BRPI0803898A2 - catalytic process for the transformation of glycerine into inputs for the petrochemical sector - Google Patents

Abstract

CATALYTIC PROCESS FOR THE TRANSFORMATION OF GLYCERIN IN SUPPLIES FOR THE PETROCHEMICAL SECTOR. The present invention relates to a catalytic process of glycerol or glycerine hydrogenation / hydrogenolysis to oxygenated compounds and hydrocarbons containing from 1 to 3 carbon atoms, using group VIu-E metal supported metal catalysts from the periodic table of elements, which were supported by conventional techniques on high specific area materials such as activated carbon powder, aluminosilicate, alumina, clays, zeolites and molecular sieves.

Description

Patent Descriptive Report for: "PROCESSOCATALYTIC FOR THE TRANSFORMATION OF 6LICERIN INTO PRODUCTS FOR THE PETROCHEMICAL SECTOR".

Field of the Invention

The present invention relates to a catalytic process corresponding to the hydrogenation / hydrogenolysis of glycerol or glycerine to petrochemical industry inputs, more specifically oxygenated compounds and hydrocarbons containing 1 to 3 carbon atoms, using metal catalysts based on inorganic salts supported on high specific area materials. .

Background of the Invention

The growing concern about global warming in this early 21st century encourages discussions about new sources of energy. Climate change, largely driven by the use of fossil fuels associated with concern for sustainable development, has made renewable energy sources extremely important. However, modern society is still very dependent on oil, which, along with coal and natural gas, represent about 40% of all energy consumed in the world. These sources are limited and expected to be depleted in the future. Therefore, the search for alternative sources of energy is of paramount importance. The viability of renewable fuels is already being discussed all over the world, which would have a much smaller impact on the planet's warming, since in the total balance CO2 emissions, which is one of the main villains of the greenhouse effect, are reduced.

One of the most pressing alternatives to contain this problem is biofuels. Because they are of plant origin, they contribute to the carbon cycle in the atmosphere and are therefore considered renewable, since CO2 emitted during burning is reabsorbed, at least in part, by the plants, thus contributing to the reduction of global carbon dioxide emission.

Among the most promising renewable fuels is biodiesel. Biodiesel is composed of fatty acid methyl or ethyl esters. Compared to petroleum-derived oleodiesel, biodiesel can reduce carbon dioxide emissions by 78%, considering area absorption by plants. It also reduces smoke emissions by 90% and virtually eliminates sulfur dioxide emissions. This product is generally obtained from the transesterification of vegetable oils with alcohols, such as methanol and ethanol, using basic or acid catalysis, or even by esterification of fatty acids in the presence of acid catalysts. From the chemical point of view, biodiesel production from vegetable oils involves a transesteresterification reaction. Vegetable oil is a triglyceride, that is, a triester derived from glycerine or glycerol. Under the presence of a basic catalyst, or even acid, and in the presence of methanol or ethanol, the oil undergoes a transesterification forming three molecules of methyl or ethyl esters of the oleovegetal fatty acids, and releasing glycerine or glycerol, according to scheme 1:

<formula> formula see original document page 4 </formula>

Scheme 1: Transesterification of vegetable oils for biodiesel production.

For each 90m3 of biodiesel produced by transesterification of vegetable oils, approximately 10m3 of glycerin is formed. This scenario indicates that the commercial viability of biodiesel goes through the consumption of this extra volume of glycerin, seeking large scale applications, adding value to the production chain. Today, the main application of glycerin is found in the cosmetics, soap and drug industry, sectors unable to absorb the volume of glycerine generated by biodiesel production alone.

Glycerol or glycerin is a three-carbon triol. It has high viscosity and boiling point, is miscible with polar substances such as water and immiscible with hydrocarbons and other nonpolar compounds. It may be an alternative source for obtaining petrochemical derivatives such as acetaldehyde, α-hydroxyacetone (acetol), 1,2-propanediol, 1,3-propanediol, epichlorohydrin, acrolein, acrylic acid and propene.

Glycerin dehydration can occur in two ways, leading to technological routes for the production of important petrochemical products. According to scheme 2, dehydration of the central hydroxyl from glycerine leads to glyceraldehyde, which may also undergo dehydration to form acrolein:

<formula> formula see original document page 5 </formula>

3-Hydroxypropanal Glycerin Acrolein

Scheme 2: Acrolein production route from daglycerine.

According to scheme 3, oxidation of acrolein leads to acrylic acid, which is an important input in the production of plastics. Acrylic acid can also lead to acrylonitrile, which is widely used as a synthetic fiber and in car interiors and panels.

<formula> formula see original document page 6 </formula>

Acrolein Ac. Acrylic Acrylonitrile

Scheme 3: Production route for acrylonitrile from daglycerine.

With respect to scheme 4, glycerine hydroxyl terminal dehydration leads to α-hydroxy acetone (acetol), which once hydrogenated forms propylene glycol. This product is widely used as an antifreeze and cooling additive in refrigeration systems, as well as playing an important role in the production of polyesters.

<formula> formula see original document page 6 </formula>

Α-hydroxyacetone glycerine Propylene glycol

Scheme 4: Propylene glycol production route from daglycerine.

Acrolein obtained by the route shown in scheme 2 may be hydrogenated to allyl alcohol and hence to dealyl chloride. As for Scheme 5, the addition of hypochlorous acid to the double bond to form halohydrin, followed by base treatment, leads to a possible epichlorohydrin production route, which is an important industrial product in the production of epoxy resins.

<formula> formula see original document page 7 </formula>

Scheme 5: Route for the production of epichlorohydrin from daglycerine.

It is even possible to imagine a paraformaldehyde and formic acid industrial route from glycerine. The first product is widely used in the chemical industry, in the manufacture of synthetic resins used as wood substitutes for furniture and partitions, as well as for fixing electronic circuits. Formaldehyde is also used in the paint, varnish, cellulose pulp industries. Formic acid has major use as a chemical intermediate in the production of some drugs, as well as as a preservative in the food industry.

The use of glycerin as a raw material to obtain petrochemical derivatives is the object of the present invention, since glycerin is a byproduct of biodiesel production, there is a danger of becoming an environmental problem, since there is no adequate demand for a volumescent volume of oil. production of that product. The fact that glycerin becomes a waste with no commercial value puts the socio-economic and environmental viability of biodiesel in check, at a time when its demand has been increasing each day due to the perception that biodiesel is a cleaner source of energy, also generating social benefits.

The scientific literature reports some examples of glycerine hydrogenation and hydrogenolysis using various homogeneous and heterogeneous catalysts.

Runberg et al. Appl. Catai. 17, (1985) 309; Wojcik and Adkins, J. Am. Chem. Sound. 55, (1933) 1294; Wang et al. Ind.Eng. Chem. Res. 34, (1995) 3766-3770 and Lahr and Shanks, Ind.Eng. Chem. Res. 42, (2003) 5467-5472 describe in recent studies that conventional catalysts for hydrogenation of alcohols, such as nickel, ruthenium and alkaladium, are not effective for glycerine hydrogenation.

Copper-based catalysts have good results in the hydrogenation of alcohols in general. These scalers demonstrate good selectivity for C-O bond cleavage and low affinity for C-C bonds. Note that all these studies involve discontinuous reactor conditions.

Chaminand et al. Green Chem. 6, (2004) 359-361 describe the hydrogenation of an aqueous glycerin solution at 180 ° C under an atmosphere of 80 bar H2 and in the presence of ZnO, carbonated (C) or Al2 O3 supported Cu, Pd or Ru catalysts. The reactions produce 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO) with good selectivity. Another important detail is the influence of the solvent (water, sulfolane, dioxane). The selectivity of 1,2-PDO increases significantly in the presence of the CuO / ZnO combination using water as a solvent. For good 1,3-PDO selectivity, studies with the Rh / C catalyst and solvent sulfolan as good results. The addition of an additive (H2WO4) helped to improve selectivity.

Dasari et al. Appl. Catai. A: Gen. 281, (2005), 225-231 describe the hydrogenation of glycerin to propylene glycol using nickel, palladium, platinum, copper / chromium catalysts. At temperatures above 200 ° C and hydrogen pressures of 200 psi, selectivity to propylene glycol decreases due to excessive hydrogenolysis.

Xie and Schlaf, J. Mol. Catai. A: Chem. 229, (2005) 151-158 demonstrated that the hydrogenolysis of glycerine to 1,2-propanediol, 1,3-propanediol using the [cis-Ru (6,6-C12-bipy) 2 (OH2) 2] catalyst ( CF3SO3) 2 in continuous flow of H2 at ambient pressure, besides being ecologically and economically viable, does not generate by-products derived from triol polymerization and decomposition under drastic reaction conditions.

Hirai et al. Energy & Fuels. 19, (2005) 1761-1762 describe a study where ruthenium is dispersed in different supports such as Y2O3, ZrO2, CeO2, La2O3, SiO2, MgO and Al2O3. These catalysts transformed glycerol into H2, CH4, CO and CO2. The catalyst with the best performance was Ru / Y203. The catalyst is pretreated at 600 ° C under a stream of H2 for one hour. After this procedure, an argon stream is used as a carrier gas. With the aid of an injection pump, a aqueous solution of glycerin is slowly dripped onto the catalyst surface, which is at a temperature of 500 ° C. The gases generated are carried and analyzed on a gas chromatograph. With a 100% conversion to aglycerin, product selectivity ranges from 60-80% for CO2 and 80-90% for H2.

Chiu et al. Ind. Eng. Chem. Res. 45, (2006) 791-795 published a paper where, after the transesterification process, calcium hydroxide in combination with phosphoric acid generates a precipitate, characterized as hydroxy-hapatite, at different pH measurements. Thus, crude glycerin can be used directly for hydrogenolysis reporting generating propylene glycol without having affected performance.

Recently, Miyazawa et al. Appl. Catai. A: Gen.318, (2007) 244-251 described the hydrogenation of glycerine propylene glycol. The use of mild reaction conditions is still a major challenge for researchers, especially in the hydrogenation stage, where normally lower temperatures disadvantage the process. The Ru / C catalyst in combination with Amberlyst (Rohm and Haas supplied ionic resin resin) showed good results. This catalyst was prepared from Ru (NO) (NO3) 3 and activated charcoal following a programmed temperature procedure under a continuous flow of air, which allowed a high surface area which, in combination with Amberlyst's acidity, makes the reaction process very more efficient.

Maris and Davis, J. Catai. 249 (2007) 328-337 described the glycerine hydrogenation on coal-supported Ruthenium and Platinum catalysts. The reaction was carried out with an aqueous glycerine solution at a temperature of 100 ° C and 40 bar hydrogen pressure, leading to the production of ethylene glycol and propylene glycol.

The prior art also contemplates some patent documents related to the hydrogenation process and glycerine hydrogenolysis.

Chinese document CN 101085719 of June 29, 2007, filed by Shanghai Huayi Acrylic Acid Co., describes a process of glycerine hydrogenation at a temperature range of 180-300 ° C and a pressure of 1.0-10.0 MPa. Glycerin / H2 molar relationship is 1:30 and the spatial velocity used was 1.0-5.0 h "1 in the presence of Cu, Co and Al metal oxides with 25% by weight demetal.

Chinese document CN 101054339 of May 31, 2007, filed by Shanghai Huayi Acrylic Acid Co., describes another method of glycerine hydrogenation using a mixture of gases and hydrogen in the presence of supported catalysts. The active component contains one or more metals such as: Ni, Co, Mn, Cu, Cr, Ca, Zn, Fe, Sn, W, Mo, V, Ti, Zr, Nb, La, Re, Ru, Rh, Pd , and Pt. The temperature used is in the range of 120-450 ° C, and the pressure between 0.2 and 30.0 Mpa. The practiced spatial velocity is in the range of 0.1 - 50.0 h, and the molar glycerin / H2 ratio was 1: (1-50). The support used comprises one or more of the following materials: zeolites, Al2O3, SiO2, MgO, TiO2, ZrO2, amorphous aluminosilicates. The generated products contain 3-100% by weight of n-propanol and one or more of methane, methanol, ethanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, acetone and glycerine.

Chinese document CN 101012149 of February 7, 2007, filed by Univ. Nanjing, refers to a 1,2-propanediol preparation method under mild conditions, which comprises: adopting copper, zinc and manganese and / or aluminum as catalyst; aerate glycerine and hydrogen continuously from the top of the reactor; hydrogenate glycerine at 200-2500 ° C under pressure of 2.5-5 MPa; extract and collect the reaction product from the catalyst bottom continuously, separate the gas; return gas for recycling; and adjust the weight ratio of the metal catalyst element.

Japanese document JP 2008044874, of August 14, 2006, filed by Nat. Inst. of Adv Ind. & Technol. eSakamoto Yakuhin Kogyo Co. Ltd., refers to a method of producing propanediols, particularly 1,3-propanediol, with a high yield through the glycerine hydrocracking method. Said method comprises hydrogenation of glycerin in the presence of an acid and a hydrogenation catalyst, where a solvent is present in the reaction system, if circumstances require. The acid is a solid at room temperature and not less than the total weight of the acid and hydrogenation catalyst relative to the total volume of glycerine and the solvent is from 1/15 to 10 g / ml.

Japanese document JP 416623,2 of October 29, 1990, filed by Sumitomo Metal Mining Co., relates to obtaining a catalyst for high activity hydrogenation by the deposition of group VI (preferably Mo and / or W) metals and group VIII (preferably Co and / or Ni) on a catalytic support comprising a porous material and the addition of a polyhydric alcohol to form an active metal complex. Said porous catalyst support material may be alumina, silica, titania, zirconia or active carbon. Polyhydric alcohol (ethylene glycol, diethylene glycol, triethylene glycol, glycerin, 2,2-diethyl-1,3-propylene glycol, etc.) is added to the deposited catalyst. Thereafter, the catalyst is dried and has extremely high activity to allow high level hydrogenation, such as deep desulphurization of hydrocarbon oils.

European Document EP 0 523 014 of July 7, 1992, filed by Novamont SpA, describes a hydrogenation process of an aqueous glycerin solution in basic medium (NaOH) at a temperature of 260 ° C (autoclave) using Ru / C catalysts, leading to the formation of 1,2-propanediol and lactic acid with 100% conversion and 75.2 and 13.4% respectively.

EP 0 523 015 of July 7, 1992, filed by Novamont SpA, describes another process of hydrogenation of an aqueous glycerin solution under Cu-Zn catalysts at 270 ° C, leading to the formation of 1,2- propanediol and 1,2-ethanediol, with conversion of 99.4% and selectivities of 84.4 and 6%, respectively.

European Document EP 0 713 849 of 17 November 1995 filed by BASF AG discloses another glycerine hydrogenation process for the production of isopropanol, n-propanol and propanediols using supported cobalt, copper, manganese or molybdenum metal catalysts and an inorganic polyacid . The yield was 95%, the pressure 3625 psi and temperature 250 ° C.

EP 0 598 228 of 18 October 1993, filed by Degussa AG, describes a process for the simultaneous production of propylene glycol and 1,3-propanediol (1,3-PDO) from hydrogenation and hydrogenolysis of glycerine / water desolutions containing 10-40 wt% deglycerin at a temperature of 300 ° C.

German DE 43 02 464 of 29 January 1993, filed by Henkel KGaA, describes the process of hydrogenation of glycerine in vapor phase, with high conversion and selectivity to 1,2-propylene glycol. The darning temperature is between 160-260 ° C, the pressure between 10-30bar and the glycerine / H2 molar ratio is 1: 600.

Analyzing the above state of the art, it is observed that most of the documents presented refer to glycerine hydrogenolysis. Although most of the above documents have as a product of interest mainly ethylene glycol, 1,2-prapanediol and 1,3-propanediol, which can also be obtained using the method of the present invention, the reaction conditions used such as spatial velocity, molarglycerin / hydrogen ratio and reaction time, together with the supported metal catalysts, have a specific effect on product conversion, which is not an obvious occurrence for one of ordinary skill in the art.

As mentioned earlier, there is a decreasing need for absorption of the glycerine filler produced as a byproduct of biodiesel production. Moreover, the demand for inputs for the petrochemical sector, especially propylene, and the search for cleaner and less environmentally friendly technologies are decisive factors that prove the need for new techniques.

Summary of the Invention

The object of the present invention is a catalytic process whereby the hydrogenation / hydrogenolysis reaction of glycerol or glycerine leads to the obtaining of oxygenated compounds and hydrocarbons containing from 1 to 3 carbon atoms, by the use of commercial metal catalysts based on inorganic metal salts of group VIII-B periodic table of the elements, which are supported in high specific area materials, using conventional methods, but with specific pressure ranges, temperature, glycerin / H2 molar ratio and spatial velocity that give it an unexpected technical result, which is not evident to a technician subject based on the above state of the art.

Description of the Figures

The present invention will be described based on the attached figures, in which:

- Figure 1 shows the mass selectivity of organic products using the catalyst containing 5% alkaly supported on 6.46 h "1 WHSV and 120: 1 molar H2 / glycerine ratio (reaction temperature = 300 ° C);

Figure 2 shows the mass selectivity of organic products using the catalyst containing 5% alkaline supported alumina with 6.46 h_1 WHSV and 120: 1 molar H2 / glycerine ratio (reaction temperature = 325 ° C);

Figure 3 shows the mass selectivity of organic products using the catalyst containing 5% alkalis supported on 3.74 h "1 WHSV alumina and 120: 1 molar H2 / glycerine ratio (reaction temperature = 350 ° C);

- Figure 4 shows the mass selectivity of organic products using the catalyst containing 5% deruthenium supported on 6.46 h_1 WHSV alumina and 120: 1 molar H2 / glycerine ratio (reaction temperature = 250 ° C);

- Figure 5 shows the mass selectivity of organic products using the catalyst containing 1% depalladium and 5% ruthenium supported on charcoal active powder with 5.45 h "1WHSV and 120: 1 H2 / glycerin molar ratio ( reaction = 300 ° C), and

- Figure 6 shows the mass selectivity of organic products using the catalyst containing 5% coal-backed active powder supported with 5.47 h_1 WHSV and 120: 1 molar H2 / glycerine molar ratio (stripping temperature = 300 ° C).

Detailed Description of the Invention

The present invention is based on the fact that the proposed catalytic method has application in a process where a glycerine charge is introduced into the hydrogen stream and over the catalytic bed, containing a supported metal catalyst, with the aid of a pump gun. Said charge reacts with hydrogen in the present catalyst under appropriate conditions of temperature, pressure, molar hydrogen / glycerin ratio and spatial velocity.

Generally speaking, the process of the present invention comprises the following steps: (a) catalyst pretreatment for activation at a temperature range of between 150 ° and 700 ° C, depending on the catalyst employed, more specifically between 250 ° and 550 ° C;

b) monitoring the reaction temperature between 200 and 550 ° C, more specifically between 225 and 350 ° C;

c) using a pressure in the range from 0 to 200 kgf / cm2, preferably from 0.01 to 10 kgf / cm2;

d) adding the glycerin through an injection pump having a glycerine / H2 molar ratio of 1: 1000, preferably 1:30 to 1: 240; and

(e) use of a spatial velocity between 0,1 and 100 h ~ 1, more specifically between 2,0 and 20 h -1, for the conversion of glycerin. This process is carried out in a test-catalytic unit equipped with a flow controller; programmer linear temperature controller and oven. To this system was coupled a gas chromatography with flame deionization detector (DIC) and equipped with a capillary column.

The hydrogenation / hydrogenolysis reaction of glycerine or glycerol leads to the obtainment of oxygenated hydrocarbon compounds containing from 1 to 3 carbon atoms, such as propene, propane, acetol, acetone, propylene glycol, ethylene glycol, acetaldehyde, ethane and methane, among others.

Typical total pressure values for said process are from 0 to 150 kgf / cm2; the reaction temperature is 150 to 550 ° C, the glycerine / hydrogen molar ratio is 1: (5-1000); and the spatial velocity is between 0.01-100 h "1.

The present invention also describes the use of supported metal catalysts, the metals belonging to group VIII-B of the periodic table of the elements. The supports used include powdered activated carbon, aluminosilicate, alumina, clays, zeolites, molecular sieves, but not limited to these examples. Catalysts may be obtained commercially or prepared by conventional, public domain methods, such as wet impregnation.

Said supported metal catalysts comprise in their composition a metal which is comprised of from 0.1% to 10% by weight of catalyst, preferably from 1 to 5% by weight. The metals are group VIII-B, preferably palladium, ruthenium, nickel and rhodium.

The catalysts used may be employed in glycerine hydrogenation / hydrogenolysis reactions as exemplified by scheme 6:

<formula> formula see original document page 21 </formula>

Scheme 6: Hydrogenation / hydrogenolysis of metal glycerine over catalysts.

The following example is for the purpose of merely illustrating the invention and facilitating its understanding, having no limiting character thereto.

Example

A catalytic test unit equipped with a flow controller, programmer and linear temperature controller and oven was coupled to a gas chromatograph with flame ionization detector (DIC) and equipped with a 50 m methyl silicon capillary column for use in hydrogenation of the glycerin.

A mass of catalyst containing 5% alumina-supported palladium was placed in the fixed delight catalyst reactor, and pretreated at 550 ° C for 30 minutes with a heating rate of 10 ° C / min under continuous H 2 flow (40 mL / min). min), to reduce the metallic sites.

The hydrogenation / hydrogenolysis reaction was conducted under a continuous flow of a glycerine in hydrogen (H2) charge. Glycerin was introduced into the hydrogen stream and onto the catalytic bed through an injection pump. The products were analyzed by a gas chromatograph fitted with a 50 m methyl silicon capillary column and a flame ionization detector (DIC) coupled in line with the catalytic testing unit.

The catalyst conversion and selectivity parameters containing 5% palladium on alumina were evaluated against catalytic tests at 300 ° C, varying the spatial velocity of the load in order to maximize propylene production.

The influence of spatial velocity (WHSV) on the selectivity of the formed products was performed by applying values between 4.8 and 6.4 h-1.

Under the best reaction conditions used, glycerine conversion was 100%. The products detected were methane, ethane, propane and propene. The temperature range from 300 ° C to 325 ° C alters the selectivities while maintaining the same H2 / glycerin molar ratio (Figures 1 and 2).

Figure 3 shows the results of the conversion of selectivity with the catalyst of 5% palladium on aluminum reaction temperature of 350 ° C and molarEh / glycerin ratio of 1:60, occurring a change in the selectivity of the products.

Figure 4 shows the conversion and selectivity results for glycerine hydrogenation / hydrogenolysis on a catalyst containing 5% alumina supported ruthenium. In this case, methane, ethane and acetaldehyde were the main products. Figures 5 and β show the conversion and selectivity results for glycerine hydrogenation / hydrogenolysis on catalysts containing 1% palladium and 5% ruthenium supported on active charcoal powder, and lastly the catalyst containing 5% palladium on charcoal supported, respectively. .

Claims (14)

1. Hydrogenation / hydrogenolysis process of a glycerine or glycerol filler in which said reaction occurs in the presence of supported metal catalysts, through the addition of glycerin or glycerol in the hydrogen gas stream and over the catalytic bed, through a pump gun, characterized by the fact that comprise the following steps: (a) catalyst pretreatment for activation at a temperature range of 150 to 700 ° C (b) monitoring of the reaction temperature of 200 to 50 ° C (c) use of pressure in the range of 0 to 200 ° C kgf / cm2 (d) addition of glycerine by injection pump having a glycerine / H2 molar ratio of 1: 1000; ee) use of a spatial velocity comprised between 0.1 and 100 h "1, aiming at the glycerin conversion. Process according to Claim 1, characterized in that in step a) the catalyst pretreatment is preferably carried out within a temperature range of 250 ° to 550 ° C. Process according to Claim 1, characterized in that in step b) the reaction temperature is preferably in a temperature range between 225 ° and 350 ° C. Process according to Claim 1, characterized in that in step c) the pressure is preferably from 0.01 to 10 kgf / cm2. Process according to claim 1, characterized in that in step d) the glycerine / H2 molar ratio is preferably between 1:30 and 1: 240. Process according to claim 1, characterized in that in step e) the spatial velocity is more specifically comprised between 2.0 and 20 h -1. Process according to any one of claims 1 to 6, characterized in that it utilizes glycerine obtained by means of transesterification processes of soybean, castor, jatropha, palm, palm, oilseed rape, cotton, sunflower, fodder turnip, babassu, coconut oil, among other oilseeds used in biodiesel production processes, or from the transesterification of vegetable oils used in frying, animal fat from domestic or industrial sewage, and in all cases glycerin is previously neutralized before hydrogenation / hydrogenolysis. Process according to any one of claims 1 to 7, characterized in that the conversion of glycerinaser to oxygenated compounds and hydrocarbons containing from 1 to 3 carbon atoms, preferably propene, propane, propylene glycol, ethylene glycol, acetol (α-hydroxy) acetone), acetone, acetaldehyde, ethanol, ethane and methane, among others. Process according to Claim 8, characterized in that the products are in the range of 10 to 100%. Process according to Claim 1, characterized in that said glycerin filler can be in the form of aqueous solution in proportions of 30-100% by weight of glycerin. Process according to any one of claims 1 to 10, characterized in that the hydrogenation reaction takes place in a system where the catalyst is in a fixed bed system in the reactor. Process according to any one of Claims 1 to 11, characterized in that the transition metals supported on the catalyst belong to the group VIII-B of the periodic table of the elements, preferably palladium, ruthenium, nickel and rhodium. Process according to any one of Claims 1 to 12, characterized in that the supports used are preferably active carbon powder, aluminosilicates, aluminas, clays, zeolites and molecular sieves. Process according to any one of Claims 1 to 13, characterized in that the metal is present in the catalyst formulation in a range of from 0.2-10% by weight, preferably from 1-5% by weight of the metal catalyst. .