BRPI0803465A2 - biokerosene and process for obtaining it - Google Patents

Abstract

BIOCHEROSENE AND PROCESS OF OBTAINING THE SAME The present invention belongs to the field of biofuels. More specifically, the biofuel of the present invention is the biokerosene obtained from the transesterification of vegetable oils in the presence of a catalyst. Additionally, the reaction of the present invention is a reaction that takes 10 minutes and the process of obtaining the biokerosene also comprises a step of purifying the obtained product. Specifically, the biokerosene obtained in the present invention has potential application as an aviation fuel.

Description

Patent Invention Descriptive Report

Biokerosene ε process for obtaining same

Field of the Invention

The present invention belongs to the field of biofuels. More specifically, the biofuel of the present invention is biokerosene obtained from transesterification of vegetable oils in the presence of a catalyst. Additionally, the reaction of the present invention is a 10 minute reaction and the process of obtaining the biosynthesis further comprises a purification step of the obtained product. Specifically, the biosynthesis obtained in the present invention has potential application as aviation fuel.

Background of the Invention

Biodiesel is defined by the American Society for Testing Materials (ASTM) as a synthetic liquid fuel originating from renewable material and consisting of a mixture of long decade fatty acid alkyl esters derived from vegetable oils or animal fats.

The frequent rise in the price of oil and the possibility of fossil fuel depletion have motivated numerous researchers to search for alternative fuel. This concern also exists on the part of environmentalists aiming to reduce the pollution caused by the use of diesel and was intensified after the Kyoto Protocol.

The use of biodiesel as a fuel has shown promising potential worldwide, being a market that is growing rapidly due to numerous advantages, such as:

- is a fuel produced from renewable sources such as vegetable oils, frying waste or animal fat. The use of waste as a raw material reduces the costs of sewage treatment and disposal.- is biodegradable. Studies show that biodiesel from oil spills and canola are easily absorbed into the environment. The use of mixtures containing 20% v / v biodiesel (B20) increases the biodegradability of diesel in the presence of water. In addition, the growth of algae in biodiesel storage tanks was observed.

- It is a non-toxic fuel as the use of biodiesel causes a substantial reduction in carbon monoxide and particulate matter emissions. In addition, it is sulfur free and aromatic, prevents the formation of soot because it has 10% v / v oxygen. Using 20% v / v diesel biodiesel reduces carbon dioxide emissions by 15.66% v / v.

Transesterification is the most common form of biodiesel production. This reaction consists of mixing an alcohol, preferably of low molecular weight, with a vegetable oil or animal fat. Also called dealcoolysis, the transesterification reaction may occur in the presence or absence of catalyst. The transesterification reaction occurs most rapidly in low molecular weight alcohol such as methanol and ethanol.

The transesterification reaction is accelerated by homogeneous or heterogeneous catalysts. Homogeneous catalysts may be acids, bases or enzymes. These catalysts have the drawbacks: the need for product purification (ester and glycerin) to remove catalyst residues and the impossibility of reuse after sandblasting. Heterogeneous catalysts can be reused after reaction and are easily removed, making the purification step of products (glycerin and ester) simpler.

In this context, this invention describes the production of biosynthesizing transesterification of coconut oil. This fuel was obtained with a high degree of purity (99% by weight of esters) using the high performance centrifugal molecular distiller prototype. Biokerosene is derived from vegetable oils and has the same characteristics as petroleum-derived kerosene. It is noteworthy that fossil kerosene contributes to environmental pollution (greenhouse effect). In this sense, it is intended to replace kerosene with a similar product of plant origin, renewable and that will contribute significantly to the reduction of pollution.

The search in the patent literature has pointed out some relevant documents that will be described below.

US 2007/0194016 discloses a method of obtaining biofuels such as biodiesel, biogasoline, biokerosene, among others, which process comprises the passage of chemical species through a dielectric macroscopic structure to a gas permeable susceptor receiving electromagnetic energy. Various types of vegetable and animal oils can be used in this process. The present invention differs from this document in that the production process comprises the use of a catalyst.

WO 2007/143803 discloses a transesterification method for the production of alkyl esters which comprises the use of a plant glyceride material and a basic or acid catalyst and a guanidine-based catalyst. The basic catalysts are NaOH1 KOH1 NaOCH3, NaOCH2CH3l KOCH3l KOCH2CH3l and the acids are H2SO4l HCl and guanidine-based catalysts are: N-alkyl guanidine, Ν, Ν'-alkylguanidine; N 1 N - dialkyl guanidine; N1N11N "- trialkyl guanidine; N1 N1 N'-trialkyl guanidine; N5 N N11 N tetraalkyl guanidine; N5 N, N11N 'tetraalkyl guanidine and Ν, Ν, N', N N" pentaalkyl guanidine. Specifically, the alkyl ester produced by the process of this document is biodiesel. The present invention differs from this document in that the alkyl ester produced is biokerosene.

US 2006/0058540 discloses a method of transesterification of vegetable oils with short chain alcohols in the presence of a catalyst. Specifically, the catalyst described herein is a salt or base of an organic compound and a carbonic acid. Specifically, the organic compound is a nitrogen-containing compound, and the basic compound is umaguanidine, such as guanidine carbonate, and 1-aminoguanidine derivatives, such as 1-aminoguanidine hydrogen carbonate. Specifically, the product obtained in the process of this document is biodiesel. The present invention differs from this document in that it comprises a product purification step obtained yielding the biokerosene.

WO 2007/025360 discloses a transesterification method which comprises the reaction between mono-, di- and triglycerides of vegetable oils and animal fats and a molar ratio short chain alcohol ranging from 3 to 15. Specifically, the reaction of this document takes place at temperatures between 80 ° C and 80 ° C. and 250 ° C, pressures greater than atmospheric pressure, stirring speeds between 400 and 1500 rpm, residence time or space time from 5 to 1000 minutes. Specifically, the alcohol used is a hydrochloride alcohol and the catalyst is a basic solid hydrotalcite based catalyst undergoing a calcination process between 250 and 900 ° C. The present invention differs from this document in that the transesterification process does not comprise a hydrotalcite based catalyst.

US 6,359,157 discloses a process of transesterification of vegetable oils and fats with short chain alcohols comprising a catalyst which is a metal salt of an amino acid or an amino acid derivative. Specifically, the catalyst used is a short chain alcohol insoluble catalyst, with catalysis being a heterogeneous catalysis. The present invention differs from this document in that the catalyst is a homogeneous catalyst and does not comprise an amino acid metal salt or amino acid derivative.

US 6,187,939 discloses a method of esterifying fatty acids and obtaining fuels comprising fatty acids which reaction with an alcohol does not comprise the use of a catalyst. Specifically, the alcohol used in this process is in supercritical states and the product obtained comprises diesel. , fuel additives and lubricating oils. The present invention differs from this document in that it does not include the use of alcohol in a supercritical state and the fact that it misunderstands the use of a catalyst.

Therefore, no document has been found in the literature that suggests or even suggests the particularities of the present invention.

It is an object of the present invention, a fuel obtained from renewable fontevegetal. Specifically, the biofuel of the present invention is biokerosene.

Specifically, the biokerosene of the present invention has characteristics similar to petroleum derived kerosene and may be used as aviation kerosene.

Also an object of the present invention is a process for obtaining the biorosene comprising the steps of:

a) reacting a mixture comprising:

- a material rich in glycerides;

a C1-C5 short chain alcohol; and

- at least one homogeneous catalyst; and

b) separate the ester and glycerin phases.

The reaction time from step a) can range from 5 minutes to 3 hours. In a preferred embodiment, the reaction time from step a) is 10 minutes.

The glyceride rich material may be a vegetable oil, an animal oil, a mineral oil as well as a mixture thereof. Specifically, the glyceride material of the present invention is coconut oil and / or babassu and the short alcohol of the present invention is ethanol.

Detailed Description of the Invention

The following examples are not intended to limit the scope of the invention, but merely to show one of the possible embodiments.

The Biokerosene of the present invention was obtained using an oil-vegetable as a feedstock, ethyl alcohol as a solvent, and catalysts. Then, the biokerosene was purified using a molecular distiller.

Glyceride Material

The term "glyceride material" refers to vegetable and / or animal oils and / or fats containing triglycerides and / or diglycerides and / or monoglycerides and / or free fatty acids. Useful glyceride materials for carrying out the invention include, but are not limited to soybean oil, cottonseed oil, coconut oil, babassu oil, corn oil, canola oil, macauba oil (Acrocomia aculeata and / or Acrocomia totai mart) palm oil, peanut oil, pequi oil (Carioear brasiliensis and / or Carioeareoriaeeous), ouricuri oil (Syagrus eoronata), jatropha oil (Jatropha eureas and / or Jatropha marcocarpa), other vegetable fats and / or animals, such as chicken, pork and / or beef tallow fats, including waste oil and fat from frying. Additionally, the "glyceride material" may be chosen from oils, neutrals, acids, crude, degummed, semi-refined and / or refined as well as the mixture thereof.

The vegetable oil corresponded specifically to babassu or beach coconut oil.

Short Chain Alcohol

The lower alcohols of the present invention are preferably chosen from alcohols of up to 5 carbon atoms. Examples of such alcohols include, but are not limited to, methanol, ethanol, propanol, butanol, isopropanol, 1-butanol, 2-butanol, isobutanol, amyl and / or isomers among others, as well as a mixture thereof.

Specifically, the solvent of the present invention should have a solvent to vegetable molar ratio ranging from 3: 1 to 15: 1 (w / w).

Specifically the solvent of the present invention is ethanol used in the 10: 1 ratio to vegetable oil.

Homogeneous and Heterogeneous Catalyst

The catalyst of the present invention is a catalyst chosen from the group which comprises basic catalysts such as NaOH, KOH, NaOCH3, NaOCH2 CH3, KOCH3, KOCH2 CH3, among others as well as a mixture thereof, guanidines such as 1.5,7 -triazabicyclo [4.4.0] dec-5-ene (TBD) 1 1,1,3,3-tetramethylguanidine (TMG) 1 among others, as well as the mixture thereof.

Specifically, the catalyst is used in molar ratio ranging from 0.01 to 3% by weight relative to vegetable oil. Specifically, in the present invention the homogeneous catalyst is NaOH and KOH and the heterogeneous catalyst is guanidine. A catalyst mass of up to 1% by weight of the vegetable oil mass being used.

Bioguerosene Production Process

The biokerosene production process of the present invention comprises the steps of:

a) reacting a mixture comprising:

- a material rich in glycerides;

a C1-C5 short chain alcohol; and

- at least one homogeneous catalyst; and

b) separate the ester and glycerin phases.

Several factors influence the outcome of the process. Examples include reaction time, temperature and proportion of reagents. Regarding the reaction time, it must be adjusted to consume all reagents. It can vary within a range of 5 minutes to 3 hours, and preferably the reaction lasts 10 minutes. The process temperature is chosen to maintain a suitable dropping speed without causing degradation to the reagents. Preferably the temperature is chosen within a range of from 20 to 80 ° C. Regarding the ratio between reagents, the molar ratio between short chain alcohol and glyceride rich material ranges from 3: 1 to 15: 1 (w / w). Specifically, the molar ratio of the present invention is 10: 1.

The production process of the present invention may be carried out in various types of reactors known in the prior art, as well as by a batch process or a continuous process.

Ester-glycerine phase separation

Phase separation is performed by any phase separation method already described in the prior art such as washing, neutralization, distillation methods such as centrifugal molecular distillation distillation, column purification, among others possible, as well as mixing of the same. The purification / separation of the present invention is performed by washing with acidified water at temperatures between 75 ° C and 90 ° C, which provides neutralization of the obtained product, then the mixture is vacuum filtered in the presence of anhydrous sodium sulfate (dehumidifying agent). ), and distillation in molecular distillers at 150 - 70 ° C and pressure between 4-90μό8Γ. Specifically, temperature of 90 ° C and pressure of 70 μόβΓ favored a higher concentration of the desired product.

The operating conditions that provided the greatest reaction conversion in the shortest time were 1 wt.% Of basic catalyst, 10: 1 ethanol: coconut oil molar ratio, 10 minute reaction time and 50 ° C reaction temperature. Characterization of the raw material

Biokerosene was produced by transesterification of beach decoction in the presence of alkaline catalysts derived from guanidine and ethyl alcohol. Coconut oil (raw material) was characterized using the following methodologies:

Example 1.1. Fatty acid identification by gas chromatographyFatty acid identification was performed by gas chromatography. Fatty acids were converted to methyl esters (FAME) and analyzed in the gas chromatograph using a DB23 column (30 m χ 0.53 mm) flame ionization detector. . Table 1 shows the composition of the decco oil. The determination of the coconut oil composition allowed the molecular dope calculation of this oil. Table 1 shows that coconut oil is mostly composed of short chain fatty acids (between C8-C14), which enables the formation of esters of low molecular weight and characteristics similar to aviation kerosene.

Table 1 - Coconut oil composition

<table> table see original document page 9 </column> </row> <table> <table> table see original document page 10 </column> </row> <table>

Example 1.2. Determination of acidity

The analysis of free fatty acids was performed according to AOCS Ca 5a - 40 methodology. The sample was dissolved in ethyl alcohol etched with sodium hydroxide. The percentage of free fatty acids was calculated in terms of oleic acid according to equation (1).

<formula> formula see original document page 10 </formula>

In this equation, mL of alkali represents the volume of sodium hydroxide used and N corresponds to the normality of sodium hydroxide. The constant28,2 is related to the molecular weight of oleic acid. The acidity of the decoc oil corresponded to 0.131% or 0.262 mg KOH / g. It is noteworthy that the determination of acidity is of fundamental importance for the choice of catalyst of the reaction, since acidity greater than 1% would cause catalyst consumption, soap formation and reduced reaction conversion.

Example 1.3. Liquid chromatography

Analysis of the composition of the transesterification reaction was performed by size exclusion liquid chromatography, also known as high performance size-exclusion chromatography (HPSEC). This analysis allowed the exact measurement of the reaction composition, ie concentration of glycerides, diglycerides, monoglycerides, esters and glycerin.

The chromatographic columns used form two WatersStyragel® HR1 and HR2 columns in series. Refractive index detector was used. The mobile phase used was tetrahydrofuran, with a flow rate of 1 mL / min at 40 ° C. Sample preparation consists of diluting 100 mg of the sample in 10 mL of this solvent (tetrahydrofuran).

Example 2. Transesterification ReactionThe transesterification reaction is influenced by several variables such as: agitation level, reaction time, reaction temperature, catalyst concentration, quantity and quality of the raw material, alcohol concentration used (measured in terms of molar ratio ethanol: coconut oil). In order to obtain a high reaction conversion in a shorter time the following operating conditions have been tested:

• Reaction temperature: 30, 40, 50, 60 and 75 ° C.

• Catalyst concentration: 0.5 to 1.5% by weight of coconut oil.

• Molar ratio: 6: 1 to 12: 1

For each assay samples were taken at the following intervals: 0.5; 1; 2; 5; 7; 10; 12; 15; 20 and 30 minutes. These samples were analyzed in HPPSEC, through which the conversion to biokerosene was determined.

The operating conditions that provided the highest reaction conversion in the shortest time were 1% by weight of basic catalyst, 10: 1 ethanol: coconut oil molar ratio, 10 minute reaction time and 50 ° C reaction temperature. Under these conditions, a 97% by weight conversion of biokerosene was achieved, ie, for every 400 grams of coconut oil used, only 12 grams of unreacted coconut oil (monoglyceride) remained.

Laboratory scale biokerosene can be obtained as follows:

Initially, coconut oil (400g) was added to the reactor (1 liter mechanical comagination reactor) and heated to the desired temperature. Then the catalyst (NaOH) was diluted in ethanol and added to the oil. After the desired time, stirring was stopped and the mixture was cooled, terminating the reaction. Then the mixture went to the rotary evaporator, in which the excess alcohol used in the reaction is distilled. Catalyst concentration corresponded to 1% w / w of coconut oil mass, while the amount of ethyl alcohol was calculated based on the number of moles of coconut oil, as detailed in Equation. Several molar ratios between ethanol and coconut oil were tested, and 10: 1 proportion provided higher conversion. Thus, for each 400 g of coconut oil, 253 g of ethyl alcohol and 4 grams of catalyst were used.

<formula> formula see original document page 12 </formula>

Where: Mwc0co is the molecular weight of coconut oil calculated on the basis of fatty acid composition.

The mixture obtained in the rotary evaporator went to a separatory funnel and two phases were obtained. The lower phase is rich in glycerin and is orange in color as a result of the catalyst residue. The upper phase consists of ester and impurities and is yellowish in color.

Example 3. Purification of Formed Products

Biokerosene purification was performed in the following steps:

Example 3.1 Washing and neutralization

After separation, the ester phase was washed with acidified water and heated to 75 ° C. A minimum amount of water, corresponding to 10% by weight of ester, was used, which enabled a reduction of ester losses by washing. The water used was acidified with drops of hydrochloric acid. Water was added to the ester and, after vigorous stirring, the mixture goes to a separatory funnel and then the acidity of the aqueous phase was measured using pH indicator paper. Normally, three washes were required to achieve a neutral pH. Various temperatures were tested and it was found that temperatures between 75 ° C and 90 ° C allowed for faster separation.

Then a small amount of dehumidifier (anhydrous sodium sulfate) was added to the ester to remove water residues. After vacuum filtration the ester moisture was determined by KarlFisher, a corresponding water content was found. 0.1%. Example 3.2. Molecular distillation

The concentration of the lower molecular weight esters was made by molecular distillation, or short path distillation as it is also known, it is an unconventional separation process indicated for the separation of homogeneous liquid mixtures containing high molecular weight thermosensitive substances (typically greater than 180g / mol) and low volatility. In this process, the mixture is fed to a distiller having an evaporator having an internal condenser. This evaporator operates under a high vacuum and provides the heat necessary for any powered molecules to volatilize. Molecules that volatilize migrate to the condenser, become liquefied and are removed from the equipment. Thus, this process gives rise to two effluent streams that are taken from the process. One made up of non-volatilized material, called waste, and another made up of molecules that volatilized during the process, called distillate.

The distillation of the biokerosene was carried out at 90 ° C and 70pbar pressure. Biokerosene was obtained in the colorless distillate and in the residue as a mixture of higher molecular weight yellowish esters. Molecular distillation allowed the complete concentration of lighter esters (C8-C14) and complete elimination of residues from the raw material (fatty acids, monoglycerides, diglycerides etriglycerides), promoting a high purity product.Example 3.3. Income Determination

Reaction yield was determined based on distilled product mass and corresponded to 90%.

Example 3.4. Product Characterization

Several analyzes were performed that allowed the characterization of the bilobososene, such as:

• reduced pressure distillation curve (performed at IPT);

· Humidity analysis (IPT and UNICAMP);

• composition (IPT and UNICAMP) • flash point (IPT)

• acidity (UNICAMP).

Table 2 lists the analyzes performed and compares with the specifications of the National Agency of Petroleum Natural Gas and Biofuels (ANP).

Table 2 - Biokerosene Properties

<table> table see original document page 14 </column> </row> <table> <table> table see original document page 15 </column> </row> <table>

Claims (16)

1. Process for obtaining biokerosene characterized in that it comprises the steps of: a. reacting a mixture comprising: a glyceride rich material in a C1-C5 short alcohol; and at least one homogeneous and / or heterogeneous catalyst, eb. separate the ester and glycerin phases. Process according to Claim 1, characterized in that the glyceride material is selected from the group comprising vegetable and / or animal oils and / or fats containing triglycerides and / or diglycerides and / or monoglycerides and / or free fatty acids. Process according to Claim 2, characterized in that the glyceride material is selected from the group comprising spawn oil, cottonseed oil, coconut oil, babassu oil, corn oil, canola oil, macauba oil, palm, peanut oil, persian oil, goldfin oil, jatropha oil, chicken fat, pork and / or beef tallow, residual frying fat and the same combinations. Process according to Claim 3, characterized in that the oil is a mixture of beach coconut oil and babassu oil. Process according to Claim 1, characterized in that the alcohol is selected from the group comprising methanol, ethanol, propanol, butanol, isopropanol, 1-butanol, 2-butanol, isobutanol, amyl and a mixture thereof. Process according to Claim 5, characterized by the alcohol ethanol. Process according to Claim 1, characterized in that the alcohol: vegetable oil molar ratio is in the range from 3: 1 to 15: 1 (w / w). Process according to Claim 7, characterized in that the molar ratio is approximately 10: 1. Process according to Claim 1, characterized in that the catalyst is selected from the group comprising NaOH 1 KOH 1 NaOCH 3, NaOCH 2 CH 3, KOCH 3, KOCH 2 CH 3, guanidines, 1,5,7-triazabicyclo [4.4.0] dec-5-ene ( TBD), 1,1,3,3-tetramethylguanidine (TMG), mixture thereof. Process according to Claim 9, characterized in that the catalyst is selected from the group comprising NaOH, KOH and guanidine. Process according to Claim 1, characterized in that the catalyst is present in a concentration of 0.01% to 3.0% by weight of the vegetable oil mass. Process according to Claim 1, characterized in that the reaction temperature is within a range of from 20 to 80 ° C. Process according to Claim 1, characterized in that step a) takes place within a range of 5 minutes to 3 hours. Process according to Claim 1, characterized in that the purification step comprises washing and neutralizing with acidified water at temperatures between 75 ° C and 90 ° C and filtration with anhydrous sodium dehydrate sulfate (dehumidifying) which provides traces of water, and / or molecular distillation at 50-180 ° C and pressure at 1-1000μόβΓ, and / or vacuum distillation at 0.1 to 20 mbar and / or distillation / evaporation on falling film or centrifugation under vacuum at 0.1 to 20 mbar Process according to Claim 1, characterized in that it has: a. 1% by weight of basic catalyst b. 10: 1 ethanol: coconut oil molar ratio c. reaction time 10 minutes; ed. reaction temperature corresponding to 50 ° C 16. Biokerosene, characterized in that it is produced by a transesterification process and is useful for use as an aviation biokerosene.