CA3027314A1 - Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass - Google Patents

Abstract

The subject matter of the invention is a mixture of liquid fuels for boilers or fuels for diesel engines with esters and alkanes, both derived from biomass and having chain lengths of between 8 and 14 carbon atoms, and the use thereof to reduce particle and nitrogen oxide emissions while the boilers or diesel engines are in operation.

Description

MIXTURE FOR FEEDING A BOILER OR ENGINE
DIESEL COMPRISING GASOLINE OR DOMESTIC FUEL AND
ESTERS AND ALKANES FROM THE PROCESSING OF
THE BIOMASS
The present invention relates to a liquid fuel mixture for boiler or diesel fuel, including particular compounds that allow reduce particulate matter and nitrogen oxide emissions from boilers and engines Diesel during their operation.
Diesel engines are powerful engines from the point of view of the fight against against the effect greenhouse gases since, at equivalent power, they emit approximately 20% of greenhouse effect less than gasoline engines. Nevertheless, they are more and more criticized because of certain emissions harmful to humans, in particular emissions from particles and nitrogen oxides. In some large cities, or even some entire regions, the air pollution by these emissions is a major problem.
Particle and nitrogen oxide emissions from diesel engines are numerous regulated countries. This is particularly the case in Europe where the limits set by the Regulations are becoming more stringent (now Euro6 standards).
This is also the case in other large countries, particularly the United States, but with very low limits in certain states such as those set by California Air Resources Board.
Particles are the subject of two categories of measures:
= measures that characterize the color of exhaust gases (measurements of fumes) = measurements of weight, diameter and number of particles.
The particles are of different sizes. There are generally four categories of fine particles: SMEs:, with a diameter of less than 10 μm, PM2.5 lower diameter at 2.5 μm, ultrafine particles with a diameter of less than 0.1 μm and nanoparticles characterized by a diameter of less than 50 nm.
Most of the particles emitted by diesel engines have a diameter of less than 1 m. They therefore represent a mixture of fine or ultrafine particles and nanoparticles. The smaller ones are considered the most dangerous for humans.
Diesel engines have made remarkable progress over the last 30 years thanks to the improvement of the quality of fuels (reduction of sulfur content), the quality of process of

2 combustion (optimization of injection systems) and gas treatment exhaust (recirculation of exhaust gases, oxidation systems catalytic and particulate filters). But despite a reduction of around 98% since about thirty years of particulate emissions from new engines, the problem of particles remains considered serious enough for some cities to come to want to ban diesel vehicles in town. This is due in particular to the fact that Diesel vehicles are a large number of years (8 to 10 years for individuals and often over 15 years for coaches and trucks).
It would therefore be very useful, in addition to measures to reduce emissions on the new vehicles and the promotion of alternative energies (vehicles electric or vehicles, for example) to find solutions for vehicles to diesel motor existing.
The same problems of emission of particles and oxides of nitrogen are encountered with liquid fuels for boilers, in particular with old boilers whose contribution to pollution by particles and nitrogen oxides is also very significant.
The objective of the present invention is to respond to these problems and to particular of provide an effective, simple and economical solution for reducing emissions engines Diesel and liquid fuel boilers.
.. For this purpose the invention proposes to incorporate in the engine fuel Diesel or in the fuel for boiler, together one or more esters and one or more alkanes in addition to those that may already be present in the fuel or the combustible.
Before the 1990s, there was no biofuel for engines Diesel while ethanol has long been used in gasoline, particularly in Brazil and the USA.
From 1992 began to be developed in France, then in Europe and in the world, the use of biodiesel which is a methyl (or ethyl) ester of vegetable oil.
Today, different types of esters are used depending on the origin of the fat that are transesterified by an alcohol: vegetable oils, animal fats or frying oils recovered. These are esters of fatty acids whose chain length is mainly between 16 and 18 carbon atoms. These products are generally incorporated into a less than 8% in unmarked diesel or they are used at 20% or 30% or

3 exceptionally pure in captive transport fleets. But the gains that we can expect in terms of particle reduction such mixtures are limited (reduction of the order of half the rate of incorporation of the esters). In addition, these esters they tend to increase the nitrogen oxides. They are submitted in Europe to EN14214 and, elsewhere worldwide, to similar standards and the rate of incorporation into the unmarked diesel is generally limited to 8% by volume, particularly for this reason.
Some other biofuels, particularly alkanes from the biomass start to be developed, whether vegetable oils or animal fats hydrotreated (treated with hydrogen to remove oxygen atoms) which have also 16 to 18 .. carbon atoms or products of the type BTL (Biomass to Liquid) from the gasification of biomass followed by Fischer Tropsch synthesis.
Other solutions are developed, still experimental, such as pyrolysis oils hydrotreated and alkanes that can be obtained by anaerobic fermentation of biomass followed by Kolbe electrolysis (patent application WO2014170603).
These hydrocarbons are interesting because they usually have a high cetane which promotes a reduction of NOx emissions. Their effect on particles rest however limited.
Moreover, the addition to fuels of various oxygenated components (alcohols or esters) a been proposed for many years, for purposes that were not the reduction particle emissions but improving other features (improvement of cold, lubricity, impact on agriculture, impact on the greenhouse effect, ...), by example:
- the use of more than 10% ethanol in diesel but this requires the presence expensive additives - incorporation of butanol into diesel (example: Energy Conservation and Management Vol 51, Issue 10, October 2010, Effects of Butanol Fuel Oil blends on the performance and emissions of a high-speed Dl diesel engine - incorporation of esters from the anaerobic fermentation of the biomass in gasoline, diesel or kerosene (patent FR 2757539A1, Dupré-Kaplan, use esters as fuels or fuels).
Tests have also been carried out for the use of aldehydes in the diesel (Reducing the Emission of Particles from a Diesel Engine by Adding an Oxygenate to the Fuel

4 Environmental Science and Technology 39 (16): 6260-5 = September 2005) in the goal reduce emitted particles, but acetaldehyde emissions, which are they are also judged dangerous, were greatly increased.
Nevertheless, none of these solutions has resulted in a satisfactory solution, which allows .. reduce particulate emissions and nitrous oxide emissions when of operation Boilers and Diesel engines.
The present invention is specifically aimed at incorporation into fuels for engine Diesel or liquid fuels for a boiler selected from diesel fuel and oil domestic:
at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, and at least one biosourced alkane with a chain length of between 8 and 14 carbon atoms, the ester (s) having a chain length of between 8 and 14 carbon atoms carbon .. incorporated in the fuel or fuel representing between 1% and 80% by volume said mixture and the alkane or alkanes of chain length of between 8 and 14 atoms of carbon incorporated into the fuel or fuel representing between 1 and 80%
volume of said mixture.
For the purposes of the invention, biobased is understood to mean products derived from biomass, it's up to say agricultural or forestry plants or organic waste.
It should be noted that biobased esters and alkanes can be distinguished from esters and alkanes of oil origin present in a mixture thanks to a dating that is based on the Mass spectrometer measurement of the proportion of the C14 isotope on the whole carbon of the molecule. Fossil products have a C14 plus content weak than .. products resulting from more recent photosynthesis.
While the esters will lower particulate emissions, it is important according the invention to add alkanes of chain length between 8 and 14 atoms of carbon in addition to those already present in the fuel or fuel, as this avoids an increase in the emission of nitrogen oxide.
The mixture according to the invention is a liquid mixture which has a variable composition.
Advantageously, such a mixture makes it possible to reduce the emissions of particles and the nitrogen oxide emissions during operation of boilers or engines Diesel, without any degradation of other emissions (nitrogen monoxide CO, hydrocarbons HC-imbricated, etc.). In addition, the invention makes it possible to ensure that the mix meets all specifications for liquid fuels and fuels, including those who are the most difficult to respect, namely the flash point which must be above 55 C and

5 calculated cetane number which must be greater than 46. In addition, the mixture according to the invention maintains the characteristics of diesel fuel and combustible boiler liquid, such as, for example, cold strength, viscosity, etc.
The esters and / or alkanes used can in particular be bio-based, that is to say, to be biofuels from agricultural or forestry biomass or waste organic products, which is also an advantage in combating the effect of tight.
Other features and advantages will emerge from the description in detail that will follow of the invention.
The invention therefore aims at a mixture intended to feed a boiler or a diesel motor, comprising:
at least one liquid fuel for a boiler or a fuel for engine Diesel selected from diesel and heating oil, and at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel, and at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel, the ester (s) having a chain length of between 8 and 14 carbon atoms carbon incorporated (s) representing between 1% and 80% by volume of said mixture, preferably between 5 and 50%, and the alkane (s) with a chain length of between 8 and 14 atoms of incorporated carbon (s) representing between 1 and 80% by volume of said mixture, preferably between 5 and 50%.
The ester (s) having a chain length of between 8 and 14 carbon atoms carbon incorporated in the mixture may be chosen from all the esters of this cut. It may be preferentially ethyl hexanoate (C8), butyl butyrate (C8), from butyl valerate (C9), butyl hexanoate (C12) and / or butyl caprylate (C14).
Preferably, it is not a question of esters of higher fatty alcohols, it is to say of alcohols obtained from the fatty acids of vegetable oils which have been reduced by example by

6 hydrogenation and which is associated with a short acid such as formic acid or acid acetic.
The alkane (s) with a chain length of between 8 and 14 carbon atoms carbon incorporated in the mixture may be selected from all alkanes of this size (connected or not connected). It may be preferentially decane, dodecane and tetradecane.
According to the invention, the specifically selected esters of chain included between 8 and 14 carbon atoms advantageously allow to continue to respect all current specifications for diesel fuels and fuels for boilers, including at an incorporation rate of between 1 and 8%, except the rate the esters thus produced are not esters.
methyl of fatty acids complying with EN14214. Also, according to a variant the invention is directed mixture as described above in which the ester (s) length chain between 8 and 14 carbon atoms represent between 1% and 8% by volume said mixed. This mixture can be distributed as an unmarked fuel in all the distribution pumps.
In addition, the esters used according to the invention can also be used at higher rates high. Also, according to another variant, the invention aims at a mixture such that described previously in which the ester (s) of chain length included between 8 and 14 incorporated carbon atoms represent between 8% and 80% by volume of said mixture that will be distributed as an unmarked fuel if approved for that purpose, be like a fuel for captive transport fleets.
Preferably, the ester (s) with a chain length of between 8 and 14 atoms of carbon present in the mixture are esters of biobased origin obtained from volatile fatty acids resulting from the anaerobic fermentation of biomass, and esterification by an alcohol.
Likewise, a mixture in which the alkane or alkanes of chain between 8 and 14 carbon atoms incorporated in the mixture are alkanes obtained by Kolbe electrolysis of volatile fatty acids from the fermentation anaerobic biomass as described in application WO2014170603 or from the biomass by gasification and Fischer Tropsch synthesis.

7 The mixture according to the invention, in addition to fuel or fuel, esters and alkanes specific lengths of chain, may possibly contain at least one additive to improve the cetane number and / or to reinforce the reduction of the particulate matter and / or reduce nitrogen oxide emissions through boiler or the Diesel engine during operation. For example, it may be tetranitromethane.
Other additives can be added to enhance other functionality mixing such as cold resistance, viscosity, etc.
The mixture according to the invention can be obtained by conventional techniques of the man of job. Preferably, it is obtained by simply mixing the constituents in a same tank or by mixing two flows in the same pipe. In the most countries such a mixture should be under the control of the Customs Service.
The invention is specifically directed to a method of manufacturing a mixture according to the invention described above, which consists of incorporating into at least one liquid fuel for a boiler or diesel engine fuel selected from diesel or oil domestic:
at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, and at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, so that the ester (s) with a chain length of between 8 and 14 atoms of incorporated carbon represent between 1% and 80% by volume of said mixture and in that the or alkanes of chain length between 8 and 14 carbon atoms incorporated represent between 1 and 80% by volume of said mixture.
Preferably, the mixture is produced at a temperature of between 10.degree.
and 50 C
in a stirred tank or in an apparatus where the different components are mix by crossing of flows.
Surprisingly and advantageously, the mixture according to the invention, incorporating esters and particular alkanes in fuels for diesel engine or in the boiler fuels, allows a very significant reduction in emissions from particles without any degradation of other emissions in particular oxide nitrogen and other emissions such as CO, HC, etc. The reduction rate of particles in mass and in number is of the order of twice the incorporation rate (30 to 40%
for 20%

8 of incorporation, 60 to 80% for 40% incorporation, 80 to 90% for 50%
of incorporation), this which is a considerable asset for reducing particulate emissions in the towns.
The reduction being parallel for the mass and the number of particles, this process does not favor not the finest particles that are the most dangerous.
.. The invention is therefore specifically aimed at the use to power a boiler or a Diesel engine, of a mixture comprising:
at least one liquid fuel for a boiler or a fuel for engine Diesel selected from diesel or heating oil, and at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel, and at least one biosourced alkane with a chain length of between 8 and carbon atoms, incorporated in the fuel or fuel, the ester (s) having a chain length of between 8 and 14 carbon atoms carbon incorporated (s) representing between 1% and 80% by volume of said mixture and the alkanes of chain length of 8 to 14 carbon atoms incorporated representative between 1 and 80% by volume of said mixture.
In particular, the invention aims to use the mixture in a boiler or an engine Diesel to reduce particulate emissions and / or reduce emissions nitrogen oxides during its operation. Advantageously, the invention also allows improve the cetane number of the fuel.
The mixture according to the invention can be used in any boiler in liquid fuel and in any diesel engine, particularly in a stationary diesel engine or a diesel motor installed on transport vehicles or boats or building site or agricultural machinery or small household appliances such as lawn mowers or tillers.
In addition to the mixture according to the invention, at least one additive may be added in the boiler and / or the engine, an additive capable of improving the cetane number and / or strengthen the reduction particulate emissions and / or reduce nitrogen oxide emissions by the boiler or the diesel engine during its operation, and / or at least one additive capable improve .. other functionality of the mixture such as cold resistance, viscosity, etc.

9 The invention is now illustrated by examples of mixtures according to the invention and emission test results on a test bench demonstrating their effectiveness.
The composition of the different mixtures tested is described in the table (examples 1 to 5 with different charge rates that represent the number of turns per minute of motor relative to the nominal number of revolutions). These mixtures are obtained by simple mixing of components in cans with manual stirring.
The measurements are carried out at the exhaust by a bay Horiba 9100 (CO, CO2, 02, HC and NOx) and a PPS PEGASOR particle analyzer on a car engine of Mark Renault The results obtained are shown in the table below:
%
Fuel mg / m3 N / cm3 CO NOx fumes charge 3.9 19000 0.3 700 85 34 170000 2.8 810 116 reference gas oil 40 43 220000 3.9 45 20 95000 2,830 60 1.5 7000 0.4 220 EXAMPLE 1 INVENTION 20 3.6 18000 0.25 764 gas oil + 10% decane + 20% butyl butyrate 30 13 62000 1.35 540 significant decrease (-31% in nb) of the 40 9 42000 0.92 343 particles 45 7 32000 0.75 350 without significant degradation of NOx 60 1.8 8500 0.23 475 EXAMPLE 2 INVENTION 20 2.3 11000 0.17 800 gas oil + 20% decane + 20% butyl hexanoate 30 15 70000 1.65 575 significant decline (-48% in nb) of 19 88000 2.2 920 222 particles slight decrease (-15%) of NOx 45 18.5 90000 2.35 880 60 1.3 6000 0.29 270 20 3.2 15000 0.23 870 EXAMPLE 3 INVENTION 30 15.5 74000 1.6 591 gas oil + 20% decane + 20% butyl butyrate 40 31 148000 3.5 significant decrease (-36% in nb) of particles 45 19 82000 2.12 960 slight decrease (-19%) of NOx 60 1.5 6800 0.32 465 1186 20 0.3 1600 0.03 1240 EXAMPLE 4 INVENTION 30 3 14000 0.22 530 30% gas oil + 20% decane + 50% butyl 40 5 23000 0.34 337 butyrate strong fall (-88% in nb) of the particles 45 slight decrease (-11%) of NOx 4.5 21000 0.42 347 1 5000 0.04 1218 EXAMPLE 5 INVENTION 5.5 5.5 28000 0.41 550 1/3 gasoil + 1/3 deca ne + 1/3 butyl 40 13 62000 1.00 566 butyrate sharp drop (-74% in nb) of the particles 45 and significant decrease (-27%) of NOx 7 35000 0.53 380 These results show that alkanes have no favorable impact significant on the particulate emissions, while esters and alkanes together allow to unexpectedly very significant reductions in particles more or less proportional to the ester level (decrease of particles of the order of twice the level of esters 5 incorporated) at the same time as a significant decrease in NOx. The example 5 is in this regard very demonstrative.
The other parameters (CO, HC) are not degraded. There is even a drop sensitive of CO. By adjusting the levels of esters and alkanes, it will thus be possible to optimize diesel engine emissions.

Claims (15)

11 A mixture for supplying a boiler or a diesel engine, comprising:
at least one liquid fuel for a boiler or a fuel for engine Diesel selected from diesel or heating oil, and at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated into the fuel, and at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, incorporated into the fuel, the ester (s) having a chain length of between 8 and 14 carbon atoms carbon incorporated (s) representing between 1% and 80% by volume of said mixture and the alkanes of chain length of 8 to 14 carbon atoms incorporated representative between 1 and 80% by volume of said mixture. 2. Mixture according to claim 1, characterized in that the ester (s) length of chain of 8 to 14 carbon atoms incorporated (s) represent between 5% and 50% by volume of said mixture. Mixture according to one of the preceding claims, characterized in that the one or alkane (s) with a chain length of 8 to 14 carbon atoms embedded (s) represent between 5% and 50% by volume of said mixture. 4. Mixture according to one of the preceding claims, characterized in that the one or alkanes of chain length of between 8 and 14 carbon atoms incorporated into the mixture are alkanes obtained by electrolysis of Kolbe fatty acids volatiles from anaerobic fermentation of biomass or alkanes from biomass by gasification and Fischer-Tropsch synthesis. Mixture according to one of the preceding claims, characterized in that the one or esters having a chain length of 8 to 14 carbon atoms incorporated into the mixture are esters whose acidic part is obtained from acids volatile fats anaerobic fermentation of biomass, and esterification with an alcohol. Mixture according to one of the preceding claims, characterized in that comprises at least one additional additive capable of improving the cetane and / or reduce particulate emissions and / or reduce emissions of oxides of nitrogen by the boiler or diesel engine running. Mixture according to one of the preceding claims, characterized in that comprises at least one additional additive capable of improving cold and / or viscosity. 8. Process for manufacturing a mixture according to one of the preceding claims, characterized by incorporating in at least one fuel liquid for boiler or fuel for a diesel engine selected from diesel or diesel heating oil :
at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, and at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, so that the ester (s) with a chain length of between 8 and 14 atoms of incorporated carbon represent between 1% and 80% by volume of said mixture and in that the or alkane (s) with a chain length of between 8 and 14 atoms carbon incorporated represent between 1 and 80% by volume of said mixture. 9. Use of a mixture according to one of claims 1 to 7 for feed a boiler or diesel engine. 10. Use according to claim 9 in a boiler or an engine Diesel for reduce particulate emissions during boiler operation or of the motor. 11. Use according to claim 9 or 10 in a boiler or an engine Diesel to reduce emissions of nitrogen oxides during operation of the boiler or engine. 12. Use according to one of claims 9 to 11 in a diesel engine for improve the cetane number of the fuel. 13. Use according to one of claims 9 to 12 in a boiler or a engine in which other additives are added to improve the cetane or to reinforce the reduction of emissions of particulate matter or nitrogen oxides. 14. Use according to one of claims 9 to 13 in a diesel engine in which other additives are added to improve cold and / or the viscosity. 15. Use according to one of claims 9 to 14 in a diesel engine fixed or diesel engine installed on transport vehicles or boats or gear construction site or agricultural machinery or small domestic machinery.