PL153363B1 - Fuel composition - Google Patents

Description

REPUBLIC POLAND PATENT DESCRIPTION 153363 Additional patent to patent no. --- Int. Cl. ⁵ C10L 1/14 Oll || l Reported: 87 09 24 / P. 267893 / in* Priority 86 09 '24 UK OFFICE PATENT Application announced: 88 08 18 RP Patent description published: 1991 10 31

Inventor ·

Patent holder: Εχχοη Chemical Patents Inc.,

Lindan / United States Λΐϋ ^ ί /

FUEL COMPOSITION

The subject of the invention is a fuel composition containing distilled fuel containing paraffin wax and wax crystal modifier at low temperatures, constituting a diesel fuel or heating oil.

A characteristic feature of mineral oils containing paraffin wax is a decrease in their fluidity with a decrease in oil temperature. · This loss of fluidity is caused by wax crystallizing in the form of flaky crystals, which then form a spongy mass, closing the oil inside. The temperature at which wax crystals begin to form is called the cloud point, and the temperature at which the wax makes the oil liquid is called the pour point

Various additives have been known for a long time which, when mixed with wax-containing mineral oils, reduce the pour point of the oil.These agents change the size and shape of the wax crystals and reduce the cohesive forces between the crystals and between wax and oil so that the oil remains liquid in the lower temperature and can drink through thick filters ·

Various freezing point depressants are described in the literature, some of which are used on an industrial scale. For example, U.S. Patent No. 3,048,479 uses copolymers of ethylene and vinyl esters with 3-5 carbon atoms, e.g. vinyl as agents reducing the pour point of oils, especially heating oils and fuels for diesel engines or jet engines. Agents of this type are also known, hereinafter referred to as depressants, being polymeric hydrocarbons based on ethylene and higher cL-olefins, e.g. propylene U.S. Patent No. 3,252,771 discusses the use of the polymers (C ^ gC gg) -ol-olein with alkali trichloride and alkali halide catalysts as sodium hydroxides for oils.

153 363

153 363 obtained by distillation, known as broad boiling point oils ", available in the United States from the early to 1960s. In the late 1960s and early 1970s, more emphasis was placed on improving the filterability of oil <5w at temperatures from cloud point to the freezing point, the ability to be determined more severely, the so-called cold filter plugging test / "Cold Filter Plugging Point - CFPP - test IP 309/80 J. There were also obtained general patents for fuel improving additives in accordance with this test. According to U.S. Patent No. 3,961,916, a mixture of copolymers is used to control the size of the wax crystals, and according to of British Patent No. 1,263,152, a copolymer with a low degree of side chain branching can be used for this purpose.

It has also been proposed, e.g., in British Patent Specification No. 1,469,016, in the case of the distillation route of fuels with a high final boiling point, to improve their low-temperature fluidity by using ethylene vinyl acetate copolymers together with the diiunalkyl furanaan copolymers previously used as pour point depressants of lubricating oils. It has also been proposed to use additives based on olefin-maleic anhydride copolymers.For example, U.S. Patent 2,542,542 uses olefin copolymers such as octadecene with maleic anhydride, an alcohol esterified such as lauTail alcohol, and according to British Patent Specification No. 2,542,542. No. 1 468 588 copolymers / C22 "C2g / ~ ol ⁰ fin with funnel anhydride with ^ t ^ t 10Nm behenic alcohol are used as co-additives for boarding fuels. According to the published Japanese patent description No. 5,654,037, copolymers of olefins with maleic anhydride, reacted with ammons

According to published Japanese Patent Specification No. 5,654,038, olefin-melonic anhydride copolymer derivatives are used as flow improvers together with ordinary middle distillates, such as ethylene vinyl acetate copolymers. The Japanese patent specification discusses the use of non-CFP copolymers as non-polymeric copolymers. olefins with maleic anhydride, where these phases should have more than 20 carbon atoms. According to British patent specification No. 2 192 012 certain differently shaped copolymers of olefins with maleic anhydride are used together with low-frequency polyene, these copolymers are not effective, when used alone as a supplement ± ·

Improving the efficiency of CFPP by introducing the additives discussed in the above-mentioned patents is achieved by changing the size and shape of the wax crystal, namely by producing mostly needle-like crystals of 10 microns or more, usually 30-100 microns. When working in diesel engines, such crystals are I do not pass through the paper filter of the vehicle, but I create a permeable layer on the filtrzze, uιnm01ioiα moans the passage of liquid fuel 1 when the engine and fuel heat up then these wax crystals can be dissolved, however, accumulated wax may clog the filters, which causes difficulties when starting the vehicle's engine and when driving in cold weather or when the heating system fails ·

With the help of a computer, it is possible to precisely and easily and conveniently determine the geometry of the n-alkane wax crystal lattice and the energetically advantageous geommery potential of the additive. These discoveries become especially clear when they are then presented graphically as using a curve plotter or graphical terminal. This method is known as particle modeling. Computer programs useful for this purpose are commercially available, especially the series of programs developed by Chemmcal Desing Ltd, O ^ IFord, England, under the name Chem- with·.

The growth of paraffin crystals takes place by associating the individual paraffin particles with their long sides to the edge of the existing paraffin plate, as schematically shown in Fig. 1 of the drawing. The association with the top or bottom side of the wafer is energetically disadvantageous as in this case only one end of the paraffin molecule chain is involved in the crystal formation. The association takes place mainly in the crystallographic plane not 001 / compare Fig. 2 / The / 001 plane has the greatest number of the strongest bonds

153 363 intermolecular, this determines the production of large, flat plates / (Fig. 3 /. The next most durable form of the crystal is / llx /, e.g. 110. The intermolecular association is strongest when the n-alkane molecules are most closed, and so the plaster / 110 / is stronger than the / 100 / plaster.

The crystal grows by the enlargement of the / 001 / plane. For this reason it is important that the edges of this plane constitute fast forward front surfaces, while / llx / e.g. / 110 / and / 100 / advancing less. Accordingly, the regulation of crystal growth is mainly controlled by the advancement of the / Hx / plane. Since the face-to-face bonds are relatively weak, generally only one molecular plane / 001 / is considered and it can therefore be assumed that in the case of the present considerations, the planes / 110 /, 411 / etc. are equal as elements of the grid 1, the relative positions of the neighboring molecules placed "side-by-side" are the same (Fig. 4/). the macroscopic appearance of the plates is dominated by the plane / 001 /. Such plates can clog filters in fuel lines, e.g. in vehicles.

The present invention solves this problem, and at least severely limits the growth of wax crystals in the direction of the / 001 / plane and the / 110/1/111 / planes. Thus, by using certain wax crystal moieties, it is possible to prepare wax-containing fuel compositions in which the wax crystals are so small at low temperatures that they can pass through filters commonly used in diesel engines and in oil heating equipment.

According to the invention, a carbonaceous compound containing wax-containing distilled fuel and wax crystal moiety at low temperatures consists in the fact that as a moOyrlkatlr it contains an additive that shapes the size of the wax crystals at low temperatures, which is a chemical compound with at least two substituent groups that have a spacing and configuration that allows them to occupy the position of the wax molecules in the / 100 / and / or / / 110 / and / or / / 111 / planes in the wax crystals, said substituent groups being alkUows, alkoisralkyl or polialkoksralkiliwe at least 10 carbon atoms in the main chain, y ^{p y} being in turn our tempera about 1 ⁰ ° C temperature for ^{d y} zjawiania the WOS ^k u ^ mpcoycja contains wax crystal size mnnejszej than 4000 nanometers.

These additives in the palm oil composition according to the invention unmoHi ^ and their occupation of wax particles in the wax crystals at the intersection of the / 001 / and / 11x / planes, e.g. planes / 110/1 / or / 111 /

The occupying of the crystal planes can be explained with reference to Fig. 4, which shows an enlarged top view of the sulfur of the crystalline paraffin plate. The view direction corresponds to the long axis of the parish chains. From each paraffin molecule, only two carbon atoms and four hydrogen atoms (the latter shown only once) can be seen because the other atoms are below the atoms shown because all the carbons in the molecule lie on One molecular symmetry plane. It can be seen from Fig. 4 that the distance) between the two molecules in the / 100 / plane and the / 110 / plane are essentially the same. These distances are designated in Figure 4 by the symbols "b" and d ", with b 0.49 nm and d" 0.45 nm. The main difference between planes / 100 / and / 110 /, or more precisely / llx /, where x is zero or an integer, is the relative orientation of adjacent paraffin particles. In the / 100 / plane, the molecular planes of the single molecules are parallel to each other, i.e. the plane angle is 0 °. In talograficznej ^ ^^ ^ not coat / IA / ^ka LAS ^k t ^p and ^{y about} the ^y lmię part teczko ^ ^ I ^y coat mark of symmetry ^Getting le ^g ającycfi olcoło molecules is 82 °. ^,

According to the invention, the additives should occupy positions in the paraffin particles which are indicated in Fig. 4 by the symbols "C" and D. This is only possible when the distance between the substituents is about 0.45 to 0.50 nm in energetically available and LAS ^{p k} t ^p and ^any OMI ^EY with ^y ^ s aszczyznami local merii ^ ^ ^ dstaWników FOH is oltoło and preferably 75-90 ° C.

The molecule can be modeled by entering its known atomic coordinates or by creating a structure according to the rules of physics with the help of kn ^ pte ^. This structure can be defined, for example, as follows: a) Calculate the fractional charges on each atom from the differences

153 363 electronegativity / wets field method / or quantum mechanics method / e.g. CNDO, Q.C.P.E. 141 «Indiana Uniwecsity; b / optimize the structure of the molecular mechanics method / compare MoOecular M ^^ haeńc ^ s ^ '', U. Kurkert and N.L. Allinger, ACS, 1982 /; c) minimizing overall energy by optimizing the conformation, i.e. by rotating around the spinning bonds.

One should be careful here, because the environment on the surface of the wax crystal is different than in the gas phase or in solution and it is possible that the additive particle crystallizes together with the paraffin in a conformation that is not the energetically most favorable conformation in the gas phase. that the additive cannot assume a conformation that is hindered by steric hindrance or by electronic factors.

Using the criteria below, it can be checked whether the additive particle fits on the / 001 / plane of the paraffin lattice in the desired positions C and D, because:

/ <1 / the distance between the substituents in the molecule should be approximately equal to the distance between two adjacent paraffin particles in the / 001 / plane intersecting the / llx / plane, i.e. it is about 0.45 nm. The relative orientation of the substituents should follow the n-alkanes in the (110) direction, namely, the plane angle between the local planes of the substituents should be about 82 °. Distance and angle can be easily measured using computer programs / s /, the additive particle should match the structure of the wax crystal lattice and in two free places in the mesh

In well-known publications, certain derivatives of phthalic acid, mmldnic acid, succinic acid and vinylZdenum olefins have been proposed as compounds to be added to oils.

Neither of these compounds corresponds to the criterion / 1 / described above, as illustrated by the following examples: a) phthalic acid diamide can at best assume the conformation shown in Fig. 3, in which the distance between the substituents and the plane angles are small. Such a conformation is energetically disadvantageous due to the spatial hindrance. Re-minimization leads to kon ^^ mac! distorted, shown in Fig. 6; b) a similar situation is in the case of mmleinic diamide, as shown in Fig. 7. Due to spatial obstruction, re-minimization pro ^^ t ^^ j. to the distorted konίοτϋ ^ ϊ, as shown in Fig. 6; c / due to steric hindrance, succinic acid cannot become kon ^^ mac! similar to a particular system, the strand αilgo according to the invention (compare Fig. 9). When rotated about a single C-C node, succinic acid adopts the conformation transformed in Figure 10.

By introducing additives known from the patents cited above, the improvement of CFPP activity is achieved by changing the size and shape of the wax crystals and producing crystals with particle sizes generally 10,000 nm or greater, typically 30,000 to

100,000 nm. When operating a diesel engine at low temperatures, such crystals do not pass through the paper fuel filter in the vehicle, but form a permeable layer / cake / on the filter. The liquid fuel may pass through the cake and when the engine and fuel are heated, the major mass of the heated fuel may be recycled, causing the wax crystals to dissolve. However, build-up of wax can clog the filters, making it difficult to start the vehicle and drive in cold weather, and can also cause collapse when using oil for heating purposes.

The following test methods were used in the trials with an additive to the state coep position according to the invention.

The temperature of wax appearance in the fuel (WAT) was measured by the differential scanning calorimetry method (DSC). In this test MALEA fuel sample / 25 microliters / it is cooled ^ ędko ^ i-± 2 ° C / min ^E, with ^p r ^yellow bk ^ę reference example adorned ^p ojemności H ^and L ^pl football, al-e ^k torej not precipitates the wax in the temperature range under consideration / e.g. As crystallization begins, the sample begins to heat up. This measurement can be carried out using the following extrapolation technique using the Meller TA 2000B method.

The wax content in the fuel is determined on the basis of the results of the DSC analysis, integrating the surface with the base line and the exothermic curve set to a specific temperature. Marking is carried out beforehand by obtaining a sample with a known content of crystallizing wax.

The average size of the crystalline wax particles is measured by analyzing the scanning method of the microgroup of the fuel sample at the magnification from 4000 to 8000 times and the

153 363 the longest dimension of at least 40 of the 88 points of the previously defined mesh. It has been found that when an average size of less than 4000 nm is achieved, the wax begins to pass along with the fuel through conventional paper filters used in diesel engines. It is preferable, however, that the quantity is less than 3000 nm, in particular less than 2500 nm and most preferably less than 2000 nm. Particular advantages regarding the passage of the wax through the filter are achieved when the wax crystals are less than or equal to 1000 nm. The crystal size achieved depends on the type of fuel and the amount of fuel additive used, but trials have shown that using the additive according to the invention, it is possible to achieve a wax particle size even smaller than the above-mentioned preferred sizes, which is important for the operation of diesel engines.

This can be demonstrated by the use of mixing the fuel through a filter paper used in VWGolf or CumIn engines at a speed of 8-15 ml / second and at a rate of 1.0 to 2.4 liters per minute and 1 m3 of filter area. at a temperature of at least 5 ° C lower than the temperature at which the wax appears, with at least 0.5% by weight of the fuel in the form of a solid wax. Both the fuel and the wax have been found to pass efficiently through the filter. If one or more of the following conditions are met.

(1) When 18-20 liters of fuel are passed through the filter, the pressure drop across the filter does not exceed 50 kPa, preferably 25 kPa, more preferably 10 kPa and most preferably 5 kPa.

(11) At least 60% by weight, preferably at least 80% and especially at least 90% by weight of wax is found in the fuel exiting the filter. What was in the original fuel.

(111) When 18-20 liters of fuel are pumped through the filter, the flow rate is kept above 60% and preferably above 80% of the initial speed.

The amount of crystals passing through the vehicle filter and the operational benefits achieved with the small wax crystals are largely dependent on the length of the crystals, but the shape of the crystals is also important. It has been found that the cubic crystals pass through the filters somewhat more easily than the flat crystals, and when they do not pass through the filter, they resist the flow of fuel. Nevertheless, it is preferable for the crystals to be flat as they can settle on the filter in greater amounts as the temperature decreases, and the amount of wax deposited before the critical length is reached may be greater than for cube crystals.

Fuels prepared according to the invention are much more advantageous than fuels prepared from distillates by known methods, using known additives. This applies to the ability to flow cold and such fuels can be used at temperatures close to the freezing point, but meeting the CFPP test is not a limitation here, because they pass this test at much lower temperatures or do not need to meet the conditions of this test. These fuels also have better low temperature engine starting properties, since with such fuels it is not necessary to heat the fuel to remove undesirable wax deposits. In addition, wax crystals tend to stay in suspension rather than waxy these layers in storage tanks as is the case with fuels containing known additives.

Distilled aliwa ^{k p y} las general boiling 1 ^2Ο -5 ° ^{Ο 0} ^ r n ^{OZ ble} t ^o considerably with regard to their boiling characteristics, n-alkane content and the content of the wax. Fuels from northern Europe generally have lower final boiling points and cloud points than fuels ^from Ei ^^ y southern. The contents wos ^ ^k u is generally hung than 1.5% / 1 at a temperature of ^O ° C below WAT /. Likewise, fuels from other countries of the world also differ in their wax content depending on the climate as well as the origin of the crude oil from which they were obtained.

Middle Eastern crude fuels typically have a lower wax content than those of Chinese or Tustrral crude oils.

The smallest size of a wax crystal that can be obtained depends on the type of fuel itself, and with some fuels very fine crystals cannot be obtained. In such cases, in order to obtain small crystals, appropriate conditions can be adjusted or mixtures prepared to facilitate the use of appropriate additives.

153 363

The wax deposition of distilled fuels consists mostly of normal alkanes which crystallize in the orthorhombic or hexagonal arrangement, as described in the literature, e.g. A.Muier, Proc.Roy.Soc. A 114, 542/1927 /, ibid. 1210, 437/1928 /, ibid. 127, 417, / 1930 /, ibid. 138, 514, / 1932 /, AESmith, O.Chem.Pys., 21, 2229, / 1953 / and PWTeare, Acta Cryst ·, 12, 294, / 1959 / · As mentioned above, when adjusting the additive molecule to the wax crystal structure, two factors are important · First, the separation of n-alkanes in selected crystal planes, as important the distances should be adjusted to the distances in the planes / 110 / and / 111 / etc · or to the directions, and to a lesser extent in the plane / 100 /.

The additive chains should occupy places / more than one place / in positions on the axes at right angles to the axis of the n-alkane chains in the crystal. These distances are of the order of 0.45 to 0.55 the closer the additive chains are and the closer the additive chains are, the more effective the additive is.In addition, although this is probably of multiple importance, the relative chain orientations of the additive molecule should preferably match the orientation of the n-alkanes in Crystals The n-alkyl chains of the additive should closely match the intermolecular distances in n-alkanes in the wax crystal along the planes / 100 / and / abbo / 110 / and / 111 /, where there is an intersection with the / 001 / plane, and should also be able to reach conformation that u ^ oil ^^^ and these chains orienting at angles similar to those in n-alkanes in the above-mentioned crystal planes It has been found that such chain arrangements and orientations in the additive molecule can best be achieved by placing them on adjacent carbon atoms in cy ^^ relationship or JtsJenool niJnasycllSi, provided ^ they cis orientations

Customization is also preferably achieved along the length :! of the wax chains and the total length of the additive chain is preferably of the same order as the average size of the wax chain. The wax deposit of the fuel or oil is usually made of n-alkanes, so this is referred to as average dimensions. The fuel klmoolysia additives according to the invention contain hence usually dioic chains, preferably i-alkyl, or chain segments that can co-exist with the wax It has been found that there should be two or more of these chains in one molecule and that they should be placed on the same side of the additive molecule. It is desirable that the additive molecule had two distinct patterns · One side * contains the cassicstallising chains of the molecules, and the other side the cc at least numerous hydrocarbon groups that can block or prevent further crystallization after the additive molecule has been in the crystal roll of the wax crystals. such that such a blocking group is halfway or approximately halfway down the co-crystallizing i-dclO chains of the additive

Klmpoiysii fuel additives of the invention are preferably compounds of the general formula 1 kforym December ^p -YR b is a ^g roup of ^E -S ^Og H ⁺ / n ^{r 1} 3 r ^2. -S ° ₃ / / / + / h No2r ² .

/ ^ ^{+ H} H ^g N ^RR , ^{-! H} 3 ^{NR 2, -S0} 2 ^Nr3r2 lu ^{b -SOgR2} group ^{-R 1} -X ^ c ^^ and lpisan above ^that a group of -YR ² or R ³ -C0NR? ^1, -C0 ₂ W NR ^ R ¹ . -C0% / / ^ NR ^ R ¹ , - Co / ^- / ^/ + / ^H 2 ^No 3 ^r1 . - ^c 2 ^W ^ MR ¹ . - ^ COR ^{1, -R 4} ° ^r1, z ^{/ - / / f /} NR ^ R ^{1 p} y wherein ^y ^^ above the supply wzorac ^h

R is a group ^e OCOR SOJ

R ⁴ R ^Ł -N / COR ³ / R Feb ¹ >

^{/ m /} or -Co / ^{m /}

2

R and R represent the groups dklL ^^ we, al ^ ksys ^ -kHotte or polyalkoxide containing at least 3 less than 10 carbon atoms in the main chain, R is a hydrocarbon radical, where the individual 3 4 and e R may be the same or different, and R i and e denotes nothing or the radical / C / -C8 / dkUrne, and in the group of formula 2 the bond CC may be / a / ethylenically unsaturated, when A and B represent it alkyl radicals, d ^^ e ^ n ^ L ^ e or substituted hydrocarbyl radicals, or / b / it may be part of the ring structure which may be aromatic, multi-aromatic or cyclldiphatic. The ring atoms in such cyclic compounds are preferably carbon atoms, but may also be nitrogen, sulfur or oxygen atoms, and then these are heterlisotic compounds

An example of an aromatic compound from which the additives to beer mixture according to the invention can be produced is the compound of formula III in which the aromatic ring may be substituted

The fuel oil additives according to the invention can also be prepared from multi-fungal compounds, i.e. small 2 or more rings, which may have different

153 363 figure. These can be / a / fused benzene structures, b) fused ring structures where none or all of the rings are benzene, cj rings joined end-to-end, d / heterocyclic compounds, ej non-aromatic or partially saturated ring systems or f / three-dimensional structures The fused benzene structures from which the compounds described above can be derived include, for example, naphthalene, anthracene, phenanthrene and pyrene.

Fused ring structures, none or all of which are benzene rings, include e.g. azulene, indene, hydroindene, fluorene, and diphenylene. End-to-end ring compounds include e.g. diphenyl.Examples of heterocyclic compounds are quinoline, pyridine, indole. 2,3-dihydroindole, benzofuran, coumarins, isocoumarin, benzohofen, carbazole and thioduphenylamine, non-aromatic or partially saturated ring systems are e.g. decalin, β-pinene, cadynene and bornylene, and examples of trimia compounds are norbornene, norloocbornane, bicycooctene,

The two substituents X and Y should be attached to adjacent ring atoms in such systems where there is only one ring, or to adjacent ring atoms in one of the rings in the case of multi-breast compounds.

In the latter case, it means that in the case of naphthalene the coasters! these may not be in the 1.8 or 4.5 position, but should be in the 1,2-, 2,3-, 3,4-, 5,6-, 6,7- or 7,8- positions.

these are reacted to form esters, amines, amd2, half-esters / half-half-esters or salts used as additives in the fuel comunition according to the invention,

Preferred additives are the secondary amn salts having a hydrogen or carbon group or groups with at least 10, and preferably at least 12 carbon atoms. Such amines or their salts can be prepared by reacting the above-described acid or anhydride with am ^ ^, or by reacting Secondary amine derivative with carblxylic acid or its anhydride, In order to produce amides from acids, it is usually necessary to remove the water and heat, It is also possible to react the carboxylic acid with an alcohol having at least 10 carbon atoms or with a mixture of alcohol and am.

The groups containing hydrogen and carbon in the substituents are preferably hydrocarbyl groups, but it is also possible to use yhlolOiCliαne hydrocarbyl groups, preferably with a halogen content, e.g. chlorine, of e.g. less than 20% by weight. The hydrocarbyl groups are preferably aliphayic groups, e.g. especially straight chain, Unsaturated hydrocarbyl groups, e.g., alkynyl, may also be used, but are not preferred,

Groups of al ^ ^ in preferably at least 10 carbon atoms, especially 10-22, e.g.

14-20 and are preferably groups with straight or multi-branched branches in positions 1 or 2, If the branch is present in more than 20% of the alkyl chains, then the branches should be furniture groups, Other groups containing hydrogen and carbon may be shorter, e.g. may have less than 6 carbon atoms, but may also have at least 10 carbon atoms. Suitable alkyl and y groups include iron, ethyl, propyl, hexyl, decyl, ddθcylwa, tetocyl, tetrol and behenyl. alkylene groups are, e.g., hexylene, octylene, dodeclenoyl and hl-xadecyl groups, but are not preferred,

According to a preferred embodiment, when the intermediate is reacted with a secondary amine, one of the substituents is preferably an amide and the other is an amine or a di-alkyl ammonium salt of the secondary amine. Particularly preferred additives are amides and amine salts of secondary amines,

In the production of fuel, according to the invention, the additives are usually used in kunminaccia with other additives, examples of which are products referred to as comb polymers. These are compounds of the general formula 4 in which D is R, CO.OR, TCO.R, R * CO.OR or OR; E is H or CH2 or D or R * and G is H or D; m> 1.0 Hmeτ / do 0.4 ^^^^^ u ^ ek J means H, R *. an aryl group, a heterocyclic group, or R * CO.OR;

X is H, CO.OR *, OCO.R *, OR * or COgH; L is H, R *, CO.OR *, OCO.R *, an aryl group

153 363 or CO 2 H; n is a number from 0.0 to 0.6 (molar ratio), where R ^ C ^ g and R ^ C ^

If necessary, another monomer can be terpolymerized

If these other additives are copolymers of © C-olefin with maleic anhydride, they can conveniently be prepared by polymerizing the monomers neat or in solution in a hydrocarbon solvent such as heptane, benzene, cyclohexane or white oil at a temperature usually in the range of 20-150 ° C. C and typically using a peroxide or azo catalyst such as benzoyl peroxide or azo-di-isobutyronitrile under an inert gas such as nitrogen or carbon dioxide * to exclude oxygen It is preferred, but not necessary, to use equimolar amounts of olefin and maleic anhydride, but a molar ratio of 2: 1 to 1: 2 may also be maintained. Examples of olefins that can be copolymerized with maleic anhydride are decee-1, dodecene-1, tetradecene, hexadecene-1 and okitadecene-1 .

The olefin copoimers with the male anhydride can be esterified in any way and it is advantageous, but not necessary, to esterify at least 50%. As alcohols, e.g. n-decane-b-1, n-dodeka-b-1, n-rttradecannb -1, n-hexadecane-11 n-octadecane-o1-1. Alcohols can also be used for the production of one methyl branch in the chain, e.g. 1-methylpeniadekaa-bll or 2-methylpeniadekaa-bll or 2-metyy © tridecanno-1Alcohol can be a mixture of normal alcohol and alcohol with one methyl branch. use any alcohols · Preference is given to using pure alcohols and not commercial Uędęce mixtures, but · if mixtures are used, then R ^! is the median number of carbon atoms in aJ-kH group, and if. aHohole odggłęzienie comprise at position 1] .u ^b 2 is ^{R 1} is a skeleton se ^g ment speed ^ and ⁿ ^ ano chain lu ·

^Y Gd mixtures are used for ^e is important not ^{learn more,} than 15% of the R ¹ have a value of ^ ^r! + 2 · ^ choice of alcohol depends of course NLT ^{d f} in npolimer ^yk-y zbua θj of the Water ^ ^ he property is ^L ei-oa ^Uy sum of ^R + R ^at VLA in the range ¹ 8 ³ 8 · Korzona value of R + R ¹ may depend on the character of ^k ^ γ / β ^ Π boiling of the fuel to which the additive is applied

These kbmbi-nuł-t polymers can also be used with fuma-buymi polymers, all from applications to European patent no. 0 153 176, 0 153 177, 85 301 047 and 85 301 048 Ι - / νι polymers There are polymers and copolymers of oe-olafin with ost ^ and ^^ let me! styrene-maleic anhydride copolymers.

Examples of other additives that can be used together with the quench compound are polyox / alkite-ohd esters, ethers, ether esters and mixtures thereof, especially those containing at least one, and preferably at least two, linear, - ^ / μ A group of / C, C, C, C, and a polyox / alkyl-buwt glycol group with a molecular weight of 100 to 5,000, especially from 200 to 5,000, where the alkyl group of this polyoxyalkylene glycol contains 1-4 carbon atoms. are known from European Patent Specification B 0061895, and other additives of this type are described in US Pat. Ammrica No. 4 491 455.

Preferred esters, ethers and ether esters useful according to the invention can be represented by the general formula RO / A / -OR, wherein R and R are the same or different and represent the groups 1, and · alkylb ^ ^ ^, n-alkyl-C / O ^/ - --łl ^k and ^- oO-C / ^O / - / C ^{H 2} / ^- - lu ^{u n-k} el-yl-C 0/0 / - / CH ^ ^n-C / 0 / - ^p rz ^y where the ^p a ^ ΖΗ ^ ο is a linno-saturated group and has 10-30 carbon atoms, and A bz-joined the polybx / low-boo / glycol segment, in which the alkaloid group has 1-4 carbon atoms and is a group such as a polyoxymeth / lebua, polyoxytitino or polyox / thymerylene group, i.e. a substantially linear group. A certain degree of branching in the form of lower alkyl side chains (such as in polyoxypropylene glycol) may be used here, but it is preferred that the glycol is essentially linbic. Substituent A may also contain nitrogen.

Generally speaking, polyethylene glycols (PEG) and polypopyenne glycols (PPG) with a molecular weight of about 200 to 2000 are generally polyethylene glycols and glycols. Fatty esters and acids with 10-30 carbon atoms are preferred for the reaction. with glycols, in the preparation of ester additives. It is preferred to use fatty acids with 18-24 carbon atoms, especially Uthenbwe acids. Esters can also be produced by esterifying polyoxinic acids or polyoxyoxinate alcohols

153 363

The polyoxyalkylene dieesters, diethers, ester-ethers and mixtures thereof are suitable as additives to the fuel composition of the invention, it being preferred to use diuesters having a narrow boiling point limit. In the course of their preparation, small amounts of monoethers and moneneters may also be formed. It is important for the proper functioning of the additive that it contains a large amount of the two-tone compound. Preference is given to using, in particular, diesters of stearic or tanic acid, or of polyethsesic glycol, polypropylene glycol or mixtures of polyalkyl glycol with polypropylene glycol.

The palm corapposition according to the invention may also contain, As flow-improving additives, ethylene unsaturated ester copolymers Unsaturated monomme which can be copo-mimatized with ι ^ Ιθπθρ include unsaturated mono- and di-esres of the general formula 5, in which Rg is hydrogen or methyl. , Rg is a group of the formula -OOCRg, in which Rg is a hydrogen atom or a linear or branched alkali radical of 1-28, usually 1-17 and preferably 1-8 carbon atoms, or Rg is a group of the formula -COORg, in wherein Rg is as defined above but with the exception of a hydrogen atom, and R? in formula 5 represents a hydrogen atom or a group of the above-described formula -COORg · Manommr, when Rg and R are hydrogen atoms and Rg is the group -OOCRg, includes vinyl alcohol esters of a mono-carboxylic acid having 1-29, and usually 1-18 carbon atoms, or Ponena-hydroxy-acid esters of 2-29, and usually 1-18 carbon atoms, or preferably monocarboxylic acid with 2-5 carbon atoms Examples of vinyl esters which can be copolymerized with ethylene are vinyl acetate, vinyl propionate and vinyl butyrate or isobutyrate, preferably vinyl acetate is used. It is preferable to use such copolymers containing 5-40%, in particular 10-35% by weight of vinyl ester. Mixtures of two copolymers, such as those described in US Patent No. 3,961,916, can also be used. It is preferred that these copolymers have an average molecular weight as measured by the vapor-phase method of 1000-10000 and especially

10005000.

The inventive fuel composition additives may also contain other polar, ionic or non-ionic compounds which in fuels have the ability to inhibit the growth of wax crystals. Nitrogen-containing polar compounds have been found to be particularly effective when used in a cat. with esters, ethers or ether-esters of glycol These polar compounds are usually salts of amines and / abboamides prepared by reacting at least one mole of an amine substituted with a hydrocarbon radical with one mole of a hydrocarbon acid having 1-4 carboxyl groups, or with an anhydride of such acid The amide esters used herein may contain 30 * 300, preferably 50-150 carbon atoms in total. These nitrogen-containing compounds are known from US Pat. No. 4,211,554. Amines having a chain of 12-40 carbon atoms are suitable, these are primary, secondary, tertiary or quaternary amines or their mixtures. Shorter-chain amines can also be used, provided that the resulting nitrogen compound is oil-soluble. For this reason, compounds with a total of 30-300 carbon atoms are usually used. The nitrogen compound preferably contains at least one straight chain in which the alkyl segment has 8-24 carbon atoms. □ ak complementary, suitable are primary amines, secondary, tertiary or quaternary amines are preferably used. Triethioyl and quaternary amine can only form amine salts. Examples of such amines are tetradecyl amine, cocoamines, hydrogenated tall amine, etc. Examples of secondary amines are dioctacedyl amine, methylnishenclcoa amine, etc. Mixtures of amines and many amines of natural origin are also mixtures of a secondary amine, preferably using the formula UNR ^ R ^, where and R ^ are αlkinow groups derived from hydrogenated tallow containing approximately 4% C ₁₄ , 31% C ₁₆ and 59% Ο _χΘ

Examples of carboxylic acids and their hydrates which are suitable for the preparation of these nitrogen-containing compounds are 1,2-cyclohexene dicarboxylic acid, cyclohexene dicarboxylic acid, cyclohexene dicarboxylic acid, and eaftaSnnodidecarboxylic acid, and eaftaSnnodidecarboxylic acid, usually with 5-thirty carbon ring atoms. According to the invention, it is preferable to use benzodiodicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. It is particularly advantageous to use phthalic acid or its ihydrate.

A preferred compound is an amide-amine salt prepared by reacting 1 mole of phthalic anhydride with 2 moles of an amine from a diuretic tall oil, and another preferred compound is a diamide, prepared by de-denaturing the salt of this amide amine.

Hydrocarbon polymers of the general formula 6, in which T is hydrogen or R *, U is hydrogen, the above-described substituent T or an aryl radical, can also be used as a component of the combination used according to the invention for improving the fuel, V is the number from 1, 0 to 0.0 (molar ratio) and W is a number from 0.0 to 1.0 (molar ratio) and R * is an alkyl radical.

These polymers can be prepared either directly from ethenically unsaturated monomers or indirectly, e.g., by liberating polymers derived from others such as isoprene and butadiene. A particularly preferred hydrocarbon polymer is an ethylene propylene copolymer, preferably 50-6C% by weight of ethylene.

The amount of additive required to produce the improved distillate product of the present invention is, depending on the fuel type, generally 0.001 to 0.5%, in particular 0.01 to 0.1% by weight of the active ingredient. amount of fuel · It is convenient to dissolve the additive in a suitable solvent and prepare a concentrate with a concentration of 20-90%, e.g. 30-80% by weight in the solvent · Suitable solvents are kerosene, heavy aromatic petrol, mineral sminwe oils, etc.

Wynnlazek z ^ ubl ^ observed below in the Examples, in which the wax crystal size was measured by placing samples of fuel in the cylinders with a capacity of 60 ml, kept in cold p ^k y ^y Niac ^h at about 8 ° C above the cloud point for 1 hour ^{y d} ustalbilioowania time of the temperature of oil · ^y s ^k Then chodzono rzyni.ę 1 ° C for odzin ^{g s} until reaching a temperature where the field ^ ^ paromar used as filter support ring of sintered diameter of 10 mm, surrounded by a metal with a ring with a width of 1 mm and supporting a silver bemmranooy filter with 200 nm openings, held in place by 2 vertical supports. This filter was placed in a vacuum device, the pressure was reduced to at least 80 kPa and the cooled fuel was fed to ^ ^ and ^ ^ r ^^ the filter with a clean pipette. The fuel was dripped into powdi producing a small puddle just covering the membrane. The puddle was left for a few minutes, then 10-20 drops of fuel were added and the puddle was allowed to drain, leaving a thin, cloudy, dull layer of wax dough moistened with fuel. Too thick a wax layer cannot be properly washed off and a very thin layer may suffer. The optimum thickness of such a layer depends on the shape of the crystals, for leaf-shaped crystals a thinner layer must be used than for ball-shaped crystals. It is important that the final pasty residue is dull. A shimmering precipitate indicates excess fuel remaining in the layer and there is no excess in the crystal and such a precipitate should be discarded.

The thinner layer is then rinsed with kiHoma with drops of betylwljsyrketone and allowed to drain. This process is repeated many times and when the washing is complete the methyl ethyl ketone disappears very quickly leaving a light dull white surface with the surface turning gray with one more drop of methyl ethyl ketone.

The washed specimen is placed in a cold desiccatilr and kept ready to be covered by the SEM assay. It may be necessary to cool the sample to preserve the wax, in which case the sample must be kept in a refrigerated box until it is transferred (in a suitable container) to the SEM test, avoiding the formation of an ice crystal on the sample surface.

Keep the boilioie sample cold during coating in order to minimize damage to the crystals. The electric contact with the base is best achieved by means of a screw holding the filter ring against the side of the seat in the base, shaped so as to keep the sample surface lying in the focal plane of the instrument. Electrically conductive paint can also be used. After the coating is applied, flSobikrlgΓaphic pictures are obtained in the usual way by means of a scanning electron microscope. The photomicrographs are analyzed to determine the average crystal size. For this purpose, a transparent sheet with 88 marked points (as dots) is attached to the photo

153 363 regularly and at equal distances in an 8-row, 11-column grid · The magnification should be such that · only a few of the largest crystals are touched by more than one dot. A magnification of 4,000 to 8,000 times is suitable. At any point of the grid, if the dot touches the dimensions of a crystal whose shape can be clearly defined, the shape can be measured. The scatter in the form of the typical Gaussian length deviation of the crystals is taken into account, as well as the Bessel correction.

The wax content is measured before and after the filters «enl ^ u by means of a scanning ka Prymat ™ differential (DSC /, such as du Pont 9900 series) arrange ^^^ a ^^^ c ^ e ^ go plot o ^ wl .erzchni ^k oło of 100 cm ² / l% of the fuel in the form of wax, with using ^s using an instrument noise caused by the change in the output value. with a typical deviation of less than 2% of the average output signal

The DSC is calibrated with an additive which produces large crystals which. is removed on the filter. Calibration is carried out at the temperature of test 1 WAT is measured of wax free fuel using DSC. Then the fuel samples from fuel tank 1 after fuel are analyzed on DSC. filtzza 1 for each fuel determines the area above the baseline, up to the WAT of the fuel during calibration · The percentage of wax remaining after the filtrzze is defined as the ratio:

go.S2— _x ioo ^^ «^ i ^^ DSC ranks for the tank sample

The temperature of the distillate fuel is determined by the typical IP-219 or ASTK-D 2500 method, or the occurrence of crystallization is measured by the WAP-ASTM D.3117-72 method, and the WAT wax appearance temperature is determined by the differential scan calorimeter method, using a scanning calorimeter Menler TA 2000B

The ability of the fuel to pass through the main filter in a vehicle with diesel engines is determined in an apparatus consisting of a typical main filter of such a vehicle, placed in an ordinary casing in the fuel line.For a 1980 VW Golf passenger vehicle with diesel engines, a type a filter is used for CrmmOts NTC series motor uses a filter

Cumnins FF 105. Fuel tank and supply system, capable of supplying half of a normal fuel tank, connecting with the injection pump used in VW Golf and feeding the fuel through the filter from the tank at a constant speed, just like in a vehicle. Also rmoOlizitjącr devices are used. measurement of pressure drop on the filter, recipe speed from the injection pump and temperature. Receivers are also provided for the collection of the pumped fuel, both • injected and excess fuel · During the test, 19 kg of fuel are placed in the tank and tested for tightness · If the tank is tight, the air temperature is set to 8 ° C above the cloud point and the system is cooled at a speed 3 ° C / hour ^ until the desired leoρerttuΓ is obtained, which is kept for at least 3 hours for the fuel temperature to stabilize · The tank is then shaken vigorously to fully disperse the wax and 1 liter of fuel is withdrawn from the tank at the collection point the samples on the discharge line and the fuel is immediately poured into the tank in the shell · The pump is then started ^^^^ and its rotation corresponds to the driving speed of 110 km / hour · For VW Golf this corresponds to 1900 rpm and the speed engine 3800 rpm The pressure drop across the filter and the speed of the fuel flow from the injection pump are followed until the fuel runs out as usual le occurs after 30-35 minutes.

If the fuel delivery to the injectors can be kept at 2 ml / second (excess fuel is at about 6.5-7 ml / second), the result is good. A drop in fuel flow to the injectors is the limit line and zero flow is defined as a negative result.

A good result may be accompanied by a continuing pressure drop across the filter, which may reach the value of 60 kPa. Usually a significant amount of muui wax pass through the filter to get this result. A very good result is characterized by a pressure drop on fiRzze not greater than 10 kPa, and the first indication of the passage of the main mass of Dsku through the filter is a pressure drop on fiRzze of less than 5 kPa. Additionally, the excess fuel fuel and the injection fuel are sampled every 4 minutes during the test. These samples together

The DSC method is compared with the samples taken from the reservoir prior to starting the test to determine the ratio of the wax passing through the filter. Pre-test fuel samples are also taken and SEM samples prepared to determine the size and type of wax crystals during the test.

The following additives were used in the examples. '

Appendix 1. N, N-dialkylammonium salt of 2-dialkylammidobenzenesuffonic acid, in which the al ^^ groups are n-ZC ^ groups. -w ³³ - 37 / »is prepared by reacting 1 mole of acid anhydride cykllcz nego-l suf0bbnnoo6lowego dwuuwoOdlnlonej with 2 moles of tallow amine in a xylene solvent, wherein the concentration of components in the reaction solution of 50% by weight.

Mleszanin ^ę rea tive ^k t ^{o E being} mixed at a temperature of ^d 1OO ° C to the boiling point of the ^{p d} c ^{h a} n Bovine ^{and Ce} condenser. Solvent and the reaction components should be anhydrous to prevent hydrolysis of the anhydride. The product is analyzed by means of a barium magnetic resonance method and the 500 MHz spectrum confirms that this compound is structured according to formula 7. The molecule model of this compound is given in Fig. 11.

Additive 2 The addition of this sten is an ethylene vinyl acetate copolymer with a vinyl acetate content of 17% by weight and a treszo weight of 3500. The 500 MHz NMR spectrum shows that the aa side chain has 8 methyl groups per 100 methylene groups.

Appendix 3. A copolymer of styrene with maleic anhydride with a molar ratio of 1: 1 is esterified by using 2 moles of an equal mixture of CgHgsOH per 1 mole of anhydride groups in the copolymer. A slight excess (5%) of alcohol and p-toluenesulfonate acid as a catalyst / 0.1 mooa / and the reaction is carried out in xylene. A compound with a molecular weight of 50,000 is obtained, containing 3% by weight of unreacted alcohol.

Appendix 4. 2-N, N-dialkilyl and sodium bicarbonate salts of 2-N, N-dialkyl and tertiary acid are prepared by mixing 1 mole of anhydride. Low fat with 2 moles of diluted ammonium tallow at ⁶⁰ ° C.

The above-mentioned additives are used for fuel improvement and the test results are given in the examples below:

EXAMPLE 1 The fuel used for Follow these characteristics: cloud point - 14 ° ^ appearance temperature t ^o wosłcu -1 ^8.6 ° C. initial boiling point 178 ° C, 20% ² 30 ° C. 90% ³ 1 ⁸ ° ^ ^ ³ ńcowa boiling point 55 ° C. contains ^k u ^ wos tempera round -25 ° C 11% by weight.

To the above described fuel introduced into each of the additives 1.2 and 3 in an amount of 250 ^g portion Wa o ^s c ^h ppm / ppm / ^ip r ^O that was carried out at a temperature of - ² 5 ° C. It has been found that the ^{desired length} of ^c-axis crystal ^g ^ wax you do not ass 1 1200 nm greater than 90% by weight of the wax passed through the filter Cummlna FF105. During the test, the pressure drop on the filter caused by the wax was checked and found that the pressure drop increased by only 2.2 kPa.

Example 11 The procedure of Example 1 was followed and the wax crystals were found to be 1300 nm long. a the highest final pressure drop across the oynoiZ filter _; 3.4 kPa.

Example IU. The fuel used was as follows: cloud point 0 ° C. zjawienia temperature ^SIU wos ^k u - ^2, 5 ^o C. ^p sys ^ę 1 Initial boiling point ⁸² ° C. 20% 220 ° C, 90% 354 ° C. ^k o ⁿ final boiling point of ³⁸ 5 ° C. ^content wos ^{k p} u r ^crib at 1.6% by weight.

To the above described fuel introduced into each of the additives 1.2 and 3, at 250 ppm, and ^p Roby ^p ditch ^d bride, at a temperature of - ^ δυ. ^ ^ a quarter of it, in that the ^{length g} of yszta ^SC ^ ^ ^k of the WOS was 1500 nm, and about 75% by weight of the wax passed through the filter Bosh 145434106th highest pressure drop across the filtzze wycGo ^! 6.5 kPa.

Example IV. Following Example 111, the length of the wax crystal was found to be 2000 nm and about 50% by weight of the wax passed through the filter, with the highest pressure drop across the filter being 35.3 kPa.

EXAMPLE The fuel described in Example HI were added 400 ppm of an additive and 1 100 ^pp m ^ 2. Vacuum addi ^{to p} ditch ^d bride, at a temperature of - ⁸ ° C ^and the temperature raoartlś ^{Æ j} wax wynoosła 1.4% Wagna ^ o . The length of the wax crystal was found to be 2500 nm, and 50% by weight of the wax passed through the filter, and the highest final pressure drop across the filter was 67.1 kPa.

153 363

When carrying out tests with this fuel, a rather rapid increase in pressure drop was found and the test failed. · It seems that, as shown in the photo, the wax crystals were flat, did not pass through the filter and produced on us. impermeable layer. The cube-shaped nasal crystals, o He did not even pass through the filter, produced a relatively loose dough on it, through which the fuel could pass until the thickness of the dough layer became so. large that the pressure drop has become too large ·

Example 6 - comparative · The fuel with the characteristics given in example ΙΧΙ was treated with 500 ppm of a mixture of 4 parts of additive 4 and part of additive 2, in tests at -8 ° C. It has been found · that the ^long-SC wax crystals wynooiła 6 ³⁰⁰ nm and passed through the filter 13% of wax by weight · This Example illustrates the best use of known additives · using which produce very good results database passage crystals through a filter · Photomicrographs of the wax crystals produce in the fuel in The tests described in Examples 1-6 are given in Figs. 1 to 6 of the drawing.

Examples I-IV show that if the crystals can pass through the filter well, very good results at low temperature can be obtained with fuels with a wax content much higher than previously possible, as well as at temperatures lower than the wax appearance temperature Until now, it has been unattainable in practice. These advantages are achieved according to the invention without recycling the fuel from the engine to heat the fuel flowing from the tank and without having to maintain a certain ratio of the amount of fuel fed to the engine to the amount of recycled fuel, and without having to maintain an appropriate ratio of the main filter area to the amount of fuel fed and without the use of prefilters. Examples I-IV also show that if the length of wax crystals is less than about 1800 nm, the fuel operation is remarkably improved.

· Przykłaad VII In this example the additive is added to one of the following destyoowanego fuel nature ^s st.yce: initial boiling point ^ę Initial 1 ⁸ 0 ° C · ^{20% 2} 23% 90 ° ^ 336 ° C · final boiling point 365 ° C · the temperature of appearance of wax t ^{o 5.5} ° C cloud point - ^3, 5 ° ^C ·

For comparison purposes, the following additives were also added to the fuel:

Additive A Mixture of ethylene vinyl acetate copolymers, one of which was the additive 2/1 parts by weight described above, and the other / 3 parts by weight / was a copolymer containing 36% by weight of vinyl acetate and had a molecular weight of 2000 and as branches 2 and 3 methyl groups on 100 methylene groups / → fire → ar 500 MHz NM /

Appendix B. Mixture of additives 4 and 2 in a molar ratio of 4: 1

Additive C A mixture of polyethylene glycol dighenate with an average particle weight of 600

Appendix D. Ethylene-propylene copolymer with an ethylene content of 56% by weight and an average weight of 60,000. These additives were used in the amounts shown in the table below. The tests were carried out using the programmed cooling method / PCT /

Attempt programmable cooling / PCT / · In this test, the fuel is subjected to a slow cooling so · to bring them into poipowónia stored cooking oil · the cold flow of fuel containing the additives are determined by the PCT in this way keep in mind that 300 ml of the fuel ^c hl ^of today ^SIU równon Ernie ^ of ^ ^^ bone ° C / h ^e a ^desired temperature, reg wk ^ ^ ^ words, it will attempt ^bE, and this temperature is kept constant for 2 hours · then removed from the surface of about 20 ml of the fuel, to prevent the formation of abnormally large wax crystals, which may form on the surface of the oil in contact with air during cooling, and which could interfere with the test procedure. The wax embedded in the bottle is dispersed with gentle agitation, then the CFPPT filter set is placed, i.e. the set used in a cold plugging test, described in detail in the Journal of the Institute of Petroleum, vol. 52, no. 510, June 1966, pages 173-185. The valve opens, creates a pressure reduced to 667 hPa and it closes when 200 ml of fuel flows through the filter into the aimed container. A good / PASS / result is obtained when 200 ml of fuel accumulate in the receptacle through a sieve with a defined size of openings within 10 seconds, and a bad result / FA1L / It is when the flow rate is too much to prove that the filter is blocked · Records the size of the holes in the sieve / mesh / ·

153 363

Example VIII. This example uses a fuel with the following ASTM-D86 ^y characteristics: {initial boiling point 190 ° C, 20% 246 ° C,

90% 346 ° C ^"k ońcowa b.p. ³⁷⁴ ° C, the appearance wos t ^o u ^{k -1,} 5 ° C, the temperature of clouding ^2, 0 ° C. To this was added ^p aliwa t ^{o y} WOO ppm part Tripartite substance given below of additives · / E / A mixture of 1 part by weight of Appendix 2 of 9 parts wagowyal Appendix 4.

/ F / Ethylene vinyl acetate copolymer, manufactured by Εχχοη Chemicals As additive ECA 5920 / G / Mixture of 1 part additive 1, 1 part additive 3, 1 part additive Dii part additive K / H / Ethylene vinyl acetate copolymer, manufactured by Amoco as additive 2042E.

/ 1 / Ethylene-vinyl propioniene copolymer, produced by BASF as an additive 5486 · / □ / no additive · / K / The product of the reaction of 4 moles of dihydrogenated tallowamine with 1 mole of pyromellitic anhydride. This reaction ^is carried out. ^{E B} ez spread uszczalni ^p * ^k and stirring at 15 ⁰ C for 6 hours under nitrogen.

In this test, determined as defined below fuel property · / i / fuel's ability to flow through a main motor filter H ° koprężnego in temppraturze -9 ° C and ^p rocent wos ^k u ^ «^ Chio ^p-limiting slaughter iltr ^f ^ ^D CAD and ^{when p} and r ^crib gives ^p axis ^y above omniin bad result. These variations are given in Table 1

Table 1

and Appendix 1 1 L.. 1 Time until the moment when the attempt is wrong % passing wax 'E 1 11 minutes ¹ 18-30% and F 1 | 16 minutes thirty% ¹ G 1 good result and 90-100% H. 1 15 minutes 1 25% l I 1 | 12 minutes 25% ¹ □ 1 9 minutes and 10% F ----------- - - _ _ u / 11 / Pressure drop on main filter as it runs time is given in Fig. 12

/ II1 / Deposition of wax palwwach was measured by cooling 100 ml of fuel in a graduated cylinder, ^k t ^o r ^y c ^hl of ^d bride, with solid ^and h ^ bone ^ l ° C / it ^d zin ^E O ^d a temperature higher tarzystnie 1 ⁰ ° C * and at least about 5 ° C for the ^d temperatures ^p aliwa ^d of tempeeatury in angle ^yellow reg leads t ^{o p} r ^{would be and} in which is maintained a fuel for a time period · Tempe ^ here ™ is and the duration of fuel this temperature depends on the destination of the fuel mianowwcie whether it is a diesel fuel or fuel for heating purposes · Preferably, this temperature is at least 5 ° C lower than ^d temperature m ^ tniθnia, and the retention time ^{of p} aliwa at this temperature is at least 4 hours. This temperature should, however, preferably be at least 10 ° C lower than the cloud point of the fuel, and the fuel keeping time at this temperature should be 24 hours or longer.

At the end of the test, the graduated cylinder is examined and the amount of wax deposition is determined visually by measuring the height of the wax layer above the cylinder bottom / 0 ml / and determining it as a percentage of the total volume / 100 ml / Above the deposited wax crystals, sticky ones can be seen the fuel and the height of this fuel layer is often a sufficient measure of the wax deposition process. Sometimes the fuel above the wax crystal layer is cloudy or the crystal layer is clearly denser towards the bottom of the cylinder. In such cases, a more precise method can be used. Namely, 5% / 5ml / fuel is gently sucked off the top and stored. Another 45% is sucked off and discarded, a further 5% is sucked off and stored, then a further 35% is discarded and finally the bottom 10% is collected when heated for dissolving wax crystals The stored samples are defined below as top, middle and bottom samples.

So that the reduced pressure used to withdraw the samples is slightly less than atmospheric, namely by 200 hPa, and that the pipette is placed only on the surface of the fuel, to avoid velocities that could disturb the wax concentration in the various layers in the cylinder. The samples t ^o ff ^ę then for 15 minu ^t ^ mperaturze at 60 ° C and examined their wax content of the above-described method of differential scanning calorimetry.

For this purpose, the Meller TA 200CB DSC is used. A sample of 25 microliters of fuel is placed in the pan for a sample and pan Comparative there is usually a kerosene and cooled with ^p rędkością ²² ° C / min with a ^d 60 ° C to a temperature higher by at least 1O ° C, preferably 20 ° C ^ lower than the wax temperature / WAT /. ^EP NAET not cooled ^SIU to the ^p r ^e dkością eye ^ 2 ° C / minute temperature ^{E of} the eye of about ^{2 L} 0 C lower than the WAT of ^d. These include ^s also lead test subjects with no build-up or cooling fuel. The size of the wax deposition is then correlated with the WAT / u or ∆ WAT "WAT of the deposited sample minus the WAT of the original fuel sample /. Negative values show the removal of wax from the fuel and positive values show a wax enrichment during deposition. The wax content can also be used as a measure of sample deposition. This is illustrated by% W ^ or Δ,% W ^ X, with 2Ϊ%% WAX in embedded sample -% WAX in original sample. Again, negative values show the removal of wax from the fuel, and positive values indicate the wax during deposition.

RDP ^d ar- Prot> s ^ c ^h odzono the fuel rod ^EDK spears ° C / h ^E from 10 ° C to a temperature ^y -9 ° C and left at this temperature for about 48 ^{g k} res odzin before okrt ^COG Lantana results. The test results are given in Tables 2, 3 and 4 and are shown graphically in Figure 13.

Table 2

Visual assessment of layers in the wax deposition process

Addition

^{K COG} many of those ⁱⁿ the AT for the samples subjected to the deposition of wax

-------------- x- _r -----------------—-------------—

Top 5% Middle 5%

Denne 10%

E. 1 and Completely cloudy 1 1 1 1 1 1 and thicker at the bottom 1 -10.80 , - <00 , -3.15 F. and Clear above 50% 1 -13.35 1 -0.80 • -0.40 G. 1 100% clear 1 1 - 78B5 1-7.40 ¹ -7.50 H. and Clear above ± 35% 1 -13.05 and -8.50 and * 0.50 AND 1 Clear above 65% 1 1 1 1 1 1 1 □ 1 100% half gel 1 - 6.20 and -6.25 , -6.40 . . J. T a b e 1 a 3 Addition 1 ^1, the WAT C ^{d p} la aliwa not, Size 1 WAT ° C ^dl and ^p e ^k r ^crib subjects 1 AND subjected to deposition myself ₍ deposition get wax 1 wax 1 1 Top 5% 1 Middle 5% , Denne 10% --AND . - J. E. and -6.00 and -4.80 ^and * 2.00 and +2.85 1 F. J -5.15 1 | -8.20 ^and * 4.35 '+4 ^, 75 1 AND G. , -7.75 -0.10 '* 0.35 , * 0.25 1 H. and -5.00 and -8.5 '-3.50 and * 4.50 1 □ «-6.20 1 ^0, 00 1 -0.05 and -0.20 1 I _ 1 . - J. It should be noted considerable you get mixed up WAT, caused by the most effective

dod ^ tkeem G.

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Table 4

Addition

^The size of AT ° C in vacuum ^{k b} e treated

and embedding sir wax ¹ Top 5% 1 middle 5% 1 Denne 10% AND - -i - _r - E. , -0.7 1 * 0.8 ♦ 0.9 F. '-0.8 1 1 * 2.1 1 ♦ 2.2 G. J ± 0.0 1 ♦ 0.3 1 ♦ 0.1 H. and -1.3 1 l -0.2 1 | ♦ 1 · 1 J. '-0.1 1 ♦ 0.0 AND ♦ 0.1

These results show that the size of the wax crystals decreases in the presence of additives and the wax crystals deposit relatively quickly. For example, fuels without additives, when cooled to temperatures below their cloud points, show little deposition of wax crystals, as the lamellar crystals mesh with each other, they cannot move freely in the liquid and a gel-like structure is created.However, when a flow improver is added to the fuel, the crystals may change, become less like plates, or rather form tens of micrometers of needles that can move freely in the liquid and settle relatively faster. This deposition of wax crystals can create problems in storage tanks and running gears. Thickened wax layers can be pulled off unexpectedly, especially when the fuel level is low or the contents of the tank are confusing, e.g. when the vehicle curves and the filter may then be blocked · □ e if the dimensions of the wax crystals can be further reduced to less than 10,000 nm, then the wax crystals are deposited relatively slowly and the anti-wax / WAS / umm makes the fuel work better than that of the fuel in which the wax crystals are deposited the size of the wax crystals can be reduced to below about 4000 nm, then it almost completely eliminates the deposition of crystals during fuel storage. If the crystal size is preferably lower than 2000 nm, then the wax crystals remain suspended in the fuel for many weeks and then the problems with fuel storage are generally completely solved · / iv / Table 5 shows the results of tests carried out with additives reducing the clogging temperature of the filter when cold / CFPP /.

Table 5

Γ Addition 1 ^and CFPP temperature in ° C 1 -1 -------------------. ¹ Temperature setback CFPP i given in ° C - - - - - | | -------- ’- - η E. -14 AND and 11 F. , -twenty '17 G. • -twenty ¹ 17 | H. ¹ -20 and 17 AND '-19 AND and 16 J. and “3 -i- - - - - - - - - - -

Table 6 shows the diagonal sizes of the wax crystals when using the additives also given in this table.

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Table 6

The size of the crystals in nanommers _t Addition ι E. 1 1 4400 ¹ F. 1 10400, G. 1 2600 i H. 1 1 10,600 J AND 1 640 i □ 1 1 thin plates above 50,000 nm

Claims (4)

Patent claims A fuel composition comprising a wax-containing distilled fuel and a wax crystal modifier at low temperatures, characterized in that the modifier comprises an additive that shapes the size of the wax crystals at low temperatures, which is a chemical compound with at least two substituent groups that have a spacing and a configuration enabling them to occupy the position of wax molecules in the / 100 / and / abbo / 110 / and / abbo / 111 / planes in the wax crystals, where these substituent groups are alkyl, alkoxyalky or polyalkoxyalkyd groups with at least 10 atoms in the main chain, ^p y ^y nHszej then at ¹⁰ ° C with a temperature ^{yp d} ojawienia ^k of the WOS komppoycja contains wax crystals of a size smaller nil 4.000 nanommirów. 2. A wax comoption containing wax and a wax crystal moiety at low temperatures, characterized by the form of a wax crystal-size additive at low temperatures, which has a chemical compound with at least two substituent groups that have spacing and configuration enabling them to occupy wax particles in the wax crystals at the intersection of the / 001 / and / llx / planes, e.g. / 110 / and / or / 111 /, where these substituent groups are alkyl, alkoxyalkyl or polyalkoxyalkyl groups at least 10 carbon atoms in the main ^EXAMPLE n ^{C ear p} y ^y wherein at nHszej 10 ° C for the ^d temperatures ^s concept and know present ^SIU wax ^k ompoz ^y tion contains wax crystals size mnnejszej nil 4.000 nanommtrów. The commooxication according to claim 2, characterized in that as subfixatdr comprises a chemical compound having at least two i-alkydivt groups with more than 2 carbon atoms and having a distance between them in the order of 0.45 to 0.55 for. A comoposition according to claim 2 or 3, characterized in that I, as modifier, comprises a chemical compound in which the plane angle between two planes of the local symmerri is ^hg r ^ u ^p n-alkHw res · 7 ⁵ -90 ° C. 153 363 ' AND FIG. 3 153 363 σ e s £ 6 ° £ 50 FIG.12 T? 0 153 363 Temperature A _{x Z} XR ^ł C. I b ^{/ Cx} y ^-r2 AND B ^ ^c Formula 2 D H and i J. 1 I c-c- . and I ι k-c- 1 i E G k L _j m Pattern b Re Rs' Pattern 5 o H 'R? T H U H. —C cH -C-C- T T L j V H U - - In 'Pattern 6 R '' S (j NH Formula 7 Department of Publishing of the UP RP. Circulation 100 copies Price: PLN 3,000