JPH08506844A - Oil additives and compositions - Google Patents

Abstract

  (57) [Summary] Petroleum fuel defoamers are used to control the foaming of blends of petroleum-based fuel oils and biofuels.

Description

Detailed Description of the Invention Oil additives and compositionsTechnical field   The present invention is directed to oil compositions, primarily fuel oil compositions, and especially the control of foaming of the compositions. About.Background technology   In the processing and transportation of hydrocarbon oils, frequently as the oil is transferred from container to container. Foaming occurs. Foaming hinders oil pumping, slowing pumping speed It may be necessary to break the bubbles and avoid oil spills. Control foaming It is desirable to be able to speed up oil transportation.   The problem of foaming is in the distillation of liquid petroleum oils, especially oils such as fuels and lubricants, Especially important. The oil is typically pumped through a pipeline or series of storage tanks. Through the distillation network, including transport.   Fuel oils derived from plant or animal sources, also known as biofuels, are burned when burned. The negative impact on the environment is believed to be relatively small and reproducible. specific Biofuel is used as a complete replacement for fuel oil such as diesel fuel oil. Can be Similarly, certain biofuels should be blended with the fuel oil in proper proportions. Can be used as a partial replacement for the oil.   Biofuels inherently have a higher degree of foaming than general fuel oils such as diesel fuel oil. Low. Unfortunately, however, a blend of biofuels and diesel fuel oils Have been found to have a higher degree of foaming than the fuel oil itself. With these fuel oil components Different foam stabilizing and surface active properties are due to a small proportion of fuel oil components It was believed that this finding is surprising. Therefore, a considerable amount of It would be desirable to add biofuels to fuel oils to increase the degree of foaming of the resulting blends. It wasn't rare.   Even more surprisingly, it is traditionally used to control the foaming of petroleum distillate fuel oils. The initial foam height at the time of stirring by the defoaming additive (hereinafter referred to as petroleum fuel defoaming agent) In the sense of reducing (foam height), It has been found that foaming in the blend can be successfully controlled.   The additive has surface-active properties by itself, and in some way other than fuel blends. It is considered that this inhibits the tendency of the component to stabilize the foam.Disclosure of the invention   Accordingly, the present invention provides, in a first aspect, a high proportion of petroleum-based fuel oil and biofuel. A fuel oil composition is provided that includes a blend with a fuel and a small proportion of a petroleum fuel defoamer. To serve.   The petroleum fuel defoamer useful in this first aspect of the present invention includes silicon-containing and non-silicon-containing antifoam agents. Both compositions are included. When the defoaming agent is a silicon-containing composition, the first aspect Foaming in a blend of, when the blend contains up to 65% by weight of biofuel Furthermore, it has been further found that it can be successfully controlled in the sense of accelerating bubble destruction. Was done.   Therefore, the present invention, in a preferred embodiment of the first aspect, comprises a large proportion of petroleum-based Blends of fuel oils and biofuels, and petroleum fuels with small proportions of silicon-containing compositions A fuel oil composition comprising an antifoaming agent, the fuel oil blend comprising 65% by weight or less of a raw oil composition. A fuel oil composition comprising a solid fuel and 35% by weight or more of a petroleum-based fuel oil. To serve.   When the defoamer is a non-silicon containing composition, a blend of petroleum-based fuel oil and biofuel Foaming in the lend occurs when the blend contains any proportion of biofuel. However, we further see that it can be successfully controlled in the sense of accelerating bubble destruction. Was issued.   Therefore, the present invention further provides, as a second preferred embodiment of the first aspect, a high proportion of stones. Blends of oil-based fuel oils with biofuels, and small proportions of non-silicon containing compositions There is provided a fuel oil composition comprising a petroleum fuel defoamer.   In this second preferred embodiment, the defoamer is preferably one or more first Alternatively, by reaction between a polyamine having a secondary amino group and a carboxylic acylating agent. It is a product that can be obtained. The petroleum-based fuel oil has one of the following characteristics: It is desirable to have three or more: specific gravity at 15 ° C. is 0.835 or less, preferably 0.825 or less, kinematic viscosity at 20 ℃ 3.10mm²Less than / second, IBP is 175 ° C or lower, FBP is 370 ° C or lower, and 90 % To 20% distillation temperature of 125 ° C. (last three characteristics are ASTM (When measured according to D86).   Furthermore, in this second preferred embodiment, the fuel oil blend is 60% by weight or more. It is desirable to include the biofuel of Is desirable.   The invention also provides, in a second aspect, a blend of petroleum-based fuel oil and biofuel. A concentrate comprising a petroleum fuel defoamer mixed with an oil, and in a third aspect, petroleum Petroleum fuels to control foaming in base fuel oil and biofuel blends Provide use of an antifoaming agent.   The present invention will be described in more detail below.BEST MODE FOR CARRYING OUT THE INVENTION Petroleum based fuel oil (In all aspects of the invention)   Petroleum-based fuel oils are middle distillate fuel oils, that is, light kerosene and dihydrogen during crude oil production. Is preferred as the fuel oil obtained as a fraction between the fuel oil fraction and the heavy fuel oil fraction. . The distillate fuel oil generally ranges from about 100 ° C to about 500 ° C (ASTM D-8 6), for example, those having a relatively high final boiling point of 360 ° C. or higher (380 ° C., etc.) Boiling at 150 ° C to about 400 ° C. The fuel oil may be atmospheric distillate oil or vacuum distillate oil, Russo or cracked gas oil or direct distillation oil and distillate oil decomposed by heat and / or catalyst Blends in any proportion may be included. The most common petroleum distillate fuels are kerosene, Jet fuel, diesel fuel, heating oil and heavy fuel oil. The heating oil may be a straight-run atmospheric distillate, or a small amount (eg 35% by weight or less) It may contain vacuum gas oil, cracked gas oil, or both. Heating oil, for example Between virgin distillate such as light oil and naphtha, and cracked distillate such as catalyst cycle stock It may consist of a blend. Minimum flammability for typical diesel fuel specifications point Is 38 ° C and the distillation point is between 282 and 380 ° C (AS See TM designations D-396 and D-975).   The fuel oil may have a sulfur concentration of 1% by weight or less based on the weight of the fuel. Preferably, the sulfur concentration is 0.2% by weight or less, more preferably 0.05% by weight. It is below, and most preferably 0.01% by weight or less. Hydrocarbon intermediate in the literature A method for reducing the sulfur concentration of distillate fuel is described, which includes solvent extraction and sulfuric acid treatment. And hydrodesulfurization.Biofuel (In all aspects of the invention)   Biofuel is one or more oils derived from animal and / or plant material. It can be used as fuel.   Oils derived from animal or vegetable material consist primarily of monocarboxylic acids (eg predominantly 1 Triglyceride of an acid containing 0 to 25 carbon atoms) represented by the following general formula: Metabolites including those (In the formula, R may be saturated or unsaturated, mainly 10 to 25 carbons. Represents an aliphatic group containing an elementary atom. Preferably R contains from 10 to 25 carbon atoms It is an aliphatic group. ) Generally, the oil contains glycerides of many acids, the number and type of which depend on the source of the oil. And may further include phosphoglyceride. The oil is a method known in the art. May be obtained by   Examples of the oil derivatives include alkanes such as methyl esters of plant or animal fatty acids. There is a kill ester. The ester can be produced by transesterification.   Therefore, when referring to oils of animal or plant material origin in this specification, Refers to oils derived from natural or plant materials or both, or their derivatives Including that.   Examples of oils derived from animal or plant material include rapeseed oil, cilantro oil, soybean oil. , Cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn Oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow and There is fish oil. Further examples include corn, jute, sesame, shea nuts and gras. It includes oils derived from und nuts and flaxseed, from which they can be prepared by methods known in the art. Can be obtained. Available in large quantities, the simple squeeze of rapeseed The fat partially esterified with glycerol as obtained by the method. Rapeseed oil, which is a mixture of fatty acids, is preferred. Rapeseed oil is generally around 11 to 19% C₁₆~ C₁₈In addition to saturated acid esters, 23-32% mono-, 40-50% Di- and 4-12% tri-unsaturated C₁₈~ C_{twenty two}Acid, mainly olein, Includes esters of the oleic, linolein and erucic acids.   The lower alkyl esters of fatty acids include the following, for example, commercially available As a mixture, lauric acid, myristic acid, palmitic acid, palmitoleic acid, Stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic acid, linoleic acid, linoleic acid, a 12 such as cosanoic acid, gadoleic acid, behenic acid or erucic acid Ethyl, propyl, butyl and especially methyl of fatty acids having .about.22 carbon atoms Ruester having an iodine value of 50 to 150, particularly 90 to 125 Can be considered. Mixtures with particularly desirable properties have from 16 to 22 carbon atoms and And mainly methyl esters of fatty acids having 1, 2 or 3 double bonds (ie 50% by weight or more). Preferred lower alkyl esters of fatty acids are It is a methyl ester of oleic acid, linoleic acid, linoleic acid and erucic acid.   Commercially available mixtures of the above type may be used, for example, to convert animal and vegetable oils and fats into lower aliphatic It can be obtained by transesterification with bisphenol and cleavage or esterification. Of fatty acids For the production of lower alkyl esters, for example sunflower oil, rapeseed oil, coene High iodine value such as doro oil, castor oil, soybean oil, cottonseed oil, peanut oil or beef tallow It is desirable to start with the fats and oils of. Lower fatty acids based on new rapeseed oil Alkyl esters are preferred.   Most of the above oils can be used as biofuels, but vegetable oils or their derivatives Preferred and particularly preferred biofuels are rapeseed oil, cottonseed oil, soybean oil, sunflower oil, Rapeseed oil, which is olive oil, palm oil, or their alkyl ester derivatives. Is particularly preferred.blend (In all aspects of the invention)   The proportion of biofuel in the blend may range from 0.1 to 99.9% by weight, It is preferably 0.1 to 90% by weight, more preferably 0.5 to 85% by weight. Defoaming When the agent is a silicon-containing composition, the proportion of biofuel is desirably not more than 65% by weight, More preferably, it is 55% by weight or less. When the defoamer is a non-silicon containing composition, The proportion of biofuel is preferably 60% by weight or more, more preferably 65% by weight or more. is there.   One or more petroleum-based fuel oils, or especially two or more biofuels It is within the scope of the invention to mix with other types of fuels and use them as blends. belongs to.   The blend may include additives other than petroleum fuel defoamers. Therefore, low temperature Flow improver, stabilizer, dispersant, antioxidant, corrosion inhibitor, cetane improver, release Emission-reducing agents, fragrances, lubricants, antistatic agents or solutions One or more co-additives such as emulsifiers may be present in the blend. Co-addition of these Agent may be added to the blend at the same time as the petroleum fuel defoamer, eg co-added with defoamer The agent may be a single additive. Alternatively, one or more co-additives may be added to the defoamer. Independently of blending with or prior to blending with petroleum-based fuel oils or biofuels. You may add.Petroleum fuel defoamer (In all aspects of the invention)   The defoamer should be insoluble in the fuel being processed, but it must be mechanically dispersed. With or without a suitable dispersant or solvent, if necessary It can be dispersed in fuel to form a stable dispersion.   As the defoaming agent, the silicon-containing composition can be used as described above. The group The composition is, for example, a block containing siloxane blocks and oxyalkylene blocks. It is desirable to contain a siloxane polymer such as a co-copolymer. Preferably, The siloxane polymer is represented by the following general formula (i). (In the formula, R represents a hydrocarbyl group, n represents an integer in the range of 1 to 3, and m represents 2 The above numbers are shown. The hydrocarbyl group is a relatively monocyclic group having 1 to 30 carbon atoms. It may be a pure hydrocarbyl group or a high molecular weight group. The group represented by R is optionally Identical at specified siloxane groups or throughout the siloxane polymer Can be different or different, and the value of n depends on the various silo in the siloxane polymer. The xane groups may be the same or different. )   Preferred polymers are block copolymers containing two or more blocks , The first block contains a siloxane group represented by the general formula (i), and the second block C includes an oxyalkylene group represented by the following general formula (ii).        (R¹-O) (ii)   The siloxane block and oxyalkylene block are divalent hydrocarbyl groups. (This may be R in general formula (i)) may be bonded to each other. Yo And each siloxane block contains at least one siloxane group represented by the general formula (i). In that case, at least one of the groups represented by R is a divalent hydrocarbyl group.   The hydrocarbyl group represented by R in the general formula (i) is a vinyl group, an allyl group, or the like. Alkenyl group; cycloalkenyl group such as cyclohexenyl group; methyl group, ethyl group Alkyl group such as phenyl group, isopropyl group, octyl group and dodecyl group; phenyl group And aryl groups such as naphthyl groups; aralkyl such as benzyl groups and phenylethyl groups Group; alkaryl group such as styryl group, tolyl group and n-hexylphenyl group; Alternatively, it may be a cycloalkyl group such as a cyclohexyl group.   The divalent hydrocarbyl group represented by R in the general formula (i) is a methylene group or an ethyl group. Ren group, propylene group, butylene group, 2,2-dimethyl-1,3-propylene group And alkylene groups such as decylene group; phenylene group and p, p'-diphenylene group Or an arylene group such as phenylethylene group, etc. . Preferably, the divalent hydrocarbyl group contains 2 to 4 consecutive carbon atoms. A It is a rubylene group.   These divalent hydrocarbyl groups have a siloxane block due to the silicon-carbon bond. Bonded to the silicon atom of the oxyalkylene block by the carbon-oxygen bond. Join the child.   The siloxane block in the copolymer is a siloxane group represented by the general formula (i) May be included, in which case the same hydrocarbyl group is bound to the silicon atom Well (eg dimethylsiloxy group, diphenylsiloxy group and diethylsiloxy group) Si group), different hydrocarbyl groups may be bound to the silicon atom (eg methyl group). Ruphenylsiloxy group, phenylethylmethylsiloxy group and ethylvinylsiloxy group Xy group).   Provided that at least one group has at least one divalent hydrocarbyl substituent. Thus, the siloxane block in the copolymer is represented by one or more general formula (i) Siloxane groups may be included. For illustration purposes only, ethylene methyl Roxy groups may be present in the siloxane block, or the siloxane block It may contain one or more siloxane groups, for example where the block is ethylene methyl. It may contain both a lucyloxy group and a diphenylsiloxy group, or The lock is an ethylenemethylsiloxy group, a diphenylsiloxy group and a diethylsiloxy group. It may contain a cis group.   The siloxane block is a trifunctional siloxane group (for example, monomethylsiloxane). Group, CH₃SiO_1.5) Bifunctional siloxane group (eg, dimethylsiloxane group, (CH³ )₂SiO), monofunctional siloxane groups (eg trimethylsiloxane groups, (CH₂)₃Si O_0.5), Or sets of these types of siloxane groups having the same or different substituents May include a match. Depending on the functionality of the siloxane group, the siloxane block , Which may be exclusively linear or cyclic or crosslinked, or of these structures It may have a combination.   The siloxane block is a monofunctional siloxane chain encompassed by the general formula (i). In addition to chain-terminating groups, organic end-blocking groups or chain-terminating organics It may contain a group. The organic end blocking group is a hydroxyl group; phenoxy Groups such as aryloxy groups; methoxy groups, ethoxy groups, propoxy groups and butoxy groups Base Alkoxy groups such as; and acyloxy groups such as acetoxy groups.   The siloxane block in the copolymer is such that (m represents a number of 2 or more. As such) containing two or more siloxane groups of general formula (i). Preferably, The siloxane block has a total of 5 to 20 siloxanes represented by the general formula (i). Group, in which case m represents a number in the range 5-20. For siloxane block The average molecular weight of the part of the copolymer that may belong may be around 50,000, , Preferably 220 to 20000. Copo that may belong to the siloxane block If the average molecular weight of the limer exceeds 50,000 or if the siloxane block is 2 Copolymers containing more than zero siloxane groups of general formula (i) Is, for example, too high in viscosity to be suitably used in the additive of the present invention. Not useful.   The oxyalkylene blocks in the copolymer each have two or more of the general formula (ii) ( Where R¹Is an alkylene group). Preferred Specifically, 60% by weight or more of the group represented by the general formula (ii) is an oxyethylene group or It is an oxypropylene group.   It is preferably present in the oxyalkylene block in an amount not exceeding 40% by weight. Other oxyalkylene groups represented by the general formula (ii) may be oxy-1. , 4-butylene group, oxy-1,5-amylene group, oxy-2,2-dimethyl- It is a 1,3-propylene group or an oxy-1,10-decylene group.   The oxyalkylene blocks in the copolymer are oxyethylene groups or Oki represented by the general formula (ii) of various kinds including one or more ropylene groups. It may be included together with a sialkylene group. That is, the oxyalkylene block is Oxyethylene group only, or oxypropylene group only, or oxyethylene group Both of the oxypropylene groups, or various types of oxypropylene groups represented by the general formula (ii) Other combinations of sialkylene groups may be included.   The oxyalkylene blocks in the copolymer are organic end-blocking groups or linkages. It may contain a chain-terminating organic group. The terminal blocking group is a hydroxyl group; Aryloxy groups such as enoxy groups; methoxy groups, ethoxy groups, propoxy groups and An alkoxy group such as butoxy group; and an alkyl group such as vinyloxy group and allyloxy group It may be a alkenyloxy group. An oxyalkylene block in which a single group is one or more May be a terminal blocking group of. For example, an oxy group with three glyceroxy groups It may be an end-blocking group of the sialkylene chain.   The oxyalkylene block in the copolymer is represented by two or more general formulas (ii) Oxyalkylene group may be included. Preferably, each block is 4-30 In number. Of copolymers that may belong to the oxyalkylene block The average molecular weight of the part is 176 ((C₂H_FourO)_FourIn the case of) However, it is preferably 176-15000. Each oxyalkylene block has two or more A copolymer obtained by containing an oxyalkylene group represented by the general formula (ii) Is not physically incompatible with oily liquids Number of phenyl groups and the part of the copolymer that may belong to the oxyalkylene block The average molecular weight of is not critical. However, in the oxyalkylene block If the average molecular weight of the part of the copolymer that may belong exceeds 200,000, or Copolymers containing more than 50 oxyalkylene groups per block Is, for example, too high in viscosity to be suitably used in the additive of the present invention. Clearly not useful.   The copolymer has siloxane blocks and oxyalkylene blocks in any phase. It may be included in a relative amount. To have the desired properties, the copolymer is a copolymer 5 to 95 parts by weight of siloxane block and 5 to 100 parts by weight per 100 parts by weight It must contain 95 parts by weight of oxyalkylene block. Preferably Means that the copolymer is from 5 to 50 parts by weight per 100 parts by weight of the copolymer. A roxane block and 50 to 95 parts by weight of an oxyalkylene block. Mu.   The copolymer may include one or more of each block, and the blocks may be linear. It may be arranged in various arrangements, such as a staggered arrangement, an annular arrangement or a branched arrangement.   The most preferable copolymer is represented by the following general formula (iii). (In the formula, p represents an integer of 2 or more, preferably an integer in the range of 4 to 30, and c is 0 to Represents an integer in the range of 2, m represents an integer of 2 or more, R²Is 1-12 carbon atoms A monovalent hydrocarbyl group, preferably a linear group such as a methyl group or an ethyl group. Represents an aliphatic group, R³Is a divalent hydrocarbyl group having 1 to 12 carbon atoms And preferably 2 such as ethylene group, 1,3-propylene group or 1,4-butylene group. Represents an alkenyl group having one or more carbon atoms, R^FourAre the same or different 2 to 10 such as ethylene group, ethylene group, 1,3-propylene group or 1,6-hexylene group Represents a divalent hydrocarbyl group having a carbon atom of^FiveIs 1 to 12 carbon sources Represents a monovalent hydrocarbyl group having a child, or a terminal group such as a hydroxyl group or hydrogen. R^Four Preferably represent different hydrocarbyl groups, most preferably ethylene groups and And a mixture of one or more of each of the 1,3-propylene groups. )   Alkenyl and siloxanes containing hydrogen atoms bonded to silicon in the presence of platinum catalysts By an addition reaction with an oxyalkylene polymer containing a terminal blocking group The block copolymers mentioned may be prepared. In addition, silicon-bonded chloroorgano Of oxyalkylene polymers whose ends are blocked with siloxane containing groups and hydroxyl groups The copolymer may be prepared by a metathesis reaction with an alkali metal salt.   Or as a defoamer, (A) Polyamine of the general formula (iv) (In the formula, A, B and C may be the same or different and each represents a hydrocarbyl group. Where x and y are integers in the range of 0 to 10). When, (B) Carboxylic acid acylating agent Non-silicon containing compositions containing products obtainable by reaction with Yes.   Desirably, the sum of x and y is in the range of 1-10. More preferably, x and y The sum is 8 or less, preferably 6 or less, more preferably 4 or less, It is also preferably 2 or less.   As used herein, the term "hydrocarbyl" refers to the rest of the molecule. A group having a carbon atom directly bound thereto and having hydrocarbon or exclusively hydrocarbon properties Means Of these, aliphatic groups (alkyl or alkenyl, etc.), alicyclic groups (Cycloalkyl or cycloalkenyl, etc.), aromatic group, aliphatic group or alicyclic group Charcoal containing an aromatic group substituted with and an aliphatic group or alicyclic group substituted with an aromatic group It may also mean a hydrogenated group. Desirably, the aliphatic groups are saturated. Not replaced Hydrocarbyl groups are preferred, but if desired they may further substitute hydrocarbyl groups. It may have as a group. The group may also be, for example, keto, halo, hydroxy, nitro. Contains non-hydrocarbon substituents such as cyano, alkoxy, and hydroxyalkyl But their presence does not replace the exclusively hydrocarbon character of the group. That is the condition. If the hydrocarbyl group is substituted, a single (mono) position Substituents are preferred. Examples of substituted hydrocarbyl groups include 2-hydroxyethyl groups, 3 -Hydroxypropyl group, 4-hydroxybutyl group, 2-ketopropyl group, eth A xyethyl group and a propoxypropyl group are included. The group may additionally, or alternatively , The chain or ring to be composed of carbon atoms may contain atoms other than carbon Yes. Suitable heteroatoms include, for example, nitrogen, sulfur and preferably oxygen. Desirably, each hydrocarbyl group has 10 or less, preferably 8 or less, more preferably It preferably contains up to 6 and most preferably up to 4 carbon atoms.   The term "hydrocarbylene" is used as well.   In a preferred embodiment of the non-silicon defoamer, the polyamine reactant is represented by the formula above. Alkylenediamine or polyalkylenepolyamine, where A, B And C are respectively 10 or less, preferably 8 or less, more preferably 6 or less, most preferably It is preferably an alkylene group containing 4 or less carbon atoms. Therefore, in the present invention And preferred polyamine reactants include ethylenediamine, propylenediamine, Simple diamines such as butylene diamine and pentylene diamine; diethylene tria Min, triethylenediamine, tetraethylenepentamine, pentaethylene Xaamine, di (methylethylene) triamine, dibutylenetriamine, trib Polyalkylene polyamines such as ethylene tetraamine and dipentylene hexaamine Are included.   The alkylene group constituting A, B and C may be one or more of the above alkylene groups, if necessary. It may be substituted by a trocarbyl group. In an even more preferred embodiment, A, B, and C are optionally one or more alkyl groups, alkenyl groups, and alkoxy groups. By a hydroxy group or a hydroxyalkyl group (most preferably a hydroxyalkyl group) It is a substituted alkylene group containing from 1 to 3 carbon atoms. As the reactant (a) Most preferred polyamines are ethylenediamine and diethylene. Triamine is included.   Each component of the polyamine reactant is a polyamine represented by the general formula (iv). It may include a mixture of polyamines. Of the mixture, the amine is optionally Alkylenediamines and polyols substituted with one or more hydrocarbyl groups Lucylene polyamine is preferred. More preferred are alkylenediamines and A mixture containing a polyalkylenepolyamine, wherein the alkylene group has 1 to 3 carbon atoms. 1 or more alkyl groups, alkenyl groups, alkoxy groups containing atoms, if necessary Alternatively, it is substituted with a hydroxyalkyl group. Most preferred polyamid Mixture of ethylenediamine and diethylenetriamine .   Carboxylic acylating agents useful as reactant (b) include one or more carboxylic acid acylating agents. Silylated groups, and sufficient hydrocarbyl to give the hydrocarbon solubility in the molecule. Including a radical. Suitable carboxylic acid acylating groups include carboxylic acid groups or derivatives thereof. And having a leaving group, ie a group capable of leaving during the reaction. The carbo Examples of acid derivatives are esters, acid anhydrides and acid chlorides, acid bromides and acid iodides. Acid halides, including other carbohydrates known in the art as acylating agents. The same effect can be obtained by using an acid derivative.   A more preferable carboxylic acylating agent is a monocarboxylic acid represented by the following general formula (v). It is a boric acid acylating agent.         R⁶COX (v) (In the formula, R⁶Represents a hydrocarbyl group, and X represents a leaving group. )   Such preferred acylating agents include naturally-occurring fats. Fatty acids and their derivatives are included. Preferably, the fatty acid or its derivative is 8 to 40, more preferably 10 to 30, even more preferably 12 to 24, most It preferably contains 12 to 18 carbon atoms. In the fatty acid composition, R⁶Is good Preferable is straight chain or branched chain alkyl or alkenyl. Most preferred fat Acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid. Including those selected from the group consisting of, succinic acid and coco fatty acids. Rare, the last four acids or mixtures thereof are most preferred.   The preferred fatty acid composition also comprises a fat having an average carbon number within the preferred range described above. It may include a mixture of fatty acids. Such particularly preferred mixtures include the above-mentioned fats. Mixtures of fatty acids, and coco fatty acid fractions and secanoic acid (iso-C₁₃A mixture of fatty acids) Mixtures of natural origin such as. Mixing naturally occurring fatty acids with other fatty acids The thing is also preferable.   The reaction product may be a mixed composition. Therefore, the product is a simple amide, di- -And higher reaction products of poly-amides, imides and / or amidines The nature of the reactants (a) and (b) and the proportion in which they are used in combination May be included if it is possible to occur. Therefore, according to the present invention The range of possible compositions is best described by the definition of reaction products. Be done.   Suitable reaction conditions for producing the above reaction products include, for example, polyamine acyl It is known in the technical field relating to promotion of chemical conversion. Therefore, the reactants (a) and (b) are Mixing (optionally in combination in the presence of each other co-solvent) reactants or forming Mix enough for the reaction to occur without raising the temperature above the decomposition temperature The reaction may be carried out by heating the material. Suitable temperatures are generally 100 ° C-3 00 ° C, the exact temperature being determined by the nature of the reactants selected. According to the invention Examples of the preparation of the products are U.S. Pat.No. 4,394,135 and EP 147,240. You can find them in the book and see them.   Other types of non-silicon antifoam agents according to the invention include the carboxylic acylating agents (b ) And one or more polyamines (a) represented by the following general formula (vi) There is something you can get. (Wherein A, B and C are as defined above, R⁷And R⁸Are the same or Can be different, R⁷And R⁸Are water, provided they are not hydrogen. It represents an elementary or hydrocarbyl group, and X and y are integers in the sum of 0-10. )   In a preferred embodiment, the polyamine reactant is a terminal N represented by general formula (vi) -Substituted or terminal N, N'-disubstituted polyamines, wherein A, B and C are each 10 Or less, preferably 8 or less, more preferably 6 or less, most preferably 4 or less It is an alkylene group containing the lower carbon atom. Therefore, the polyamine reactant is Tolylenediamine, Propylenediamine, Butylenediamine and Pentylenediamine N-substituted or terminal N, N'-disubstituted derivatives of simple diamines such as amines; and die Tylene triamine, triethylene diamine, tetraethylene pentaamine, pen Taethylene hexaamine, di (methylethylene) triamine, dibutylene tria Polyalkyl compounds such as amine, tributylene tetraamine and dipentylene hexaamine Included are terminal N-substituted or terminal N, N'-disubstituted derivatives of renpolyamines.   In a more preferred embodiment, the R of the polyamine reactant is⁷And R⁸Each independently water Represents an elementary or aliphatic hydrocarbyl group. This aliphatic hydrocarbyl group is preferred Or straight-chain or branched-chain alkyl groups, oxyalkyl groups or hydroxyalkyl groups. It is a ru basis. Most preferably, the group is a hydroxy group such as a 2-hydroxyethyl group. It is a rukyll group.   A particularly preferred amine is R⁷And R⁸One of them is hydrogen. Also hope Preferably, the sum of x and y in the polyamine is 8 or less, preferably 6 or less. Yes, more preferably 4 or less, and most preferably 2 or less.   The polyamine reactant is a polyamine in which each component is a polyamine represented by the above general formula. It may include a mixture of mines. If necessary, one or more amines may be included in the mixture. Terminal N-substituted or terminal N, N'-disubstituted, substituted by the above hydrocarbyl groups Substituted alkylenediamines and terminal N-substituted or terminal N, N'-disubstituted polyalkyls Lene polyamine is preferred. Most preferred are alkylenediamines and polyamines. A mixture containing alkylene polyamine, wherein the alkylene group has 1 to 3 carbon atoms. Including one or more alkyl groups, alkenyl groups, alkoxy groups or It is substituted with a hydroxyalkyl group.   The polyamine reactant also comprises a mixture of polyamines of general formula (iv), It may comprise a combination with a mixture of polyamines of general formula (vi).   The degree of acylation of the polyamine (a) generally depends on the primary amine present in the polyamine. And the number of secondary nitrogens, ie the number of sites that can be acylated, of the reactants (a) and (b) It is defined by the mixing ratio and the reaction time. 1 mole of polyamine and 1 mole The product may be formed by reaction with the above carboxylic acylating agents. Preferably By the reaction of 1 mole of polyamine with 2 moles or more of a carboxylic acylating agent, The product is formed. More preferably, a polyamine is used with a carboxylic acylating agent. Is completely acylated to form the product. In this specification, The term "complete" acylation refers to the addition of all of the polyamines on the polyamine with the addition of the acylating agent (b). Used to define a reaction in which the amino group undergoes a condensation reaction. Therefore, " Under "complete" acylation, what is the exact nature of the condensation reaction with the acylating agent (b)? Regardless, the amino group of each polyamine will release one equivalent of water by the reaction. It   A particularly preferred embodiment of the non-silicon containing defoamer is that the product is of the general formula (iv ) Or 1 mol of the polyamine of (vi) and the monocarboxylic acid acyl of the general formula (v) defined above. 2 mol This is the case where it can be obtained by the reaction between the above and. The product is It can be obtained by completely acylating a lyamine with the above-mentioned acylating agent. The case is most desirable.   For all aspects of the invention, the concentration of antifoam agent in the fuel oil composition is determined by the weight of the fuel oil. The weight ratio to the amount may be, for example, in the range of 0.1 to 10,000 ppm, Preferably 0.5-5,000 ppm, most preferably 1-100 ppm (effective Ingredient). A particularly desirable concentration is in the range of 1 to 20 ppm.Concentrate   Concentrates are a convenient means of adding antifoam agents to bulk fuel oils. The addition is Any method known in the art may be used. Concentrates may also be prepared as described above, if desired. The co-additive is preferably added as an oil solution, preferably 3 to 75% by weight of the additive. May preferably comprise 3 to 60% by weight, most preferably 10 to 50% by weight. . Examples of carrier liquids are petroleum oils such as naphtha, kerosene, diesel oil and heating oil. Organic solvents containing hydrocarbon solvents such as fractions; sold under the trademark "Solvesso" Aromatic hydrocarbons such as aromatic fractions such as; and hexane, pentane, and And paraffin hydrocarbons such as isoparaffin. The carrier liquid is, of course, Nonetheless, it should be selected in view of compatibility with additives and fuel blends. Book With respect to a second aspect of the invention, the fuel batch of the bulk fuel blend to which the concentrate should be added. Lend is preferred as the carrier liquid.   Add antifoam agents to bulk fuel blends by other methods known in the art. Good. The co-additive may be added to the bulk fuel blend at the same time as the defoamer or at a different time. .   The invention is described below by way of example only for illustration.Example Fuel used in the examples   Two petroleum-based fuel oils and biofuels having the properties shown in Table 1 are described in the book below. Used in the examples of the invention. Both fuel oil is diesel fuel, while raw fuel The fuel used was rapeseed oil methyl ester. Examples of antifoam agents useful in the present invention (I) Non-silicon containing compositionExample 1   Dissolve oleic acid (282g, 1.0mol) in toluene (250ml) I understand. Diethylenetriamine (DETA) (34.3 g, 0.33 mol) Dissolve in ruene (100 ml) and add a slight stoichiometric excess of DETA Used to ensure sufficient acylation of all amino groups. Amine solution Slowly added to the stirred acid solution over 1 hour. An exotherm occurs during the addition The reaction temperature rose to 13 ° C. After the amine addition is complete, the reaction mixture is Heat and reflux for 7 hours 45 minutes. Dean Stark trap during the reflux Water (17 ml, theoretical 18 ml) was collected at. After reflux Toluene was removed by distilling the reaction mixture at a pot temperature of 150 ° C. It was A vacuum of 500 mm Hg was applied to remove the last traces of solvent from the product. .   The resulting product was a waxy solid. The IR spectrum of the product is olein There was no evidence of acid (peak at frequency 1711). However Consistent with formation of secondary and tertiary amine groups, ie acylation was virtually complete There were peaks at frequencies 1665 and 1590 that ran.Examples 2 and 3   Using similar reaction conditions, the fully acylated reaction products shown in Table 2 below are produced. I made it. Examples 4 and 5   As shown in Table 3, 1 mol of diethylenetriamine and 2 mol of monocarboxylic acid The reaction scheme used for the synthesis of Examples 1-3 above in the reaction with an acylating agent. Reaction conditions similar to the above were adopted.   In each of the examples, the main product is represented by the following general formula. It was In this case the acylating agent (b) corresponds to RCOOH, ie It is a completely acylated product in the sense of the specification, and it is a polyacylated product with the addition of the acylating agent (b). All amino groups of the min undergo a reaction, releasing 3 mol of water per mol of DETA .Examples 6-14   Adopting reaction conditions similar to those used for the synthesis of Examples 1-3, The products shown in Table 4 below were produced.   In each example, 1 mole of polyamine was added in excess of 2 moles of acyl. Reacted with agent. (Ii) Silicon-containing composition The defoaming agent A contains a siloxane block and an oxyalkylene block, and It is a block copolymer possessed by the applicant which falls under the general classification. Antifoam A is , Is commercially available for the treatment of middle distillate fuel oils.Examples of the present invention   The fuel oil composition defined in Table 5 was prepared using a WARING blender. It was prepared by the laboratory blending method. Between biofuels and petroleum-based fuel oils The foaming degree of each blend was determined by adding the defoaming agent or defoaming agent A of Example 4 Hand-wash and dry 100 ml of test fuel oil in a 4 ounce bottle. Using a test procedure that involves stirring and then allowing the bottle to rest on a stable, flat surface. It was measured. The bubbles generated by shaking are sufficient to reveal a clear surface of the liquid surface. Record the length of time (in seconds) until it is destroyed to a certain degree as one measurement of the degree of foaming. It was The longer the foam breaking time, the higher the foam stability.   As shown in the results in Table 5, the non-silicon-containing defoaming agent was used for all fuel oil A-containing antifoam agents. Blends and odors containing Fuel Oil B and 60 wt% or more biofuel The foam breaking time was significantly shortened.   The silicon-containing defoaming agent is used for all oils containing fuel oil A and biofuel up to 60% by weight. Lend, and for all blends containing Fuel Oil B and up to 70 wt% biofuel The foam breaking time was significantly shortened. These results show that silicon-containing defoamers are generally Is effective in fuel oil blends containing up to about 65% biofuel by weight. Suggest.   The degree of foaming of each blend in Table 5 was further measured according to the initial foam height obtained by shaking. Measured. In Table 5, the foam heights of the fuel oil compositions containing antifoaming agents are Shown as a percentage of foam height for the treated blend (in brackets).   From the results of blended foam height, the initial foam height was generally higher with the addition of petroleum fuel defoamer. It was shown that

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Claims (1)

[Claims] 1. A fuel oil composition comprising a major proportion of a petroleum-based fuel oil blended with a biofuel, and a minor proportion of a petroleum fuel defoamer. 2. The composition of claim 1, wherein the defoamer is a silicon-containing composition. 3. The composition of claim 2, wherein the silicon-containing composition contains a block copolymer containing siloxane blocks and oxyalkylene blocks. 4. 4. The composition of claim 2 or 3, wherein the fuel oil blend comprises up to 65 wt% biofuel and up to 35 wt% petroleum-based fuel oil. 5. The composition of claim 1, wherein the defoamer is a non-silicon containing composition. 6. The composition according to claim 7, wherein the antifoaming agent is a product obtainable by a reaction between a polyamine having one or more primary or secondary amino groups and a carboxylic acylating agent. 7. The reaction product is a) a polyamine of the general formula (iv) And b) a monocarboxylic acid acylating agent of the general formula (v) R ⁶ COX (v) (wherein A, B and C may be the same or different and each represents a hydrocarbylene group, and R ⁶ is Represents a hydrocarbyl group, X is a leaving group, and x and y are those whose sum is an integer in the range of 0 to 10). . 8. 8. The composition of claim 7, wherein the reaction product is obtainable by reaction between 1 mole of polyamine and 2 moles or more of a monocarboxylic acylating agent. 9. The composition according to claim 7, wherein the reaction product is obtainable by complete acylation of a polyamine with a monocarboxylic acid acylating agent. Ten. Said product can be obtained by reaction between a polyalkylene polyamine and a monocarboxylic acid acylating agent selected from the group consisting of stearic acid, oleic acid, secanoic acid and coco fatty acid fractions, or mixtures thereof. The composition according to any one of claims 7 to 9. 11. 11. The composition of claim 10, wherein the product is obtainable by the reaction between diethylenetriamine and stearic acid. 12. 12. The composition of any one of claims 5-11, wherein the fuel oil blend comprises 60 wt% or more biofuel. 13. 13. The composition of claim 12, wherein the fuel oil blend comprises 65% or more biofuel by weight. 14. 14. The composition according to any one of claims 1 to 13, wherein the biofuel is a methyl ester of rapeseed oil. 15. 15. The composition of any one of claims 1-14, wherein the petroleum-based fuel oil is a middle distillate of petroleum. 16. The composition according to any one of claims 1 to 15, which comprises 0.5 to 5000 ppm by weight of an antifoaming agent. 17. A concentrate comprising a petroleum fuel defoamer mixed with a blend of petroleum-based fuel oil and biofuel. 18. The use of petroleum fuel defoamers to control foaming in blends of petroleum-based fuel oils and biofuels.