples 1 and 2 of the present invention and the quality standards based on 100% of the biodiesel. The biodiesel produced by the present invention showed good performance within the quality criteria.

Table 1. Biodiesel Performance and Quality Standards

Claims (6)

Ti-MN composite catalyst, wherein M represents a platinum group metal and is at least one metal of Pt, Pd, Ir, Ru, and N is a group 2 metal, characterized in that at least one metal of Be, Mg, Sr, Ba Catalyst for Biodiesel Production The ratio of the material used in the Ti-MN composite catalyst is a mixture of Ti and M in a weight ratio of 100: 1 to 1: 1, the ratio of the N metal to the sum of Ti and M metal. Is a catalyst for producing biodiesel, characterized in that the mixture is used in a weight ratio of 10: 1 to 1: 10 The Ti-MN composite catalyst according to claim 1, wherein the Ti-MN composite catalyst is a platinum metal of TiCl ₄ or titanium tetraisopropoxide and a platinum group metal of M metal; platinum chloride, platinum nitrate, or palladium metal; palladium chloride, palladium nitrate, or iridium. Mix one or more metal compounds of iridium chloride or ruthenium metal as a metal and ruthenium chloride or ruthenium nitrate, and beryllium metal as group 2 metal as N metal, beryllium chloride or beryllium nitrate, or magnesium metal as magnesium chloride or magnesium nitrate or barium. Barium nitrate, barium chloride or strontium as a metal is mixed with strontium nitrate or strontium chloride as a metal and at least one metal compound is mixed in a nitrate, sulfuric acid or hydrochloric acid solution at 60 ° C. to 150 ° C. at 60 rpm or more for 3 hours. Manufacturing The method for producing biodiesel catalysts, characterized in that to obtain a Ti-MN complex catalyst. The Ti-MN composite catalyst is coated on the surface of a pellet or bead of ceramic material, plastic, glass or metal material having a diameter of 0.1mm to 15mm, and the Ti-MN composite catalyst is coated with The amount of pellets, soybean oil, rapeseed oil, palm oil, edible oil, fish oil, bovine oil, chicken oil, pork oil, jatropha oil, cassava oil, canola oil, corn oil, sunflower oil or two or more animal or vegetable oils And a weight ratio of the biodiesel production catalyst, characterized in that used in a weight ratio of 1: 100 to 10: 1. M represents a platinum group metal and is a metal of at least one of Pt, Pd, Ir and Ru, and N is a Group 2 metal to form a Ti-MN composite catalyst, characterized in that at least one of Be, Mg, Sr, and Ba. It is coated on the surface of pellets or beads made of ceramic, plastic, glass, or metal with a diameter of 0.1mm to 15mm and placed in the reactor.The amount of beads or pellets coated with the Ti-MN composite catalyst and the amount of animals and plants to be used as raw materials in the reactor The weight ratio of the fruit is 1: 100 to 10: 1, and it is used as a raw material for the animal and vegetable oil. Refined and dephosphorized soybean oil, rapeseed oil, palm oil, waste cooking oil, fish oil, beef oil, chicken oil, pork oil. Add one or two or more of jatropha oil, cassava oil, canola oil, corn oil and sunflower oil, and stir for at least 5 minutes at a temperature between 250 ° C and 380 ° C at atmospheric pressure for at least 5 minutes. Then, the method for producing a biodiesel, characterized in that number of times to remove the pellet or bead is coated, and the catalyst, obtained by distillation at 190 ℃. M represents a platinum group metal and is a metal of at least one of Pt, Pd, Ir and Ru, and N is a Group 2 metal to form a Ti-MN composite catalyst, characterized in that at least one of Be, Mg, Sr, and Ba. Soybean oil dephosphorized within the range of 1,000 to 100,000 per hour after filling the fixed bed reactor by coating the surface of pellets or beads of ceramic material, plastic, glass or metal material of 0.1mm to 15mm in diameter, Rapeseed oil, palm oil, waste cooking oil, fish oil, bovine oil, chicken oil, pork oil, jatropha oil, cassava oil, canola oil, corn oil, sunflower oil or two or more kinds of raw oils are passed through a catalyst layer at 380 ° C at atmospheric pressure. Method for producing biodiesel, characterized in that after the cracking reaction at a temperature between ℃ and distillation at 190 ℃.