KR101386077B1 - Preparation method of methanol from glyceline by liquid phase catalytic radical reaction - Google Patents

Abstract

The present invention relates to a method for manufacturing a methanol-based biofuel from a glycerin by an aqueous phase radical reaction. More specifically, a glycerin, produced as a byproduct when manufacturing a biofuel, is manufactured into a solution and conducted with a radical reaction, caused by peroxide or ozone. A metal catalyst is added so as to produce volatile vapor through a decompressing reaction in a solution phase, and continuously condense the vapor. As main products, methanol, and ethanol are manufactured, and aldehydes and organic acids are produced as byproducts for useful purposes.

Description

Preparation method of methanol from glyceline by liquid phase catalytic radical reaction}

The present invention is to prepare a glycerin produced as a by-product in the production of biodiesel as an aqueous solution, and then radical reaction by hydrogen peroxide or ozone and a metal catalyst are added to continuously condense the volatile vapor produced by the reduced pressure reaction in the solution and the resulting vapor It is to provide a method for producing a fuel.

As the use of fossil fuels increases rapidly with the development of the industry, the atmospheric concentration of carbon dioxide increases, so the human disaster of climate change is foreseen, but the use of renewable energy, which is a solution to solve this problem, is still very small. Biodiesel is used as a diesel fuel as one of the transportation biofuels. Since 2006, BD0.5 is currently being sold as a commercial agreement between biodiesel and the Ministry of Knowledge Economy, allowing oil refiners to mix biodiesel within 5%. In 2007, there were 15 biodiesel producers, with annual production capacity of 600,000 tons and actual production of 90,000 tons (Korea Environmental Policy and Evaluation Institute, 2007.Environmental Economic Analysis of Biofuels (Biodiesel, Bioethanol) And expansion measures.).

Biodiesel is mainly used mixed with ordinary diesel oil, and depending on the mixing ratio, it is BD5 (5% biodiesel + 95% general diesel), BD20 (20% biodiesel + 80% general diesel), and BD100 (100% biodiesel). Divided. To use biodiesel as fuel in diesel vehicles, there is no need to modify the engine.

 To produce biodiesel, catalysts and alcohols are used to produce glycerin and biodiesel at specific temperatures and pressures. All kinds of oils extracted from animals and plants can be used as fuel for biodiesel production, but most of them use vegetable oils (Future Research Institute. 2005. Economic analysis and analysis of crops that can be used as industrial raw materials (bioenergy). Policy support measures). Biodiesel's type of plant depends on the geographic climate and soil in each country. Rapeseed in northern Europe, soybean in the US, and palm oil, mainly in the equator, are the main raw materials for biodiesel production. Coconut and sunflower are also widely used raw materials (Samsung Economic Research Institute, 2006. Reasonable introduction of bio fuel).

Specifically, as shown in the schematic diagram below, methanol and a base catalyst are added to the crude oil to react, separated, neutralized with acid, and purified to produce biodiesel. In addition, glycerin is produced as a by-product in the process of separating and reacting methanol and a base catalyst to the crude oil.

One molecule of triglycerides reacts with three molecules of alcohol under a catalyst as shown in the chemical reaction accompanying the production of glycerin as a by-product of the production of biodiesel, and one molecule of glycerin (or glycerol) and three types of biodiesel Is generated.

Biodiesel oils, unlike petroleum diesel, are biodegradable, non-toxic and dramatically reduce emissions and toxic substances during fuel combustion. Biodiesel oil is now somewhat more expensive than petroleum diesel because of its widespread use worldwide. Currently, the world's vegetable oils and animal fats are not sufficient to replace liquid fuels, and their fuel supply capacity is only about 20-25% of the maximum demand. The methyl ester of vegetable oil (BD) has several advantages over other renewable energy and clean engine alternative fuels. Therefore, if methanol is produced using by-product glycerin, the production cost of biodiesel can be greatly reduced. Methanol has a variety of manufacturing methods, it is usually produced by distilling the liquid produced from wood, coal, natural gas, petroleum gas. Glycerin is used as a raw material for the synthesis of methanol, thereby replacing the fossil fuel.

Glycerol (glycerol) is a colorless, odorless liquid, also called glycerin (glycerine). Viscosity is very strong. Glycerin is a trihydric alcohol with three hydroxyl groups. Colorless and sticky liquid, hygroscopic, slightly sweet, melting point 20 ℃, boiling point 290 ℃.

Glycerin is not only used as a synthetic raw material such as glyphtal resin, but also as a lubricant or an ointment, a desiccant and a spice in tobacco and cosmetics, and furthermore, a defroster and a coolant. And an important material having a very wide application such as printing ink. Therefore, it is manufactured not only by such fat-and-oil decomposition but also by the synthetic method which uses propylene as a raw material, and the board is used as a natural product and a synthetic product today.

These water-soluble glycerin have a high molecular weight and are bound by glycosidic bonds and thus are not easily degraded. In order to decompose these polymers, a strong chemical reaction is required. In the present invention, a radical generator such as hydrogen peroxide or ozone is used, and metal ions are introduced as radicals to produce radical species and chemical species having high energy . The production of radicals is accelerated by the addition of transition metals such as iron and copper, vanadium, nickel and magnesium and metal salts such as silver, platinum, rhodium and paradium. The radical reaction destroys the polymer chains and at the same time contributes to the formation of alcohols. For example, when hydrogen peroxide is used as a radical initiator, OH radicals are produced and attack the polymer chains of glycerin and alginate to produce alkyl radicals, which react with OH ions to produce alcohol. The alcohol produced is decomposed in the presence of OH radicals and finally converted to carbon dioxide. Therefore, when alcohols are produced, it is important to separate them and recover them to the final product. In addition, the removal of the alcohol produced has the advantage of accelerating the production of alcohol because the equilibrium proceeds to the product direction by the Leshatrier law.

Thus, the inventors While studying the method of using glycerin, which is produced as a by-product in the production of biodiesel, as a biofuel, after preparing glycerin as an aqueous solution in the production of biodiesel, an aqueous solution was used to produce a radical reaction by hydrogen peroxide or ozone and a metal catalyst. After condensation, the volatile vapor produced by the pressure reduction reaction in the solution and the condensed vapor are condensed into water, alcohol, aldehyde, ethylene glycol, etc., and the condensate can be distilled to remove water to form volatile organics. By confirming that the present invention was completed.

It is an object of the present invention to provide a method for producing a biofuel from glycerin.

It is still another object of the present invention to provide a method for preparing volatile organics from glycerine, wherein methanol is a main component and aldehyde or glycol is a byproduct.

 The present invention to achieve the above object

1) dissolving glycerin in water;

2) adding a metal catalyst to the glycerin solution of step 1);

3) adding a radical initiator to the mixture of step 2);

4) maintaining the reaction pressure of the mixture of step 3) below the vapor pressure of the desired volatile organics to react to generate steam; And

5) It provides a method for producing a biofuel from glycerin comprising the step of condensing the vapor of step 4) to obtain a volatile organic matter.

In addition,

1) dissolving glycerin in water at 0.01 to 30 parts by weight relative to the total weight of the solution;

2) adding ferric sulfate (Iron (III) sulfate, Fe ₂ (SO ₄ ) ₃ ) to the solution of step 1) in an amount of 0.01 to 0.1 parts by weight based on the total weight of the mixture;

3) adding hydrogen peroxide to the mixture of step 2) in an amount of 0.1 to 0.5 parts by weight based on the total weight of the reactants and reacting at room temperature for 1 to 10 hours;

4) aliquoting the reactant of step 3) and distilling at 50 to 100 mbar at 50 to 100 ° C. in a rotary vacuum distillation to obtain steam; And

5) It provides a method for producing a volatile organic substance of methanol is the main component and aldehyde or glycol by-product from the glycerin comprising the step of condensing the steam of step 4) to -40 ℃ to 25 ℃ temperature to obtain a volatile organic substance .

In the manufacturing method according to the present invention, by adding a metal catalyst and a radical initiator to the glycerin of the polymer produced as a by-product during the production of biodiesel, a strong radical reaction occurs, so that volatile organic substances can be produced. It can be used as a useful biofuel to replace fossil fuels because it can greatly reduce the production cost of biodiesel, is biodegradable, non-toxic, and can drastically reduce emissions and toxic substances during fuel combustion.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the manufacturing method of the biofuel which has methanol as a main component from glycerin by a liquid radical reaction.
Figure 2 is a graph showing the results confirmed by gas chromatography mass spectrometry of the substance produced after the glycerin decomposition reaction in a batch reactor 150 ℃.
Figure 3 is a graph showing the results confirmed by gas chromatography mass spectrometry of the substance produced after the glycerin decomposition reaction in a batch reactor 200 ℃.
Figure 4 is a graph showing the results confirmed by gas chromatography mass spectrometry of the substance produced after the glycerin decomposition reaction in a batch reactor 250 ℃.
FIG. 5 is a graph showing the results of confirming the composition% of a substance produced after glycerin decomposition in a rotary vacuum distillation machine at 90 ° C. using a gas chromatography mass spectrometer. FIG.
6 is a schematic diagram showing a glycerin decomposition experiment method at 150 ℃ electric.
Figure 7 is a schematic diagram showing a glycerin decomposition method in a rotary vacuum distillation.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for producing a biofuel from glycerin comprising the following steps:

1) dissolving glycerin in water;

2) adding a metal catalyst to the glycerin solution of step 1);

3) adding a radical initiator to the mixture of step 2);

4) maintaining the reaction pressure of the mixture of step 3) below the vapor pressure of the desired volatile organics to react to generate steam; And

5) condensing the vapor of step 4) to obtain volatile organics.

In the production method according to the present invention, step 1) is a step of dissolving glycerin (glyceline) in water.

The glycerin may be, but is not limited to, glycerin produced during the manufacture of biodiesel or glycerin produced for industrial purposes.

In the production method according to the invention, step 2) is a step of adding a metal catalyst to the glycerin solution.

The metal catalyst is preferably one kind of transition metal selected from the group consisting of iron, copper, nickel, vanadium, chromium and manganese or one kind of precious metal salt selected from the group consisting of platinum, rhodium, palladium, gold and ruthenium. One is not limited to this.

In addition, the metal catalyst is preferably any one selected from the group consisting of ferric sulfate, copper sulfate, silver chloride, ammonium vanadate and platinum chloride, but is not limited thereto.

The metal catalyst may be added at 0.01 to 3.0 parts by weight based on the total weight of the mixture.

When out of the above range, when added in less than 0.01 parts by weight, there is a problem that the activity of the radical initiator is lowered, when added in excess of 3.0 parts by weight, the activity of the radical initiator occurs quickly, the problem that the yield of volatile organics is lowered have.

In general, the radical reaction is increased by the reaction of metal ions due to the effect of reducing the reaction activation energy by the catalytic action of metal ions and the role of promoting the redox reaction as an electron transfer path of the metal ion.

In the preparation method according to the invention, step 3) is a step of adding a radical initiator to the mixture.

The radical initiator is preferably hydrogen peroxide or ozone.

The radical initiator may be added in 0.1 to 30 parts by weight based on the total weight of the reactants.

When the amount is less than 0.1 parts by weight, it is difficult to degrade glycerin.

Since the water-soluble polymer glycerin of the present invention has a high molecular weight and is bound by glycosidic bonds, it is not easily decomposed, but the hydrogen peroxide and ozone of the present invention are a strong oxidative force of OH radicals generated by reaction with metal ions. Since the organic matter is oxidized, it is preferable to use a radical generating agent such as hydrogen peroxide or ozone which causes a radical reaction in the present invention.

In the production method according to the present invention, step 4) is a step of generating a vapor by maintaining the reaction pressure of the mixture below the vapor pressure of the desired volatile organics.

The reaction is preferably a reaction temperature of 10 to 300 ℃, a reaction pressure of 0.1 to 1000 mbar, 80 to 300 ℃, the reaction pressure is more preferably 100 to 500 mbar, but is not limited thereto.

When out of the above range, when the reaction temperature is maintained in the range of less than 10 ℃, more than 300 ℃, there is a problem that the production yield of volatile organics is lowered, the reaction pressure is produced at a pressure of less than 100 mbar, the production of volatile organics There is a problem that the steam production rapidly increases due to the violent reaction, and when the pressure is maintained above 500 mbar, there is a problem that the production yield of volatile organics is lowered due to the decrease in the steam production rate.

In the manufacturing method according to the present invention, step 5) is a step of condensing steam to obtain volatile organics.

The condensation is carried out at -40 ° C to 25 ° C, but is not limited to the temperature.

If it is out of the above range, there is a problem that the generated steam freezes below -40 ℃, if maintained above 10 ℃, there is a problem that the volatile organic vapor condensation is lowered to lower the alcohol yield.

The volatile organic material is preferably one or more selected from the group consisting of ethanol, methanol, alcohol, aldehyde and ethyl glycol, but is not limited thereto.

It is preferable to further include the step of increasing the reaction direction and speed by continuously removing the generated volatile organics, but is not limited thereto.

The method may further include removing water contained in the prepared volatile organic material through fractional distillation.

The reduced pressure reaction may vaporize only the generated volatile organics even though complex chemical reactions occur in the reactor, and condense these vapors to produce volatile organics as a final product.

Such a reduced pressure reaction allows the selective increase in yield by continuously removing volatile organics, while simultaneously maintaining the equilibrium in the direction of reactant production, and simultaneously increasing the reaction rate of the product.

According to Leshatrier's law, the reaction proceeds in the direction of decreasing the pressure, and the reaction equilibrium may proceed in the direction of increasing the product because the pressure is continuously reduced by the decompression reaction. Achievement and yield increase can be achieved.

In the present invention, the optimum decomposition conditions are set in consideration of the effect of the type and concentration of the radical initiator, the decomposition temperature and time on the decomposition rate when the radical decomposition with respect to glycerin, and the generated steam facilitates steam production by reducing the pressure of the reactor. It is aimed to obtain a volatile organic substance whose main product is ethanol or methanol as a final product by condensing and recovering the vapor containing the reactant continuously.

Specifically, the destruction of the polysaccharide polymer is a strong oxidizing power of OH generated by the reaction of hydrogen peroxide, ozone, and the like with a metal ion, which utilizes a reaction of oxidizing organic matter. Hydrogen peroxide is generally supplied in a weakly acidic state because it decomposes more at pH 6 and above and increases at higher pH. Hydrogen peroxide is mainly used for the oxidation reaction. It is easy to think that oxygen is generated in the molecule because the oxygen or the active oxygen is in the molecule. However, the two oxygen atoms in the molecule of hydrogen peroxide practically have no distinctive property. The reason for the excellent reactivity between hydrogen peroxide and ozone is that the binding force of OO in the molecule is weak. Unlike the reaction with an inorganic compound, the reaction with an organic compound acts as a weak oxidizing agent. Hydrogen peroxide and ozone oxidize and decompose various substances because the OO bond is destroyed and the radical is generated when the metal catalyst exists. The reaction path and the type of material produced are very different depending on the composition and characteristics of the reactants. Depending on the reaction pH and the catalyst used, different reactions such as the same organic substances cause different results. In particular, hydrogen peroxide is relatively non-toxic, easy to handle, and the byproducts produced during the oxidation reaction are considered to be environmentally safe because they are very low in toxicity. In addition, it is water and oxygen when it decomposes spontaneously and it is advantageous in terms of environmental safety, ease of use and selective oxidation reaction compared with other oxidizing agents. Looking at the properties of hydrogen peroxide, hydrogen peroxide is very stable because the following equilibrium reaction proceeds only in the forward direction in an acidic solution.

H ₂ O ₂ + OH ^- HOO ^- + H ₂ O (1)

Furthermore, hydrogen peroxide reacts with hydrogen ions, producing oxonium.

H ₂ O ₂ + H ^{+ -} & gt ^; HOOH ₂ ^{+ -} (2)

These oxonium ions increase the stability of hydrogen peroxide by making hydrogen peroxide molecules electrophilic. When nucleophile substances are present in the solution rather than hydrogen peroxide such as acids, alcohols or ketones, protonation occurs to produce new electrophilic intermediates which in turn react with hydrogen peroxide, thereby increasing the consumption of hydrogen peroxide .

In the alkaline solution of hydrogen peroxide is OH ^- and generates (perhydroxyl ion) ^- HO ₂ reacts with.

H ₂ O ₂ + OH ^- HOO ^- + H ₂ O pk = 16.6 (20 ° C) ----- (3)

This equilibrium reaction proceeds as the alkalinity increases. Since HOO ^- is more than 200 times more reactive than OH ^- , decomposition reaction of hydrogen peroxide occurs.

^{_{HOO - + H 2 O 2 →}} H 2 O + OH - + O 2 -------- (4)

Therefore, the presence of organic compounds that can attack HOO ^- in alkaline solutions occurs competitively in the above reactions, thus accelerating the decomposition of hydrogen peroxide. Hydrogen peroxide, on the other hand, has the property of generating free radicals in the presence of metal ions of low oxidation state in acidic or neutral state. When hydrogen peroxide is activated, OH and HO ₂ are formed, and their redox potentials are as high as 2.8 V, which allows oxidative decomposition of the electrophilic organic compounds.

Glycerin is not easily decomposed because it has a high molecular weight and is bound by glycosidic bonds. In order to decompose these polymers, a strong chemical reaction is required. In the present invention, a radical generator such as hydrogen peroxide or ozone is used, and metal ions are introduced as radicals to produce radical species and chemical species having high energy . The generation of radicals is accelerated by the addition of transition metals such as iron and copper, vanadium, nickel, and magnesium and noble metal salts such as silver, platinum, rhodium, and palladium. The radical reaction destroys the polymer chains and at the same time contributes to the formation of alcohols. For example, when hydrogen peroxide is used as the radical initiator as in the following chemical reaction formula, OH radicals are produced and the polymer chains of glycerin and alginate are attacked to generate alkyl radicals, which are reacted with OH ions to produce alcohol. In addition, since OH has an electrophilic property in reaction with an organic substance, the reaction with a compound having an electron donor group in the polysaccharide proceeds much faster.

The present invention also provides a method for preparing a volatile organic substance, wherein methanol is a main component and aldehyde or glycol is a by-product from glycerin comprising the following steps:

1) dissolving glycerin in water at 0.01 to 30 parts by weight relative to the total weight of the solution;

2) adding ferric sulfate (Iron (III) sulfate, Fe ₂ (SO ₄ ) ₃ ) to the solution of step 1) in an amount of 0.01 to 0.1 parts by weight based on the total weight of the mixture;

3) adding hydrogen peroxide to the mixture of step 2) in an amount of 0.1 to 0.5 parts by weight based on the total weight of the reactants and reacting at room temperature for 1 to 10 hours;

4) aliquoting the reactant of step 3) and distilling at 50 to 100 mbar at 50 to 100 ° C. in a rotary vacuum distillation to obtain steam; And

5) condensing the vapor of step 4) to a temperature of −40 ° C. to 25 ° C. to obtain volatile organics.

In the manufacturing method according to the present invention, it may further comprise the step of ashing the reactant of step 3) in an electric furnace.

The ash temperature is preferably 100 to 300 ° C., and the ash time is 1 to 10 hours. When the ash temperature is out of the above range, the reaction temperature is less than 100 ° C. and is maintained in the range of more than 300 ° C., yield of volatile organics is produced. There is a problem that this is lowered.

< Example  1> Preparation of Volatile Organics from Glycerin

<1-1> Preparation of Glycerin Solution

<1-1> glycerin

270 mL of 99.0% purity glycerin prepared from large purified gold was used.

<1-2> Ferric sulfate  Preparation of aqueous solution

Molecular weight of ferric sulfate 400 g / mol to calculate the amount of 0.0387 mol (Mole) ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) (Showa Chemical Co., Ltd.) to be added to the glycerin solution of Example <1-1> The density of ferric sulfate after multiplying 0.0387 mol by 3.03 g / cm ³ multiply And the purity of ferric sulfate was 0.8. As a result, it was confirmed that 6.3 ml was required. Thus, 15.48 g of ferric sulfate was dissolved in 1 L of water, and then 6.3 ml of the ferric sulfate was added to 270 ml of glycerin solution.

<1-3> Preparation of aqueous hydrogen peroxide solution

Molecular weight of hydrogen peroxide 34 to calculate the amount of 0.387 mol (Mole) 30% hydrogen peroxide (H ₂ O ₂ , large purified gold) to be added to the glycerin solution to which the ferric sulfate was added in Example <1-2> g / mol times 0.387 mol, hydrogen peroxide density 1.463 g / cm ³ multiply And the purity of hydrogen peroxide was 0.3. As a result, it was confirmed that 30 ml was required. At this time, ferric sulfate (0.0387 mol) was prepared in a ratio of hydrogen peroxide (0.387 mol) and 1:10. Accordingly, 30 ml of hydrogen peroxide was added to the glycerin solution to which ferric sulfate was added, followed by reaction at room temperature for 6 hours.

<1-4> Preparation of Volatile Organics Using Glycerin in Electric Furnace

An electric furnace was used to fractionate the reactants of Example <1-3> and perform a hydrolysis reaction of a polysaccharide such as glycerin. The manufacturer of the electric furnace is JISICO, and the model name is Electric muffle furnace.

Specifically, in order to check the degree of glycerin decomposition by temperature, the temperature was set at 150 ° C., 200 ° C. and 250 ° C., respectively, and a 100 ml batch reactor containing a glycerin solution was added to the electric furnace and allowed to react for 6 hours at room temperature. Cooled down to The whole amount was recovered and distilled under reduced pressure into a hot water bath at 90 ° C. and 300 mbar in a rotary vacuum distillation machine to condense the steam to a temperature of −5 ° C.

<1-5> In a rotary vacuum still  Preparation of Volatile Organics Using Glycerin

Glycerin was decomposed for each temperature of 150 ℃, 200 ℃ and 250 ℃ by ash in the electric furnace of Example <1-4> and hot water bath 90 ℃, 300 directly in a rotary vacuum distillation without going through Example <1-4> Distillation under reduced pressure to mbar condensed the steam to a temperature of -5 ° C. The manufacturer of the rotary vacuum distillation machine is BUCHI and the model name is described in the following [Table 1].

Vacuum Controller BUCHI V-800 Rotavapor BUCHI R-250 Heating Bath BUCHI B-490 Vacuum Pump BUCHI V-500 Constant Temperature Circulator Cole Parmer

< Experimental Example  1> by temperature Batch  Analysis of the results of decomposition of glycerin in the reactor

<1-1> Batch  Analysis of Glycerin Decomposition Results in Reactor 150 ℃

Further performing the steps of Example <1-4> in a batch reactor 150 ℃ In order to analyze the volatile organic compounds generated by the decomposition of glycerin, gas chromatography mass spectrometry (GCMS) was used.

Specifically, the gas chromatography mass spectrometers were the model names GC-2010 and GCMS-QP2010 plus of Shimadzu. 270 ml of the glycerin solution of Example <1-1> and 6.3 ml of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) prepared in Example <1-2> and hydrogen peroxide prepared in Example <1-3> 30 ml of (H ₂ O ₂ ) was added thereto and reacted at room temperature for 6 hours, and then reacted at 150 ° C. in a batch reactor. The condensate was distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation unit at a thickness of 0.25 μm, length of 30 m, and Organics were measured using a DB-WAX column with a diameter of 0.32 mm. The measuring method is to raise the oven temperature of the gas chromatography mass spectrometer from 10 ℃ to 240 ℃ 10 minutes per minute from 80 ℃ and give a final holding time of 5 minutes to measure the total measurement time to 21 minutes [Table 2], [ Table 3] and [FIG. 2].

Batch  Composition% of substance produced after glycerin decomposition at 150 ℃ Peak # Substance Area (%) One Acetaldehyde (CAS) Ethanal 4.34 2 Formicacid, methylester (CAS) Methylformate 1.65 3 1-propen-2-ol (CAS) Isopropenylalcohol 0.89 4 Methanol (CAS) Carbinol 23.49 5 2-Propanol (CAS) Isopropyl alcohol 16.16 6 Ethanol (CAS) Ethylalcohol 10.74 7 Water (CAS) Ice 16.73 8 2-Propanone, 1-hydroxy- (CAS) Acetol 0.73 9 Aceticacid (CAS) 2.16 10 Formic acid (CAS) Bilorin 14.1 11 Benzaldehyde, 2-hydroxy-6-methyl- 0.49 12 1,2-Benzenedicarboxylic acid, diethyl ester (CAS) Ethyl phthalate 8.53

Batch  Composition% of substance produced after glycerin decomposition at 150 ℃ Peak # Retention time Furtherance
(%) Substance The rescue One 1.157 4.34 Acetaldehyde (CAS) Ethanal CH ₃ CHO

2 1.256 1.65 Formic acid, methyl ester (CAS) Methyl formate HCOOCH ₃

3 1.402 0.89 1-propen-2-ol (CAS) Isopropenyl alcohol C ₃ H ₆ O

4 1.706 23.49 Methanol (CAS) Carbinol CH ₃ OH

5 1.865 16.16 2-Propanol (CAS) Isopropyl alcohol CH ₃ CHOHCH ₃

6 1.902 10.74 Ethanol (CAS) Ethyl alcohol C ₂ H ₅ OH

7 2.628 16.73 Water (CAS) Ice H ₂ O

8 4.705 0.73 2-Propanone, 1-hydroxy- (CAS) Acetol C ₃ H ₆ O ₂

9 5.928 2.16 Acetic acid (CAS) Ethylic acid C ₂ H ₄ O ₂

10 6.253 14.10 Formic acid (CAS) Bilorin HCOOH

11 7.711 0.49 Benzaldehyde, 2-hydroxy-6-methyl- C ₈ H ₈ O ₂

12 11.341 8.53 1,2-Benzenedicarboxylic acid, diethyl ester (CAS) Diethyl phthalate C ₁₂ H ₁₄ O ₄

<1-2> Batch  Analysis of Glycerin Decomposition Results in Reactor 200 ℃

Further performing the steps of Example <1-4> in a batch reactor 200 ℃ In order to analyze the volatile organic compounds generated by the decomposition of glycerin, gas chromatography mass spectrometry (GCMS) was used.

Specifically, the gas chromatography mass spectrometers were the model names GC-2010 and GCMS-QP2010 plus of Shimadzu. 270 ml of the glycerin solution of Example <1-1> and 6.3 ml of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) prepared in Example <1-2> and hydrogen peroxide prepared in Example <1-3> 30 ml of (H ₂ O ₂ ) was added thereto and reacted at room temperature for 6 hours, and then reacted at 200 ° C. in a batch reactor. The condensate was distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation unit at a thickness of 0.25 μm, length of 30 m, and Organics were measured using a DB-WAX column with a diameter of 0.32 mm. The measuring method is to raise the oven temperature of the gas chromatography mass spectrometer from 10 ℃ to 240 ℃ 10 minutes per minute from 80 ℃ and give a final holding time of 5 minutes to measure the total measurement time to 21 minutes [Table 4] and [ 3].

Batch  Composition% of substance produced after glycerin decomposition at 200 ℃ Peak # Substance Area (%) One Acetaldehyde (CAS) 4.13 2 Propanal (CAS) Propionaldehyde 6.63 3 2-Propanone (CAS) Acetone 1.43 4 Methanol (CAS) Carbinol 1.75 5 2-Propanol (CAS) Isopropylalcohol 7.84 6 Ethanol (CAS) Ethylalcohol 11.38 7 1-Propanol (CAS) 6.53 8 Water (CAS) Ice 18.36 9 Furan, 2,3-dihydro- 22.34 10 2-Propen-1-ol (CAS) Allylalcohol 5.28 11 2-Propanone, 1-hydroxy- (CAS) Acetol 6.3 12 2-Cyclopenten-1-one, 2-methyl- (CAS) 2-Methyl-2-cyclopentenone 1.47 13 Aceticacid (CAS) 3.66 14 1,3-Dioxolane-4-methanol, 2-ethyl- (CAS) 2-ETHYL-4-METHYLOL-1,3-DIOXOLANE 0.74 15 Ethanone, 1- (2-hydroxy-5-methylphenyl)-(CAS) 1-Hydroxy-2-acetyl-4-methylbenzene 2.16

<1-3> Batch  Analysis of Glycerin Decomposition Results in Reactor 250 ° C

Further performing the steps of Example <1-4> in the batch reactor 250 ℃ In order to analyze the volatile organic compounds generated by the decomposition of glycerin, gas chromatography mass spectrometry (GCMS) was used.

Specifically, the gas chromatography mass spectrometers were the model names GC-2010 and GCMS-QP2010 plus of Shimadzu. 270 ml of the glycerin solution of Example <1-1> and 6.3 ml of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) prepared in Example <1-2> and hydrogen peroxide prepared in Example <1-3> After adding 30 ml of (H ₂ O ₂ ) and reacting at room temperature for 6 hours, the reaction mixture was reacted at 250 ° C. in a batch reactor, and the condensate distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation unit was 0.25 μm thick, 30 m long, and Organics were measured using a DB-WAX column with a diameter of 0.32 mm. The measuring method is to raise the oven temperature of the gas chromatography mass spectrometer from 10 ℃ to 240 ℃ 10 minutes per minute from 80 ℃ and give a final holding time of 5 minutes to measure the total measurement time to 21 minutes [Table 5] and [ 4].

Batch  Of the material produced after the glycerin decomposition reaction in the reactor 250 ℃ Area % Peak # Compound Name Area (%) One Acetaldehyde (CAS) Ethanal 8.19 2 Propanal (CAS) Propionaldehyde 8.26 3 2-Propanone (CAS) Acetone 4.95 4 Methanol (CAS) Cabinol 7.19 5 2-Propanone (CAS) Isopropyl alcohol 9.5 6 Ethanol (CAS) Ethyl alcohol 21.79 7 Furan, 2,3-dihydro- 4.43 8 2-Butanol (CAS) sec-Butanol 2.24 9 1-Propanol (CAS) Propanol 20.01 10 5-Methyl-3-propyl-isoxazole 13.46

< Experimental Example  2> Degradation analysis of glycerin in rotary vacuum distillation machine at 90 ℃

Rotary vacuum distillator of the above <1-5> at 90 ℃ In order to analyze the volatile organic compounds generated by the decomposition of glycerin, gas chromatography mass spectrometry (GCMS) was used.

Specifically, the gas chromatography mass spectrometers were the model names GC-2010 and GCMS-QP2010 plus of Shimadzu. 270 ml of the glycerin solution of Example <1-1> and 6.3 ml of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) prepared in Example <1-2> and hydrogen peroxide prepared in Example <1-3> After adding 30 ml of (H ₂ O ₂ ) and reacting at room temperature for 6 hours, a condensate distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation machine was prepared using a DB-WAX column having a thickness of 0.25 μm, a length of 30 m, and a diameter of 0.32 mm. Organic matter was measured. The measuring method is to raise the oven temperature of the gas chromatography mass spectrometer from 10 ℃ to 240 ℃ 10 minutes per minute from 80 ℃ and give a final holding time of 5 minutes to measure the total measurement time to 21 minutes [Table 6] and [ 5].

Composition of Substances Produced after Glycerin Decomposition at 90 ° C in a Rotary Vacuum Distillation Unit Peak # Compound Name Furtherance(%) One Acetaldehyde (CAS) Ethanal 7.49 2 2-Propenal (CAS) Acrolein 4.49 3 Methanol (CAS) Carbinol 20.55 4 Ethanol (CAS) Ethylalcohol 14.2 5 Water (CAS) Ice 12.95 6 2-Propanone, 1-hydroxy- (CAS) Acetol 18.13 7 Aceticacid (CAS) 4.5 8 2-Furancarboxaldehyde (CAS) Furfural 2.26 9 cis-5-hydroxy-2methyl-1,3dioxane 2.21 10 Formic acid (CAS) Bilorin 3.39 11 Formicacid, ethylester (CAS) ethylformate 4.32 12 trans-4-hydroxymethyl-2-methyl-1,3-di 1.42 13 trans-4-hydroxymethyl-2-methyl-1,3-di 1.11 14 Ethanol, 2- (ethenyloxy)-(CAS) vinylon 0.71 15 1,2,3-Propanetriol (CAS) Glycerol 2.28

To 270 ml of glycerin was added 6.3 ml of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) and 30 ml of hydrogen peroxide (H ₂ O ₂ ) and reacted at room temperature for 6 hours at 150 ℃, 200 ℃ and 250 ℃ by temperature in batch reactor. After the reaction, the condensate distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation unit was measured with a gas chromatography mass spectrometer. First, the composition (%) of the main products methanol and ethanol was measured to be 23.49% and 10.74%, respectively, at 150 ° C in a batch reactor. Second, in the batch reactor 200 ℃, the composition (%) of the main products methanol and ethanol was measured to 1.75% and 11.38%, respectively. Third, the composition (%) of the main products methanol and ethanol was measured at 7.19% and 21.79%, respectively. Condensate distilled under reduced pressure at 90 ° C. in a rotary vacuum distillation unit without a batch reactor was measured with a gas chromatography mass spectrometer. The composition of the main products, methanol and ethanol (%), was 20.55% and 14.2%, respectively.

Claims (15)

1) dissolving glycerin in water;
2) adding a metal catalyst to the glycerin solution of step 1);
3) adding a radical initiator to the mixture of step 2);
4) maintaining the reaction pressure of the mixture of step 3) below the vapor pressure of the desired volatile organics to react to generate steam; And
5) A method of producing a biofuel from glycerin comprising the step of condensing the vapor of step 4) to obtain volatile organics.
The method of claim 1, wherein the glycerin of step 1) is dissolved in water by 0.01 to 30 parts by weight based on the total weight of the solution.
The metal catalyst of claim 1, wherein the metal catalyst in step 2) is selected from the group consisting of platinum, rhodium, palladium, gold and ruthenium or at least one transition metal selected from the group consisting of iron, copper, nickel, vanadium, chromium and manganese. A method for producing a biofuel from glycerin, characterized in that one kind of precious metal salt is selected.
The method according to claim 1, wherein the metal catalyst in step 2) is any one selected from the group consisting of ferric sulfate, copper sulfate, silver chloride, ammonium vanadate and platinum chloride.
The method of claim 1, wherein in step 2) the metal catalyst is added in an amount of 0.01 to 3.0 parts by weight based on the total weight of the mixture.
The method of claim 1, wherein the radical initiator of step 3) is hydrogen peroxide or ozone.
The method of claim 1, wherein the radical initiator of step 3) is added in an amount of 0.1 to 30 parts by weight based on the total weight of the reactants.
The method of claim 1, wherein the reaction of step 4) has a reaction temperature of 10 to 300 ° C and a reaction pressure of 0.1 to 1000 mbar.
The method of claim 1, wherein the reaction of step 4) has a reaction temperature of 80 to 300 ° C and a reaction pressure of 100 to 500 mbar.
The method of claim 1, wherein the condensation of step 5) is performed at -40 ° C to 25 ° C.
The method according to claim 1, wherein the volatile organic material of step 5) is made of one or more from the group consisting of ethanol, methanol, alcohol, aldehyde and ethyl glycol.
The method of claim 1, further comprising increasing the reaction direction and speed by continuously removing the volatile organics generated in step 5).
1) dissolving glycerin in water at 0.01 to 30 parts by weight relative to the total weight of the solution;
2) adding ferric sulfate (Iron (III) sulfate, Fe ₂ (SO ₄ ) ₃ ) to the solution of step 1) in an amount of 0.01 to 0.1 parts by weight based on the total weight of the mixture;
3) adding hydrogen peroxide to the mixture of step 2) in an amount of 0.1 to 0.5 parts by weight based on the total weight of the reactants and reacting at room temperature for 1 to 10 hours;
4) aliquoting the reactant of step 3) and distilling at 50 to 100 mbar at 50 to 100 ° C. in a rotary vacuum distillation to obtain steam; And
5) A method for preparing a volatile organic substance, wherein methanol is a main component and aldehyde or glycol is a byproduct from glycerin, comprising the step of condensing the steam of step 4) to a temperature of -40 ° C to 25 ° C.
14. The method of claim 13, further comprising the step of ashing the reactant of step 3) in an electric furnace, wherein glycerol is the main component and aldehyde or glycol is a byproduct from glycerine.
15. The method according to claim 14, wherein the ash temperature is 100 to 300 DEG C, and the ash time is 1 to 10 hours, wherein methanol is a main component and aldehyde or glycol is a by-product.

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