JP2006516996A5 - - Google Patents

Description

The introduction of cerium oxide in the fuel serves more than one purpose. The primary purpose is to act as a catalyst in reducing toxic exhaust emissions in the combustion of fuel. However, a diesel engine can serve another purpose. Diesel engines are widely used that contain traps of dust generated from the combustion of diesel fuel. The presence of cerium oxide in the trap helps burn and remove the dust that accumulates in the trap. In fact, such use exists in commercial operations. Therefore, certain automobiles, mainly those devised by Peugeot, have an in-vehicle system that starts the engine after cerium oxide is taken into the fuel. However, this Ri complex systems der, an appropriate amount of additive to be supplied to the fuel, requires a lot of electronic control. In effect, the in-vehicle system allows the particulate filter to be regenerated to last longer .

Accordingly, the present invention provides for adding cerium oxide and / or doped cerium oxide, and optionally one or more fuel additives, to the fuel prior to introducing the fuel to a vehicle or other device having an internal combustion engine. A method for improving fuel efficiency for an internal combustion engine is provided.

Thus, the introduction of cerium oxide eliminates the need for a vehicle fuel management system. Fuel efficiency can be obtained from the introduction of cerium oxide particles in the fuel.

The particles can be introduced into the fuel at a variety of different points. There are particular advantages with regard to introducing particles at their various different points. In particular, cerium oxide can be introduced at the refinery, typically with processing additives. This is of course the earliest point at which cerium oxide can be added and means that the resulting fuel already contains additives at the refinery and does not need to be introduced at a later stage. However, if desired, it may be added in depot fuel company, it introduction amount means the resulting Rukoto customized to the requirements of individual companies. Cerium oxide can also be added to storage tanks at public or private refueling facilities, or distributed to fuel when supplied to vehicles. This has the advantage of maximum particle dispersion stability.

The main purpose of adding cerium oxide to the fuel is to increase the economics of the fuel, but the presence of particles in the fuel will regenerate it at the same time if a diesel soot filter is present. It is recognized to promote. The effect of cerium oxide is generally to allow regeneration at low temperatures . This has the advantage that filters, usually ceramic materials, are generally less prone to cracking.

Such dopant ions should be elemental divalent or trivalent ions, which are rare earth metals, transition metals or metals of the periodic table IIA, IIIB, VB or VIB to provide oxygen vacancies. . They should also be sized to allow the introduction of ions into the surface region of the cerium oxide nanoparticles. Therefore, metals with a large ionic radius should not be used. For example, transition metals in the first and second rows of transition metals are generally preferred over those described in the third row. Ceria acts as an oxygen activator and exchange medium during a redox reaction. However, since ceria is a ceramic material, it has low electronic conductivity and low surface activity against chemical adsorption of reactive species. Transition metal additives are particularly useful in improving these situations. In addition, the polyvalent dopant may itself have a catalytic effect.

Typically this doped oxide is
Formula: Cel _x M _x O ₂
[ Wherein M is the above metal or metalloid , in particular Rh, Cu, Ag, Au, Pd, Pt, Sb, Se, Fe, Ga, Mg, Mn, Cr, Be, B, Co, V, Zr, Ti and Ca, and Pr, Sm and Gd, and x is a value of 0.3 or less, typically 0.01 or 0.1 to 0.2. ]
Or
Formula: [(CeO ₂ ) _1-n (REO _y ) _n ] _1-k M ′ _k
[ Wherein M ′ is the above metal or metalloid other than rare earth elements, RE is a rare earth element, y is 1 or 1.5, n and k may be the same or different, and 0 0.5 or less, preferably 0.3 or less, typically 0.01 or 0.1 to 0.2. ]
Have Further details are given in Applicant's PCT application specification GB2002 / 005013, to which reference should be made.

In general, cerium oxide particles have a size not exceeding 1 micron, in particular 300 nm or less, for example 1 to 300 nm, specifically 1 to 150 nm, in particular 10 to 50 nm, in particular 1 to 20 nm.

It is preferred to coat the particles to prevent agglomeration. For this purpose, the particles of the organic acid, the presence of the coating agent is anhydride or ester or a Lewis base, may be comminuted in an organic solvent. It has been found that oxide coatings can be significantly improved in processes involving intact coatings. Furthermore, the products obtained can often be used directly without intermediate steps. Thus, in some coating procedures, it is necessary to dry the coated particles prior to dispersing in a hydrocarbon solvent.

The particles subjected to this process should have as large a surface area as possible and preferably the particles have a surface area of at least 10 m ² / g prior to coating, preferably a surface area of at least 50 or 75 m ² / g, for example 80~150m having ² / g or 100 to 300 m ² / g,.

Coating agent, preferably an organic acid, anhydride or ester or a Lewis base. The coating agent is preferably an organic carboxylic acid or anhydride, those typically having at least 8 carbon atoms, for example 10 to 25 carbon atoms, especially 12 to 18 carbon atoms, such as stearic An acid etc. are mentioned. It will be appreciated that the carbon chain may be saturated or unsaturated and may be ethylenically unsaturated, for example oleic acid. Similar description applies to that available anhydride. They are preferably dicarboxylic anhydrides, in particular alkenyl succinic anhydrides, in particular dodecenyl succinic anhydride , octadecenyl succinic anhydride and polyisobutenyl succinic anhydride. Other organic acids may be used in the process of the present invention, as anhydrides and esters include those derived from phosphoric acid and sulfonic acid. Esters are typically aliphatic esters, for example alkyl esters in which both the acid and ester moieties have from 4 to 18 carbon atoms.

The coating method can be performed in an organic solvent. Preferably the solvent is non-polar and preferably also non-hydrophilic . It may be an aliphatic or aromatic solvent. Typical examples include toluene, xylene, gasoline, diesel fuel, and hevier fuel oils. Of course, the organic solvent used must be selected to apply to the desired end use of the coated particles. The presence of water must be avoided; the use of an anhydride as a coating aids in eliminating the presence of water.

The coating method involves grinding the particles to prevent the formation of agglomerates. Techniques used for this purpose include high speed stirring or tumbling and include the use of colloid mills, ultrasound or ball mills. A ball mill is preferred. Further details of such coatings can be shown in PCT / GB02 / 02312.

In general, cerium oxide particles have been found to be stable in fuel or in fuel addition packages due to the presence of detergent. In this regard, it has been recognized that lubricants are detrimental because they can cause precipitates to form. Specific cleaning agents that can be used in accordance with the present invention include basic nitrogen-containing cleaning agents. Such cleaning agents must be ashless (ie they are metal free). Suitable detergents include amides, amines, Mannich bases and succinimides, which are preferred. Preferably the detergent is succinimide having an average of at least 3 nitrogen atoms per molecule . The succinimide is preferably aliphatic and may be saturated or unsaturated, especially ethylenically unsaturated, such as alkyl or alkenyl succinimide. Typical detergents are generally alkyl or alkenyl succinic acylating agents having at least 35 carbon atoms in the alkyl or alkenyl group, and alkylene polyamines having an average of at least 3 nitrogen atoms per molecule. Formed from a mixture. Preferably, it includes polyisobutenyl succinic acylating agents derived from polyisobutene having a number average molecular weight of 500 to 10,000 and cyclic and acyclic moieties having an average composition of triethylenetetramine to pentaethylenehexamine. It can be formed from the resulting ethylene polyamine. Thus, the chain is typically the molecular weight 500 to 2,500, in particular having a 750 to 1500, those having a molecular weight of about 900 and 1300 are particularly useful. However, succinimide with an aliphatic chain having a molecular weight of about 2100 is also useful. Further details can be shown in US-A-5,932,525 and 6048373 and EP-A-432,941, 460309 and 1,237,373.

Typically, the concentration of cerium oxide in the additive is 0.1 to 10% by weight , generally 0.5 to 5% by weight.

If cerium oxide is added at the refinery, it really can be added without anything else. Typically, additives introduced at refineries include cetane number improvers, cold flow improvers and antioxidants. Thus, the composition according to the invention can introduce one or more of these. However, cerium oxide generally does not improve the cetane number, so it is unlikely to be added with them.

Typical additives that may be used in the fuel composition (especially diesel fuel) include the following, as conventionally used:
Non-polar organic solvents; such as aromatic and aliphatic hydrocarbons, such as toluene, xylene, and volatile oils, and mixtures thereof and sold under the trademark “SHELLSOL” from the Royal Dutch / Shell Group and “EXXSOL” from the ExxonMobil Group Is mentioned.
Polar organic solvents; especially alcohols, generally aliphatic alcohols such as 2-ethylhexanol, decanol and isotridecanol,
Detergents; for example hydrocarbyl-substituted amines and amides, such as hydrocarbyl-substituted succinimides, such as polyisobutenyl succinimides,
Dehazers; eg alkoxylated phenol formaldehyde polymers such as the commercially available “NALCO” ^™ 7D07 (by Nalco) and “TOLAD” ^™ 2683 (by Petrolite ),
Defoaming agent; commercially available as, for example, polyether-modified polysiloxane, “TEGOPREN” ^™ 5851 (by Th. Goldschmidt), Q 25907 (by Dow Corning ) or “RHODORSIL” ^™ (by Rhone Poulenc),
Ignition modifiers; for example aliphatic nitrates, such as 2-ethylhexyl nitrate and cyclohexyl nitrate,
Rust inhibitor; for example, Germany Mannheim Rhein Chemie, as "RC4801" from or those commercially available as HiTEC ^(R) 536 from from Ethyl corporation, i.e., polyhydric alcohol esters of succinic acid derivatives
Flavoring agent ;
An antioxidant; for example, phenols such as 2,6-di-t-butylphenol, or phenylenediamine such as N, N′-di-sec-butyl-p-phenylenediamine, etc.
Metal activity reducing agents; such as salicylic acid derivatives, such as N, N′-disalicylidene-1,2-propanediamine, and lubricants; such as polar compounds, especially fatty acids and esters and amides. Typical acids are C ₂ -C have ₅₀ chain and / or aromatic, polybasic acids, e.g., dimers of dicarboxylic acids, such as unsaturated acids (such as oleic or linoleic acid), and in particular ortho OH Included are hydroxy aromatic carboxylic acids having groups, such as salicylic acid, particularly those substituted by a group possessing at least 10 carbon atoms. Typical esters are such acids and alcohols (typically C ₁ and C ₅ aliphatic alcohols or polyhydric alcohols such as glycols, glycerol or pentaerythritol or poly (oxyalkylenes) having eg 5 oxyalkylene groups. Derived from alcohol ). The ester of the polybasic acid may be partial. Particular esters include glycerol mono- and di-esters such as glyceryl monooleate , sorbitan monooleate and pentaerythritol monooleate, and salicylic acid esters. Other lubricants that can be used include esters derived from carboxyphenols and polyols and aminoalkylmorpholines. Some such agents are (by Ethyl Corporation) EC831, P631, (by Infinium) P633 or P639, or "HITEC" ^{(Trade Mark)} 580, commercially available as TOLAD 2670 and 9103 Baker Petrolite slit (Baker Petrolit) And those described in WO 98/01516 and 98/16596.

The demulsifier is, for example , commercially available as TOLAD 2898 from Baker Petrolite.

Unless otherwise specified, the concentration of (active matter) of each additive in the fuel is typically 1000 ppmw or less (parts per million (parts) of diesel fuel weight), particularly 800 ppmw or less , for example 1-1000 , 1-800, or 1-20 ppmw.

The same or similar additives can be used for other fuels recognized by those skilled in the art (eg, gasoline ).

Claims (14)

A method according to claim 1, comprising adding a cerium oxide doped with a divalent or trivalent metal or metalloid which is a rare earth metal, transition metal or metal of the periodic table IIA, IIIB, VB or VIB. . A method according to any preceding claim, wherein the cerium oxide and / or the doped cerium oxide is coated with an organic acid, anhydride or ester or Lewis base. Succinic anhydride, dodecenyl succinic anhydride, octadecenyl succinic anhydride or polyisobutenyl succinic anhydride, The method of claim 10. A method according to any preceding claim, wherein cerium oxide and / or doped cerium oxide is added to the fuel at the refinery . Cerium oxide and / or doped cerium oxide can be used as a cleaning agent, dehazer, anti-foaming agent, ignition improver, anti-rust agent, flavoring agent, oxidation A method according to any preceding claim, added with one or more of an inhibitor, metal deactivator, lubricant or demulsifier. 20. A process according to claim 19, wherein the cleaning agent is a succinimide containing an average of at least 3 nitrogen atoms per molecule . Succinimide is derived alkyl or alkenyl succinic acylating agents, and the alkylene polyamine mixture containing an average of at least 3 nitrogen atoms per molecule having at least 35 carbon atoms in the alkyl or alkenyl part, claim 20. The method according to 20. Succinimide is derived from ethylene polyamines having an average composition from polyisobutenyl succinic acid acylating agents and triethylenetetramine obtained from polyisobutene having a number average molecular weight of 500 to 10,000 to pentaethylenehexamine (average Composition) 21. The method of claim 20, wherein: 27. The method of claim 26 , wherein cerium oxide and / or doped cerium oxide is added in an amount not exceeding 10 ppm. 32. The fuel additive according to any one of claims 29 to 31, wherein the cerium oxide is defined in one or more of claims 2 to 11. 34. The fuel additive according to claim 33, wherein the cleaning agent is a succinimide having an average of at least 3 nitrogen atoms per molecule . Succinimide, alkyl or alkenyl succinic acid acylating agent having at least 35 carbon atoms in the alkyl or alkenyl part and is derived from an alkylene polyamine mixture having an average of at least 3 nitrogen atoms per molecule, according to claim 34, wherein Fuel additive. Succinimides, Ru is derived from ethylene polyamines having an average composition from polyisobutenyl succinic acid acylating agents and triethylenetetramine obtained from polyisobutene having a number average molecular weight of 500 to 10,000 to pentaethylenehexamine, claim 34. The fuel additive according to 34. Moreover, in any one of Claims 32-38 containing 1 or more of a dehazer, an antifoamer, an ignition improving agent, a rust preventive agent, a fragrance | flavor agent, antioxidant, a metal deactivator, a lubricant agent, or an emulsion breaker . The fuel additive as described.