MXPA99004040A - Heavy oils with improved properties and an additive for the same - Google Patents

Abstract

The additive described consists essentially of a selected oxalkylated fatty amine or fatty amine derivative and a special mineral salt compound, preferably a metal soap. Said additive for heavy oils produces good emulsification and dispersion of asphaltenes and other high molecular compounds thereby resulting inter alia in increased storage stability, improved pumpability due to reduced viscosity of the oil and longer operational life of the filter systems. Further, said additive produces better combustion of heavy oils. The effective additive quantity for said oils amounts to 2 to 2,000 ppm. The oilsdescribed are specially adequate to be used as fuel for industrial installations and power stations and as fuel for boat motors.

Description

HEAVY OILS THAT HAVE IMPROVED PROPERTIES AND AN ADDITIVE TO THEMSELVES DESCRIPTIVE MEMORY The invention relates to an additive for improving the properties of heavy oils and heavy oils and heavy oils containing this additive. Heavy oils are obtained in the processing of petroleum types (crude oils) and are residues of processing operations such as distillation and atmospheric pressure or reduced pressure, thermal or catalytic cracking and the like. From the chemical point of view, these residual furnace fuels or residual machinery fuels (oils from C ships) essentially include paraffinic, naphthenic and aromatic hydrocarbons, some of high molecular weight. The high molecular weight components, also called asphaltenes, are not present in dissolved form, but in a more or less dispersed form, which increases to numerous problems. In this way, asphaltenes and otherwise poorly soluble or insoluble compounds (eg, oxygen compounds, nitrogen compounds and sulfur compounds) and aging products, in the absence of effective dispersants, are separated from the oily phase, forming an extremely undesirable two-phase system. In addition, in the presence of water, or even only moisture, mud formation can occur. All these compounds and higher molecular weight contents in the heavy oil also adversely affect the combustion process of the oil, for example due to the intense soot formation. Heavy oils, particularly in the form of heavy fuel oils (marine fuel oils) and mixtures of heavy fuel oils and heavy distillates (interfuel oils) are used in large quantities, mainly as kiln fuel in industrial plants and stations of energy and as a fuel of machinery for relatively low combustion internal combustion engines, in particular marine machines. Therefore, numerous proposals have already been made in the prior art for additives which aim to exclude the most beneficial properties described from heavy oils of furnace fuel and machinery fuel oils, i.e., in particular the formation of two phases by asphaltenes and other fractions of higher molecular weight, mud formation and deterioration of combustion. Thus, FR-A-2 172 797 describes basic iron salts of organic acids and FR-A-2 632 966 describes a mixture of iron hydroxide and a basic calcium soap as auxiliaries to increase combustion of heavy oils. US-A-4 129 589 recommends highly basic and oil-soluble magnesium salts of sulfonic acids as oil additives. The most recent publication EP-A-476 196 describes, as an oil additive, a mixture comprising essentially (1) at least one oil soluble manganese carbonyl compound, (2) at least one neutral salt soluble in oil or basic alkali metal or alkaline earth metal or an organic oil component; and (3) at least one oil soluble dispersant selected from the group consisting of succinimides. In addition, US-A-5 421 993, which discloses alkoxylated fatty amines and fatty amine derivatives as corrosion inhibitors, demulsifiers and substances for reducing the thawing temperature for crude oils, should be mentioned. It has now been found that the combination of alkoxylated fatty amine compounds and organic metal salts is a particularly effective additive for heavy oils, in particular with respect to emulsifying and / or dispersing asphaltenes, mud and the like and also with respect to an improvement in the combustion of oil. The additive according to the invention essentially includes: a) 1 to 99% by weight, preferably 20 to 80% by weight, and in particular 40 to 60% by weight, of at least one amine compound of the formula (1) ) following: where n is 1, 2, 3 or 4, A is a radical of formulas (II) to (V) R / RN (~) (i) (ll) R n = 2 n = 1 wherein R is a Cß to C22 alquilo alkyl, preferably a Cß to C-i alquilo alkyl and m is 2, 3 or 4, preferably 2 or 3, x is a number from 5 to 120, preferably from 10 to 80, R1 is H, CH3 or H and CH3, wherein the oxyalkylene radicals are arranged randomly or in blocks, and b) 1 to 99% by weight, preferably 20 to 80% by weight, and in particular 40 to 60% by weight, of at least one oil soluble or neutral oil-dispersible or basic metal salt compound containing a metal of the first major group of the Periodic Table of the Elements, the second major group, the first subgroup, the second subgroup, or the fourth subgroup, of the sixth subgroup, of the eighth subgroup or of the group of the lanthanides (rare earth metals) of the Periodic Table of the Elements and a carboxylic acid, sulfonic acid, phosphoric acid ester or sulfuric acid ester containing a radical hydrocarbon in each case from 8 to 40 carbon atoms, p preferably 12 to 30 carbon atoms, as an acid component, the weight percentages are based on the additive. The component a) of the additives according to the invention is an amine compound according to the formula (I). These alkoxylated fatty amines and fatty amine derivatives are prepared by conventional alkoxylation methods, by reacting an amine in accordance with radical A in formula (I) with one mole of ethylene oxide alone (R1 is H and the radical of polyoxyalkylene includes units of ethylene oxide) or with one mole of x of propylene oxide alone (R1 is CH3 and polyoxyalkylene radical includes propylene oxide units) or with one mole of x of ethylene oxide and propylene oxide simultaneously or in succession (R1 is H and CH3 and the polyoxyalkylene radical includes ethylene oxide and propylene oxide units which are present in a random or block distribution). The reaction is generally carried out at a temperature of 100 to 180 ° C in the presence or absence of an alkaline catalyst or acid alkoxylation in the absence of air. The preferred amine compounds as component a) correspond to the following formula (IV): O) b- (CH2CH2?) C-H (VI) wherein n is 1, 2, 3 or 4, A is a radical of the formulas specified above (II) to (V), a is a number from 5 to 30, preferably 8 to 20, b is a number of 5 to 50, preferably 10 to 30, and c is a number from 0 to 40, preferably 0 to 20. The amine compounds of formula (VI) and their preparation are described extensively in US-A-5 421 993 mentioned at the beginning. , which is incorporated herein by reference. They are obtained by alkoxylation of amines of the specific formula (II) to (V), initially with ethylene oxide and subsequently with propylene oxide, with the addition of bases such as alkali metal hydroxides. The reaction is carried out in stages at a temperature of preferably 100 to 160 ° C. The amount of catalyst / base used is generally 0.5 to 3.0% by weight, based on the initial amine used. The molar amount of ethylene oxide and propylene oxide per mole of initial amine corresponds to the specific values of a and b and the values of c. In detail, reference is made to said document US-A-5 421 993. The following summary gives examples of suitable amine compounds (ai to aß) according to formula (I) as component a): TABLE 1 Preferred metals in the metal salt compounds of component b) are alkali metals or alkaline earth metals (first and second major group of the Periodic Table of the Elements), copper or silver (first subgroup), zinc or cadmium (second subgroup) ), titanium or zirconium (fourth subgroup), molidebno, chromium or tunsgteno (sixth subgroup), iron, cobalt or nickel (eighth subgroup) and lanthanium cerium or ytterbium (from the lanthanide group). Particularly preferred metals are alkaline earth metals, such as barium, beryllium, calcium or magnesium, copper, zinc, zirconium, molybdenum, iron, nickel, cerium or ytterbium. Preferred acids in the metal salt compound of component b) are aliphatic carboxylic acids having from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms. The aliphatic radical can be branched or unbranched, saturated or unsaturated. The aliphatic carboxylic acids are preferably fatty acids having from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms. The aliphatic carboxylic acids and fatty acids may be of the synthetic or natural type, and may be present as such or as a mixture of two or more acids. Examples which may be mentioned are octanoic acid (caprylic acid), decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadenoic acid, (stearic acid), ecoxanoic acid ( arachidic acid), docosanoic acid (behenic acid), dodecenoic acid (lauroleic acid), tetradecenoic acid (myristoleic acid), hexadecenoic acid (palmitoleic acid), octadecenoic acid (oleic acid), 12-hydroxyoctadecenoic acid (ricinoleic acid), octadecadienoic acid ( linoleic acid), and ocadecatrienoic acid (linoleic acid), as well as coconut fatty acid, tallow fatty acid, palm kernel fatty acid and the like. In addition to said (simple) fatty acids, dimer fatty acids are also preferred acidic components. These dimeric fatty acids correspond to the formula (VII) HOOC-R2-COOH (VII) in which R2 is a divalent hydrocarbon radical having 34 carbon atoms (R2 is therefore the radical containing 34 carbon atoms and is formed in the dimerization of an unsaturated fatty acid containing 18 carbon atoms to give a dicarboxylic acid having a total of 36 carbon atoms). As is known, they are prepared by dimerizing unsaturated fatty acids of C-is, for example oleic acid, linoleic acid, linolenic acid or tallow fatty acid (dimerization is understood to combine two identical molecules to form a new molecule, the dimer, per addition reaction). The fatty acids of C-? 8 are generally dimerized at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst. The resulting dicarboxylic acid (which is dimeric fatty acid) corresponds to the formula VII given, when R2 is the divalent connecting member that is formed in the dimerization of the fatty acid of Ci8, they hold the two -COOH groups and have 34 carbon atoms. carbon. R 2 is preferably an acyclic (aliphatic) radical or monocyclic or bicyclic (cycloaliphatic) radical having 34 carbon atoms. In general, the acyclic radical is a branched alkyl radical (substituted) and mono unsaturated to saturated tri- no having 34 carbon atoms. Generally, the cycloaliphatic radical likewise has from 1 to 3 double bonds. The preferred dimer fatty acids described are generally a mixture of two or more dicarboxylic acids of formula VII having structurally different radicals R 2. The dicarboxylic acid mixture frequently has a higher or lower content of trimeric fatty acids, which were formed in the dimerization and were not removed in the treatment of the product by distillation. Similar mixtures are obtained from natural products, for example, in the production of pine extract rosin. Subsequently, some dimeric fatty acids can be specified as formulas, in which the hydrocarbon radical that supports the two -COOH groups is an acyclic, monocyclic or bicyclic radical: CH 3 (CH 2) 8'CH- (CH 2) 7"COOH CH 3 (CH 2) 7-CH = C (CH 2) 7" COOH CH3 (CH2) 5-CH-CH-CH = CH- (CH2) 7-COOH / CH3 (CH2) 5"CH CH- (CH2) 7" COOH \ / CH =CHOH COOH (CH2) 8 (CH2) ) 7 CH (CH2) 8-C? H CH CH (CH2D8-COOH) / \ / CH CH / \ / \ / CH CH CH CH CH CH CH CH \ / \ CH CH = CH- (CH2) 4CH3 CH3 (CH2) x4 x CH \ C / H / (CH2) 4 (CH2) 4 CH3 CH3 The dimer fatty acids described are commercially available under the name "dimerized fatty acids", or "dimeric fatty acids" and, as mentioned above, may have a higher or lower content of trimerized fatty acids. Preferred acids in the metal salt compound of component b) are, in addition, aliphatic or aromatic sulfonic acids having from 8 to 40 carbon atoms, preferably from 12 to 30 atoms, in the aliphatic or aromatic radical. Here also, the aliphatic radical can be branched or unbranched, saturated or unsaturated. The aromatic sulfonic acid is preferably a benzene sulfonic acid having an alkyl or alkenyl radical containing from 12 to 30 carbon atoms. Among these representatives, metal soaps are particularly preferred as component b). The organic metal salt to be used according to the invention as component b) can be prepared by the methods described in the prior art. The reference made in this case in particular to the publications mentioned at the beginning. FR-A-2 172 797, FR-A-2 632 966, US-A-4 129 589 and EP-A-476 196, which are incorporated herein by reference. The organic metal salts to be used according to the invention should be oil-soluble or at least oil-dispersible. In addition, these refer to neutral or basic product. The last one is the preferred one. The term "basic", as it is known, describes the metal salts in which the metal is present in a stoichiometric amount higher than the organic acid radical. The basic metal salt products which will be used according to the invention, therefore have a pH of generally 7.5 to 12, preferably from 8 to 10. The additive according to the invention is prepared by mixing the components together a) and b) with or without the use of a solvent or dispersion medium. Suitable dispersion solvent means of this type are lower or higher alcohols such as ethanol, and isopropanol, butanol, decanol, dodecanol and the like, lower or higher glycols and their monoalkyl or dialkyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, tetrapropylene glycol. and the like, boiling hydrocarbons lower than aliphatic, aromatic or cycloaliphatic mediums such as toluene, xylene, naphtha and the like, light to medium-heavy mineral oils, oil distillates, natural or synthetic oils and derivatives thereof and mixtures of two or more of these solvents. The two compounds, composed of amine and metal salt compound, generally bind at an atmospheric pressure and at a temperature of 15 to 100 ° C, preferably 20 to 70 ° C. The heavy oils according to the invention have a content of the described additive. The active amount of the additive in the heavy oil can vary within wide limits. Generally, the oil contains from 2 to 2000 ppm of additive, preferably 100 to 1000 ppm. The additive according to the invention and the heavy oils containing this additive have a property profile which is particularly desired and this is mainly due to the high unexpected synergy of the combination according to the invention of components a) and b) . In this way, the additive is present in the oil in dissolved or highly dispersed form. Even in oils having a high content of asphaltene and / or other higher molecular weight compounds, all those insoluble fractions are highly emulsified or dispersed. The same also applies in the case of sludge, so sludge formation is significantly excluded or at least greatly reduced. further, the additive according to the invention is a highly effective combustion enhancer. This ensures the complete combustion of heavy oils with the simultaneous reduction in soot formation. Therefore, heavy oils according to the invention meet a surprisingly higher degree with the requirements mentioned at the beginning. As a result of said actions, the additive according to the invention leads to the oils which, in addition, also have in particular the following advantageous properties: an improved storage stability (reduced sedimentation of insoluble constituents), improves the ability to pump due to their low viscosity, longer operating life of the filter system, improved injection behavior in combustion devices, which additionally contribute to optimizing combustion and increased protection against corrosion for all devices due to the high inhibition of corrosion by the additive. The heavy oils according to the invention are therefore mainly used as kiln fuel for industrial plants and power stations and likewise for marine machinery machinery fuel. The invention is now described in more detail by means of examples and comparison examples. Component a) of the additive according to the invention: As component a), the use is made of the compounds ai, a3 and a5 of Table 1. Component b) of the additive according to the invention: As component b), the use it is made of the bi and b2 products described in more detail later. Bi Product: The fatty acid used to prepare bi product is a distilled fatty acid consisting of a mixture of high distillate oil fatty acid and resin acid having a molecular weight of about 300 g / mol. Lot: FeCI3 0.85 1 density 1.48 g / cm3 NH3 0.785 1 density 0.91 g / cm3 Fatty acid 0.22 1 density 0.94 g / cm3 Water 0.20 1 Petroleum distillate 0.80 1 density 0.82 g / cm3 0.85 1 of FeC, 0.22 1 of fatty acid, 0.20 1 of water and 0.80 1 of petroleum distillation at room temperature (15 to 30 ° C).

The 0.785 1 NH is slowly introduced (exothermic reaction) into this mixture while stirring. The mixture is heated with stirring at 80 to 90 ° C, giving an aqueous phase and an organic phase. The phase formation can be completed by adding more petroleum distillate. The two phases are separated one from the other (decanted), where the organic phase is centrifuged further to separate the residual water. The organic phase contains the desired iron carboxylate compound. Product b2: The fatty acid used to prepare product b2 is an alkylbenzenesulfonic acid having a molecular weight of about 322 g / mol. Lot: FeCI3 44 ml density 1.48 g / cm NH3 34 ml density 0.91 g / cm Acid 13 ml density 1.06 g / cm3 Water 16 Distillate of 84 density 0.82 g / cpr oil The product b2, an iron alkylbenzene sulfonate, is prepared in a similar to the product bi. Additives according to the invention: EXAMPLE 1 a) 40% by weight of compound a- b) 60% by weight of the organic iron salt in accordance with the bi-product EXAMPLE 2 a) 60% by weight of compound a3 b) 40% by weight of the organic iron salt in accordance with the product b2 EXAMPLE 3 a) 50% by weight of compound as b) 50% by weight of the organic iron salt according to the bi-product The additives according to the invention of examples 1 to 3 are prepared by mixing components a) and b together ) (mix temperature from about 20 to about 60 ° C). In accordance with a preferred process, component a) is first introduced and heated to about 40 to 50 ° C under stirring and under a nitrogen atmosphere. Component b) is subsequently stirred at said temperature under a nitrogen atmosphere, where the additive according to the invention is prepared. If the mixture is cooled to room temperature it does not have the desired viscosity and / or the separation phase is observed; this phenomenon can be eliminated by adding an effective amount of an organic solvent such as petroleum distillate. Testing of the additives according to the invention: The additives of examples 1 to 3 are tested with respect to the dispersibility of asphaltene and the increase of combustibility in heavy oils. For the asphaltene dispersibility test, a solution containing asphaltene is first prepared. - Preparation of a solution of asphaltenes in toluenes: To prepare this solution, a residual oil containing asphaltenes is subjected to an extraction that, in detail, is carried out in the following manner. In a first step, approximately 30 g of residual oil is mixed in a glass vessel with approximately 300 ml of ethyl acetate. The mixture is stirred for two hours at 40 ° C and subsequently allowed to stand for 24 hours, where it is filtered through a simple pore filter. In the second step, the filter residue is placed inside a common extraction cup for Soxhiet extraction and extracted for approximately two hours using again approximately 300 ml of ethyl acetate, the paraffin fraction in the filter layer passes within the ethyl acetate phase. In a third step, the resin fractions are dissolved in another way by Soxhiet extraction using approximately 300 ml of pentane. In a fourth step, the asphaltenes are subsequently extracted using approximately 300 ml of toluene, which produces the desired solution of asphaltenes in toluene. - Test of additive according to the invention in asphaltene dispersibility: This test is carried out in accordance with standards ISO 10307-1: 1993 ASTM D4370-32 (hot filtration). For this, 30 g of concentration to almost 10% by weight of asphaltene solution in toluene is first mixed with 100 ppm of pentane. 700 ppm of additive of each of the examples 1, 2 and 3 and are stirred separately in three of said solutions asphaltene-toluene / pentane at room temperature. These three test solutions are subsequently treated in accordance with these standards.

Result: the additives according to the invention comply with the test. - Testing of the additives according to the invention to increase the combustibility of heavy oils: This test is carried out in accordance with the indications of VID 2066, part 1 (VDI is Verein deustscher Ingenieure [Association de German Engineers], the additives of Examples 1, 2 and 3 are used in an amount of 500 ppm, 700 ppm, and 900 ppm. Result: the additives according to the invention comply with the test.

EXAMPLES OF COMPARISON 1 TO 3 In comparison examples 1 to 3, the compounds a-i, a3 and bi are each used individually. The three test solutions are subjected to the same test methods as the examples according to the invention. Result: none of the test solutions comply with the asphaltene dispersibility test or the combustibility increase. The additives according to the invention therefore have a high unexpected efficiency with respect to the dispersion of asphaltenes in heavy oils and also with respect to the combustion of heavy oils; this could result from a surprisingly high synergy of the components of additive a) and b). Due to the advantageous actions of the new additive, the oils according to the invention also have especially those properties which are particularly desired for use in industrial plants, power stations and marine heavy machinery.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - The use of an additive that essentially includes a) from 1 to 99% by weight of at least one amine compound of the following formula I: wherein n is 1, 2, 3 or 4; A is a radical of the formulas (II) to (V) n = 2 n = 1 wherein R is a C6 to C22 alkyl, preferably a C6 to C2 alkyl, and m is 2, 3 or 4, preferably 2 or 3; x is a number from 5 to 120, preferably from 10 to 80; R1 is H, CH3 or H and CH3, wherein the oxyalkylene radicals are arranged randomly or in blocks, and b) from 1 to 99% by weight of at least one salt compound soluble in oil or neutral dispersible in oil or metal basic metal containing the first main group of the Periodic Table of the Elements, the second main group, the first subgroup, the second subgroup, or the fourth subgroup, the sixth subgroup, the eighth subgroup or the lanthanide group (metals rare earths) of the Periodic Table of the Elements and a carboxylic acid, sulfonic acid, phosphoric acid ester or sulfuric acid ester containing a hydrocarbon radical in each case from 8 to 40 carbon atoms as the acid component, Weight percentages are based on the additive, as an emulsifier and dispersant and as a combustion enhancer for heavy oils.

2. The use according to claim 1, wherein the component (a) is an amine compound of the following formula (VI): A- (CH2CH20) a- (CH2CHO) b- (CH2CH2?) C-H (VI) CH3 n wherein n is 1, 2, 3 or 4; A is a radical of the formulas specified above (II) to (V); a is a number from 5 to 30, preferably 8 to 20; b is a number from 5 to 50, preferably 10 to 30 and c is a number from 0 to 40.

3. The additive according to claim 1 or 2, further characterized in that component b) is a metal salt compound. containing a metal selected from the group consisting of alkali metals, alkaline earth metals, copper, silver, zinc, cadmium, titanium, zirconium, molybdenum, chromium, tungsten, iron, cobalt, nickel, lanthanum, cerium and ytterbium and containing an acid selected from the group consisting of aliphatic carboxylic acids having from 8 to 40 carbon atoms, dimer fatty acids having 36 carbon atoms and aliphatic or aromatic sulfonic acids having from 8 to 40 carbon atoms.

4. The use according to claim 1 or 2, wherein the component (b) is a metal salt compound, the metal is an alkaline earth metal, copper, zinc, zirconium, molybdenum, iron, nickel, cerium and ytterbium, and the acid component is a fatty acid having from 8 to 40 carbon atoms, a dimeric fatty acid having 36 carbon atoms or an aliphatic or aromatic sulfonic acid having from 8 to 40 carbon atoms. ^ ~ 5.- The use in accordance with one or more of the claims 1 to 4, where it contains from 20 to 80% by weight of component a) and 20 to 80% by weight of component b). 6. The use in accordance with one or more of the claims 1 to 4, where it contains from 40 to 60% by weight of component a) and 40 to 60% by weight of component b). 7. Use according to one or more of the claims 1 or 6, where it has a pH of 7.5 to 12. 8. The use of the additive according to one or more of claims 1 to 7 in industrial plants, power stations or marine machineries.