JP5020830B2 - Low emission combustion using multi-component metal combustion catalysts - Google Patents

Description

  The present invention relates to novel compositions and novel methods for improving the efficiency of fossil fuel combustion sources. The use of a fuel soluble catalyst consisting of platinum and at least one additional metal reduces the production of contaminants of the type caused by incomplete combustion, such as particulates, unburned hydrocarbons and carbon monoxide.

  Diesel engines have many important advantages over Otto type engines. In particular, fuel economy, ease of repair and long service life are raised. However, from the point of view of exhaust gas, there are more severe problems than spark-ignition facing parts. The exhaust gas problem relates to particulates, nitrogen oxides (NOx), unburned hydrocarbons (HC) and carbon monoxide (CO). When engine operation improvements are made to reduce particulates and unburned hydrocarbons in diesel engines, NOx emissions tend to increase.

  Post-treatment devices such as diesel particulate filters (DPF) and diesel oxidation catalysts (DOC) have been proposed to reduce emissions of particulates and gaseous hydrocarbons and carbon monoxide from diesel engines. While these devices are particularly emphasized in older engines, efficiency improvements are needed in newer engines. In all cases, efficiency is required because most are expensive due to the cost of the precious metal used. It would be desirable to reduce the cost of DOC or DPF devices or reduce them together.

  It has been believed that the way to achieve this is to employ a fuel-borne catalyst (FBC), however, they are not always effective when used at relatively high levels (concentrations). is not. FBC produces ash, and data published in the European VERT program show that the number of ultrafine particles increases dramatically above baseline at high FBC dosages of 20 ppm or 100 ppm cerium. ing. However, in the case of binary metals used at 0.5 / 7.5 or 0.25 / 4 ppm, no significant increase in the number of ultrafine particles is observed. At low levels of FBC, there are no separated ultrafine oxide particle peaks and the metal oxide is contained in the soot with a complete particle size distribution. It is desirable to reduce the contribution of metal ash to the overall engine emissions. In the case of the engine emission standards established in 1998, the particulate emission is limited to 100,000 μg / hp-hr (0.1 g / hp-hr). The cerium FBC used at 30 ppm in the fuel represents a metal catalyst introduction load into the engine corresponding to 6000 μg / hp-hr of metal, or roughly 6% of the raw engine emissions.

  By reducing the emission of particulates, HC and CO directly from the diesel engine, more directly from the current level, the aftertreatment device can be eliminated or the frequency of the catalyst load or soot cleaning cycle It is necessary to provide a diesel fuel containing FBC that has such a high effect that it can be reduced.

  The problem of the present invention is that the post-treatment device can be eliminated or the frequency of the catalyst load or the soot washing cycle can be reduced by directly reducing the emission of particulates, HC and CO from the diesel engine. It is to provide a diesel fuel comprising an effective fuel soluble catalyst (FBC).

  In the case of diesel engines, it is an advantage of the present invention that improvements can be achieved without the use of aftertreatment devices such as filters or catalysts such as diesel particulate filter (DPF) or diesel oxidation catalyst (DOC).

  If an aftertreatment device such as DOC or DPF is applied, the device will be improved in emissions from diesel engines so that it will have improved performance with less valuable metal usage. This is a further advantage of the present invention.

  The fuel used according to the present invention consists of a carbonaceous fuel, such as a fossil fuel, containing low or very low levels of catalytic metal additives. The catalytic metal additive is preferably soluble or dispersible in the fuel and comprises a platinum and cerium and / or iron composition.

  In one aspect, the present invention comprises a base fuel consisting of a distillate fraction and a fuel soluble catalyst consisting of platinum and cerium and / or iron, with 0.05 to 0.5 ppm platinum, for example 0.1 to 0.00. Provided is a diesel fuel for diesel engine power that requires less after-treatment equipment and generates less particulates, characterized by the use of 5 ppm and cerium or iron at a level of 5 to 10 ppm. Preferably, the sulfur content of the diesel fuel is less than 0.05%. In a preferred embodiment, cerium and / or iron is present at a total concentration of 0.5 to 8 ppm.

  In another aspect of the present invention, at least one other catalyst comprising a fuel soluble platinum group metal composition and a cerium fuel soluble compound to reduce emissions of particulates, unburned hydrocarbons and carbon monoxide. The compound is added to the diesel fuel at a level of 0.05 to 0.5 ppm platinum, for example 0.1 to 0.5 ppm, and cerium and / or iron to 5 to 10 ppm, and the diesel engine is operated with this diesel fuel. A method is provided for reducing the generation of particulates, hydrocarbons and carbon monoxide from a diesel engine directly at the engine outlet prior to contact with an oxidant or particulate collection device.

  From another point of view, the present invention provides a pilot fuel with a multi-way catalyst composition containing as little as 0.0005 to 0.15 ppm platinum and 0.5 to 8 ppm cerium and / or iron as a total concentration. It can be described as providing a method for improving the combustion of pilot fuel in a dual fuel diesel engine operating primarily on natural gas, characterized by the addition.

  Viewed from another aspect, the present invention provides a multi-component combustion catalyst comprising a platinum composition and a cerium and / or iron composition at a low level of 0.0005 ppm platinum and 0.5 ppm cerium and iron, fuel or combustion air. And a method for burning carbon-containing fuel, characterized in that the fuel is burned with air in the presence of the catalyst.

  In another aspect, the present invention provides a multi-component combustion catalyst comprising a platinum composition and a cerium and / or iron composition at a level of about 0.0005 to 2 ppm platinum and about 1 to 25 ppm cerium and iron, fuel or Mix with combustion air and burn the fuel with air in the presence of this catalyst, reducing the level of platinum composition and cerium and / or iron composition to a low level of 0.0005 ppm platinum and 0.5 ppm cerium and iron The multi-component combustion catalyst is mixed with fuel or combustion air, and the fuel is burned with air in the presence of the catalyst.

  Furthermore, the present invention provides a platinum composition and a cerium and / or iron composition as at least part of the processing conditions using higher catalyst concentrations, eg, 0.5 to 2.0 ppm platinum and 7.5 to 15 ppm cerium. A multi-component combustion catalyst comprising platinum at a level of 0.0005 to 0.15 ppm and cerium and iron at a level of 0.05 to 1.0 ppm and mixed with fuel or combustion air; A combustion method of a carbon-containing fuel characterized by burning is provided.

With the use of the diesel fuel of the present invention, particulate, HC and CO emissions can be directly eliminated without the use of after-treatment devices such as filters or catalysts such as diesel particulate filter (DPF) or diesel oxidation catalyst (DOC). Can be reduced.
In addition, when applying post-processing equipment such as DOC or DPF, the equipment has the advantage of improved performance with less valuable metal usage.

  In addition to other advantages and improvements of the present invention, the use of low and ultra-low levels of individual and combined catalysts includes a number of reductions in catalyst solids accumulated or consumed in the system. It is important from a viewpoint. The present invention can reduce contaminants without the use of an aftertreatment device, and can facilitate aftertreatment by reducing particulate formation and increasing the carbon deposit combustion capacity. Cerium and iron levels can be reduced to levels as low as 0.05 ppm, and platinum levels can be reduced to levels as low as 0.0005 ppm. The processing method uses an effective level within the low and ultra-low level range at times and conditions where one or more noticeable improvements are achieved.

  As mentioned above, the present invention relates to improved combustion of diesel fuel, typically including fossil fuels, such as any of the fuels derived from typical petroleum, including distillate fuels. The diesel fuel can be any of the formulations disclosed in the above-mentioned prior patent application, hereby incorporated by reference in its entirety. The fuel may be a diesel fuel, for example No. 2 diesel fuel, no. 1 diesel fuel, jet fuel, eg, Jet A, or No. 1 Analogues similar in boiling point and viscosity to one diesel fuel, distillate distillate fuels including ultra-low sulfur content diesel fuel (ULSD) and “monoalkyl ester-based oxidized fuels”, ie fatty acid esters, preferably triglycerides It may be one or a blend selected from the group consisting of biologically derived fuels such as those containing methyl esters of fatty acids derived from, for example, soybean oil, canola oil and / or tallow.

  Jet A and diesel no. 1 is considered equivalent in the present invention, but is covered by different ASTM specifications. Diesel fuel is covered by ASTM D975, “Standard Specification for Diesel Fuel Oils”. The term ultra-low sulfur content diesel fuel (ULSD) has a sulfur level of no more than 0.0015 wt% (15 ppm). 1 or NO. 2 means diesel fuel and some jurisdictions require low aromatic hydrocarbon content, for example, 10% by volume or less.

  The term low aromatic ultra-low sulfur diesel fuel (LA ULSD) as used herein means that this component in the fuel is no more than 10% by volume, and preferably from 1 to 8%, especially from 2 It means having an aromatic content of 5%.

  The table below shows no. Typical analysis results for two diesel and low aromatic ultra-low sulfur content diesel fuel LA ULSD are shown below in addition to a formulation containing biodiesel components (LA ULSD containing FBC and 20% biodiesel).

  Biologically derived fuels are conventionally referred to as “biodiesel” in the literature. Biodiesel typically contains a small amount of a diesel fuel blend, typically on the order of 1 to 35%, such as 15 to 25%. The blend typically contains about 20% biodiesel and the biologically derived fuel component is a “monoalkyl ester-based oxidized fuel”, eg, soybean oil, canola oil and / or It consists of fatty acid esters such as tallow, preferably triglyceride-derived fatty acid esters. As used herein, the term “fatty acid ester” refers to polyols and substituted alcohols, etc., but preferably volatile alcohols such as C1-C4 alcohols (preferably methyl), esters of 2-methoxyethyl and It is intended to encompass any compound in which the alcohol moiety is readily removed, including benzyl esters of fatty acids containing about 8 or more (eg, 8 to 22) carbon atoms and mixtures of such esters. Volatile alcohols are highly preferred. Methyl ester is the most preferred ester reactant. Suitable ester reactants can be prepared by the reaction of diazoalkanes with fatty acids, or obtained by fatty acid alcoholization that occurs naturally in fats or oils.

  Suitable fatty acid esters are derived from synthetic or natural, saturated or unsaturated fatty acids and include positional and geometric isomers. Suitable preferred saturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, isomustic acid, isomalgaric acid, myristic acid, caprylic acid, and anteisoaracadic acid Is included. Suitable preferred unsaturated fatty acids include myristic acid, palmitolic acid, ricinoleic acid, linoleic acid, oleic acid, elaidic acid, linolenic acid, eleosteric acid, arachidonic acid, erucic acid, and erythrogenic acid. Particularly preferred for use herein are mixtures of fatty acids obtained from soybean oil, palm oil, safflower oil, rapeseed oil, canola (low erucic acid), and corn oil. Fatty acids can be used as such and / or after hydrogenation, and isomerized and purified. For example, rapeseed oil is a good raw material for C22 fatty acids, C16-C18 fatty acids are obtained from tallow, soybean oil, or cottonseed oil, and shorter chain fatty acids are obtained from coconut, palm kernel, or Bavasu oil. It is done. Lard, olive oil, peanut oil, sesame oil, and sunflower oil are other natural fatty acid sources.

  Preferred esters included in biodiesel are lower alkyl esters such as methyl, ethyl, propyl and butyl, especially methyl esters of soybean oil or tallow fatty acids. The following is a spec (performance table) of the biodiesel (B100) set by the National Biodiesel Board in December 2001, which is also adopted for the purpose of clarifying and defining the present invention. Thus, biodiesel is defined as a monoalkyl ester of a long chain fatty acid obtained from vegetable oil or animal oil for use in compression ignition (diesel) engines. This spec is for pure (100%) biodiesel before use or before blending with diesel fuel. In the United States, a blend of 20% biodiesel and 80% diesel fuel has a considerable track record. Biodiesel (B100) can be used, but blends of diesel fuel and more than 20% biodiesel should be evaluated on a case-by-case basis until further performance is achieved. Equivalents having the same essential function and having a composition change of up to 50%, preferably 20% or less can also be used. In some cases, other sources mentioned above can only blend 2% biodiesel with 98% diesel fuel.

  One product of this type is marketed by the members of the National Biodiesel Board under the trade name Biodiesel and has been identified as “Methyl Soyate, Rapeseed Oil (RME), Methyl Taloate”. The manufacturer also refers to the fuel as "a fuel made from a monoalkyl-based oxidized fuel, vegetable oil or animal oil". It is said to contain 11 wt% oxygen. They describe the product as methyl ester from a lipid source, CAS No. 67784-80-9.

  The process of the present invention employs a multi-metallic catalyst that is fuel soluble, preferably containing fuel soluble platinum and cerium or iron or both cerium and iron. Cerium and / or iron is typically used at a concentration of 0.5 to 20 ppm and platinum is 0.0005 to 2 ppm, with a preferred level of cerium and / or iron being 5 to 10 ppm, such as 7.5 ppm, Platinum is then used at a level of 0.0005 to 0.5 ppm, for example 0.15 ppm or less, and in some cases 0.1 ppm or less, ie 0.01 to 0.09 ppm. In some embodiments, the treatment process initially requires a higher catalyst concentration or is done as needed, but not at intervals or the entire treatment that was previously required. In some cases, the platinum concentration can be as high as 1 ppm and, if necessary, as high as 2 ppm. Cerium and / or iron has a cerium and / or iron level of 2 to 10 ppm, such as 3-8 ppm, and platinum is 0.05 to 0.5 ppm, such as 0.1 to 0.5 ppm, eg, typical In some operations, 0.15 ppm is used. The following tests performed at these levels show surprising results in engine emissions.

  The preferred ratio of cerium and / or iron: platinum is 100,000: 1 to 3: 1, for example 100: 1 to 20,000: 1, but more typically 50,000: 1 to 500: 1. Preferred ratios and tests within the above range have shown surprising effects when cerium and / or iron: platinum has a ratio of 75: 1 to 10: 1. A formulation using 0.15 ppm platinum, 10 ppm cerium and 5 ppm iron is typical. Another preferred formulation contains 0.15 ppm platinum and 7.5 ppm cerium. The advantage of low levels of catalyst (about 3 to 15 ppm total), preferably 12 ppm or less and more preferably 8 ppm or less is the reduction of ultrafine particles resulting from metal oxide emissions. Data published from the European VERT program show that the number of ultrafine particles increases dramatically over baseline at high FBC dosages of 20 ppm or 100 ppm cerium. However, in the case of 0.5 / 7.5 or 0.25 / 4 ppm binary metal, no significant increase in the number of ultrafine particles is observed. At low levels of FBC, there was no separate ultrafine oxide peak and metal oxide was found to be included in the soot beyond the overall particle size distribution. A further advantage of the low dose rate predicted by the present invention is a reduced contribution of metal ash to the overall engine emissions. According to the 1998 US engine emission standard, the particulate emission is limited to 100,000 μg / hp-hr (0.1 g / hp-hr). The cerium FBC used at 30 ppm in the fuel represents a metal introduction load on the engine corresponding to 6000 μg metal / hp-hr, or roughly 6% of the raw engine emissions. Therefore, low level catalysts used in the present invention of less than 8 ppm and preferably less than 4 ppm as binary or ternary metal FBCs, for example, have a catalyst load of only 800-1600 μg / hp-hr or It only contributes to 0.8-1.6% of baseline soot emissions. This is an advantage of reducing metal ash emissions, and reduces the contribution of FBC to the overall particulate matter discharge or the metal ash load on downstream emission control devices.

  The fuel is a detergent (eg, 50-300 ppm), a lubricating additive (eg, 25-about 500 ppm), other additives, and a suitable fuel soluble catalytic metal composition, eg, 0.1-2 ppm fuel soluble. Platinum group metal compositions such as platinum COD or platinum acetylacetonate and / or 2-20 ppm fuel soluble cerium or iron compositions such as cerium, cerium octoate, ferrocene, iron oleate as soluble compounds or suspensions , Iron octoate, and the like. The fuel can be combusted without the need for other processing equipment, especially for high level control of diesel.

  The combination of low concentrations of platinum and iron and / or cerium in the fuel is the same as for very high concentrations of cerium, iron or other metals without platinum in reducing the deposition or emission of carbon or soot As effective. Metal concentrations of several ppm in the combination are as effective as 30-100 ppm when using iron and / or cerium alone.

  In one aspect, the present invention mixes a multi-component combustion catalyst comprising a platinum composition and a cerium and / or iron composition with low levels of 0.0005 ppm platinum and 0.5 ppm cerium and iron with fuel or combustion air. And in the presence of this catalyst, the fuel is burned with air, treated using an effective catalyst level under times and conditions to achieve one or more significant improvements. In one aspect, low catalyst levels can be used as at least part of a processing method that includes high initial dosing and / or using intermittently high catalyst levels.

  The present invention also has significant advantages for use in the field of dual fuel diesel engines that operate primarily on natural gas but use pilot fuels such as regular diesel fuels that are more smoky. In some cases, the catalyst concentration according to the present invention can be as low as 0.0005 to 0.15 ppm or less, such as 0.1 ppm or less of platinum and as a total concentration of only 0.5 to at least part of the processing conditions. Low catalyst levels as described above can contain up to 8 ppm cerium and / or iron. In some cases, it may be useful to use 0.05 ppm or less of platinum and a total catalyst level of 5 ppm or less.

  These binary and ternary platinum-based combinations can coexist with standard additive components for distillation fractions and distillation residue fuels such as pour point reducing agents, antioxidants, corrosion inhibitors and the like.

Among other cerium compounds, cerium III acetylacetonate, cerium III naphthenate, and other soaps and the like such as cerium octoate, cerium oleate and stearate, neodecanoate, and C6 to C24 alkanoates Is good. Many of the cerium compounds are trivalent compounds conforming to the formula: Ce (OOCR) ₃ , where R = hydrocarbon, preferably C2 to C22, and aliphatic, alicyclic, aryl and alkylaryl. Cerium is preferably at a concentration of 1 to 15 ppm cerium w / v, for example 4 to 15 ppm of the fuel. Preferably, cerium is supplied as a cerium hydroxy oleate propionate complex (cerium 40 wt%) or cerium octoate (cerium 12 wt%). A preferred level is the lower limit of this range.

Among iron compounds, iron soaps such as ferrocene, ferric and ferrous acetylacetonates, octanoates and stearates (usually commercially available as Fe (III) compounds), iron naphthenates, There are iron torate and other C ₆ to C ₂₄ iron alkanoates, iron pentacarbonyl Fe (CO) ₅ and the like.

  Some platinum group metal compounds such as 1,5-cyclooctadiene platinum diphenyl (platinum COD) are described in Patent Document 1, Patent Document 2 and Patent Document 3, and can be used as a platinum source. Other suitable platinum group metal catalyst compositions include platinum group metal acetyls, including substituted (eg, alkyl, aryl, alkylaryl substituted) and unsubstituted acetylacetonates, which are commercially available or can be readily synthesized. Includes fatty acid soaps of acetonates, platinum group metal dibenzylidene acetonates, and tetramine platinum metal complexes such as tetramine platinum oleate. Platinum is preferably at a concentration of 0.05 to 2.0 ppm platinum w / v (mg / l), for example, about 1.0 ppm or less of the fuel. A preferred level is the lower limit of this range (eg, 0.15-0.5 ppm). Platinum COD is the preferred form of platinum added to the fuel. Cerium or iron is typically used in concentrations that give 0.5 to 25 ppm of metal and 0.0005 to 2 ppm of platinum, with preferred levels of cerium or iron being 5 to 10 ppm, such as 7.5 ppm, and platinum being 0 Used at levels of 1 to 0.5 ppm, for example 0.15 ppm. A preferred ratio of cerium and / or iron: platinum is 100,000: 1 to 10: 1, for example 50,000: 1 to 500: 1. Illustratively, a formulation using 0.0015 ppm platinum and 10 ppm cerium and 5 ppm iron has a (cerium + iron): platinum ratio of about 10,000: 1. An alternative exemplary composition includes 0.0015 ppm platinum and 10 ppm iron and 5 ppm cerium. Another composition contains 3 to 10 ppm of a combination of Ce and Fe for 0.1 to 0.5 ppm of platinum. Another fuel of choice comprises 0.05 to 0.5 ppm platinum and 0.5 to 10 ppm cerium and / or iron, in particular 3 to 8 ppm total concentration of cerium and / or iron.

  Combustion according to the present invention can be an emulsion with water in which the oil phase is emulsified with water containing 1 to 30% water based on the weight of the diesel fuel. In a preferred form, the emulsion is predominantly of the water-in-oil type and preferably contains surfactants, lubricants and / or corrosion inhibitors in addition to the other components described above. Suitable emulsion forms and additives can be found in US Pat. Combustion can improve combustion efficiency and reduce particulates without the use of oxidation catalysts or particulate filters to promote diesel engine exhaust gas control. Also, good carbon combustion in an open flame combustion source can reduce carbon deposition on the heat exchanger surface and lower the soot oxidation temperature of the downstream heat recovery device.

The fuel of the present invention, which includes a base fuel and a fuel soluble catalyst based on low levels of platinum and cerium and / or iron compounds, provides better engine emissions than those of the prior art, and also provides a diesel oxidation catalyst (DOC). ) Or when used with an aftertreatment device such as a diesel particulate filter (DPF) gives unexpected results with NO ₂ as a percentage of PM, HC, CO, NOx and NOx. Particulate reactors, partial filters or NOx absorbers can also be used and have the advantage of reducing engine emissions of the present invention. The term “diesel particulate filter” refers to a device known in the prior art as an exhaust gas filter that reduces particulate emissions by capturing a portion of the particulate within a complex internal structure. They must be regenerated or replaced as deposits accumulate. They can take any suitable structure, for example ceramic, metal, SiC or wire mesh. The term “diesel oxidation catalyst” has traditionally been used as an exhaust treatment catalyst that reduces emissions of particulates, hydrocarbons and carbon monoxide by contacting the catalyst surface at a particulate capture location, such as in a diesel particulate filter. Means a device known in the art. The effect of the discharge results and FBC engine with catalytic aftertreatment device for reducing the NO ₂ and particulate emissions, see below Examples. While not wishing to be bound by any theory, it expected more excellent results in the engine outlet exhaust as well as the post-processing apparatus, a sufficient amount of platinum to produce an excess amount of NO ₂ is absent And the presence of low levels of cerium and / or iron is believed to produce some NO ₂ or other species sufficient to promote the oxidation of carbon in the microparticles. NO ₂ causes strong inflammation in the lungs and is produced in large quantities by the traditional use of highly catalytic aftertreatment devices such as DOC, DPF or combinations thereof. Overall results of NO ₂ produced is limited, and low platinum concentration, small but however expected microparticles generated more than the decrease of the (resulting other species in the same incomplete oxidation) and are generated at the same time opened due to the presence of sufficient amounts of cerium and / or iron to control the amount of NO ₂ was. Unlike the prior art, the present invention has been found that large amounts of NO ₂ are not necessarily required and, of course, has found a way to provide exhaust gases that are less irritating to humans.

  The following examples are intended to further illustrate and illustrate the present invention and should not be construed as limiting the invention in any way. Unless otherwise noted, all parts and percentages are by weight.

  This example describes the preparation of a low emission diesel fuel according to a preferred embodiment of the present invention, but the fuel is an alternative aircraft kerosene grade 55 (available from Colonial Pipeline Company) analyzed above. Jet A and the same boiling point and viscosity as No. 1 diesel) additives (TFA4690-C detergent 100 ppm, Texaco lubricant 225 ppm) and 0.15 ppm platinum and 7 supplied as platinum COD Blended using a fuel soluble catalyst (FBC) containing 0.5 ppm cerium hydroxy oleate propionate complex (solution containing 40 wt% cerium). These ppm values are the metal weight mg per liter of fuel. The fuel was used in testing 1998 DDC Detroit Diesel Series 60, 400 hp engines, and highway no. Results were significantly improved compared to 2 CARB ULSD (California Air Resources Board Ultra Low Sulfur Diesel) fuel. The test data is summarized in the table below, where the FTP test results, transition compositions are given for the various fuels tested.

  In view of the fact that CARB ULSD fuel has been the subject of considerable research and development, it is surprising that it does not give improved results compared to the present invention which includes FBC catalysts containing low levels of platinum and cerium. is there. Thus, the present invention greatly reduces the range of contaminated emissions without the need for a difficult and expensive process to achieve the ultra-low sulfur content that was considered essential for particulate control. It will provide a practical approach.

  This example shows the results of testing on a 1998 DDC series 60 engine using a commercial ultra-low sulfur diesel using platinum and cerium binary FBC with a total of 4 ppm metal and a standard sulfur fuel and control ULSD. . The results are summarized in the following table.

  The table above shows the improvement in FBC treated fuel in treated ultra-low sulfur content diesel (ULSD) versus control ULSD without additives, HC (54%), NOx (5%), PM (25%) and Shows fuel economy (1.4%).

Three 20 minute hot transient test cycles were performed on a 1990 DTA-446 International 7.6 liter engine. NOx, the average emissions NO and NO ₂ and particulates were measured in g / hp-hr units, shown below.

Commercially available No. Baseline emissions of 2 (> 3000 ppm sulfur) and ULSD (<15 ppm sulfur) and similar NO ₂ emissions are shown as a percentage of total NOx species in 17 and 18% of total nitrogen species. In the case of ULSD, the fine particles were slightly low at 0.244 g / hp-hr.

A high contact diesel oxidation catalyst with a PGM load of 75 g / cuft and a low contact wire mesh filter (LCWMF) with a platinum group metal (PGM) load of 14 g / cuft was discharged into the exhaust in ULSD fuel. When used with the bimetallic platinum / cerium FBC at 5 / 7.5 ppm, the particulates were reduced by 59%, while NO ₂ emissions increased to 58% of the total nitrogen oxide species. The cerium additive was cerium hydroxyoleate propionate and the platinum additive was platinum COD.

When DOC was removed, the particulate reduction efficiency dropped slightly to 57%, but NO ₂ was only 25% of the total nitrogen oxide species. Furthermore, both fine particles and NO ₂ were unexpectedly reduced when operated with treated fuel for 25 hours.

The unexpected positive result observed in the test is that the standard no. When FBC was added to either 2D or ULSD, both particulate emissions and NO ₂ proportions decreased. No. In the 2D case, the treated fuel (Pt / Ce = 0.15 / 7.5 ppm) reduced the fines by 15% from 0.253 to 0.215 and from 17% to 13%. In the case of ULSD, adding FBC to the fuel (Pt / Ce = 0.5 / 7.5 ppm) reduces the particulates from 0.244 to 0.207, while NO ₂ from 18% to 12%. Decreased by 15%. Thus, the use of FBC alone or together with a contact post-treatment device has the advantage that particulates and other emissions can be reduced. The high contact DOC advocated by the prior art as helping to reduce particulates through the generation of NO ₂ is less effective here than FBC in reducing particulates and has an adverse effect on NO ₂ generation It has been shown. This has not been disclosed in the prior art.

  An engine dynamometer test was conducted on a Cummins 275 hp, 8.3 liter diesel engine meeting the 1991 California and US Environmental Protection Association federal emission standards. The test cycle is an EPA transient test protocol according to the US Federal Test Procedure (FTP).

  This transient cycle is described by the% maximum torque and% speed at each 1 second interval of a test cycle spanning 1199 seconds. The first 5 minutes of the cycle is referred to as the New York Non-Freeway (NYNF) portion of the test and represents a city run that includes significant idle time. The second 5 minutes is called the Los Angeles Non Freeway (LANF) part. This test part also represents a city run, but does not include a lot of idle time. The third 5-minute portion of the test is called the Los Angeles Freeway (LAF) portion. This corresponds to high-speed driving on a freeway (highway). The last 5 minutes is a repeat of the NYNF part.

These four parts give a 20 minute EPA transient cycle. The results represent the average of three “hot start” repeat tests for each fuel.
The result is a standard No. containing 386 ppm sulfur. 2 graphically shows the reduction in hydrocarbon (HC), carbon monoxide (CO), nitric oxide (NOx) and particulate (PM) emissions for each test fuel compared to emissions from the two highway control fuels.

  The addition of binary platinum / cerium fuel soluble catalyst (FBC) at a concentration of 0.15 ppm platinum and 7.5 ppm cerium metal into the fuel produced an 11% particulate reduction in FIG. 1 (No. 2D + FBC). For comparison between a commercially available ultra-low sulfur content diesel fuel and a 9 ppm sulfur content fuel, it was run without FBC, and as shown in the figure (ULSD), a standard no. There was a 6% reduction in particulates relative to 2D. This same ULSD treated with a fuel soluble catalyst at a concentration of 0.15 ppm platinum and 7.5 ppm cerium metal was the baseline No. Compared to 2D or untreated ULSD, the highest reduction in HC, CO and NOx was 13% PM reduction. These data show that FBCs in standard or ultra-low sulfur content fuels are effective in reducing engine emissions, including particulate reduction. The results are summarized in FIG.

  In another test with a baseline different from Example 4 on a 1990 model Cummins 8.3 liter engine made with 1991 Federal Emission Standards, three “hot starts” in a 20 minute transient cycle Baseline No. Operated with 2D fuel. The discharged amount was measured as 0.189 g / hp-hr. The ultra-low sulfur content diesel fuel (ULSD) operation had a small particulate reduction of 0.182 μg / hp-hr. NO2 emissions maintained 15-16% of total nitrogen oxide emissions with either baseline fuel.

No. in bimetallic FBC with 0.15 ppm platinum and 7.5 ppm cerium. In the 2D treatment, the decrease in fine particles was 13%, 0.164 g / hp-hr, and the decrease in NO ₂ was from 0.8 g / hp-hr to 0.6 g / hp-hr. This is in contrast to the traditional approach to particle reduction using a high contact device to convert NO to NO ₂ . Two fuel sulfur particulate emissions can be converted to sulfur. The 13% PM reduction is surprising for low level FBC and it is important to give minor PM reduction achieved from ULSD alone.

Further tests have shown that the effect of bimetallic FBC is maintained in ULSD fuel at a ratio of 0.5 ppm Pt to 7.5 ppm Ce. A 12% PM reduction relative to baseline ULSD was achieved while maintaining low NO ₂ emissions.

  A similar replica test performed on a 1998 Detroit Diesel 12.7 liter engine is depicted in FIG. 2 and No. 5 at 0.5 ppm Pt / 7.5 ppm Ce treatment rate. The FBC particulate reduction in the 2D fuel was 11% and the untreated ULSD fuel was a 15% reduction. When added to ULSD fuel, the FBC is untreated. Increased to 28% particulate reduction over 2D fuel baseline.

  These results are shown in No. It confirms FBC's ability to reduce engine PM emissions when added to 2D or ULSD fuel. The results are summarized in FIG.

  Testing on a 1990 International Harbister 7.6 liter engine was performed using FBC treated with 0.15 / 7.5 ppm FBC. 2D fuel showed 15% particulate reduction. For comparison, a commercial ULSD without FBC gave a 3% PM reduction. When FBC was added to ULSD at a dose rate of 0.15 / 7.5 ppm, the microparticles decreased by 18%, and when used in low aromatic ULSD, FBC showed a 29% microparticle reduction. The results are summarized in FIG.

  A series of tests were conducted on a 1995 Navistar 7.6 liter engine equipped with a transient response engine dynamometer. No. 3 hot test cycles Performed at the baseline of 2D fuel (> 3000 ppm sulfur) and then used in ULSD (<15 ppm sulfur) for each of the different FBC additives.

Additive A is 0.15 / 4/4 ppm Pt / Ce / Fe; Additive B is 0.15 ppm / 7.5 ppm Ce; and Additive C is 0.15 / 5.6 / 2.4 ppm Pt / Ce. / Fe. All additives contain the same commercially available detergent to ensure catalyst stability. In all three additives showed HC, CO, similar results in NOx and NO _2. Additives A and C are both baseline Nos. Compared to the 25% reduction in PM relative to 2D, the fine particle reduction with binary metal additive B was slightly better at 32%. Blend additives to ULSD in all cases gave unexpectedly good reduction in NOx and NO _2.

  In some applications, the use of ternary metals has a cost advantage over binary metals or is preferred for use in the regeneration of exhaust gas aftertreatment devices such as DOC, DPF, wire mesh or combination systems.

  The above description is intended to enable the skilled artisan to practice the invention. There is no intention to detail all possible variations and modifications as will become apparent to those skilled in the art upon reading this description. However, it will be appreciated that such changes and modifications are encompassed within the scope of the invention as found in the foregoing description and the appended claims. The claims are intended to cover specified elements and steps in an arrangement or sequential combination effective to meet the intended purpose of the invention, unless otherwise specified.

USP 4,891,050 USP 5,034,020 USP 5,266,083 USP 5,743,922

  The present invention can achieve a reduction in particulate, HC and CO emissions directly without the use of a post-treatment device such as a filter or catalyst, for example, diesel particulate filter (DPF) or diesel oxidation catalyst (DOC). Useful as diesel fuel.

  Further, when combining aftertreatment devices such as DOC or DPF, the use of the fuel of the present invention is advantageous because the device has improved performance with less valuable metal usage.

FIG. 1 is a graph summarizing data from Example 3, in which low concentrations of platinum / cerium fuel soluble catalyst (FBC) are evaluated in several fuels of diesel engines. FIG. 2 is a graph summarizing data from Example 6, where platinum / cerium fuel soluble catalysts (FBC) at low concentrations are evaluated in several fuels of diesel engines. FIG. 3 is a graph summarizing data from Example 7, in which low concentrations of platinum / cerium fuel soluble catalyst (FBC) are evaluated in several fuels of diesel engines.

Claims (1)

The including multi-component combustion catalyst platinum composition and cerium and / or iron compositions, mixed with diesel fuel of low aromatic content,
Combustion of the low-fragrance diesel fuel with air in the presence of the multi-component combustion catalyst in a process condition using an effective amount of catalyst under time and conditions to reduce the amount of produced particles and increase the combustion capacity of carbon deposits It consists to Rukoto,
In the multi-component combustion catalyst, the level of platinum is 0.0005 ppm to 2.0 ppm, and the level of cerium and / or iron is 0.5 ppm to 10 ppm,
The ratio of the cerium and / or iron to the platinum is 75: 1 to 10: 1;
The low aromatic content diesel fuel has a sulfur content of less than 0.0015% by weight,
The aroma component content of the low aroma content diesel fuel is 1 to 8% by weight,
Combustion method of the carbon-containing fuel, characterized in that.