SA98180885B1 - Heavy oils with improved properties and an additive - Google Patents

Abstract

power and as a motor fuel for use in marine engines. Abstract: The invention relates to an additive comprising essentially a selected alkoxylated fatty amine or a fatty amine derivative and a special mineral salt compound, preferably a mineral soap. This heavy oil additive emulsifies or disperses well asphaltene and other high molecular weight compounds, and in addition, among other things, gives increased stability, improved pumpability due to lower viscosity of the oil, and extended service lives of filtration systems. In addition, it creates an improved combustion of heavy oils because the effective amount of additive in these oils ranges from 2 to 2000 ppm. The described oils are particularly suitable as furnace fuels in industrial units and power stations

Description

Y — _— ALES oils have improved properties and additive Full Description

background of the invention

The invention relates to an additive to improve the properties of cheavy oils and to heavy oils that are

sale contains this additive.

Heavy oils are obtained when processing petroleum (crude oils) and are oo residues of processing processes such as distillation and cracking at atmospheric pressure or at low pressure;

thermal or catalytic and the like. From a chemical point of view; Including furnace fuels

This residual or residual motor fuels (dirty oils) are primarily C

paraffinic hydrocarbons; And naphthenic and aromatic

aromatic; Some are of high molecular weight. High molecular weight components are not present;

0 also called asphaltenes ¢ in dissolved form; But in a dispersed form ly i which causes many problems. “lll the asphaltenes and other similar compounds (Aiea soluble or insoluble (Je) for example oxygen compounds, nitrogen compounds, sulfur compounds and aging compounds; in the absence of effective dispersants separated from the oil phase, forming a highly undesirable two-phase system.

1 in the presence of water; or even just moisture; can additionally; slag formation to occur. All of these compounds have Alle molecular weight and contents found in heavy oil; effect

last

Cro in addition; adversely affects the oil combustion process; For example, as a result of the intense build-up of soot and heavy oils; particularly in the form of heavy fuel oils (marine fuel oils) and mixtures of heavy fuel oils and heavy distillates (internal fuel oils); It is used in large quantities; primarily as furnace fuel in industrial units and power stations, and as engine fuel for relatively slow-burning internal combustion engines, especially marine engines. Therefore; In the previous art; Numerous proposals have already been made for additives intended to eliminate the non-described properties of heavy furnace fuel oils and motor fuel oils; This means; as AD and other high molecular weight fractions; especially asphaltenes; Formation of two phases by asphaltines, slag formation and poor combustion. 0 French patent No. 71779791 describes basic iron salts of organic acids and coll and calcium iron hydroxide soap French patent No. 1716779773 describes a mixture of basic iron hydroxide as additional materials to improve the combustion of oils heavy. Highly basic, oil-soluble calcium soap, US Patent No. 7985841; Magnesium salts are very in demand A fad as additives to oil. The leaflet describes the sulfonic acids vo carbonyl compound (1) comprising mainly: Unda European 71197 as an oil additive; or alkali metal salt (1) and 0 At least one carbonyl manganese soluble manganese JE At least one neutral or basic alkaline earth metal salt at least one oil-soluble dispersion Selected (Y) 5 in oil for constituent an organic acid; in addition to this, succinimides may also be mentioned from the group consisting of succinimides © Damm

— $ —

US Patent No. 0471947; which describes g fatty amines and fatty amine derivatives treated with alkoxy group 0 as corrosion inhibitors ¢ and as cdemulsifiers and pour point depressants for crude oils.

© It has now been found that a combination of alkoxylated fatty amine compounds and organic mineral salts is a particularly effective addition to heavy oils. In particular, Lad is concerned with emulsifying and/or dispersing asphaltenes, sludge and the like, and also with regard to improving oil combustion.

0 General description of the invention The sale addition according to the invention mainly includes:

(a) .1 to 789 by weight; 01 to ZA is preferred by weight; particularly from 0 to #70 by weight; of at least one amine compound of formula (1) below (0) [1-(010RT-)mer 1 R Ve and of which n is 1 or 1 or of Ps AYo

Q -— —- and it is a split in formats 01 to MV) (I / R—N \ n=2 (un) R \ N— / R n=1 07 R—N—(CHy) J NT 2)m —- \ n=3 0 (CHp) J 2)m es \ / \ 8 c020 \ n=4 R Cua be alkyl der,©-m© ¢ preferably alkyl cm + and “be? Or et JF preferably? or oF x be a number from © to 001 preferably from 01 to Av 0 and lg be 1 or “CH; or 11”CH where the oxyalkylene moieties are The blocks JS J 5f Lil pe 4d 5 ¢ (Y) are from 1 to 730 by weight; preferably from 71 to ZA by weight; in particular from 46 to 0 wt.; of at least one metal salt compound that is soluble in oil or dispersible in a substance

the oil; neutral or basic containing a metal of the first major group of the periodic table of elements or the second major group; or from the first subgroup; or from the second subgroup; or from the fourth subgroup; or from the sixth subgroup; or of subgroup VIII or of de sana the lanthanide group (rare earth metals© of the periodic table of the elements and a carboxylic acid” or “aes sulfonic acid ¢” or The acid ester of phosphoric acid phosphoric sl «acid is an acid ester of sulfuric acid that contains a hydrocarbon moiety in each of the cases of (MA) 56 carbon atoms carbon atoms “and preferably from 11 to Ve a carbon atom” carbon atoms as a component (ana) in percentages by weight

0 based on sale add. (©) and component (a) of the additive according to the invention is an amine compound with the formula oD) These fatty amines and alkoxylated fatty amine derivatives are prepared by conventional alkoxylation methods; By reacting an amine according to its moiety in formula (I) with x mole of ethylene oxide alone (R') 11 is formed and the polyoxyalkylene Vo moiety includes oxide units (ethylene oxide (pli) 0 with X moles of propylene oxide alone (for 18 to be CH; the polyoxyalkylene moiety includes propylene oxide units 0 with X moles of ethylene oxide and propylene oxide simultaneously or in succession (RY) be H: 11 and the polyoxyalkylene moiety includes ethylene oxide units 0 and propylene oxide Allg propylene oxide is found in a random distribution or in

last

—~ 7 _ agglomeration). The reaction is generally carried out at a temperature ranging from Yeo C to YA 2 in the presence or absence of an alkaline or acidic catalyst for the introduction of the 0-alkoxy group in the absence of air. Preferred amine compounds such as component 0 (corresponds to formula (VI) below: (VD A (CH,CH,0) a cy HO);— (CH,CH,0)7— H CH, oo and with: oy or a or “2 or z be i in the forms (ID) through (V) specified above; 8 | be a number from © to Fe Preferably « to 01 P | )| be a number from * to 00, preferably from 01 to 1 be a number from zero to ofr, preferably from zero to 10; and the amine compounds of formula (VI) and their preparation are described in the US Patent No. 5,421,993 mentioned at the beginning; which are incorporated here for reference. It is obtained by alkoxylation on the amines of the formulas of (V)MJD) specified; At the beginning with ethylene oxide, then with propylene oxide, with the addition of Jie bases, alkali metal hydroxides, and the reaction is carried out in stages at a temperature preferably ranging from 001a to 100 m and the amount of catalyst / base used in general ranges from 1.5 to 77 by weight; Based on the starting amine used 0 and the molecular amount of ethylene oxide and propylene oxide AYo

A — _ oxide per mole of initiating amine corresponds to the will determined by the bya and © values. And in detail; Reference is made to US Pat. No. 2,471,947. The following summary gives examples of amine compounds suitable a) to (ag) according to formula ( ) as compound (e): cd 1 es ce [bv fa] rR] em ri 01 0 uncommon Sa AER cee [Fo rt© and the preferred minerals in the metal salt compound for component B are alkali metals or alkaline earth metals (major group 1 and 2 of the periodic table of elements) ¢ copper copper 0 silver (subgroup one); zinc or cadmium (subgroup two); titanium or zirconium zirconium (subgroup IV); molybdenum “0.” or chromium a5 SH or tungsten (subgroup VI); iron “cobalt” or nickel ( sub-group VIII); beryllium ¢ and calcium or magnesium; and copper etching; And zinc zine « AYo

zirconium; molybdenum; iron and nickel; And cerium or ytterbium metata: 16 riyals. The preferred acids in the metal salt compound of compound (b) are the 6 carboxylic acids having from * to £0 carbon atom; Preferably from VY to 71 carbon atoms. The aliphatic fissure may be unbranched or branched; saturated or unsaturated. It is preferred that aliphatic carboxylic acids are fatty acids with from + to Ee a carbon atom; Preferably from 11 to IT carbon. Aliphatic carboxylic acids and fatty acids may be of the synthetic or natural type and may exist as is or as a mixture of two or more acids. Examples that can be mentioned are octanoic acid (caprylic acid), decanoic acid (capric acid), and dodecanoic acid (lauric acid). tetradecanoic acid (myristic acid ¢) (acid 0), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid ¢), eicosanoic acid (¢ (arachic acid Sli Jf), docosanoic acid (behenic acid), dodecenoic acid (lauroleic acid) and tetradecenoic acid 117820606006 myristoleic acid ¢ (acid 0) and hexadecenoic acid (palmitoleic acid)

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- 11. - and octadecenoic acid (oleic acid) and VY-hydroxyoctadecenoic acid (12-hydroxyoctadecenoic acid) linoleic acid (linoleic acid) octadecadienoic acid and octadecatrienoic acid (linolenic acid) plus coconut fatty acid ¢, tallow fatty acid and palm kernel fatty acid kernel fatty acid, etc. In addition to the aforementioned fatty acids (simple), dimeric fatty acids are also preferred ingredients. These VIDs correspond to the formula dimeric fatty acids

HOOC-R2-COOH (VII) Ve, therefore RY) forms a divalent VE carbon atom with a hydrocarbon forming a hydrocarbon radical RY with a fatty a esdimerization of a carbon atom and it forms at the dimer of VE is The radical that contains dicarboxylic acid has a carbon atom to give an 18-unsaturated dicarboxylic acid containing 7 carbon atoms). (las) 1 As it is known; It is prepared by dimerizing unsaturated fatty acids containing VA a carbon atom; For example, oleic acid; or linoleic acid ¢ or linolenic acid or tallow fatty acid (dimer 0 means the fusion of two identical molecules to form one new molecule; a dimer “dimerized by addition reaction). Fatty acids that have YA, Ayo, are generally dimerized

- 11 - A carbon atom at a temperature ranging from 1010 °C to YOu °C; preferably from 181 M to “Yr. M” with or without a dimerization catalyst and the resulting dicarboxylic acid 40 (which is a dimeric fatty acid corresponding to Formula VII given;

Cis dimerization acids form a divalent connecting member which forms at an 82 Cua o fatty dimer; It has two COOH groups - and it has a VE carbon atom. Preferably, BER is aliphatic Lala (an acyclic Ala), a monocyclic, or a bicyclic (cycloaliphatic with YE carbon atom). The acyclic moiety is generally The alkyl moiety is branched (substituted) and monounsaturated to triple unsaturated with 4 carbon atoms. Similarly, the cycloaliphatic radical has generally from 1 to ?00 double bonds (double) The preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of formula 711 having structurally different moieties 182. The mixture of dicarboxylic acids often has a “trimeric fatty acid” content More or less dicarboxylic acid was not removed when the product was run by distillation.Dimerization mixtures formed when the similar Allg 1 dimerization is obtained from natural products, for example in the production of rosin colophony of pine extract and below, some dimeric fatty acids may be specified as formula; And the hydrocarbon radical is warm

_ 1 Y — monocyclic or monocyclic « is an annular moiety - COOH bearing two groups (53 radical 'bicyclic' or dicyclic -continued food os _CH _(CHpg—COCH)

TP1

CH Cor 1 “CH==CH-—(CH,);CH; re

CH, foo (Ha

ZCH_ tar _(CHp)7—COCH fi 8 fH

CH_CHCH

CHy(CH)T he “CH

Nie

CH, o which came in the description are available commercially under dimeric fatty acids and double fatty acids and as “dimeric fatty acids” the name “double fatty acids” or “double fatty acids” above; They can have a high or low content of fatty acids that have been made triglycerides. CH,(CHp)g— I (CH,);— COOH

CH; (CHp)7== CH== C= (CH,);— COOH

CHj(CHp)s— cH +43 CH=—CH—(CH;);—— COOH

CH, (CHp)s— ¢ SH (CHp)y—COOH

CH=CH

AYo

Fatty - The preferred acids in the metal salt compound for component (b) are; Furthermore it; furthermore, aliphatic or aromatic sulfonic acids having from + to 48 carbon atoms; Preferably from 11 to Fe carbon atoms; in the aliphatic or aromatic part, and here too; The unbranched aliphatic radical may be oo or de iia saturated or unsaturated. It is preferable that the aromatic sulfonic acid be a benzene acid with an alkenyl radical or an alkyl radical containing between 11 and 11 carbon atoms. Among the examples mentioned; Mineral soaps are particularly preferred as component (b). The salt of the organic metal to be used according to the invention can be prepared as component (b) by the methods described in the previous art. In this case, reference may be made in particular to the publications mentioned at the beginning, French Patent No. 71,779,741, French Patent 77,677,977, US Patent No. 0716874, and European Application No. 776197; which are incorporated here for reference. The organic metal salts to be used according to the invention AL shall be oil soluble or at least dispersible in oil. in addition to; It relates to a neutral or basic product, the latter being preferred. The expression basic el is well known; Describes mineral salts in which the metal is present in a stoichiometric amount higher than the organic acid moiety. Therefore, the basic mineral salt products to be used according to the invention have a pH number that generally ranges from OY JY, preferably from + to .01. The additive is prepared according to the invention by mixing the components (e) 5 (B) together; With or without the use of Bly 0 solvent or dispersant. Suitable media for solvents and dispersants of this type are AYO alcohols

- yg or “isopropanol or isopropanol ¢ ethanol ethanol Jes nS minor or alcohols or dodecanol 001 A “0006”; and the like; or “decanol” butanol J sil sul dialkyl or large or small monoalkyl dialkyl and monoalkyl ethers glycols slag propylene glycol; propylene glycol of which ethylene glycol glycol; tetra-ethylene glycol; tetra-ethylene glycol “diethylene glycol” “hydrocarbons and the like”; small to medium cycloaliphatic or aliphatic hydrocarbons tetrapropylene glycol Cyclic aromaticdy she; or aliphatic and the like naphtha and naphtha “xylene” xylene toluene Boiling point such as toluene Light to medium-heavy mineral oils Oil distillates Natural and synthetic oils and their derivatives thereof and mixtures of two or more of these solvents.The two components, 0 the amine compound and the metal salt compound, are generally combined together to atmospheric pressure and to a temperature of 71°C, preferably from 17°C to 100°C. Ne ranges from and the heavy oils according to the invention show the additive content described.The effective amount of the additive in the heavy oils can vary over large limits. and in general; The oil contains 1,000 to 1,000 ppm of additive; Preferably from 000001 over between? to 1 ppm. Those containing this additive have heavy oils and the additive according to the invention and heavy oils in the form of a property being particularly preferred; This may be initially as a result of the unexpectedly high cooperation of the combination according to the invention of compounds (E) and (T). Therefore, the additive is present in the oil in dissolved or highly dispersed form. Even in oils with a high content of asphaltenes 0

AYo

o — 3 —- asphaltenes and/or other high molecular weight compounds; All of these insoluble fractions are highly emulsified or dispersed. The same applies in the case of slag materials; So that the formation of slag is excluded Lia to a large degree or decreases to a significant degree at least. the additive according to the invention; Furthermore it; Be a high impact combustion improver. It ensures complete combustion of heavy oils with a simultaneous decrease in soot formation. Therefore, the heavy oils according to the invention satisfy to a surprisingly high degree the requirements stated at the beginning. As a result of the aforementioned deeds; The additive according to the invention gives rise to oils which have an additionality; Also in particular are the following characteristics: improved storage stability (low sedimentation of insoluble components); Allie's pumpability due to its low viscosity; long operating life of the 0 filter isotope; Chase injection system with combustion devices; This contributes additionally to optimizing combustion. Increased corrosion protection for all devices due to the high corrosion inhibition by the additive. Therefore, heavy oils according to the invention are primarily used as furnace fuels for industrial units and power plants, and similarly as motor fuels for marine engines. OY) the invention will be described in more detail by way of examples and comparative examples. vo _ compound (a) sald the additive according to the invention: as an off component) the compounds (a) to (a.) and (ah) from Table 1 will be used. compound (b) of the additive according to the invention : as component (B); Products (< (x <) oy described in more detail below will be used. AYO

Product (B,): The fatty acid used for the preparation of the product (< 1) is a hia fatty acid consisting of a mixture of a distillate pine oil stearic acid and a resinous acid having a molecular weight of about 10 g/mol. Batch po | taya aa | AT rem | ew He then mixed an amount of AO liter of (FeCl;) and 0.17 liter of stearic acid; Veg liter of Avg cela liter of distillate with each other at a temperature of Room temperature (from 10°C to 0°C).More liters of NH were introduced slowly (exothermic reaction) into this mixture with stirring.The mixture was heated with stirring to between 66°C to 0°C, which gave an aqueous phase and an organic phase. The formation of the phase can be completed by adding more distillate. The two phases are separated from 0 from each other (clarification);" Lain The organic phase is centrifuged further to separate the remaining water. The organic phase contains the required iron carboxylate. Product (re) The fatty acid used to prepare product (b”) is an alkylbenzenesulfonic acid having a molecular weight of about ¥YY g/mol. Veo Ao

the product has been prepared (vo); It is an alkylbenzene iron alkylbenzenesulfonate ¢ in a similar manner to the product (< 1). Additions according to the invention: Example: (1) ee 200 (2) by weight organic iron salt fron ly For compound (b;). Example (?): 1) 2000 by weight of compound (b) + (b) Tee by weight of an organic iron salt according to compound (b,). AYo

A —_ \ — Example (9): a) Zoe by weight of compound (ah). b) 780 by weight of an organic iron salt according to compound (b;).

Additives were prepared according to the invention ABS from 1 to ¥ by mixing components (a) and (b) together (degree

1 The mixing temperature is from about 17°C to about ¼ ofp To and according to preferred procedure; Component (a) Yi is introduced and heated to about 0 m to 6 m with stirring and under an atmosphere of nitrogen, then the component (b) is stirred at the mentioned temperature, an atmosphere of nitrogen is created, thus preparing The additive according to the invention. If the mixture cooled to room temperature does not have the required viscosity and/or you notice a “shall” separation, this phenomenon can be eliminated by adding

0 significant amount of an organic solvent such as petroleum distillate. Additive Testing According to the Invention: Additives tested for Examples 1 to ? As for the possibility of dispersing asphaltene Cyndi g the ability of heavy oils to burn. To test the possibility of dispersing asphaltene, YJ prepares a solution containing asphaltene. 1 Prepare a solution of asphaltene in toluene: toluene to prepare this solution; A leftover oil containing asphaltene is subjected to extraction, which is; in detail; It is implemented as follows. in the first step; About 1 gm of the leftover oil is mixed in a glass beaker with about 00 ml ethyl acetate and AYO

- 1 hour; Then it was filtered YE The mixture was stirred for 2 hours at 50 m; Then leave it to settle for a while through a microporous filter. And in the second step; The filter residue was placed in the extraction loop

Jaton and extracted for about 2 hours using a normal Soxhlet extractor in paraffin filter cake; The paraffin part passed ethyl acetate again from ethyl acetate and in the third step; The resin portions were similarly dissolved. ethyl acetate JAY) to the acetate phase by extractor 1 using about mL pentane. And in the fourth step, 0 ; Which produced toluene 000 ml of toluene using about asphaltene. ASTM 14370 - 32 of 150 10307 - 1: 1993 This test is carried out according to standards, toluene in toluene asphaltene g of asphaltene solution Vo YJ mixing and to do so; hot (0 ml) Two girls. 700 ppm of 001 resistivity by weight was stirred with 701 about and 7; and 3 separately in three such solutions of asphaltene 0 addition from each of the examples pentane at room temperature. Then, solutions were treated toluene - asphaltene eo These three tests are according to the mentioned standards. Result: The additives according to the invention satisfy the test. AYe

or -

Testing of additives according to the invention in terms of improving the combustibility of heavy oils:

This test was carried out in accordance with VDI Directive 2066 Part 1 (VDI is the German Association of Engineers);

Example additives were used FY 1 at an amount of 5050 ppm

Ves ppm; and 00 ppm. Result: the additives according to the invention satisfy

° Ba to test.

Comparative examples from 1 to “:

In the comparative examples 1 to oF the compounds (bf) to (+) and (b;) were used separately.

The three test solutions were subjected to the same test methods as the examples according to the invention.

Result: None of the test solutions met the asphaltene dispersibility test, the 0 improvement in combustibility test.

Thus, the additives according to the invention have an unexpectedly high dispersion efficiency

Asphaltene in heavy oils and also for the combustion of heavy oils; It may result

for the surprisingly high cooperation of additive components (a) and (b). As a result of the characteristic effects of a substance

new addition; The Bay oils of the invention also have in particular those properties which Vo are particularly desirable for use in industrial units; power stations and engines

Heavy Navy.

AYo

Claims (1)

Y \ _ _ Claims 1 1 - A process for improving the dispersion of asphaltene contained in fuel oils " - heavy; comprising incorporation into said heavy fuel oils containing asphaltene; for an amount ranging from ? to Yeo ppm; for parts of oil mentioned (a) and (b) Cun having: 1 © ) at least one amine compound of the formula (1) below: 13 00-(0H01T0) for Ser R For and with A © be 1 or or of of oF As 4 be Bd is selected from the group consisting of the forms of (ID) Y (17). n=2 R No 1" / R n=1 coe VY \ n=3 cure, er \ / \ RN "1 n=4 AYo -yy- Cua NO 8 is CoCr alkyl and is of oF FY and is a number of AY Je 01 RTs IY being 11, “CH or CHys H in which the oxyalkylene VA moieties are arranged randomly or in clusters; And 4 ab) is a metal salt compound that is soluble in oil or dispersible in oil; Yo is neutral or basic and contains a metal selected from the group consisting of alkali metal 7, alkaline earth metal, and copper; and silver ¢ YY and zinc; cadmium ¢, titanium ¢, zirconium ¢ YY 5 molybdenum; and chromium; and tungsten; and Y¢ 1:08 iron and cobalt » and nickel nickel; and lanthanum + cerium “cerium YO” and ytterbium “ytterbium” ¢ and an organic acid component selected from the AY group consisting of “carboxylic acid” sulfonic acid Yv; an ester is an addition of phosphoric acid; an ester pasa TA of sulfuric acid; And each aforementioned ester or addition contains a YA hydrocarbon moiety with from A to 560 carbon atoms as the acid component ©0 and emulsifying and/or dispersing the aforementioned asphaltene in heavy fuel oil1 mentioned. 17- The process mentioned in Claim (1), whereby the said fuel is “fuel for an industrial unit or a power station.” 1 * - The process in claim (1), whereby said fuel 7 is a marine engine fuel. AYO s1; - The process contained in claim (1), whereby component (b) is a metal salt compound containing a metal selected from the group consisting of Alkali metals; chromium, tungsten 6, iron ciron 1, cobalt, nickel ¢, lanthan ¢, cerium 1" and ytterbium; It contains an acid selected from the group consisting of “eA” aliphatic carboxylic acids with from + to 60 4 carbon atoms, double fatty acids with TT carbon atoms, and 0 aliphatic sulfonic acids and aromatic ones 8 to 50 carbon atoms. 1 * - The process mentioned in claim (1), whereby component (b) is Y a metal salt compound containing a metal selected from the group consisting of an alkaline earth metal »and copper ; your weight; zirconium ¢ ¢ and molybdenum » iron ¢ iron and nickel © and ccerium and ytterbium. 1 1 - The process mentioned in claim (1), in which component (1) is an amino compound Y of the formula: (VD) free (CH,CH,0)7— (CH,CHO )y (CH,CH,0);7H 1 I | } ¥ AYo Y 4 — — and with: n © be 1 or oY or a or 4 A 1 be a split in the form chosen from the set consisting of (1) od (V) 7 In claim (1); A and e is a number from © to 91 obs 1 is a number from Jo 00 Ve and is a number from zero to 40 . 1 1 - The process in claim 1 (in which from 7A to Y 7544 by weight of component A) and from 71 to 744 by weight of component B are present in 7 total weight of component ( A) and (B). b) In “ _ the total weight of component (a) and (b). 1 4- The process included in claim (1), in which there are from 14 to 2501 by weight of component (1) and from 7560 to 7760 by weight of component (b) in the total weight of component () and (f). b). ._ component (a) from component (b) in the total weight of components (1) and (b). AYo