JP2008525555A - Fuel composition - Google Patents

Abstract

A fuel composition for an engine that reduces emission of NOx, fine particles, and the like from a compression ignition engine.
A fuel composition comprising a major amount of fuel suitable for a compression ignition engine, the fuel comprising one or more hydrocarbon components having a boiling point in the boiling range of diesel, wherein at least one of the hydrocarbon components. One is preferably at least one of the at least one hydrocarbon component for the purpose of reducing emissions of NOx and optionally particulates from the compression ignition combustion chamber of the compression ignition engine into which the fuel composition is introduced. Treated with a metal-adsorbing or absorbing material in a different physical phase from the hydrocarbon component to reduce the level of metal, more preferably at least one heavy metal, most preferably zinc. And the treatment includes the fuel composition comprising physical separation of hydrocarbon components from the metal adsorbent or absorbent phase, a process for its production, and optionally NOx from the engine and optionally Emission reduction method of particles.
[Selection figure] None

Description

  The present invention relates to fuel compositions, methods for their production, and methods for using the compositions in the operation of compression ignition engines.

  It is known to treat hydrocarbons through filterable or adsorbent materials such as fuller's earth or charcoal, as disclosed for example in US-A-2090007, US-A-2338142 or GB-A-614636. It has been.

  GB-A-437023 is such as fuller earth, clay or other adsorptive catalyst under conditions of high temperature and overpressure sufficient to maintain cracked hydrocarbons having a boiling point in the approximate gasoline boiling range to be substantially liquid. A method for purifying cracked hydrocarbons treated with a solid active adsorbent is disclosed. This method first removes a relatively unstable low-boiling component from the hydrocarbon, i.e., part or all of dissolved gas, propane, butane and the corresponding unsaturated product, and performs a stable fractionation on the hydrocarbon. And, while hot, the purified hydrocarbon is subjected to the purification treatment to lower the vapor pressure of the hydrocarbon.

  US-A-3529944 discloses a method for transparent and stabilizing liquid hydrocarbons subject to oxidative degradation, in particular jet fuel. In this method, a material that promotes oxidative degradation of the fuel, such as polyphenyl-substituted lower alkane or lower alkylene, alkanol ester of citric acid or acetoxyethyl monobutyl ether, is added to the jet fuel, and the liquid hydrocarbon is added to the solid particulate adsorption medium. Through which micro-impurities and oxidative degradation products are removed and then a stabilizing material is added that stabilizes the liquid hydrocarbon against further oxidative degradation. Suitable adsorbent materials (column 6, lines 22-25) include various natural or synthetic clays, treated or untreated fuller's earth, attapulgite, silica gel and adsorbent catalysts. In the embodiment, jet fuel is filtered with attapulgite clay.

  US-A-4225319 blends gasoline decomposed with an adsorbent-treated catalyst into a fuel composition for an internal combustion engine in order to suppress carburetor deposition. In column 2, lines 57-62, a number of well-known adsorbents such as silica, alumina, silica-alumina, charcoal, carbon black, magnesium silicate, aluminum silicate, zeolite, clay as useful adsorbents for the treatment of catalytically cracked gasoline. , Fuller soil, magnesia, etc. The adsorbent used in the examples is silica gel.

US-A-5951851 relates to a process for removing elemental sulfur from liquids, in particular fuels such as gasoline, jet fuel, diesel, kerosene, and fuel additives such as ale. This method contacts a sulfur contaminated liquid with layered double hydroxide (or hydrotalcite) Mg ₂ AlNO ₃ ; mH ₂ O or Mg ₃ AlNO ₃ ; mH ₂ O, where m is the hydration number. That's it. In Example 1, attapulgous clay, molecular sieve 5Å, silica gel, alumina, bayerite, tetraphenylphosphonium-montmorillonite, Kao-EG. 9.4Å, Kao-tetraethylene glycol, Al ₁₃ pillared montmorillonite, tetramethylammonium-montmorillonite, palygorskite-PF1-s, kaolinite KGa-1, Kao-cellosolve, and iron (III) montmorillonite are elemental The hydrotalcite class of Al ₂ LiCl, Mg ₂ AlNO ₃ , Mg ₂ FeNO ₃ , MgFeNO ₃ and MgAlNO ₃ are particularly effective in removing elemental sulfur, whereas sulfur is ineffective. It has been shown.

  New Encyclopedia Britannica, Macropaedia, Volume 4, 15th Edition, 1984, ISBN O-85229-413-1, pages 700-706, includes nine groups based on changes in atomic structure and chemical composition: , (1) allophane, (2) kaolinite, (3) halloysite, (4) smectite, (5) illite, (6) chlorite, (7) vermiculite, (8) sepiolite, attapulgite and palygorskite, and (9 ) Classified as mixed layer clay mineral.

  Group (8) sepiolite, attapulgite and palygorskite are described as fibrous clay minerals, which have as a major structural element an amphibole double silica chain oriented parallel to the c-axis.

Diesel fuel can contain a number of trace metals. The content of these metals depends on many factors, including the source of the crude oil from which the fuel is derived, the type of refinery process used, and the handling, transportation, storage and distribution history of the fuel.
US-A-2090007 US-A-2338142 GB-A-614636 GB-A-437023 US-A-3529944 US-A-4225319 US-A-5951851 GB-A-960493 EP-A-0147240 EP-A-0482253 EP-A-0613938 EP-A-0557516 WO-A-98 / 42808 US-A-4208190 WO-A-94 / 33805 WO-A-94 / 17160 US-A-5490864 WO-A-98 / 01516 New Encyclopedia Britannica, Macropaedia, Volume 4, 15th Edition, 1984, ISBN O-85229-413-1, pages 700-706. Danping Wei and H.C. A. An article by Spikes, “The Lubricity of Diesel Fuels” Wear, III (1986) 217-235.

At least one hydrocarbon component in the diesel fuel composition to reduce the level of trace metal contaminants present in the hydrocarbon component in the diesel fuel composition, more preferably the level of heavy metals, most preferably zinc. In a physical phase different from the hydrocarbon component, in a liquid adsorbent or absorbent material (eg, in a liquid form that is immiscible with the hydrocarbon component (including those having minimal or low solubility), or a solid, preferably a solid It is unexpectedly this time that when this fuel composition is used in a compression ignition engine and output, the emission level from the fuel composition, in particular, the emission level of NOx and optionally fine particles is lowered. Was also found. The treatment includes a method of physically separating hydrocarbon components from the metal adsorbent or absorptive phase, for example, by decantation of immiscible liquid, filtration, vortexing, centrifugation, and gravity separation.
For the purposes of this disclosure, “heavy metal” is defined as a metal having an atomic number of 20 or greater.

  According to the present invention, a fuel composition comprising a major amount of fuel suitable for a compression ignition engine, the fuel comprising one or more hydrocarbon components having a boiling point in the boiling range of diesel, the hydrocarbon component At least one of the at least one hydrocarbon component preferably for the purpose of reducing emissions of NOx and optionally particulates from the compression ignition combustion chamber of the compression ignition engine into which the fuel composition is introduced. Treated with a metal adsorbent or absorbent material in a different physical phase from the hydrocarbon component to reduce the level of the species metal, more preferably the level of at least one heavy metal, most preferably the level of zinc And the treatment provides a fuel composition comprising physical separation of hydrocarbon components from the metal adsorbent or absorbent phase.

  The metal adsorbing or absorbing material is preferably selected from fibrous clay minerals, diatomaceous earth, graphite, charcoal, polymeric adsorbents or absorbents, ion exchange resins, and complexing or chelating agents. These materials may be in liquid form (including those having minimal or low solubility) that are immiscible with the hydrocarbon component, or solid, more preferably solid. The complexing agent or chelating agent preferably includes molecules having one or more functional groups that act as ligands, form complexes, or are metal-attracting.

  Sepiolite, attapulgite and palygorskite group of fibrous clay minerals must contain at least one mineral of sepiolite, attapulgite and palygorskite group. The term “fuller earth” is used in publications in a number of different ways, but in the context of the present invention, “fuller earth” means at least one fibrous clay mineral of the sepiolite, attapulgite and palygorskite groups. Means. One type of fuller's earth contains a mixture of montmorillonite and palygorskite.

The fibrous clay mineral is preferably sepiolite, attapulgite or fuller's earth.
The polymeric material may be a polyophene such as polyacrylate or polystyrene, polyester, polyether, polyamide, polyamine and polysulfone materials such as AMBERLITE XAD-4, AMBERLITE XAD-7 and AMBERLITE XAD-16 nonionic high on silica gel Preference is given to selecting from molecular adsorbents and polyethyleneimine on silica gel (obtained from Aldrich). These polymeric materials are in solid form, bound to solid, or in liquid, suspended or dissolved form that is immiscible (including those with minimal or low miscibility) with the hydrocarbon component.

Examples of diatomaceous earth are preferably DAMOLIN MOLER (obtained from Damolin) and HYFLO SUPER CEL (obtained from Aldrich).
Complexing or chelating agents include amines, amides, polyamines, but not limited to cyclic polyamines including porphyrins, derivatives of N, N′-disalicylidenepropanediamine, sulfides, sulfones, sulfoxides, sulfonates, thiols Sulfur materials such as, anionic materials such as carboxylates, alcohols, ketones, phenols, and oxygen species such as ethers including polyethers and cyclic polyethers (crown ethers), and cryptands, oxazoles and their derivatives It is preferable to select from species containing both nitrogen and oxygen atoms. The complexing agent or chelating agent is in solid form, bound to the solid, or in a liquid, suspended or dissolved form that is immiscible (including having minimal or low miscibility) with the hydrocarbon component. is there.

The ion exchange resin is selected from some of the products obtained from inorganic species such as silica gel and polymers having functional groups such as sulfonates and carboxylates, for example Aldrich under the trade names AMBERLITE, AMBERLIST, DOWEX and SEPHADEX. Is preferred.
The at least two blends of hydrocarbon components are preferably treated with a metal adsorbent or absorbent material.

  According to the present invention, preferably at least one metal level, more preferably at least one heavy metal level, most preferably zinc level in at least one hydrocarbon component having a boiling point in the diesel boiling range. Treating the at least one hydrocarbon component with a metal adsorbent or absorbent material to reduce fuel, and to form a fuel suitable for a compression ignition engine, before or after the treatment, There is also provided a process for producing the fuel composition of the present invention comprising the step of optionally blending one hydrocarbon component with at least one other hydrocarbon component having a boiling point in the diesel boiling range.

  The method blends at least two hydrocarbon components having a boiling point in the boiling range of diesel and forms the resulting mixture into a metal adsorbent or absorbent material to form a suitable fuel for a compression ignition engine. It is preferable to include the process of processing by.

Furthermore, according to the present invention, there is also provided a method of operating a compression ignition engine including the step of introducing the fuel composition of the present invention into a combustion chamber of the compression ignition engine.
Furthermore, the present invention provides a method for reducing the release of NOx and optionally particulates from a compression ignition engine comprising the step of introducing the fuel composition of the present invention into the combustion chamber of the compression ignition engine.

Furthermore, according to the present invention, there is also provided a method of using the fuel composition of the present invention in a compression ignition engine for the purpose of reducing NOx and optionally particulate emissions from the compression ignition engine.
Furthermore, the present invention also provides a method for reducing NOx and optionally particulate emissions from a compression ignition engine comprising the step of replacing the fuel composition in the compression ignition engine with the fuel composition of the present invention.

  As used herein, the term “reduced, reduced or reduced” refers to a diesel fuel composition that has not been treated with a metal adsorbent or absorbent material, or has not been treated with a metal adsorbent or absorbent material. It means comparing appropriately with the case of using physical components.

  The method of adsorption or absorption of trace metals on clay is not completely understood. One possible method is to bind the metal to the surface in the same way that the metal binds to the ligand. The ligand functions as an electron donor and attracts metal atoms or ions.

Fuel compositions with which the present invention is concerned include fuel compositions for automotive compression ignition engines, as well as other various engines such as ships, railways and stationary engines, and industrial applications for heating (eg boilers). There is gas oil. Note that the non-automotive fuel does not contain a residual (non-distilled) component.
The base fuel itself may contain a mixture of two or more different diesel fuel components and / or may contain additives as described below.

Such diesel fuel compositions typically contain a liquid hydrocarbon middle distillate gas oil, such as a petroleum derived gas oil. Diesel fuel compositions generally have a boiling point of 150-400 ° C. in the normal diesel range, depending on grade and application. The diesel fuel composition has a density at 15 ° C. (for example, according to ASTM D4502 or IP 365) of usually 750 to 1000 kg / m ³ , preferably 780 to 860 kg / m ³ for automobiles, and cetane number (ASTM D613). Is 35 to 120, more preferably 40 to 85. The initial boiling point is usually in the range of 150 to 230 ° C, and the final boiling point is in the range of 290 to 400 ° C. The kinematic viscosity at 40 ° C. (ASTM D445) may suitably be 1.5-6 mm ² / s.

Such industrial gas oils contain a base fuel that may contain a fuel fraction such as kerosene or gas oil obtained from conventional refinery processes that improve crude feedstock into useful products. Such fractions preferably contain components in the range of 5 to 40 carbon atoms, more preferably 5 to 31, even more preferably 6 to 25, most preferably 9 to 25, and at 15 ° C. of the fraction. The density of 650 to 1000 kg / m ³ , the kinematic viscosity at 20 ° C. is 1 to 80 mm ² / s, and the boiling point range is 150 to 400 ° C.

  Non-mineral oil-based fuels such as Fischer-Tropsch derived fuels, biomass derived materials, biofuel components such as fatty acid methyl esters, or shale oil may optionally be formed or present in the fuel composition. Such Fischer-Tropsch fuels can be derived from, for example, natural gas, natural gas liquids, petroleum or shale oil, petroleum or shale oil processing residues, coal or biomass.

  The amount of Fischer-Tropsch derived fuel used in the diesel fuel composition may be 0.5 to 100% by volume, preferably 5 to 75% by volume, based on the total diesel fuel composition. The fuel composition may contain Fischer-Tropsch derived fuel, desirably 10% by volume or more, more preferably 20% by volume or more, and still more preferably 30% by volume or more. The fuel composition particularly preferably contains 30 to 75% by volume, in particular 30 or 70% by volume, of Fischer-Tropsch derived fuel. The balance of the fuel composition is composed of one or more other fuels.

The industrial gas oil composition preferably contains more than 50%, more preferably more than 70% by weight of the Fischer-Tropsch derived fuel component.
Such Fischer-Tropsch derived fuel components can be isolated from the (hydrocracked) Fischer-Tropsch synthesis product in any fraction of the middle distillate fuel range. The normal boiling point of the fraction is the boiling range of naphtha, kerosene or gas oil. Since Fischer-Tropsch products in the boiling range of kerosene or gas oil are easy to handle, for example in a domestic environment, it is preferred to use such Fischer-Tropsch products. The product suitably contains a fraction having a boiling point in the range of 160-400 ° C, preferably up to about 370 ° C, with more than 90% by weight of the fraction. Examples of Fischer-Tropsch derived kerosene or gas oil are EP-A-0583836, WO-A-97 / 14768, WO-A-97 / 14769, WO-A-00 / 11116, WO-A-00 / 11117, WO-A-01 / 83406, WO-A-01 / 83648, WO-A-01 / 83647, WO-A-01 / 83634, WO-A-00 / 20535, WO-A-00 / 20534, EP- A-1101813, US-A-5766274, US-A-5378348, US-A-5888376 and US-A-6204426.

Fischer-Tropsch products preferably contain more than 80% by weight of iso- and normal-paraffins, more preferably more than 95% by weight and less than 1% by weight of aromatics. The balance is a naphthenic compound. The sulfur and nitrogen content is very low and is usually below the detection limit of these compounds. For this reason, the sulfur content in the fuel composition containing the Fischer-Tropsch product can be greatly reduced.
The fuel composition contains sulfur preferably 5000 ppmw (weight ppm) or less, more preferably 500 ppmw or less, or 350 ppmw or less, or 150 ppmw or less, or 100 ppmw or less, or 50 ppmw or less, most preferably 10 ppmw or less.

The base fuel itself may or may not contain additives. For example, when added to a base fuel at a refinery, the additives may include antistatic agents, pipeline drag reducers, flow improvers (eg, ethylene / vinyl acetate copolymers or acrylate / maleic anhydride copolymers). A small amount of one or more additives selected from coalescence), lubricants, antioxidants, and wax settling inhibitors.
Detergent-containing diesel fuel additives are known and commercially available. Such additives may be added to diesel fuel at a level intended to reduce, remove or retard the accumulation of engine deposits.

  For the above purposes, examples of suitable cleaning agents for use in fuel additives include polyolefin-substituted succinimides or succinimides of polyamines such as polyisobutylene succinimide or polyisobutylene amine succinimide, aliphatic amines, Mannich bases or amines and polyolefins. (For example, polyisobutylene) maleic anhydride. Succinimide detergents are described, for example, in GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98 / 42808. Particularly preferred are polyolefin substituted succinimides such as polyisobutylene succinimide.

  The additive may contain components other than the cleaning agent. For example, lubricity enhancers; defogging compositions such as those containing alkoxylated phenol formaldehyde polymers; antifoams (eg polyether modified polysiloxanes); ignition modifiers (cetane improvers) (eg 2-ethylhexyl nitrate ( EHN), cyclohexyl nitrate, di-tret-butyl peroxide and those disclosed in US Pat. No. 4,208,190, column 2, line 27 to column 3, line 21); rust inhibitors (e.g. propane-tetrapropenyl succinate) 1,2-diol half ester, or polyhydric alcohol ester of succinic acid derivative, succinic acid derivative having an unsubstituted or substituted aliphatic hydrocarbon group having 20 to 500 carbon atoms on at least one α-carbon atom, for example, Pentaerythritol diester of polyisobutylene substituted succinic acid); corrosion inhibitor; Perfume; Antiwear agent; Antioxidant (for example, phenols such as 2,6-di-tert-butylphenol or phenylenediamines such as N, N′-di-sec-butyl-p-phenylenediamine) Metal deactivators; and combustion improvers.

  It is particularly preferable that the additive contains a lubricity enhancer, particularly when the fuel composition has a low sulfur content (eg, 500 ppmw or less). In fuel compositions without additives, it is convenient for the lubricity enhancer to be present at a concentration of less than 1000 ppmw, preferably 5 to 1000 ppmw. Suitable commercially available lubricity enhancers include esters or acid-based additives. Other lubricity enhancers are described in, for example, the following documents in connection with the above-mentioned patent documents, in particular the use in low sulfur content diesel fuels.

Danping Wei and H.W. A. An article by Spikes, “The Lubricity of Diesel Fuels” Wear, III (1986) 217-235.
WO-A-94 / 33805: Cold flow improver for enhancing the lubricity of low sulfur fuels WO-A-94 / 17160: Carboxylic acid (carbon) as a fuel additive for friction reduction in diesel engine injection systems Contains specific esters and alcohols (having 1 or more carbon atoms) of 2 to 50 atoms, in particular glycerol monooleate and di-isodecyl adipate.
US-A-5490864: Specific dithiophosphoric diester-dialcohol as an anti-wear lubricant additive for low-sulfur diesel fuels WO-A-98 / 01516: In order to give anti-wear lubricity effects especially to low-sulfur diesel fuels Specific alkyl aromatic compounds having at least one carboxyl group bonded to an aromatic nucleus

  Moreover, it is preferable that an additive contains an antifoamer, More preferably, it contains an antifoamer combining a rust inhibitor and / or a corrosion inhibitor, and / or a lubricant.

  Unless otherwise stated, the (active matter) concentration of each additive component in the additive-containing fuel composition is preferably 10000 ppmw or less, more preferably in the range of 0.1 to 1000 ppmw, advantageously 0.1 to 300 ppmw, for example 0. The range is from 1 to 150 ppmw. The (active matter) concentration of the defogging agent in the fuel composition is preferably in the range of 0.1 to 20 ppmw, more preferably 1 to 15 ppmw, even more preferably 1 to 10 ppmw, and advantageously 1 to 5 ppmw. The (active matter) concentration of the ignition improver is preferably 2600 ppmw or less, more preferably 2000 ppmw or less, and conveniently 300 to 1500 ppmw.

  If desired, the aforementioned additive components are mixed together in an additive concentrate, preferably with a suitable diluent, and dispersed in the fuel in an amount suitable for obtaining the composition of the present invention. It's okay.

  In the case of a diesel fuel composition, the additive is usually a detergent or a diesel fuel compatible diluent (which may be a carrier oil (eg mineral oil)), for example, optionally together with other components as described above, Contains polyether (which may or may not be capped), toluene, xylene, white spirit and non-polar solvents such as those sold by Shell under the trademark "SHELLSOL".

The total content of additives is suitably 0 to 10,000 ppmw, preferably less than 5000 ppmw.
As used herein, the amounts of ingredients (concentration, ppmw, weight%) are those that exclude the active component, ie, the volatile solvent / diluent material.

The treatment according to the invention can be applied as appropriate before or after the additive is blended with the fuel component.
The present invention uses fuel compositions in direct injection diesel engines, such as rotary pumps, in-line pumps, unit pumps, electronic unit injectors or conventional rail type, or indirect injection diesel engines or homogeneous charge compression ignition engines. Or can be used if intended for use. This fuel composition may be suitable for heavy and / or light diesel engines.

  As described above, the fuel composition can be used for heating, for example, when used in a boiler. Such boilers include standard boilers, low temperature boilers and condensation boilers, and are typically used for heating industrial or household water such as space heating and water heating.

In diesel fuel compositions, hydrocarbons can be supplemented by oxygenates such as esters known to be used in diesel fuel.
In the process according to the invention, the treatment with the metal-adsorbing or absorbing material is carried out with hydrocarbons in the liquid phase, very conveniently at ambient temperature. This treatment can be carried out at atmospheric pressure, which is very convenient at ambient temperature.

If it is known that a particular hydrocarbon refinery component or combination / component of a fuel component is at least primarily responsible for the presence of the metal to be removed, this component or combination of components is at least another carbonization While blended with hydrogen refinery components to form a fuel composition, it can be treated with a metal adsorbent or absorbent material, but a pre-blended fuel composition can also be treated. .
The invention is further illustrated by the following examples. In the examples, unless otherwise indicated, parts and percentages are by weight and the temperature is in ° C.

Example 1
The fuel described in Example 1 is as shown in Table 1.

Fuel A is a Hungarian commercial fuel according to EN590, which has not been further processed. The fuel B is obtained by processing the fuel A through a clay column as described below.
Comparing the characteristics of fuels A and B shown in Table 1, it can be seen that the physical properties (density and cetane number) were not essentially changed even by clay treatment. It can also be seen that the aromatic (mono-, di- and tri-) content and sulfur content were essentially unchanged due to the distillation characteristics.

Metal content and filtration The metal content of fuel A was measured using the following method ICP-MS (inductively coupled plasma mass spectrometry). In this method, a metal-containing fuel is sprayed into a spray chamber to form a fine spray. Here, after removing the large droplets, 1-2% of the sample solution is put into plasma inductively coupled. Plasma is created in a quartz tube by the interaction of a strong magnetic field and flowing argon. The plasma discharge is a high temperature of about 1000 ° C. In ICP-MS, the plasma is used to generate positively charged ions. When ions are generated in the plasma, they pass through the interface to the mass spectrometer. At the interface, positive ions are focused on a quadruple mass spectrometer. The analysis results (ppbw) are shown in Table 2.

  A glass wool layer was attached directly above a glass column having a height of about 1 m and a diameter of 7.5 cm having a tap at the bottom and a loose glass cap at the top, and then charged with dry powdery clay. The clay was packed approximately 40 cm onto the column tap and then prevented with glass wool to prevent the clay from falling into the tap.

  Ambient temperature (20 ° C.) fuel A was then injected into the column to a depth of 25-30 cm above the clay. The flow rate was adjusted to 1 liter / hour and the fuel was regularly filled to the top of the column. A total of 50 liters was passed through the column. The 1 liter that first permeated was discarded and then a 5 liter sample (Sample B) was collected. The second, fourth, sixth, eighth and final samples (fuel B) were tested for metal content. These average values (ppbw) are as shown in Table 2 below.

It should be noted that the levels of chromium (Cr), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn) and zinc (Zn) all decreased after the clay treatment. The decrease in zinc level was particularly noticeable.
The metal level can be further reduced by optimizing the process operating conditions, passing the fuel through a solid second bed, or other means.

  The clay used is attapulgite (manufactured by Millwhite) having a mesh size of 30 to 60 (0.500 to 0.250 mm) obtained from Wilfish Smith Limited. Other suitable clays include, for example, fuller earth with a mesh size of 30-60 obtained from Aldrich, and Steely Bentonite & Absorbents Ltd. There is a grade 30-60 sepiolite obtained from

Release behavior Next, the release behavior of fuels A and B was tested using the automobile shown in Table 3. This table represents the two main light fuel injection systems: direct injection (DI) and indirect injection (IDI).

Fuels A and B were tested using the automobile in the order shown in Table 4.

Each test consisted of a standard ECE + EUDC cycle (ECE 1505M 11s 221) and measured total hydrocarbons, NOx, CO, CO ₂ and particulates using a 2 + 2 ++ 1 bagging strategy. Two cars were tested for one fuel during each day of testing.
1st: Test preparation for both cars for fuel A 2nd: Release test for VW Golf and VW Passat for fuel A 3rd: VW Golf and VW Passat for test preparation for both cars with fuel A, fuel change, and fuel B Release test 4th: Release test of VW Golf and VW Passat for fuel B

  In order to avoid contamination by trace metals in the clay-treated fuel, tests were conducted from lacquer-lined fuel cans and non-metal fuel lines to the fuel pumps of each automobile. Fuel samples were retained at the end of each release test and subjected to elemental analysis. This confirmed that trace metal contamination did not occur during the course of the test.

The results of the release test are shown in the following tables: Table 5 (NOx), Table 6 (fine particles), Table 7 (CO), Table 8 (total hydrocarbons), and Table 9 (CO ₂ ). . In the table, all units are g / km.

As can be seen from the 7-9 Table, CO, total hydrocarbons and CO _2, or no change in the fuel A and B, there is no essentially unchanged. These gains, that is, the improvement in the level ratio (%) of NOx and fine particles when fuel B is used compared to the case where fuel A is used, are shown in the following tables, that is, Table 10 (NOx) and 11th. It is shown in the table (fine particles).

Example 2
The fuel described in Example 2 is as shown in Table 12.

Fuel C is a diesel fuel containing 275 ppmw of sulfur. Fuels D, E, F, and G are fuel C on DAMOLIN MOLER (diatomite obtained from Damolin), AMBERLITE XAD-7 (polymer adsorbent obtained from Aldrich), and silica gel, respectively, as described below. It has been processed through polyethylenelemine (obtained from Aldrich) and AMBERLYST 15 (ion exchange resin obtained from Aldrich).
The density of fuels C to G was essentially unchanged by this treatment.

Metal content and filtration The metal content of fuel C was measured using the technique described for fuel A. The results are shown in Table 13 below.
Fuel C was then treated at ambient temperature (20 ° C.) with a metal absorbing or adsorbing material, DAMOLIN MOLER, AMBERLITE XAD-7, polyethylenemine on silica gel, and AMBERLYST 15, each as described below. G was produced.

  The fuel D was obtained by treating the fuel C in a column having a tap of about 1 m and a diameter of 7.5 cm having a tap at the bottom. About 250 g of dry solid was loaded on top of the glass wool layer of the column. This solid packed to approximately 20 cm above the column tap. The fuel was once passed through the first ~ 100 ml discarded column.

Fuels E, F and G were obtained by treating fuel C in a column having a tap of about 50 cm in height and a diameter of 2 cm. In each case, about 40 g of solid was loaded on top of the glass wool layer of the column. This solid was packed to approximately 30 cm above the column tap. These fuels were once passed through the first ~ 100 ml discarded column.
Fuels D to G were then tested for metal content. These average values (ppbw) are as shown in Table 13 below.

  It should be noted that the levels of copper (Cu), iron (Fe) and zinc (Zn) decreased after treatment with each metal absorbing or adsorbing material. The decrease in zinc level was particularly noticeable.

  The level of metal in the fuel can be further reduced by optimizing the process conditions, passing the fuel through a second contact step with a metal-absorbing or adsorbing material, or alternatively. During engine operation, it may be desirable to further reduce metal levels to optimally reduce NOx and particulate formation.

From the data, it is very clear that NOx and particulate emissions were reduced by treating Fuel A with clay. This reduction, more fuel characteristics (Table 1), or CO, is achieved without giving essentially influence the release of total hydrocarbons and CO ₂ (the 7-9 Table).

  Similar reductions in NOx and particulate emissions are expected when pretreating fuel hydrocarbon components with metal-absorbing or adsorbing materials such as those described above, particularly those that significantly reduce the zinc level in the fuel. It is.

Accordingly, the present invention improves, i.e. reduces, emissions from a compression ignition engine comprising the step of pretreating at least one hydrocarbon component of the fuel used in the compression ignition engine with a metal absorbent or adsorbent material. Means are also provided.

Claims (10)

  A fuel composition comprising a major amount of fuel suitable for a compression ignition engine, the fuel comprising one or more hydrocarbon components having a boiling point in the boiling range of diesel, wherein at least one of the hydrocarbon components is A level of preferably at least one metal in the at least one hydrocarbon component for the purpose of reducing the emission of NOx and optionally particulates from the compression ignition combustion chamber of the compression ignition engine into which the fuel composition is introduced; More preferably treated with a metal adsorbing or absorbing material in a different physical phase from the hydrocarbon component in order to reduce the level of at least one heavy metal, most preferably zinc. The fuel composition comprising physical separation of hydrocarbon components from the metal adsorbent or absorbent phase.   The fuel composition according to claim 1, wherein the metal adsorbing or absorbing material is selected from fibrous clay minerals, diatomaceous earth, graphite, and charcoal.   The fuel composition according to claim 1, wherein the metal adsorbing or absorbing material is selected from a polymeric adsorbent or absorbent and an ion exchange resin.   The fuel composition according to claim 1, wherein the metal adsorbing or absorbing material is selected from a complexing agent or a chelating agent.   In order to reduce the level of preferably at least one metal, more preferably at least one heavy metal, most preferably zinc, in at least one hydrocarbon component having a boiling point in the boiling range of diesel, Treating at least one hydrocarbon component with a metal adsorbent or absorbent material, and to form a fuel suitable for a compression ignition engine, before or after said treatment, said at least one hydrocarbon component The method for producing a fuel composition according to any one of claims 1 to 4, further comprising a step of optionally blending with at least one other hydrocarbon component having a boiling point in the boiling range of diesel.   Blending at least two hydrocarbon components having a boiling point in the boiling range of diesel, and treating the resulting mixture with a metal adsorbent or absorbent material to form a fuel suitable for a compression ignition engine The method of claim 5 comprising:   The operating method of a compression ignition engine including the process of introduce | transducing the fuel composition of any one of Claims 1-4 in the combustion chamber of a compression ignition engine.   A method for reducing the emission of NOx and optionally particulates from a compression ignition engine comprising the step of introducing the fuel composition of any one of claims 1 to 4 into a combustion chamber of a compression ignition engine.   A method of using a fuel composition according to any one of claims 1 to 4 in a compression ignition engine for the purpose of reducing the emission of NOx and optionally particulates from the compression ignition engine. A method for reducing the release of NOx and optionally particulates from a compression ignition engine comprising the step of replacing the fuel composition in the compression ignition engine with the fuel composition of any one of claims 1-4.