SE204373C1 - - Google Patents

Description

Inventors: RJ De Gray and LN Killian Priority Required from October 24 and 27, 1960 (USA) The present invention relates to the storage of photogenic type carbohydrates, in particular to an agent having bactericidal properties, which can be added directly to the carbohydrate layer for the control and prevention of fungal and bacterial action on a phase in such a layer in contact with an aqueous phase during storage, and on a carbon layer layer treated in this way.

It is a matter of choice that the hydrocarbon fuels, if they are stored in man, e.g. at oil refineries, distribution centers and in fuel tanks, almost constantly contain small amounts of water at the bottom. Some species of bacteria and fungi, which are normally found in groundwater and surface water, have been shown to live in the water at the bottom of such storage vessels, where they receive their nourishment from the carbohydrate phase as well as free saving elements, which are in the storage vessel's water phase. This metabolism was responsible for the consumption of a certain amount of petroleum product and corrosion in the containers and leads to general product enlargement by the formation of rust, hydrogen sulphide, rubbery products, peroxides, acids, colored substances and tradiform materials between the aqueous phase and the hydrocarbon phase.

Bacteria are eaten especially in high-carbon carbohydrates with a long carbon chain length for dietary and consequently bacterial effects, as described, and are more widespread and much more difficult to regulate in kerosene stocks than in petrol stocks, which are stored above the corresponding water bottoms. Gasoline usually has a breath point below 232 ° C and often below 205 ° C. Even if the temperature is 232 ° C, the percentage boiling above 205 ° C exceeds 10%. At least 40% of gasoline's constituents co- Dupl. at 23 b: 4/02; 45 1: 9/00 ka below 121 ° C. Photographs include those products of which at least 30% boil above 205 ° C or of which not more than 15% boil below 121 ° C or bath. Kerosene is almost always non-lead treated, ie. does not contain any tetraalkyl lead compounds. This includes diesel fuel, which is a fraction of crude oil boiling between 149 and 371 ° C, at least 90% boiling above 205 ° C, and the aviation fuel for turbojet and jet aircraft. These latter industries are mixtures of petroleum fractions, produced to meet a number of claims and which may have a boiling range between about 38 and 315 ° C, preferably between about 66 and 288 ° C. The following value is shown for the ashing of a special product, namely JP-4, which is a petroleum fraction with a relatively fast distillation interval.

Distillation% evaporation132 ° C% evaporation188 ° C 90% evaporation243 ° C Residue, volume percentage 1, Loss1, Sulfur, weight percent max. 0.4 Freezing point — 60 ° C Cal / kg, min10200 Flash point — 12 ° C SO about boils about 35% Above 205 ° C. In JP-5 boils 80-90%. over 205 ° C. In kerosene with a narrow boiling range between 149 ± 14 ° C, the lace flagon component boils below 121 ° C.

In addition to kerosene, the kerosene appears to stabilize the water-in-industry emulsions, sbin 2 is called frau slime and tradartar material, which is produced by microbiological action, and consequently a large part of this compound remains suspended in the kerosene phase and has a tendency to clog filters and strainers in storage and transport aids and filters in engines, which use kerosene as fuel.

Filter clogging Or a particularly serious problem with jet aircraft, which are operated with the industry p0. kerosene base ph due to the consequences of a shutdown. The tendency for filter clogging in jet engines Or moreover, increased ph due to the design of these engines and their operating characteristics. The industry volume, which is consumed by a jet engine, is very large and can amount to as much as 3800 liters per hour or more. In volumes of this magnitude, a very low concentration of contaminants can quickly produce a considerable amount of residue in the engine filter system. In addition, instead of a single fuel tank, a jet aircraft usually has a jumble of interconnected cells with innumerable straight points, where water can accumulate and where bacterial action can continue. In many jet fuel cells practically inaccessible to aircraft, especially of the military type, these are cleaning or flushing and the microbiological effect remains undiminished.

For the control of fungal and bacterial action in the storage of hydrocarbon fuel, it has previously been proposed to treat the aqueous phase in each storage vessel with an effective, bactericidal substance. However, it is clear that in the case of fuel tanks or fuel cells connected to engines, the treatment of this salt is not always possible. In addition, such a control method becomes impractical and uneconomical when it is necessary to monitor the bacterial problem in an entire industry distribution system due to the large number of faults in a small system.

A main object of the present invention requires an agent with bactericidal action, which can be incorporated directly into a photogen-type flask, that the agent with bactericidal action is carried with the kerosene when it is transferred from one storage vessel to another, including its 6-verb : king through the fuel system of the engine in which it is finally burned. In this way, effective control of the bacterial action can be achieved before the use of the industry, by all means only added to the kerosene for its storage. For successful completion of this, the bactericidal agent must apparently satisfy a number of requirements. The agent must, of course, be present in the kerosene in such a radiation that a lethal concentration can be incorporated into the industry. The selected agent must also function as one. powerful bacterium & dare. It has been shown that certain agents can initially regulate bacterial development, but that they are active for only a limited time, because the bacteria adapt to the agent and induce one. immunity to it. For control of the indicated problem, the adaptation is apparently not intrada and the agent with bactericidal action must, however. the bacteria.

In addition, the chosen agent must not alter the behavior of the kerosene as a fuel. This is a special answer requirement to satisfy, cla the industry Or intended shs industry for military jets due to the exact specifications, especially with regard to ph freedom frail provisions, which such industry 'piste meet. In addition, the bactericidal agent must be sufficiently surfactant to penetrate below the phase boundary carbonate water into the aqueous phase to act on the bacteria where they are actually alive, but at the same time it must not exhibit such a surface activity that it produces an undue amount of emulsifying water. -in-oil a. Yet another requirement for the agent to have balanced extraction properties. This means that the agent is not too easily extracted with water, as otherwise an undue amount of the agent will be burned to the water bottoms in the first tanks in the distribution system, which leads to insufficient amounts of agent remaining in the kerosene. to be active against the bacteria in the remaining tanks in the system or in the fuel tank of the engine itself. At the same time, however, it is important that a certain part of the agent is extracted into the water bottoms of the tanks, which are contacted in series, so that a lethal concentration builds up in them.

According to the present invention, it has been found that the stated spirit levels can be achieved, whereby the stated criteria are met by an optimal salt, by adding to the photogen before its storage salts a small amount of a more lipophilic than hydrophilic, oxygenated organoborphane purifier containing at least one or a mixture of glycol borate compounds of the following general formula: O / \ RB-OX van X represents vate, \ / 0/0 \ or R-O-BR \ 0 / van i R represents an α- or β-alkylene group in - neh011ande 3 — about 12 carbon atoms. The glycol borate compounds, as anyandas composition hdray, can. Mit is prepared by reacting orthoboric acid in a moldy ratio of 1: 1-3: 2 with the corresponding glycol of the formula.

II HO — C— [CJn — C — OH III van i n denotes 0 or 1 and the converted valences were bound at vale or at straight or branched chain alkyl groups to give a total of frail 3 to about 12 carbon atoms.

In the formation of compounds of the given formula, van in X denotes vate, the glycol and boric acid are reacted together in equimolar amounts. Two moles of reaction water are formed per each mole of acid and glycol used in the reaction. The water may possibly be depleted, however, it is usually desirable to deplete at least some of the air in the water. In the formation of compounds, van in X denotes / O \ -B R \ 0 /, the glycol and boric acid are reacted together in equimolar four oohs and per mole of acid and glycol used in the reaction, 2.5 moles of water must be precipitated. In the formation of the compound, van in X denotes 0 / \ R — O — B R \ o /, boric acid is reacted with a glycol in a ratio of 2: 3 and 3 moles of water are precipitated each mole used in the reaction.

When the water of reaction is removed, it is preferably separated from the brine, such as by blowing with nitrogen at a slightly elevated temperature or by distillation. Due to the low boiling point of these compounds, the removal of an undesirable amount of water by simple boiling causes a certain loss of product, which evaporates. In this case, the reaction water is preferably removed by azeotropic fractionation. Typical examples pd. solvents, which can be used elsewhere for this purpose, Oro benzene, toluene and xylene.

According to the present invention, the protecting agent may contain at least one triarylborate of the formula R 'z / RR' R 'van in R and denote vale or lower alkyl groups having preferably up to 3 carbon atoms. Examples Oro triphenylborate, tritolylborate, trixylylborate, tricumenylborate, triethylphenylborate () and trimethylethylphenylborate.

According to another embodiment of the invention, the protecting agent may contain a boron alkyl compound of the following formula: R 'used in R represents an alkyl group (straight or branched chain), containing from 2 to about 12 carbon atoms, and R denotes irate or R and van in R may be the same or different f Or the different positions of R in the molecule.

The amount of drilling association that was added to the industry will vary depending on several factors. It has generally been found that in order to achieve complete bacterial control, the water bottoms must build up a concentration of about 0.04% by weight of elemental boron. The amount of glycol borate in the kerosene, which is preferably expressed as boron, can be determined from this value together with the ratio of kerosene to water and the determination of the distribution ratio of the boron compound between the kerosene and water phases. The latter determination can be easily performed for any compound by simply adding the compound to a cheek mixture of kerosene and water, the amount of elemental boron in the kerosene and water phase being analyzed separately, after which the larger number is divided by the smaller one. With respect to p0. the amount of water must not only be determined by the water in a tank, but must also take into account the number of tanks in the distribution system, through which the kerosene is transferred, since normally each tank will have a new mass of water for sterilization. The choice of boron compound will determine how much of the boron compound will be extracted into the aqueous phase in the first tank and how much will remain in the kerosene for distribution between the kerosene and the water in subsequent tanks in the distribution system. In the case of glycol borate compounds in general, the boron compound will be less water-soluble or water-extractable the longer the carbon chain length in the glycol portion of the boron compound. Butylene glycol borate Or, for example, more water soluble. hexylene glycol borate. Viii triarylborate compounds in general, the boron compounds will be less water extractable the greater the number of carbon atoms Or in the R and R 'substituents molecule of the given general formula. In the case of boron alkyl compounds in general, the boron compound will be less water-extractable due to the number of carbon atoms Or in the alkyl groups of the molecule. Tributylborate Or, for example, more water-soluble On trioctylborate. Thus, a smaller amount of more water-soluble formation will be required in the kerosene in the first tank, which contains water, to achieve a concentration. of 0.05% live in the water. However, since a larger amount of a more water-soluble boron compound would migrate to the first body of water with which the kerosene is contacted, a smaller amount of boron compound would remain in the kerosene. for residual tanks, the water bottoms of which are to be brought into contact with the kerosene, a less water-soluble boron compound. From this it appears that the choice of boron association for a system will depend at least in part on how far through a tank distribution system treatment is required. It should also be noted that each photogenic charge does not have to contribute a heft and the hall lethal dose of boron to the water bottoms of each tank, since subsequent photogenic batches containing a boron compound will eventually build up the boron content of the water to the lethal level. The special agent or mixtures of agents to be used, and the required amounts thereof in the kerosene, must obviously be prepared for the special distribution system taking into account the above-mentioned shelf points. As a useful starting point, however, a quantity of compound for the presence of about 0.0001-0., 0004% by weight should be considered, calculated on the kerosene, which is the smallest quantity which will offer any significant effect at the first contact. (Namely 0.0001% triarylborate compound or 0.0002% glycol borate compound or 00004% boralkyl compound.) The boron compound in the kerosene to produce between 0.0004 and 0.006% by weight of boron is usually preferred, especially when two or more tanks are to be treated. (Namely 0.0004--0.004triarylborate or 0.0005-0.006% glycolborate or 0.0010.006% boron alkyl compound.) The use of amounts in excess of 0.01% is not required and usually cannot be economically justified.

A surprising aspect of the present invention is that much less boron content is required in the aqueous phase in the form of the more lipophilic hydrophilic organoboron boron compounds for inhibiting bacterial action than that required by known treatment methods, with waterborne boron compounds being added directly to the water bottoms in storage tanks. kerosene. As growth occurs viii the phase boundary, the transfer of the boron compound passes from the kerosene to the water with necessity through this phase boundary. This is not the case when the boron compound from the beginning is present in the aqueous phase, since part then there is no transfer from the aqueous phase to the kerosene phase.

The boron compound can be added directly to the kerosene in the required amounts. Optionally, a concentrate of the boron compound can be prepared by using a mutual solvent and the concentrate can then be mixed into the kerosene to produce the desired amount of boron.

The invention is further described in several examples of embodiments of the invention. The following test on kerosene can be used in simulating actual conditions in storage tanks for such kerosene above water bottoms and correlates with these conditions. This test involved contact between a photogenic kit containing boron compounds of the invention, and water in a ratio of the test involved the use of a device containing a large wheel with sixteen spokes. Ph each spoke Oro fixed two bottles similar to 473 nil Mason bottles, with the openings facing each other. Each bottle unit Or filled with 400 ml of kerosene to be tested and 4 ml of water. A polished steel rod is included in each bottle assembly, so that the bacteria's effect and corrosion can be observed and affected. of the rust formation on the bacterial development would mimic that which occurs under real storage conditions. The water was taken from an artificial lake, which contains bacteria similar to those which viii examination showed to be found in the water in the tank bottoms. The wheel is then rotated at Ire vary / minute for 48 hours to study the bacterial growth. Each bottle unit was turned upside down twice on each vary of the wheel and consequently the contents of the bottles fluttered back and forth six times every minute during the test. This movement mimics what Hader in a storage tank, when large volumes of kerosene are introduced or stored and contained in the thought in a rolling motion.

For the 48 hours, the bacterial population was determined by a standard plate method, in which the plates were inoculated with a sample of a given size, taken from the water bottoms and with progressive ten-potency dilutions thereof. To accomplish this, a 1 ml sample of Iran water is pipetted into the petroleum distillate water mixture and transferred to a sterile petri dish. Then pour about 20 ml of sterile nutrient solution into the bowl at a temperature of 40 ° C and shake the contents until the mixture is complete. The mixture on the plate is then allowed to cool to room temperature, after which the yarn solidifies. The plate was then watered and placed in an incubator, which was milled at 37 ° C. After culturing for 48 hours, the colonies are shaved using an illuminated, cross-shaded fait. The numbers given as a result of the test are bacteria per ml of sample. Tables 1, 2 and 3 show the results of these tests on kerosene, treated and untreated with a bactericidal agent according to the invention. The kerosene used in these tests was a material that met the industry specifications for JP-4.

TABLE 1 Rh's & Glycolborate Additive, Miming / Or concentration at 0.002ml weight percent boron none (kerosene base) 5500000 21,3-propanediol borate (1: 1 equation) 350 mole percent 1,3-propanediol borate (1: 1 compound) + 50 mole percent 2-Methyl-2,4-pentanediolborate (1: 1 compound) 1 41,3-butanediolborate (1: 1-compound) 3200 2-Methyl-2,4-pentanediolborate (1: 1-compound) 6300 Reported results show It is clear that 1,3-propanediol borate gives optimal results, based on contact with only one body of water. It Mir of the stated results is observed, that the more the number of carbon atoms is in the glycol, which forms the boron compound, the less effective for the agent at the first contact .. As a correlation ph this, it has been found that alit because the number of carbon atoms in the glycol, which forms the boron association, increases, the amount of elemental boron transferred to the aqueous phase is reduced. In addition, since the number of carbon atoms in the glycol, which forms the boron compound, Ras, the greater the amount of elemental boron which remains in the kerosene after the first contact is treated by the remaining tanks in the distribution system. For this reason, it is often undesirable to use in admixture a glycol borate compound, which is derived from a short chain glycol, and a glycol borate compound, which terrifies a longer chain glycol. This is especially the case, nat. The 1,3-propanediol borate compound was used because it itself has only limited solubility in the kerosene.

. Because the trixylyl borate is the least water extractable, it is less effective at first contact. Since more boron remains in the kerosene phase after the first contact, on the other hand, the trixylyl borate agent will be carried through the distribution system to a larger number of tanks.

TABLE 3 Understanding Boron alkyl additive at 0.004% by weight boron Shaving / ml 1 non-flake (kerosene base) 5500000 2 triethylborate 4000 3 tripropylborate 700 4 tributylborate 100 triamylborate 6 trihexylborate 9 7 dihexylborate 8 trioctylborate 0 9 tridecylborate boronate The compounds according to the invention have a very high bactericidal action at very low concentrations. Minot when in contact with a body of water give boron compounds, in which the number of carbon atoms in the alkyl groups are between 6 and 10 carbon atoms, give optimum results.

All kerosene shaving / ml 6. compositions listed in Tables 1, 2 and 3 successfully passed the Erdco Coker test according to ASTM-D1660. Denim testing is used to determine a kerosene fuel on combustion purity and is currently considered the most reliable test for predicting the actual performance of industries in turbojet and jet engines. Other compositions than 1 did not show a significant difference from the composition 1 with respect to the amount and properties of precipitates formed, indicating that the agents of the invention with bactericidal action do not adversely affect the base fuel with respect to deposition rate or any other means of use. in a turbo one engine or jet engine.

Claims (8)

Patent claim: Process for protecting kerosene against degradation due to inicrobiological action, in particular when stored in a tank containing water at the bottom, characterized in that a protective additive containing at least one glycol borate of the general formula is added to the kerosene: / \ RB-OX \ / 0 van in X denotes vate, / 0 \ / 0 \ BR or R — O — BR van in R denotes an α- or β-alkylene group having 3-12 carbon atoms, the amount of addition being equivalent to about 0.0001-0.006 weight percent live in relation to the total amount of the resulting mixture kerosene plus additive. 2. Set according to claim 1, characterized in that R represents the radical, as Urror from 1,3-propanediol. 3. A kit according to claim 1, characterized in that the protective agent contains a mixture of glycol borate compounds, wherein R in one of the grains is a propanediol and in another grains of a hexanediol. 4. A kit according to claim 1, characterized in that the protecting agent contains at least one triarylborate compound having the form: 0 \ x 0 RR 'IR' \ / van in R and R 'denote vate or a legal alkyl group, in an amount for providing at-millstone 0.0001% by weight boron, calculated on the kerosene. 5. A kit according to claim 4, characterized in that the triarylborate consists of triphenylborate. 6. according to claim 4, characterized in that the triarylborate consists of tritolylborate. 7. Mt according to claim 1, characterized in that the protecting agent contains at least one boron alkyl compound of the formula: R-O-B-O-R van R represents an alkyl group having 2 to about 12 carbon atoms and R 'represents vate or R and van in R may be the same or different for different positions of IT in the molecule, in an amount to produce at least 0.0004% by weight of boron, calculated on the kerosene. 8. Photogen-type carbonate mixture which can be stored Above water bottoms, especially kerosene based on jet fuel, characterized by a more lipophilic than hydrophilic, oxygenated organoboron compound, which protects the photogen-type carbonate from degradation caused by microbiological action at the phase boundary radian kerosene and water wherein a set according to any one of claims 1-7 is used. Cited publications: Patents from France 1,074,952.