JP2023552631A - Use of detergent additives - Google Patents

Abstract

Use of detergent additives in fuel compositions to reduce microbial cultures. The present invention relates to a wide variety of fuel compositions, including diesel fuel, heating fuel, aviation fuel, marine fuel, and the like. [Selection diagram] Figure 1

Description

The present invention relates to the use of detergent additives in fuel compositions to reduce microbial culture.

Fuel tanks and distribution systems provide an environment in which microorganisms can grow. There are three main types of spoilage and corrosive hydrocarbon-utilizing microorganisms in fuel systems: bacteria, yeasts, and molds, the latter two often referred to as fungi. Microorganisms are ubiquitous and can infect fuels at any point in the distribution chain, survive and multiply in the water/aqueous phase associated with fuels, and transfer their nutrients across the fuel/water interface. (most nutrients diffuse into cells in aqueous solution). Microorganisms require substantial amounts of elements such as carbon, hydrogen, sulfur, nitrogen, and phosphorous, trace amounts of other elements, and some forms of oxygen. The rate and type of microbial growth depends on factors such as aqueous phase pH, oxygen availability, ambient temperature, and nutrient availability. Optimal cultivation is achieved in a temperature range of 15°C to 40°C and a neutral/slightly acidic pH. Most of these conditions are met in the fuel tank and distribution system, thereby providing an ideal environment for microbial culture. Water as one major factor worsens the situation and cannot be completely eradicated due to condensation effects, tank roof leaks, poor housekeeping, etc. Therefore, fuel storage systems are never sterile and, at best, the goal is to limit microbial culture to acceptable levels by employing good housekeeping practices.

There are several undesirable consequences of microbial culture in fuel systems. One such result is Microbially Induced Corrosion (MIC), which is corrosion caused or promoted by microorganisms.

Microbial cells can exist in planktonic (single cells floating/swimming in the fuel) or sessile (attached to surfaces) form. Biofilms are formed when a collection of microorganisms (mainly bacteria) irreversibly adhere to a surface and begin to excrete slimy extracellular biopolymers. Biofilms enhance microbial interactions and provide greater access to nutrients, environmental stability, and protection from viruses and biocides. These microbial communities can adhere to the sidewalls and bottom of fuel storage tanks and cause microbially induced corrosion (MIC).

MIC is one of the most serious consequences of microbial culture. Aerobic bacteria produce organic acids, deplete the oxygen supply, and create an oxygen-deficient zone around them. An oxygen gradient develops, causing the formation of anodic corrosion pits. Sulphate Reducing Bacteria (SRB) can increase this corrosion by producing _H2S , HS, and _S2 , all of which are highly aggressive to steel.

Other consequences of microbial culture in the fuel system are blockage of filters, valves, and pipelines, increased pump wear, and production of biosurfactants that can cause stable water turbidity and coalescer ineffectiveness. In particular, fungi have been implicated in filter blockages in vehicle fuel systems. Fuel filter clogging is often caused by mold growth, which manifests as a mat of hyphae (long filaments of fungus) at the fuel/water interface. Loss of product quality, malodor, cloudiness and discoloration, and syringe fouling can also be undesirable consequences of microbial culture.

Biofuels (eg, FAME) can play a role in replacing fossil fuels to meet greenhouse gas emissions reduction goals. Globally, many countries have established or are developing biofuels directives, and some countries (e.g. Indonesia) have introduced B30 (30% biofuels), which Much higher than the current EU directive level of B7 (7% biofuel). However, it is well established that biodiesel and blends thereof are more susceptible to microbial cultivation than conventional hydrocarbon diesel, especially at EU directive level. The reasons cited for this are that FAME is easier for microorganisms to digest and is more hygroscopic than conventional diesel, resulting in more free water entrainment.

Gas-to-liquid (GTL) technology currently converts _CH4 /methane from natural gas - the cleanest burning fossil fuel - into a high-quality liquid that would otherwise be produced from crude oil. Convert into fuel products. GTL fuel can help reduce local emissions in conventional diesel vehicles. GTL fuel also has other uses, such as as a synthetic marine fuel in inland waterway vessels in conventional marine diesel engines. GTL fuel is more biodegradable than conventional diesel due to its negligible aromatic content and simple structure (fully saturated), but may be more susceptible to microbial culture than conventional diesel. It is known that there is. Fuel handling and storage conditions for microbial culture may be considered more stringent for inland waterway vessels than for road applications due to the potential presence of water in the tanks during bunkering and on board the bunker vessel.

In the past, attempts have been made to solve cases of microbial spoilage in fuels and fuel systems. Currently, chemical treatments such as biocides and biostats are used in conjunction with physical control methods such as good housekeeping, sedimentation, filtration, centrifugation, and heat treatments to control and eliminate microbial cultures in fuel systems. used in

Unfortunately, chemical treatments are toxic by their nature and their handling presents serious health, safety, and environmental concerns. Commonly used isothiazolinone chemicals are, for example, skin sensitizers. Additionally, waste biomass must be disposed of after chemical treatment, which can be time consuming and expensive.

Therefore, it would be desirable to provide alternative ways to reduce microbial culture in fuels and fuel systems.

According to the present invention, there is provided the use of detergent additives in fuel compositions to reduce microbial culture.

According to another aspect of the invention, a method is provided for reducing microbial culture in a fuel composition, the method comprising introducing a detergent additive into the fuel composition.

It has been discovered that use of the detergent additives described herein can reduce microbial cultures in fuel compositions to which the detergent additives are added. Thus, the present invention can result in a reduction in microbial spoilage events in a wide range of fuel compositions.

1 is a graphical representation of experimental data generated in Example 1. 5 is a graphical representation of the experimental data set forth in Table 5 below, and in particular, the average dry biomass weight after 4 and 12 weeks of the fuels tested in Example 2 below, with and without additives. (g) is shown. 5 is a graphical representation of the experimental data set forth in Table 5 below, in particular the following implementations with and without Performance Additive Package 2, Performance Additive Package 3, Detergent Additive 1, and Detergent Additive 2. Figure 2 shows the average dry biomass weight (g) for all fuel formulations tested in Example 2.

As used herein, provided is the use of a detergent additive in a fuel composition to reduce microbial culture in the fuel composition.

In the context of this aspect of the invention, the term "reducing microbial culture" encompasses any degree of reduction in microbial culture. Microbial culture may be measured by any suitable method, such as the biomass method described in the Examples below. The reduction in microbial culture is more than 10% compared to microbial culture in similar fuel compositions without detergent additives, especially during the period that the fuel composition is stored in the fuel tank, e.g. for a period of up to 12 weeks. , preferably 20% or more, more preferably 50% or more, particularly 70% or more. As used herein, the term "reducing microbial culture" also encompasses the prevention of microbial growth in the first place.

The present invention relates to a wide range of fuel applications such as diesel fuel, heating fuel, aviation fuel, marine fuel, and mixtures thereof. Preferred fuel applications include diesel fuel and aviation fuel.

The first essential ingredient herein is a cleaning additive, which removes and/or prevents the accumulation of combustion-related deposits within the engine, particularly within the fuel injection system such as the injector nozzle. means an agent (preferably a surfactant) capable of acting to do so. Such materials are sometimes referred to as dispersant additives.

Detergent-containing diesel fuel additives are known and commercially available. Examples of suitable detergent additives include, but are not necessarily limited to, polyolefin-substituted succinimides or succinimides of polyamines, aliphatic amines, Mannich bases or amines, polyolefin maleic anhydrides, and quaternary ammonium salts, and mixtures thereof. Not limited. Preferred detergent additives for use herein are nitrogen-containing detergents. In one embodiment, the detergent additive for use herein is a polyolefin substituted succinimide, such as polyisobutylene succinimide. In another embodiment, the detergent additive for use herein is a quaternary ammonium salt.

Many of the above detergents are nitrogen-containing detergents. Since nitrogen is an essential nutrient for microorganisms, it is particularly surprising that the nitrogen-containing detergents described above were found to reduce microbial culture when included in fuel compositions.

Fuel additives can promote water entrainment in the fuel due to their surfactant properties, especially at high treatment rates, and can also act as a food source, providing additives containing the essential nutrient nitrogen. This is especially important. Therefore, it would be reasonable to assume that fuels blended with performance additives, particularly nitrogen-containing performance additives such as nitrogen-containing detergents, are more conducive to microbial attack. Surprisingly, the inventors have discovered that detergent additives, such as nitrogen-containing detergents, surprisingly have been found to inhibit microbial culture in fuel compositions. In particular, detergent additives such as nitrogen-containing detergents have surprisingly been found to inhibit microbial cultures in fuel compositions, where the microorganisms are fungal species. This is particularly advantageous since filamentous fungi are involved in filter blockage problems.

The detergent additive preferably contains from 5 ppmw to 10000 ppmw, preferably from 5 ppmw to 1000 ppmw, more preferably from 5 to 500 ppmw, and even more preferably from 10 to 200 ppmw of active detergent, based on the total fuel composition. present in the fuel composition at levels.

In one embodiment of the invention, the detergent additive is a component of a detergent additive package along with one or more other additive components. Examples of other suitable additive components are provided in more detail below.

The diesel fuel compositions described herein can include diesel base fuel in addition to detergent additives.

Diesel base fuel is petroleum-derived low sulfur diesel containing less than 50 ppm sulfur, such as ultra-low sulfur diesel (ULSD) or zero sulfur diesel (ZSD), which is used in internal combustion engines. Any petroleum-based diesel suitable for use may be used. Preferably, the low sulfur diesel contains less than 10 ppm sulfur.

The preferred petroleum-derived low sulfur diesel for use in the present invention complies with the EN590 standard. It typically has a density of 0.81 to 0.865, preferably 0.82 to 0.85, more preferably 0.825 to 0.845 g/cm ³ at 15°C, a cetane number of at least 51 (ASTM D613) and a kinematic viscosity (ASTM D445) of 1.5 to 4.5, preferably 2.0 to 4.0, more preferably 2.2 to 3.7 mm ² /sec at 40°C.

In one embodiment, the diesel base fuel is conventional petroleum derived diesel.

A further preferred component of the fuel compositions herein is biodiesel fuel. Biodiesel fuel is a fuel derived from biological materials.

The biodiesel component is preferably present in the fuel compositions at a level of 5% v/v or more up to 50% v/v, preferably from 5% v/v to 30% v/v, such as 7% It is present at levels of v/v, 10% v/v, 20% v/v, and 30% v/v.

In one embodiment of the invention, the fuel compositions herein do not include a biodiesel component (i.e., so-called "B0" fuel).

A preferred biodiesel component for use herein is fatty acid alkyl ester (FAAE). It is known to include fatty acid alkyl esters (FAAEs), particularly fatty acid methyl esters (FAME), in diesel fuel compositions. Examples of suitable FAAEs include rapeseed methyl ester (RME), palm oil methyl ester (POME), and soy methyl ester (SME). FAAEs are typically derived from biological sources and are typically included to reduce the environmental impact of fuel production and consumption processes or to improve lubricity.

FAAEs, of which the most commonly used in the context of diesel fuels are methyl esters, are already known as renewable diesel fuels (so-called "biodiesel" fuels). They contain long chain carboxylic acid molecules (generally 10 to 22 carbon atoms long), each with an alcohol molecule attached to one end. Organically derived oils such as vegetable oils (including recycled vegetable oils) and animal fats (including fish oils) are subjected to a transesterification process with alcohols (typically C ₁ -C ₅ alcohols) to produce typical In particular, the corresponding monoalkylated fatty esters can be formed. This process is suitably catalyzed with either an acid or a base (eg, the base KOH) and converts the triglycerides contained in the oil from their glycerol backbone to the fatty acid component of the oil. FAAEs can also be prepared from used cooking oils and can be prepared from fatty acids by standard esterification.

In the present invention, the FAAE may be any alkylated fatty acid or mixture of fatty acids. The fatty acid component is preferably derived from biological sources, more preferably from vegetable sources. They may be saturated or unsaturated; in the latter case they may have one or more double bonds, preferably up to 6 double bonds. They may be linear or branched, cyclic or polycyclic. Suitably they contain 6 to 30, preferably 10 to 30, more preferably 10 to 22 or 12 to 24 or 16 to 18 carbon atoms, including the acid group -CO ₂ H. has. FAAEs typically contain a mixture of different fatty acid esters of different chain lengths depending on their source.

Preferred FAAEs for use in the present invention are selected from natural fatty oils, such as tall oil, rapeseed oil, coconut oil, or soybean oil.

The FAAE is preferably a C ₁ -C ₅ alkyl ester, more preferably a methyl, ethyl, propyl, (preferably isopropyl) or butyl ester, even more preferably a methyl or ethyl ester, especially a methyl ester. In one embodiment herein, the FAAE is selected from coconut oil methyl ester (POME) and rapeseed oil methyl ester (RME), and mixtures thereof.

Generally, it can be either natural or synthetic, purified or unpurified ("crude").

FAAEs may contain impurities or by-products as a result of the manufacturing process.

The FAAE preferably includes the remainder of the fuel composition and/or the amount to which it is added, taking into account the intended use to which the composition will be applied (e.g., in which geographic region, at what time of year). Conforms to specifications applicable to base fuel. In particular, the FAAE preferably has a flash point (IP ³⁴ ) higher than 101°C, a kinematic viscosity at ⁴⁰ °C (IP 71), density of 845 to 910 kg/m ³ at 15 °C, preferably 860 to 900 kg/m ³ (IP 365, EN ISO 12185 or EN ISO 3675), water content of less than 500 ppm (IP 386), lower than 360 °C T95 (temperature at which 95% of the fuel has evaporated, measured according to IP 123), an acid number (IP 139) of less than 0.8 mg KOG/g, preferably less than 0.5 mg KOH/g, and less than 125 grams per 110 g of fuel, Preferably it has an iodine number (IP 84) of less than 120 grams or less than 115 grams of iodine (I ₂ ). It also preferably contains (e.g. by gas chromatography, GC) less than 0.2% w/w free methanol, less than 0.02% w/w free glycerol and more than 96.5% w/w. Contains esters of. Generally, it may be preferred that the FAAE complies with European Standard EN 14214 for fatty methyl esters for use as diesel fuel.

Two or more FAAEs may be added to the diesel fuel composition according to the present invention, either separately or as a pre-prepared blend.

The FAAE is typically present as a blend (i.e., physical mixture), optionally with one or more other fuel components (such as a diesel base fuel), and optionally with one or more fuel additives. It can also be incorporated into fuel compositions. The FAAE is advantageously incorporated into the fuel composition before the composition is introduced into an engine operated with the fuel composition.

The fuel compositions herein can include paraffinic gas oils in addition to or in place of the diesel base fuels described above. Paraffinic gas oils suitable for use in the present invention may be derived from any suitable source so long as they are suitable for use in fuel compositions, particularly diesel fuel compositions.

Suitable paraffinic gas oils include, for example, Fischer-Tropsch derived gas oils and hydrogenated vegetable oil (HVO) derived gas oils, and mixtures thereof.

Preferred paraffinic gas oils for use herein are Fischer-Tropsch derived gas oil fuels. The paraffinic nature of Fischer-Tropsch derived gas oil means that diesel fuel compositions containing it have a high cetane number compared to conventional diesel.

Although Fischer-Tropsch derived gas oils are the preferred paraffinic gas oils for use herein, the term "paraffinic gas oils" as used herein refers to gas oils derived from hydroprocessing of vegetable oils (HVO). It also includes paraffinic light oil. The HVO process is based on oil refining technology. This process uses hydrogen to remove oxygen from triglyceride vegetable oil molecules and split the triglycerides into three separate chains to produce paraffinic hydrocarbons.

If present, the paraffinic gas oil (i.e., Fischer-Tropsch derived gas oil, hydrogenated vegetable oil derived gas oil) is preferably at least 95% w/w, more preferably at least 98% w/w, even more preferably at least 99% w/w. It consists of 5% w/w, most preferably up to 100% w/w of paraffinic components, preferably iso and normal paraffins, preferably 80% w/w or more of isoparaffins.

"Fischer-Tropsch derived" means that the fuel or base oil is a synthetic product of or is derived from a Fischer-Tropsch condensation process. The term "non-Fischer-Tropsch derived" may be interpreted accordingly. Fischer-Tropsch derived fuel is sometimes referred to as GTL (gas-to-liquid) fuel.

The Fischer-Tropsch reaction converts carbon monoxide and hydrogen into longer chain, usually paraffinic hydrocarbons, i.e.
n( CO+2H ₂ )=(-CH ₂ -) _n +nH ₂ O+heat. Hydrogen:carbon monoxide ratios other than 2:1 may be used if desired.

The carbon monoxide and hydrogen themselves can be derived from either organic or inorganic, natural or synthetic sources, typically natural gas or organically derived methane. More recently, techniques for obtaining carbon monoxide and hydrogen from other sources, including more sustainable sources, have been investigated and used. For example, starting with carbon dioxide and water, the water can be electrolyzed to obtain free hydrogen, typically using electricity from sustainable sources. This hydrogen can react with carbon dioxide in a "reverse aqueous shift reaction" to obtain a source of carbon monoxide. This carbon monoxide can then be reacted with the remaining hydrogen in a typical Fischer-Tropsch synthesis process. Because of the use of electrolysis, some of these manufacturing processes are referred to as "Power-to-liquids."

Gas oils, kerosene fuels and base oil products can be obtained directly from the Fischer-Tropsch reaction or indirectly, for example by fractionation of Fischer-Tropsch synthesis products or from hydrotreated Fischer-Tropsch synthesis products. can. Hydrotreating involves hydrocracking to adjust the boiling range (see, for example, UK Patent No. 2077289 and European Patent No. 0147873) and/or to improve cold flow properties by increasing the proportion of branched paraffins. can be accompanied by hydroisomerization. EP 0 583 836 discloses that the Fischer-Tropsch synthesis product is first hydrogenated under conditions such that it does not undergo substantial isomerization or hydrocracking (which hydrogenates the olefins and oxygen-containing components). and then hydroconverting at least a portion of the resulting product under conditions such that hydrocracking and isomerization occur to yield a substantially paraffinic hydrocarbon fuel or oil. A two-stage hydrogenation process is described. The desired diesel fuel fraction may then be isolated, for example, by distillation.

Other post-synthetic treatments such as polymerization, alkylation, distillation, cracking-decarboxylation, isomerization and hydrogeno-reforming are used as described, for example, in US Pat. No. A-4125566 and US Pat. No. A-4478955. The properties of the Fischer-Tropsch condensation product may be modified as described.

Typical catalysts for the Fischer-Tropsch synthesis of paraffinic hydrocarbons contain metals from group VIII of the periodic table, in particular ruthenium, iron, cobalt or nickel, as catalytically active components. Suitable such catalysts are described, for example, in EP 0 583 836.

An example of a Fischer-Tropsch based process is the SMDS (Shell Middle Distillate Synthesis) described in "The Shell Middle Distillate Synthesis Process" by van der Burgt et al. (see above). This process (sometimes referred to as Shell "Gas-to-Liquids" or "GTL" technology) converts syngas derived from natural gas (primarily methane) into heavy long-chain hydrocarbon (paraffin) waxes. produces a diesel range product, which can then be hydroconverted and fractionated to produce liquid transportation fuels such as gas oil and kerosene. A version of the SMDS process that utilizes a fixed bed reactor for the catalytic conversion step is currently used at Pearl GTL in Bintulu, Malaysia and Ras Laffan, Qatar. Kerosene and (gas) oil prepared by the SMDS process are commercially available, for example, from Royal Dutch/Shell Group of Companies.

Due to the Fischer-Tropsch process, Fischer-Tropsch derived gas oils are essentially free or contain undetectable levels of sulfur and nitrogen. Compounds containing these heteroatoms tend to act as poisons to the Fischer-Tropsch catalyst and are therefore removed from the syngas feed. Furthermore, normally operated processes produce no or substantially no aromatic components.

For example, the aromatic content of Fischer-Tropsch gas oil is typically less than 1% w/w, preferably less than 0.5% w/w, more preferably 0.1% w/w, as measured by, e.g., ASTM D4629. %w/w.

Generally speaking, Fischer-Tropsch derived fuels have relatively low levels of polar components, particularly polar surfactants, compared to, for example, petroleum derived fuels. It is believed that this may contribute to improving defoaming and fog removal performance. Such polar components can include, for example, oxygen-containing additives and sulfur- and nitrogen-containing compounds. Low levels of sulfur in Fischer-Tropsch derived fuels generally indicate low levels of both oxygenated additives and nitrogenous compounds, as all are removed by the same treatment process. .

Preferred Fischer-Tropsch derived gas oil fuels for use herein are typically in the range of 160°C to 400°C, similar to the distillation range of petroleum-derived diesel, preferably having a T95 of 360°C or less. is a liquid hydrocarbon middle distillate fuel with a distillation range of . Fischer-Tropsch derived fuels also tend to be low in undesirable fuel components such as sulfur, nitrogen and aromatics.

Preferred Fischer-Tropsch derived gas oils for use herein meet the EN15940 standard.

Preferred Fischer-Tropsch derived gas oil fuels typically have a molecular weight of 0.76 to 0.80, preferably 0.77 to 0.79, more preferably 0.775 to 0.785 g/cm ³ at 15°C. density (measured according to EN ISO 12185).

Preferred Fischer-Tropsch derived gas oil fuels for use herein have a cetane number (ASTM D613) greater than 70, preferably from 70 to 85, most preferably from 70 to 77.

Preferred Fischer-Tropsch derived gas oil fuels for use herein are 40 mm 2 /s in the range of 2.0 mm ² /s to 5.0 mm ² /s, preferably 2.5 mm ² /s to 4.0 mm ² /s. It has a kinematic viscosity (measured according to ASTM D445) at °C.

Preferred Fischer-Tropsch derived gas oils for use herein have a sulfur content (ASTM D2622) of 5 ppmw (parts per million by weight) or less, preferably 2 ppmw or less.

Preferred Fischer-Tropsch derived gas oil fuels for use in the present invention are those manufactured as a separate end product that is suitable for sale and used in applications requiring specific properties of the gas oil fuel. It is. In particular, it exhibits a distillation range that falls within the range normally associated with Fischer-Tropsch derived gas oil fuels, as discussed above.

The fuel composition used in the present invention may include a mixture of two or more paraffinic gas oils, such as two or more Fischer-Tropsch derived gas oil fuels.

If present, the Fischer-Tropsch derived component (i.e., Fischer-Tropsch derived gas oil) used herein preferably contains no more than 3% w/w, more preferably 2% w/w by weight of the Fischer-Tropsch derived component. % w/w or less, even more preferably 1% w/w or less cycloparaffins (naphthenes).

If present, the Fischer-Tropsch-derived component (i.e., Fischer-Tropsch-derived gas oil) used herein preferably contains no more than 1% w/w, more preferably 0% by weight of the Fischer-Tropsch-derived component. Contains less than .5% w/w olefins.

The diesel fuel compositions described herein for use in the present invention are particularly suitable for use as diesel fuels, where the fuel compositions are diesel fuel compositions and have excellent cold fluidity. Due to its properties it can be used in arctic applications as a winter grade diesel fuel.

For example, a cloud point (EN 23015) of -10°C or less or a cold filter plugging point (CFPP) (measured by EN 116) of -20°C or less is found in the fuel compositions herein. It could be possible.

Generally speaking, in the context of the present invention, fuel additives may be added to the fuel composition in addition to the detergent additives already mentioned.

Unless otherwise stated, the (active substance) concentration of each such additive in the fuel composition preferably ranges from 1 to 400 ppmw, such as at most 10000 ppmw, more preferably from 1 to 1000 ppmw, advantageously from 1 to 200 ppmw. be. Such additives may be added at various stages during the manufacture of the fuel composition. Additions to base fuel in refineries include, for example, antistatic agents, pipeline drag reducers, middle distillate flow improvers (MDFI) (e.g. ethylene/vinyl acetate copolymers or acrylates). /maleic anhydride copolymers), lubricity improvers, antioxidants and wax anti-settling agents.

Other ingredients that may be incorporated as fuel additives, such as in combination with the detergent additives, include lubricity enhancers, dehazing agents such as alkoxylated phenol formaldehyde polymers, antifoaming agents (e.g. commercially available polyether modified polysiloxanes), ignition improvers (cetane improvers) (e.g., 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate, di-tert-butyl peroxide, and U.S. Pat. No. 4,208,190, column 2, lines 27-3) (as disclosed in line 21), rust inhibitors (e.g. propane-1,2-diol half ester of tetrapropenylsuccinic acid, or polyhydric alcohol esters of succinic acid derivatives, wherein the succinic acid derivative is polyhydric alcohol esters having an unsubstituted or substituted aliphatic hydrocarbon group containing 20 to 500 carbon atoms in at least one of its α-carbon atoms, e.g. pentaerythritol diester of polyisobutylene-substituted succinic acid); Corrosion inhibitors, fragrances, anti-wear additives, antioxidants (e.g. phenols such as 2,6-di-tert-butylphenol, or N,N'-di-sec-butyl-p-phenylenediamine) phenylenediamine), metal deactivators, antistatic additives, and mixtures thereof.

In a preferred embodiment of the invention, other additive components in the detergent additive package include corrosion inhibitor additives, metal passivators, antioxidants, metal deactivators, flavoring agents, etc.; selected from a mixture.

The invention particularly provides that the fuel composition is suitable for use in direct injection diesel engines, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, or in indirect injection diesel engines, or in HCCI engines. may be applicable where it is intended to be used or used. The fuel composition may be suitable for use in high horsepower and/or low horsepower diesel engines, as well as engines designed for on-road or off-road use.

In order to be suitable for at least the applications listed above, the final fuel composition is preferably a diesel fuel composition that preferably meets the EN590 standard (October 2017).

When a GTL base fuel is included in the fuel compositions herein, it is preferred that the final fuel composition fuel meets the EN15940 standard (2019).

The present invention may also be applicable where the fuel composition is used or intended to be used in stationary applications such as heating oil systems, heating oil burners, and/or stationary generators. .

Heating oil compositions suitable for use herein have properties according to standard DIN 51603 (2020).

The invention will be illustrated with reference to the following non-limiting examples.

Example 1
In Example 1, four fuel samples were used, as shown in Table 1 below.

Test Procedures Test Microorganisms A defined inoculum with known hydrocarbon decomposition capacity was used, for example a contaminated field diesel sample. 1 ml was taken from the contaminated field diesel sample and used to inoculate a 70:30 ml ratio aqueous medium/fuel mixture. This was done for each of the fuels in Table 1 above and cultured for 8 days to form a culture or microbial community. Incubation was performed in the dark at 25°C. 100 μl from the aqueous phase of each microbial community was then used to inoculate the microcosms.

Microcosm Setup A stainless steel coupon (to promote biofilm growth) was inserted into the vial. 5 ml of Bushnell Haas nutrient medium (aqueous phase) was decanted and covered with 5 ml of fuel. The microbial community was then inoculated with either GTL fuel or B7 culture. Therefore, two inocula were derived from one field sample.

Test Protocol Microbial culture and diversity were evaluated over a period of one month by dry biomass weight to determine culture yield. This is a simple technique designed to give a direct measurement of total microbial load at the end of the experiment. The culture visible at the interface was captured, solvent washed to remove fuel residue, dried in an oven, cooled, and weighed. The results of Example 1 are shown in FIG. In Figure 1, the fuel sample keys are as follows:
GA1 = GTL fuel (added) (crowd 1)
GU1 = GTL fuel (no addition) (crowd 1)
DA1=B7 fuel (added) (crowd 1)
DU1=B7 fuel (no addition) (crowd 1)
GA2 = GTL fuel (added) (crowd 2)
GU2 = GTL fuel (no addition) (crowd 2)
DA2=B7 fuel (added) (crowd 2)
DU2=B7 fuel (no addition) (crowd 2)

As can be seen from FIG. 1, there was a reduction in biomass growth in the fuel containing Performance Additive Package 1 (containing PIBSI detergent additive) compared to the comparison fuel that did not contain the Performance Additive Package. This is especially surprising for nitrogen-containing cleaners considering that nitrogen is a nutrient for microorganisms.

Example 2
The fuel used in Example 2 is shown in Table 5 below. Each fuel contained EN590 base fuel or GTL EN15940 base fuel with or without FAME and with or without performance additive package/detergency additive as indicated. The physicochemical properties of the EN590 base fuel used in this example are shown in Table 3 below. The physicochemical properties of the GTL fuel used in this example are shown in Table 4 below. FAME in B7 fuel (containing 7% biofuel) was derived from SME/RME. The FAMEs used in the B30 fuels (each containing 30% biofuel) were derived from SME/RME and POME. The FAME used in B50 fuel (containing 50% biofuel) was derived from POME.

The additives used are as follows:
Performance Additive Package 2: Contains detergent additives. None of the other ingredients present in Performance Additive Package 2 have a biocidal effect. Performance additive package 2 is used in all fuel formulations except EN 590 B0.

Performance Additive Package 3: Contains detergent additives. None of the other ingredients present in performance additive package 3 have a biocidal effect. Performance Additive Package 3 is used in GTL and EN590 B0 fuel formulations. Performance additive package 3 is a special additive formulation tailored for heating fuel formulations that typically do not contain FAME. The fuel formulations tested herein also do not contain FAME.

Detergent Additive 1: PIBSI detergent additive (used in EN 590 B7 fuel formulations).

Detergent Additive 2: Quaternary ammonium based detergent additive (used in EN 590 B7 fuel formulations).

The test protocol was the same as in Example 1, and the observed microbial culture for all tested fuel types based on total biomass dry weight over a three-month period (two time points, 4 weeks and 12 weeks). We conducted an evaluation. Three replicate microcosms were set up for each time point. One microbial community was used as inoculum.

The results are shown in Table 5 below. FIG. 2 is a graphical representation of the data shown in Table 5, specifically the average dry biomass weight after 4 and 12 weeks for all fuels tested in Example 2 with and without additives ( g).

FIG. 3 is a graphical representation of the data shown in Table 5, in particular, the samples tested with and without Performance Additive Package 2, Performance Additive Package 3, Detergent Additive 1, and Detergent Additive 2. Average dry biomass weight (g) for all fuel formulations is shown. Thus, in Figure 3, the block entitled "Perf Additive Package 2" represents the average dry biomass weight (g) for all formulations shown in Table 5 containing Performance Additive Package 2; The block entitled "Perf Additive Package 3" represents the average dry biomass weight (g) for all formulations shown in Table 5 containing Performance Additive Package 3, and the block entitled "None" The block entitled "Det Additive 1" represents the average dry biomass weight (g) for all formulations shown in Table 5 without the performance additive package and detergent additive; Representing the average dry biomass weight (g) for all formulations shown in Table 5 containing Detergent Additive 1, the block titled "Det Additive 2" contains Detergent Additive 2. Table 5 represents the average dry biomass weight (g) for all formulations shown in Table 5.

Claims (13)

Use of detergent additives in fuel compositions to reduce microbial cultures. The use according to claim 1, wherein the detergent additive is selected from polyolefin-substituted succinimides or succinimides of polyamines, aliphatic amines, Mannich bases or amines, polyolefin maleic anhydrides, and quaternary ammonium salts, and mixtures thereof. . 3. Use according to claim 1 or 2, wherein the detergent additive is a polyolefin-substituted succinimide, preferably polyisobutylene succinimide. 3. Use according to claim 1 or 2, wherein the detergent additive is a quaternary ammonium salt. Use according to any one of claims 1 to 4, wherein the detergent additive is present in the fuel composition at a level of 5 ppmw to 10000 ppmw. Use according to any one of claims 1 to 5, wherein the detergent additive is a nitrogen-containing detergent. Use according to any one of claims 1 to 6, wherein the detergent additive is a component of a performance additive package. Use according to any one of claims 1 to 7, wherein the fuel composition is selected from diesel fuel compositions, heating oil compositions, aviation fuel compositions and marine fuel compositions. Use according to any one of claims 1 to 8, wherein the fuel composition is a diesel fuel composition. 10. The use according to claim 9, wherein the diesel fuel composition comprises a petroleum-derived diesel base fuel. 11. The use according to claim 9 or 10, wherein the diesel fuel composition comprises a paraffinic base fuel selected from hydrotreated vegetable oils, Fischer-Tropsch derived base fuels, and mixtures thereof. Use according to any one of claims 9 to 11, wherein the diesel fuel composition comprises a biodiesel component, preferably a fatty acid alkyl ester. A method for reducing microbial culture in a fuel composition, the method comprising the step of introducing a detergent additive into the fuel composition.