JP2005538204A - Diesel fuel composition containing components based on biological raw materials obtained by hydrogenating and decomposing fatty acids - Google Patents

Abstract

The present invention relates to a fuel composition for a diesel engine. The fuel composition comprises 0.1 to 99% by volume of a component or mixture of components prepared from biological raw materials originating from plants and / or animals and / or fish. This fuel composition contains 0 to 20% by volume of oxygen-containing components. Both components are mixed with diesel components based on crude oil and / or fractions from the Fischer-Tropsch process.

Description

  The present invention includes components based on vegetable and / or animal lipids and / or fish oil, diesel components based on crude oil and / or fractions from the Fischer-Tropsch process, and optionally oxygen-containing components. The present invention relates to a fuel composition for a diesel engine.

  At present, fuels mainly containing components derived from crude oil are used as fuels for diesel engines. The purpose of the climate agreement in Kyoto is to eliminate the negative effects of human activities on the atmosphere, or climate. The EU has agreed to reduce carbon dioxide, methane and other greenhouse gas emissions by 8% by 2010 relative to the 1990 level. One of the challenges of EU agricultural policy is to find ways to use excess products from agriculture and to promote fuel self-sufficiency. Thus, an EU directive has been created that includes a requirement that at least 2% of the petroleum and diesel fuel consumed in 2005 should be of biological origin. One of the requirements of this directive is expected to increase the proportion of biological components to about 6% by 2010. This directive will be effective in all EU countries in the near future.

At present, the most common component of biological origin in fuel is rapeseed oil methyl ester (referred to as RME). The RME is used either as it is or as a mixture with fuel. Disadvantages of RME are poor miscibility with diesel fuel, and poor storage stability especially under low temperature conditions and poor performance at low temperatures compared to conventional diesel fuel (EN590). . In addition, it causes engine fouling and increases nitrogen oxide (NO _x ) emissions. A by-product of the RME production process is glycerol. This can be a problem when large quantities of product are produced. Other vegetable oil esters can be produced in a similar manner, and the methyl esters of fatty acids are commonly known as FAME (fatty acid methyl esters). These FAMEs can be used for the same applications as rapeseed oil methyl ester. However, FAME has a negative effect on the quality of diesel fuel, especially at low temperatures, and the use of FAME in the fuel increases the emission of nitrogen oxides. In some cases, FAME and RME can cause smoke or increased particle emissions when the engine is operated at low temperatures.

  Treatment of vegetable oils and animal lipids results in degradation of the ester and / or fatty acid structure and saturation of the hydrocarbon chain double bonds to yield about 80-85% n-paraffin product relative to the amount of starting material. It is done. This product can be mixed directly with diesel fuel, but the fuel so produced has the problem of poor performance at low temperatures. Furthermore, n-paraffins having fatty acids with high carbon numbers have a high freezing point (typically about + 10 ° C.) and are waxy. Therefore, the use of these compounds in diesel fuel, at least at low temperatures, is limited.

WO 2001/049812 discloses a method for producing diesel fuel in which the molar ratio of iso-paraffin to n-paraffin is at least 21: 1. In this process, a feedstock containing 50% or more C ₁₀ -paraffin is contacted with the catalyst in the isomerization reaction zone.

  WO 2001/012581 discloses a process for producing methyl esters that are useful as biological diesel fuels. Here, the mixture of fatty acid and triglyceride is esterified in one phase. In this method, the solution is formed from fatty acids, triglycerides, alcohols, acid catalysts and cosolvents at temperatures below the boiling point of the solution. A co-solvent is used to form a single phase, and then the solution is maintained for a time sufficient for acid-catalyzed esterification of the fatty acid to occur. Thereafter, the acid catalyst is neutralized, and the base catalyst is added to transesterify the triglyceride. Finally, the ester is separated from the solution. A biofuel containing an ester having a glycerol content of less than 0.4% by weight is thus obtained.

  US Pat. No. 6,174,501 discloses a method for producing oxidized diesel fuel of biological origin. This oxidized biological diesel fuel comprises a mixture of transesterified triglycerides.

  Finnish patent 100248 discloses a two-stage process for the production of middle distillate from vegetable oil. This production method is based on hydrogenation of a fatty acid or triglyceride of a vegetable oil to obtain n-paraffin, and then isomerization of the n-paraffin to obtain a branched chain paraffin.

  Any gas, droplets and solid particles present in the atmosphere in amounts that are harmful to human health and / or adversely affect animals, plants and various substances are considered air pollutants. Air pollution comes primarily from three emission sources (ie, industry, energy production and traffic).

  The hazards of particle release arise from the fact that the substances and compounds have heavy metals and other carcinogenic and mutated compounds. The particles present in the exhaust gas are small and therefore harmful to health.

  Greenhouse gas allows the radiation from the sun to reach the earth, but prevents heat radiation from escaping from the earth into space. Therefore, greenhouse gas contributes to global warming. One of the most important greenhouse gases is, for example, carbon dioxide released during the combustion of fossil fuels.

  Nitrogen oxide is an acidifying compound. This oxidation can, for example, damage plants or cause species changes in surface water. Nitrogen oxide also reacts with oxygen to give ozone. This phenomenon especially contributes to air quality in cities.

  As indicated in the above teachings, there is a need for high quality fuel compositions for diesel engines that contain components of biological origin, and there is a need for quality for diesel fuel under low temperature operating conditions. ing. In addition, the fuel must be more environmentally friendly than prior art solutions.

  The present invention seeks to provide an environmentally friendly diesel engine fuel composition comprising components of biological origin and having quality requirements for diesel fuel under low temperature conditions.

  The diesel engine fuel composition of the present invention comprising components of biological origin comprises at least one component prepared from biological raw materials obtained from plants, animals or fish, crude oil from a Fischer-Tropsch process, and It consists of a diesel component based on the fraction and / or a component optionally containing oxygen.

  The characteristics of a fuel composition for a diesel engine comprising components of biological origin are set forth in the appended claims.

Surprisingly, it has been found that the diesel fuel composition of the present invention comprising components of biological origin also meets the quality requirements for diesel fuel under low temperature conditions. The diesel fuel composition of the present invention is as follows:
a) 0.1 to 99% by volume, preferably 0.1 to 80% by volume, of a component or mixture of components prepared from biological raw materials originating from plants and / or animals and / or fish;
b) 0-20 volumes of an oxygen-containing component selected from the group consisting of aliphatic alcohols (eg, methanol and ethanol), ethers, fatty acid esters (eg, methyl esters and ethyl esters), water, and mixtures containing them. %;
Here, components a) and b) are mixed as emulsions or dissolved in diesel components based on crude oil and / or fractions from the Fischer-Tropsch process.

  Component a) (referred to herein as a biological component) prepared from biological raw materials originating from plants and / or animals and / or fish, hydrogenates and decomposes fatty acids and / or fatty acid esters. Obtaining n-paraffins as hydrocarbons having 6 to 24 carbon atoms, typically products having 12 to 24 carbon atoms, and optionally isomerizing hydrocarbons, typically n-paraffins To obtain iso-paraffin. The hydrocarbon is preferably isomerized.

  The biological raw material originating from plants and / or animals and / or fish is selected from the group consisting of vegetable oils, animal lipids, fish oils and mixtures thereof containing fatty acids and / or fatty acid esters. Examples of suitable materials include wood-based lipids and oils and other plant-based lipids and oils (eg, rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybean oil, assami oil , Olive oil, flaxseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil and lipids contained in genetically engineered breeding plants, animal-based lipids (eg lard, tallow, fish oil and milk) Lipids) and reused lipids from the food industry and mixtures thereof.

  The basic components of typical plant or animal lipids are triglycerides, ie, triesters of glycerol and three fatty acid molecules having the structure shown in Formula I below.

Wherein R ₁ , R ₂ and R ₃ are hydrocarbon chains, and R ₁ , R ₂ and R ₃ may be saturated or unsaturated C ₆ -C ₂₄ alkyl groups. Can vary considerably with different origins of biological raw materials)

  N-paraffins, iso-paraffins or mixtures thereof prepared from biological raw materials can be used as diesel fuel based on the properties desired for the diesel fuel. The fraction from the Fischer-Tropsch process typically contains high levels of n-paraffins. And optionally, the fraction can be simultaneously isomerized or used as such during the processing of components of biological origin or components separated therefrom.

  The biological component can be produced, for example, by a method comprising at least two steps and optionally utilizes a counter-current operation principle. In the first hydrodeoxygenation step of this method (optionally convection is performed), the structure of the biological raw material is broken to remove compounds containing oxygen, nitrogen, phosphorus and sulfur and light hydrocarbons as gases. The Thereafter, the olefinic bonds are hydrogenated. In the second isomerization step (optional convection) of this process, isomerization is performed to obtain branched hydrocarbon chains, thereby improving the low temperature properties of the paraffin.

  Biological raw materials originating from plants, animals or fish containing fatty acids and / or fatty acid esters selected from vegetable oils, animal lipids, fish oils and mixtures thereof are used as feedstocks.

  High quality hydrocarbon components of biological origin (especially useful as diesel fuel components, isoparaffinic solvents and lamp oils) have high cetane numbers (can be as high as over 70) Obtained as product. Also, turbidity points below −30 ° C. can still be achieved with cetane numbers above 60. This method can be adjusted depending on the desired cetane number and turbidity point.

  Advantages of the diesel fuel composition of the present invention include superior performance at low temperatures and superior cetane number compared to prior art solutions using FAME-based components such as RME. Problems with low temperature performance can be avoided by isomerizing waxy n-paraffins having more carbon atoms than fatty acids to give isoparaffins. The properties of the product thus obtained are excellent, especially for diesel applications, since n-paraffins typically have a cetane number greater than 70 and isoparaffins greater than 60, It has the effect of improving the value. This obviously increases the value as a diesel component. Furthermore, the turbidity point of the isomerized product can be adjusted to a desired level, for example, -30 ° C or lower. In contrast, the turbidity point of RME is about 0 ° C., and n-paraffin is less than + 15 ° C. In Table 1 below, the properties of isomerized biological components, RME and commercial diesel fuel are compared.

  When using the diesel fuel composition of the present invention, engine fouling is significantly reduced and the noise level is clearly reduced compared to similar conventional fuels of biological origin containing FAME components. Furthermore, the concentration of the composition decreases. This composition does not require any changes in automotive engineering or logic. The high energy content per unit volume may show further advantages compared to RME.

  The properties of the diesel fuel composition of biological origin according to the present invention are consistent with those of a high quality diesel fuel based on crude oil (no aromatics present and no impurity residues compared to FAME) .

  The emission of nitrogen oxides by the fuel composition of the present invention is lower than similar FAME-based products, and the emission of particles is clearly lower and the percentage of carbon in the particles is low. Significant improvements in the release of fuel compositions of biological origin are very important to the environment.

  The invention will now be illustrated by the following examples, which are not intended to limit the scope of the invention.

Example 1
Table 2 below shows the release of a conventional diesel fuel (EN 590 (D1)) used in summer Europe, with 60 volume% hydrogenated and isomerized tall oil (TOFA) and 40 volume% Europe. Compared to the release of the composition containing the summer diesel fuel EN590.

Example 2
Table 3 below shows the release of diesel fuel-based high quality reformed crude oil (DITC manufactured by Fortum Oyj) commercially available in Finland, with 30 vol% hydrogenated and isomerized tall oil ( TOFA) and a composition containing 70% by volume DITC, or a composition containing 30% by volume tall oil methyl ester (MME) and 70% by volume DITC.

Claims (8)

A fuel composition for a diesel engine,
a) prepared from biological raw materials originating from plants and / or animals and / or fish by hydrogenating and decomposing fatty acids and / or fatty acid esters to obtain hydrocarbons (optionally isomerized) 0.1 to 99% by volume of the component or mixture of components to be treated;
b) 0 to 20% by volume of oxygen-containing components;
Wherein the components a) and b) are mixed as an emulsion or dissolved in a diesel component based on crude oil and / or fractions from the Fischer-Tropsch process Fuel composition. 2. The fuel composition comprising 0.1 to 80% by volume of a component or mixture of components prepared from biological raw materials originating from plants and / or animals and / or fish. Fuel composition. The fuel composition according to claim 1 or 2, wherein a product obtained from the biological raw material is isomerized. The fuel composition according to claim 1, 2 or 3, wherein the biological raw material is selected from the group consisting of vegetable oils, animal lipids, fish oils and mixtures thereof. The biological raw material is wood-based lipid or oil or other plant-based lipid or oil, lipid contained in genetically modified breeding plants, animal-based lipid, milk-containing lipid, food industry reuse The fuel composition according to claim 1, wherein the fuel composition is a lipid obtained by mixing the mixture or a mixture thereof. The biological raw material is rapeseed oil, rapeseed oil, canola oil, tall oil, sunflower oil, soybean oil, assami oil, olive oil, flaxseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, lard, 6. The fuel composition according to claim 5, wherein the fuel composition is tallow or fish oil. 7. The oxygen-containing component is selected from the group consisting of aliphatic alcohols, ethers, fatty acid esters, water, and mixtures containing them. Fuel composition. Components prepared from biological raw materials originating from the plants, animals or fish hydrogenate and decompose fatty acids and / or fatty acid esters to obtain n-paraffins as products having 12 to 24 carbon atoms. The fuel composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the fuel composition is obtained by isomerizing n-paraffin to obtain iso-paraffin.