SU399145A1 - METHOD OF OBTAINING HYDROCARBON FUEL FOR ENGINES FOR INTERNAL COMBUSTION ENGINES - Google Patents

Description

one

This invention relates to gelled hydrocarbon fluids that are used in internal combustion engines, in particular gas turbine engines; such gelatinized hydrocarbon liquids are suitable for use as aircraft fuel.

Such gelatinized hydrocarbon liquids are needed, used as fuel for aircraft engines that can be transported through pipelines from one tank to another or from tank to the engine, but which, in the event of an accident or spill, quickly take on the original gel structure, and thus minimize distribution of ogp in case of fire.

A known method for producing a gel-like hydrocarbon fuel by thickened with metal-containing soap.

However, gelatinized hydrocarbon liquids in this way do not return to their original gel-like state when they are subjected to mechanical stress or transported through pipelines. In addition, due to the high metal content and pain sensitivity of the gel to water and other floor liquids, such gelatinized hydrocarbon liquids are unsuitable for use as a fuel for internal combustion engines.

In order to eliminate these drawbacks, it has been proposed to use as a thickener a polymeric material containing polar groups, forming associative bonds between polymeric materials with the formation of a transverse polymeric structure.

Associative bonds are those resulting from electrostatic attraction between polar and / or dipolar groups, and these bonds can be broken and restored again without

any change in the nature of the polar groups.

The energy of the groups should be at least as much as the energy of the hydrogen bonds resulting from

the interactions with the OH-groups of ROH and the -0 RORi groups in hydrocarbon liquids, where R and RI are alkyl groups. Communication energy should not be commensurate in magnitude or

to be more bond energy than a typical C – C covaleptic bond. The hydrocarbon liquid may contain small amounts of other liquids, such as ethers and esters, ketones and nitronaraffins, especially in

those cases when energ associative

connection in a hydrocarbon fluid above the minimum set. However, since the nature of the fluid influences the associative link energy of any given source, the energy of the associative link is reduced; with an increase in the fluid's fluidity, but this irichina hydrocarbon liquids should not contain significant amounts of prototypes that mix with them, such as methanol.

Polar groups, which can be simple or rather complex, have the ability to form associative bonds with similar groups in polymers of the same type, or the associative binding can be dried, and the pairs can be combined with each other and preferably with so that these complementary groups interacting with each other are contained in different polymers.

When using the described gel-like hydrocarbon liquids as fuel for aircraft engines, it is desirable and desirable that the gelatinization of the hydrocarbon liquid, i.e., its mixing with gelling ageit, is carried out and carried out before the aircraft is filled with fuel. In this way, it is possible to minimize the transportation of gelatinized liquid through pipelines at Pasomas iomoishchi.

Simple polar groups contain a single polar group, which provides for the formation of hydrogen bonds and bonds that arise as a result of the interaction between ions or between strong dipoles, such as, for example, that occur in ion pairs with a separated charge.

Suitable hydrogen bonds are those formed between hydroxyl, carboxyl, amine, amidium, and mercaptan groups, either between groups of only one type, or between two types of these groups. The formation of hydrogen bonds can also occur between one of these groups and oxygen (or sulfur) in ethers and, finally, between one of the above groups and the tertiary base. Among the suitable bonds between strong dipoles are the bonds that arise between such ions as betaines and sulfobetaines, quaternary ammonium salts, and sodium (or other metals) acid salts.

Suitable bonds between ions occur in the case of tertiary bases and acidic groups of carboxylic acids, sulfonic acids, phosphonic acids, as well as sulfate hemi-esters and phosphate esters, between amines and sulfonic acids, between amines and phosphonic acids, and also between polyvalent metallic ions, and calcium, magnesium and aluminum, and acid groups. The associative bonds between such ions are strong, as well as the bonds between quaternary ammonium bases and hemi-esters of sulfuric acid or sulfonic acids, which are among the strongest bonds that can be used in the proposed method.

Complex polar groups can be formed in solvated polymers due to the presence of many weak polar groups that mutually reinforce each other; this is the result of a certain arrangement of such groups in the polymer segment, which is insoluble and, therefore, is destroyed only in the hydrocarbon liquid. Among the weak polar groups that can mutually reinforce each other and are capable of decouple the associative binding of complex polar groups are the ether atom of ether, ether carbonyl and nitrile.

These polar groups, simple or complex, must be present in polymers and relative to these groups they must have an average number of functionalities in the minimum case — more than two, and in the optimal variant — more than 10.

The weaker the binding energy or the larger the molecular weight of the polymer, the more important the function of the polymer should be; the functionality of the polymer can reach 100 or even more in polymers with molecular weights of the order of a million or more, containing sex groups that are capable of forming associative bonds of medium strength (for example, COOH-P2) or weaker bonds.

0.1-10% by weight of a used iolimer is added to the liquid to be gelled.

Even if metal ions are present in the polymers used to obtain the proposed gel-like compositions, the amount of metal introduced in this way into the hydrocarbon is so significant (due to the high effectiveness of the gelling agent) that it can be acceptable even if the gel-like product is supposed to be used as a motor fuel.

The solvated polymer may be soluble in the gelled liquid or it may be in the form of particles that swell in the liquid. In the first case, the polymer chains are linked through associative bonds to adjacent polymer chains, and in the latter case, the swollen particles are bonded to each other using associative bonds between polar groups of closely spaced particles. In both cases, a three-dimensional polymer structure is formed, which is solvated by a liquid and thus provides gel formation.

In cases where the polymer is dissolved in a liquid, the gel effect of this polymer is enhanced by the introduction of fine particles of combustible material, also containing polar groups, capable of forming associative bonds with polar groups of the dissolved polymer. Such particles provide a high content of functional nodal points in the transversely bound structure. In this case, it is desirable that the polar groups in these particles are complementary to the polar groups of the dissolved polymer, so that associative links arise mainly between the particles and the dissolved polymer.

The best option is such a gelation option, where soluble polymer containing polar groups is used in association with polymer particles that swell in an organic liquid and contain complementary polar groups.

In another embodiment, the particles used in conjunction with a soluble polymer are combustible material that is not solvated by liquid, but contains polar groups. Such materials include carbon black, cellulosic fibrous substances or crystalline compounds that are obtained as the reaction product of n-butyrolactone with long chain amines derived from coconut oil. The mentioned particles may consist of such crystalline organic substances, which are mono- or poly-doped aromatic compounds containing carboxyl, hydroxyl, amine, amide, sulfonium, phosphonium and other polar groups.

The most preferred size of the particles used is in the range of 0.01-5 μm; in cases where the particles are polymers that swell in a liquid, as a result of the swelling, the size of the particles (and hence their volume) may increase tenfold or more by comparison with the original volume. These figures characterize the optimal size of particles in the unswollen state.

The molecular weight of the soluble polymer should be at least not less than 10,000 (meaning the average viscosity molecular weight), and it is desirable that it be at least about 100,000. When using a lower concentration of polymer, its molecular weight should be less than dca 1,000,000 and more. However, half measures, the molecular weight of which is higher than 10, cannot be used in a concentration exceeding 3% of the weight of the gelled liquid.

Swollen polymer particles, regardless of whether they play the role of a primary gel or nodal, reinforcing

the effect of gelation of points, respectively, includes in its composition a polymer which could be soluble in a liquid, but which has a three-dimensional structure formed by covalent or associative bonds, causing the lipid to swell in a liquid. In this case, the degree of swelling depends on the amount (dense :) of crosslinks in the polymer and can vary from 0.1 to 10% depending on the nature of the polymer and the liquid. The crosslink density is the percentage of those portions in the polymer chain that are crosslinked. The cross-linking of the polymer in the particles can be achieved by using an appropriate amount of difunctional monomer or by using comonomers containing groups that

are capable of forming cross-links as a result of the condensation reaction or the help of a strong association. As polymers used as gelling agents according to dannol y

It is convenient for the method to use polymers obtained by the freedoms of 10 radical polymerization, since this is one of the simplest ways to obtain} and them. For ispolzovapp as geleobrazoateley in hydrocarbons, mainly aliphatic) nature solvatiruem) 1e polymers and long chain esters of unsaturated acids and 1enasyschennyh alcohols, e.g. stearnlovye lauryl, octyl, 2-ethylhexyl and hexyl esters of acrylic methacrylic acids and the corresponding esters of acids with a long and vinyl alcohol, for example vinyl stearate, etc. As monomers

using also the corresponding long chain ethers of unsaturated alcohols, for example, vinyl octadecyl ether. In addition, polymers of various alkenes are suitable, such as butadiene, isonrene

and isobutylene, as well as non-crystalline polymers of ethylene and propylene.

As gelling agents in aromatic hydrocarbons (or, mainly, aromatic), a number of similar ones are used.

polymers and, moreover, analogs with a whiter short chain, for example, polymers ethoxyethylmethacrylate 1, methyl methacrylate and egylacrylate, as well as polymers on ocH; i ie vin l benzenes, air polymer of styrene and vinyl toluene.

The term includes c (M olimers, since the corresponding polar groups in appropriate amounts can be introduced into the olimer by using 1

comonomer containing gruii1. Comonomers suitable for the introduction of simple polar groups such as acidic include acrylic and methacrylic acids, maleic anhydride, vinyl sulfonic acid, styrene sulfonic acid, and intraphosphate.

and phosphonium efframes of unsaturated () P-containing compounds, such as, for example, hydroxyisopropyl methacrylate ester. Vinylpyridine, vinyldimethylamine, H, M-dimethylaminoethyl methacrylate and Greg-butylamidioethyl methacrylate are used as comonomers suitable for the introduction of simple polar groups having the basic character. Groups such as sulfone are introduced into the polymer using vinylmethyl sulfone. After the polymer has been obtained, some preferred highly ionic and dipole groups can be introduced into it. This is done, for example, by neutralizing acidic groups or by forming quaternary ammopium bases on the main groups.

Monomers suitable for use with those containing weak polar groups (in combination) that can ensure the formation of complex fields of groups in solvated values include dipilmethyl ether, vinylmethylketone, methyl methacrylate, methyl acrylate, methacryloyitrile, vinyl chloride and vinyl acetate. These monomers contribute to the formation of side chains or segments that are not solvated by the hydrocarbon liquid and which thus ensure the existence of complex polar groups in the main polymer chain solvated by the hydrocarbon liquid.

Another class of polymers suitable for use in accordance with this method includes hydrocarbon polymers, for example, those which are prepared by nc alkenob.

Such polymers are usually obtained by ion polymerization and, since the polar groups to be contained in the final polymer can deactivate the ionic catalyst used to initiate the polymerization, they usually first obtain the hydrocarbon polymer and then modify it by introducing the polar groups necessary for the polymerization. the formation of associative links. Suitable hydrocarbon polymers for the above purposes are non-crystalline polymers and copolymers derived from monomers such as ethylene, propylene, isobutylene, butadiene, isonrep, and other higher a-alkenes, such as alkenes, obtained from the processing of crude oil. Natural rubbers are also used. These polymers are then modified to introduce the desired polar groups.

In cases where the hydrocarbon polymer contains residual unsaturation, i.e., one or another number of multiple bonds, polar primers are introduced through the addition reactions, for example, by addition of thiols (such as for example thioglycolic acid), aldehydes, halogens, or by eksdirovanie. In some of these cases, the groups thus introduced need to be modified to ensure the formation of the desired sex groups; for example, halide or hydroxyl groups resulting from the addition of aldehydes through multiple bonds of a hydrocarbon polymer can be modified in this way. In addition, the corresponding polar groups are introduced by means of an addition reaction to certain carbonate-containing soils over the unsaturated groups of the polymer. In those cases when the hydrocarbon polymer contains a small number of multiple bonds or they are almost completely absent,

the desired polar groups are introduced into said hydrocarbon polymer by means of substitution reactions, for example, by halogenation, chlorosulfirophene, chlorocarbonylation, phosphorylation or maleinium. When the hydrocarbon polymer contains aromatic rings (for example, styrene copolymers), the desired polar groups are introduced using classical substitution reactions in the aromatic core.

Solvated polymers are typically condensation type polymers such as polyesters, aromatic polyoxides and aromatic bicarbonates, the molecular weight of which should be

quite high.

The strength of the gel obtained in organic liquids by this method may vary widely depending on specific requirements. To reduce fluid flow in the event of a spill (especially important when it comes to fuel), it is desirable that the gel strength be sufficiently high; however, there are certain strength limitations, since the gelled

fuel must be able to move as a result of mechanical action from the fuel tank to the engines. This restriction largely depends on the location of the fuel tanks and lipias, according to

which receives fuel to the engine.

You can provide special systems

allowing to regulate the gel "urgency"

in gelatinized fuels.

Roughly, the ability to adjust the gel strength within the desired limits is as follows. Opened at both ends, a cylinder with a diameter of 20 cm and a height of 20 cm in height that was also internally tilted was placed vertically on a flat, level plate so that

so that the lower end of the cylinder is snug against the plate. The cylinder is then filled with a gelled fluid intended for testing. L liquids allow for sufficient time for the gel-like structure to be restored by nolost, the cylinder being raised vertically upward, thus leaving the entire mass of gel-like liquid to stand without support on the plate. This weight is deposited and spreads over

a plate. If the mass spreads on a plate in such a way that the layer obtained on the plate has an average thickness of about 1 mm or less, then the gel is not sufficient to, to some extent, improve the safety of the operation with said fuel. If the mass remains on the plate in the form of a layer, the maximum height of which is at least 10 cm, then special designed fuel systems will be required in order that such fuel, when used as fuel in aircraft, can be moved from tanks to engines. As an example of such a system, you can specify flexible, soft fuel tanks operating under external pressure.

If the gelled liquid spreads to such an extent that the average thickness of the formed layer lies in the region of 0.5-5 cm, then conventional or slightly modified fuel systems can still be used. All on-off gel-like fuels are satisfactory in terms of safety, they can be stored in fuel tanks, pumped and used in aircraft gas turbine engines.

Example 1. A 5% solution of a copolymer of stearyl methacrylate and dimethylaminoethyl methacrylate (98: 2), having a molecular weight of about 500,000, is shifted in kerosene with an equal in weight of 50% solution of a copolymer of stearyl methacrylate and methacrylic acid (98: 2), having a molecular weight of 500,000, in kerosene. In the resulting mixture, a gel-like structure is formed, which is disrupted by mechanical action and quickly restored when this effect is stopped. A lump of gel is burning, not spreading, in a compact mass.

Example 2. A mixture of 120 parts of acetone, 80 parts of isopropanol, 25.7 parts of stearyl methacrylate, 0.92 parts of ethylene glycol dimethacrylate, 0.5 parts of isopropyloxane and 45 parts of a 45% aqueous solution of polymethyl methacrylate with terminal carboxyl groups, having The average molecular weight, on the order of 10,000, reacts with glycidyl methacrylate at reflux for 30 minutes. A mixture of 141.6 parts of stearyl methacrylate, 5.14 parts of glycol dimethacrylate and 3 parts of isonyl peroxydicarbonate was refluxed for 3.5 hours, after which the kiln was continued for another 0.5 hour. The product is a 45% dispersion of particles of a cross-linked polymer stabilized in a mixture of acetone and isopropanol by solvated polymethyl methacrylate chains attached to it. 90% of the organic liquid is removed and the polymer is introduced into kerosene in an amount of 10% by weight of kerosene. Polymethyl methacrylate values, initially solvated in a mixture of acetone and isopropanol, lose their solvation shell.

but then the polymer particles swell in the kerosene and a gel is formed, which is destroyed by the action of the mechanical force and quickly restored. Gel-like. Mass burns

Do not spread out.

Example 3. Latex of a copolymer of 2-ethnylsxylacrylate of n acrylic acid (9: 1), having a weight average molecular weight of 4-10, is prepared by the method of aqueous emulsion

polymerization. The copolymer was dissolved in kerosene, added latex to the boiling mixture of kerosene and cyclohexane, taken in the ratio 9: 1, at such a rate that water did not get into the boiling mixture. At a concentration of 2.5%

copolymer kerosene is slightly gelled due to the formation of associative bonds between carboxyl groups.

Example 4. Styrene, butadiene and acrylic acid sonolymer latex (60:30:10)

obtained by the method of water-emulsion polymerization. It is added to kerosene as described in figure 3, but since, because of the presence of butadiene, the soyolimer has a certain number of randomly arranged cross-links, the polymer particles do not dissolve in the kerosene, but gradually spread throughout its volume, gradually swell. The latex of a copolymer of 2-ethylhexnlacrylate and dimethylaminoethyl methacrylate (4: 1) with an average molecular weight of 500,000, obtained by water-emulsion polymerization, is dissolved in kerosene as described in Example 3. When the 1.0% disbox of the carboxyl-containing polymer is displaced with equal in volume of a 1% solution of an amine-containing sonolimer in kerosene, a gel is formed, as a result of the occurrence of associative bonds between the carboxyl groups of the swollen particles and the amino group of the dissolved sooi Imera.

EXAMPLE 5. 8 parts of carbon black are dispersed in 100 parts of a 2% solution of the amine-containing copolymer described in the previous example, in kerosene. In this case, a strong gel is formed due to the occurrence of associative bonds between the amino groups of the copolymer and the carboxyl groups present on the surface of the carbon black particles.

Example 6. A 0.5% solution of N-cocohydroxybutyramide in kerosene is mixed with a 0.5% solution of a polymer, onisanium in yrimer 3, in kerosene at 50 ° C. The solution is cooled to room temperature, resulting in the crystallization of K-cocohydroxybutyramide in the form of fine particles. In this case, the formation of a gel is observed as a result of the occurrence of associative bonds between the amide groups of the particles and the carboxyl groups of the dissolved copolymer.

Example 7, including calcium acetate, is added to 100 parts of a 1% polymer solution,

described in example 3, in kerosene at 140 ° C.

Acetic acid is distilled off and, when the solution is cooled to room temperature, a gel is formed as a result of the associative cross-linking of the carboxyl groups of the dissolved copolymer due to the formation of calcium salts.

Example 8. 500 parts of a 1% solution of the ammonium-containing copolymer described in Example 4 are heated in kerosene to 120 ° C and 1 part of propanthone is added. The mixture is cooled to room temperature; in this case, gelation occurs as a result of the occurrence of associative bonds between sulfobetaine zwitterionic groups.

Example 9. By the method described in Example 3, a copolymer of 2-ethylhexyl acrylate, acrylic acid and dimethylaminoethyl methacrylate (96: 2: 2) is obtained, the weight average molecular weight of which is 3-10. This copolymer was dissolved in kerosene to give a 1% solution. This solution is gelled as a result of the formation of associative bonds between the carboxyl and amipic groups of the copolymer.

Example 10. A copolymer of 2-ethyl hexyl acrylate and acrylamide (90:10) with a molecular weight (weight average) of the order of 2-10 is prepared and dissolved in kerosene in a manner similar to onnsagumine in example 3. A 1% solution is gelatinized as a result of the formation of associative phosphorus. s between the amide groups of the solvent copolymer.

Example I. 5 parts of a copolymer of lauryl methacrylate and hydroxypropyl methacrylate (1: 1), having a weight average molecular weight of about 2-10, are dissolved in 95 parts of hot (60-70 ° C) kerosene. After cooling to room temperature, the formation of a weak gel is observed (as a result of the associative binding of the hydroxyl groups of the copolymer).

Example 12. A 1% solution of the carboxyl-containing copolymer described in example 3 in decahydronaphthalene is mixed with a 1% solution of the amine-containing copolymer described in example 4 in decahydronaphtalene in the ratio 5: 1. Gel formation is observed, and a similar, but slightly weaker gel is obtained when using a 0.5% solution of gelling agents.

Example 13. The amino-containing, ip copolymer used in Example 12 is replaced by a copolymer of 2-ethyl hexyl acrylate and pyridine (4: 1) with a weight average molecular weight of 500,000. At the same time, similar results are obtained. The formation of a gel is observed due to the occurrence of associative bonds between acidic and basic groups.

Example 14. By means of dispersion polymerization in kerosene, a dispersion of particles of a maleic CQ styrene copolymer with styrene (1: 1) is obtained. The weight average molecular weight of the copolymer obtained is at a level of 210. The copolymer thus distributed is then subjected to modifications in kerosene, adding diddecylamine in a ratio of 2: 3.5 and heating the reaction mixture to a temperature of 100 ° C. The resulting amide resulting from the reaction is dissolved in kerosene. The 3% solution of the reacted copolymer in kerosene is a gel-like mass, the formation of

which is due to the occurrence of associative bonds between the carboxyl compound and acid amide.

Example 15. 500 parts of a 2% solution of the substituted acidic amide described in Example 14 are heated in kerosene to 140 ° C and 2 parts of zinc acetate are added. This temperature was maintained until acetic acid was distilled off, and then the solution was cooled to room temperature;

this results in the formation of a gel as a result of the formation of associative cross-links between the carboxyl primers of the acid amide and the two-charged zinc cations. The reason for the creation of gel

The structure is the formation of zinc salts of acid amides.

Example 16. 1 part of dimethyl sulfate was added to 500 parts of a 1% solution of the amine-containing copolymer described in Example 4,

in kerosene, and the mixture is pagreyut to 60 ° C for 1 hour, then cooled to kompatpy temperature. The quaternary ammonium salt thus obtained is treated with an ion exchange resin of the main character,

to get quaternary ammonium hydroxide. This solution is mixed with an equal in weight of a 1% solution of a 2-ethyl hexyl acrylate sonomer and vinyl sulfonic acid (95: 5) having a weight average molecular weight of 2-10 in kerosene. The resulting mixture forms a very strong gel due to the presence of strong associative bonds between acid groups and quaternary ammonium hydroxide.

Example 17. A solution of 7 parts of a graft copolymer of poly aryl methacrylate (average molecular weight of about 10) and polymethyl methacrylate (with an average molecular weight of about 10,000) —a average of about 30 side chains on one main polymer chain at 20 h. xylene is diluted with 73 parts of an aliphatic hydrocarbon (boiling in the range of 140-190 ° C). The polyauryl methacrylate backbone of the copolymer remains a solvated mixture of hydrocarbons, but the polymethyl methacrylate side chains lose the solvation shell and weak dipoles of the ester carbonyl groups reinforce each other.

friend, form a complex polar group. In this case, the formation of a gel is observed due to the occurrence of associative bonds between these complex polar groups located along the main polymer

chains. In all the examples, Avtur Avtur / 50 Avnaiopnip kerosene is used as kerosene. Similar results are obtained when using other types of aviation-type kerosene, such as for example the well-known IP1 and IP5 kerosene, aviation gasoline for turbines (Avtag) and the well-known IP4 gasoline. In cases where the gel-like liquids described in the examples are obtained by mixing two polymer solutions and when these liquids are intended to be used as fuel for aircraft engines, polymer solutions are mixed immediately before filling the fuel tanks. PRIORITIES 3 ABOUT AND 1. Method for producing gel-like hydrocarbon fuel for internal combustion engines by means of hardening, expansion of hydrocarbon fuel, which is due to the fact that, with a pellicle, the characteristics of fuel and fuel and an increase in gelatinization, as a thickener, polymeric material is used that contains polar groups that form associative bonds between polymer materials to form a cross-linked structure. 2. A method according to claim 1, characterized in that a thickener with a molecular weight of not more than 10,000 is used in an amount of 0.1-10 weight. %