DE3645178C2 - New substd. hydrocarbyl cpds. - Google Patents

Abstract

Substd. hydrocarbon cpds. of general formula (I) are new, where Y = SO3(-)N(+)(R3)3, SO2NR3- or SO3-, X = Y, -CON(R3)-, -CO2(-)-, N(+)(R3)3-, -R4-CO.O-, -NR3CO-, -R4O-, R4O.CO-, -R4-, -N(COR3) or N(+)(R3)3.Z(-)-, Z(-) = -SO3(-) or -CO2(-), R1, R2 = alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10C in the main chain, R3 = hydrocarbyl (identical or different), R4 has no significance or, and the C-C bond in the gp. A-C-C-B can either be (a) an ethylenically unsatd. bond, if A and B are alkyl, alkenyl or substd. hydrocarbyl, or (b) part of an aromatic, polyaromatic or cycloaliphatic cyclic structure. More specifically, R1, R2, R3 = hydrocarbyl, esp. at least 10C straight-chain alkyl

Description

The invention relates to fuels or fuels and in particular Middle distillate fuels, which are substituted hydrocarbon compounds, as a crystal modifier suitable are included.

Alkyl derivatives with long n-alkyl groups of difunctional Compounds and their use as modifiers for paraffin crystals are with respect to alkenylsuccinic acids in US-PS 34 44 082, with respect to maleic acid compounds in US-PS 42 11 534 and with respect Phthalic acid compounds in GB-PS 29 23 645 and in U.S. Patent Nos. 4,375,973 and 4,402,708.

The object of the invention is to provide new compounds for To provide as modifier for the paraffin crystals in distillate fuels suitable and that are a significant reduction in size the paraffin crystals formed below 4000 nm and even below 2000 nm, and preferably below 1000 nm, if these modifiers alone or in combination with other known modifiers used for paraffin crystals.

To solve this problem, petroleum distillates are proposed, which new substituted hydrocarbon compounds contain, as indicated in the main claim, wherein Preferred oils are evident from claims 2 to 5.

When the C-C bond is part of a cyclic compound is, then the ring atoms in these are preferably carbon atoms, However, heteroaromatic compounds can also be used be in which the ring contains N, S or O atoms.  

Examples of aromatic compounds, of which the Additives can be made have the following Formula in which the aromatic group is substituted can be:

Alternatively, these compounds may be polycyclic Compounds are received, so from those who Two- or multi-ring structures of various kinds to have. They can be (a) condensed benzene structures, (b) fused aromatic ring structures in which not all rings are benzene rings, (c) aromatic rings, which are connected to their ends or (d) aromatic heterocyclic Be connections.

Condensed benzene structures, of which the compounds can derive, for example, naphthalene, Anthracene, phenathrene and pyrene. Compounds in which the Rings are connected at their ends, for example Diphenyl compounds.  

Suitable heterocyclic compounds are derived, for example of quinoline, indole, 2: 3-dihydroindole, benzofuran, Coumarin and iso-coumarin, benzothiophene, carbazole and thiodiphenylamine.

The two substituents X and Y must be adjacent Ring atoms stand in the ring, if only one ring is present, or on adjacent ring atoms in one of the rings, if the compound is a polycyclic compound is. In the latter case, this means that at Naphthalene compounds do not contain these substituents the 1,8-position or 4,5-position but in the 1,2-, 2,3-, 3,4-, 5,6-, 6,7- or 7,8-position.

The compounds used according to the invention are prepared by that you have both functional groups in these Compounds with amines, alcohols, quaternary ammonium salts etc. are implemented. If the compounds are amides or Amine salts, secondary amines are preferred which a group containing hydrogen and carbon containing at least 10 carbon atoms. Such Amides or salts can be prepared thereby that the acid or anhydride with a secondary Amine or alternatively an amine derivative with a carboxylic acid or an anhydride of these converts. The distance from Water and heating are generally required to get the amides from the acids. alternative The carboxylic acid can be mixed with an alcohol that is at least Contains 10 carbon atoms, or with a mixture  of an alcohol or an amine.

When using the compounds as fuel additives are the substituents R¹ and R² preferably 14 to 20 carbon atoms and are preferably straight chain or branches in the 1- or 2-position. The others Hydrogen and carbon containing groups can be shorter, for example less than 6 carbon atoms contain or may optionally be at least Have 10 carbon atoms. Suitable alkyl radicals are including methyl, ethyl, propyl, hexyl, decyl, dodecyl, Tetradecyl, eicosyl and docosyl (behenyl).

Particularly preferred compounds are the amides or Amine salts of secondary amines. Although two substituents for the cyclic derivatives described above necessary, it should be borne in mind that these cyclic compounds one or more further substituents at the ring atoms of the cyclic compounds can contain.

These compounds are as fuel additives for mineral oils, the paraffinic waxes contained and less when lowering at the oil temperature be fluid, suitable. This reduction in fluidity is due to the crystallization of the paraffins to platelike Crystals, which are a spongy mass form and hold the oil in this. The temperature, at which the wax crystals begin to form, is commonly referred to as the cloud point (Cloud Point), and the temperature at which the Paraffins prevent a flow of the oil becomes common referred to as the pour point.

It is known that many additives as modifiers  act for the paraffin crystals, if they be mixed with paraffin-containing mineral oils. These Links modify the size and shape of the Paraffin crystals and reduce the cohesive forces between the crystals and between the paraffin and the oil so that the oil at lower temperatures remains fluid.

They are the most diverse pour point depressants in literature and commercially available (See EP 00 30 099, EP 02 03 693, US 44 02 708 and US 44 81 013).  

The improvement of CFPP efficacy by the Installation of these known additives is achieved on a modification of the size and shape of the formed Paraffin crystals, called needle-like crystals with a general particle size of 10 μm or larger and generally from 30 to 100 μm. When operating diesel engines or heating systems lower temperatures generally go these crystals not through the filters, but form one permeable filter cake on the filter, so that the liquid fuel can pass through, with the Paraffin crystals subsequently dissolve when the diesel engine or the heating system has warmed up and the Main part of fuel by recirculated fuel is heated. However, this can lead to the Paraffin crystals block the filters, causing difficulties when starting or starting and also to problems when starting in cold weather or in case of failure of the preheating system for the fuel can lead.  

Surprisingly, it was found that when used the oils according to the invention are particularly small Paraffin crystals can be obtained by the filters of conventional diesel engines and heating systems pass through and not on the filter a filter cake form.

The amount of the distillate fuel such. Eg diesel or fuel oil added compound is located in a range of 0.001 to 0.5 wt%, for example at 0.01 to 0.10 wt .-%, based on the weight of Fuel.

the compound becomes practically in a suitable solvent dissolved to a concentrate of 20 to 90 and For example, 30 to 80 wt .-% in the solvent to build. Suitable solvents are kerosene, aromatic Naphtha products and mineral lubricating oils.

The invention allows that distillate fuel oils having a boiling range of 120 to 500 ° C and a paraffin content of at least 0.5 wt .-% at a temperature of 10 ° C below the Paraffin-forming temperature can be produced the paraffin crystals at this temperature with an average particle size of less than 4000 nm and sometimes less than 2000 nm, where depending on the type of fuel, the crystals size below a micron.

The wax or paraffin forming temperature (WAT) of the fuel is determined by means of differential scanning Calorimetry (DSC) determined. This test will be a small sample of a fuel of 25 μl with a Speed of 2 ° C / min. together with a comparative sample  cooled the same thermal capacity, which but no paraffin precipitates in the temperature range in question shows, such as kerosene. It an exothermic effect is observed when crystallization begins in the sample. For example, the WAT value of the fuel by extrapolation at one Mettler TA 2000 B device can be measured.

The paraffin content is carried by the DSC recording Integrating the range derived from the baseline and the exothermic curve up to the specified Temperature is enclosed. The calibration will be done in advance with a known amount of crystallizing paraffin carried out.

The average particle size of the paraffin crystals is determined by analysis of an electronically scanned photomicrograph a fuel sample at a magnification determined from 4000 to 8000, with the longitudinal axis of 50 crystals measured in a predetermined grid becomes. It was found that the paraffin crystals over an average size of less than 4000 nm through standard paper filters, as with diesel engines be used, go through with the fuel oil, although it is preferred, the size below 3000 nm and preferably below 2000 nm and in particular below 1000 nm, the actually achievable Size of the origin of the fuel and the Type and amount of additive used, however, it has been found that these sizes and even smaller can be achieved.

The possibility of such small paraffin crystals in Obtaining the fuel or fuel, results in significant Advantages of operating diesel engines, what you get thereby can show that before that for removal  fuel stirred by settled paraffin crystals through a diesel filter with 8 to 15 ml / sec. and 1.0 up to 2.4 liters per minute per m² of filter surface at one Temperature of at least 5 ° C below the paraffin forming temperature with at least 1% by weight of the fuel in the form of solid paraffin particles. Either Fuel and paraffin run successfully through the filter if one or more of the following Criteria are met:

• (i) if 18 to 20 liters of fuel through the Filter gone through and the pressure drop on the filter not more than 50 kPa, preferably 25 kPa and especially 10 kPa and at best 5 kPa;
• (ii) if at least 60% and preferably at least 80% and in particular at least 90 Wt .-% of the paraffin present in the fuel after the DSC test in the fuel is determined, which emerges from the filter;
• (iii) when you pump through from 18 to 20 liters Fuel through the filter a flow rate that always has over 60% of the original Flow rate and preferably over 80% of this remains.

The fuels of the invention show excellent advantages compared with previous ones Middle distillate fuels, the addition of conventional Improved additives in their cold flow properties have been. For example, the fuels are at Temperatures in the vicinity of the pour point operational and are not limited by the fact that they  Do not fulfill CFPP test. As a result, these meet Fuels or fuels the CFPP test at considerably lower temperatures or it must be these experimental conditions not be fulfilled at all. The fuels also have an improved cold start behavior lower temperatures, as they are not on the circulation of warm fuel to dissolve the unwanted Paraffin deposits are dependent.

The best effects are usually achieved when the oils according to the invention in combination with other additives are used to improve the cold flow properties of distillate blowing oils used although they are also used alone can.

The compounds are preferably used together with the compounds known as comb polymers used.  

Examples of suitable comb polymers are fumarate / vinyl acetate and in particular those described in EP-A 01 53 176, 01 53 177 and 85/3 01 047 and 85/3 01 048, and esterified olefin / maleic anhydride Copolymers and the polymers and copolymers of alpha olefins and esterified copolymers of styrene and maleic anhydride.

Examples of other additives are polyoxyalkylene esters, ethers, esters / ethers and theirs Mixtures, in particular those containing at least 1 and preferably 2 linear saturated C₁₀ to C₃₀ alkyl radicals and a polyoxyalkylene glycol moiety having a molecular weight from 100 to 5000, preferably 200 to 5000 contain, wherein the alkyl radical in the polyoxyalkylene glycol Contains 1 to 4 carbon atoms. These connections are described in EP 00 61 895 A2 and US-PS 44 91 455.  

The oils according to the invention can also be used with ethylenic unsaturated ester copolymers, the flow improvers are to be used. The unsaturated monomers, which can be copolymerized with ethylene are including unsaturated mono- and diesters.  

Examples of vinyl esters copolymerized with ethylene are vinyl acetate, vinyl propionate and Vinyl butyrate or isobutyrate, with vinyl acetate being preferred becomes. Preferably, the copolymers contain 5 to 40 and preferably 10 to 35% by weight of vinyl ester. You can also mixtures of two copolymers, as for example in US-PS 39 61 916 is described. Preferably These copolymers have an average Molecular weight determined by the vapor phase osmometry from 1000 to 10,000, and preferably 1000 to 5000.

The oils of the invention may also in combination with other polar Compounds, namely ionic or nonionic Compounds, which are used in the fuels have the potential as inhibitors of crystal growth the paraffin crystals to act. in this connection are especially polar nitrogenous compounds suitable and are in general amine salts or amides by the reaction of at least a molar proportion of one with hydrocarbon substituted amine with a molar fraction a carboxylic acid having 1 to 4 carboxylic acid groups or their anhydrides are obtained; it can also esters / amides be used, the 30 to 300 and preferably Contain 50 to 150 carbon atoms in total. These Nitrogen compounds are described in US-PS 42 11 534.  

Hydrocarbon polymers can also be used as part of Additive combination of the following general formula be used:

in which
T = H or R '
U = H, T or an aryl radical
v = 1.0 to 0.0 (molar ratio)
w = 0.0 to 1.0 (molar ratio)
and wherein R 'is an alkyl radical.

These polymers can be directly derived from ethylenically unsaturated Monomers or indirectly by hydrogenation of monomers, such as isoprene, butadiene, etc. obtained polymers become.

Particularly preferred hydrocarbon polymers are Mixed polymers of ethylene and propylene with an ethylene content preferably from 20 to 60% by weight, in general be prepared by homogeneous catalysis.

When combined with known additives in general  30 to 60 wt .-% of the compound defined in claim 1 be used.

The additive system can usually be provided as a concentrate be that of the bulk of the fuel or middle distillate is added. These concentrates can vary depending on Wish to include other additives. The concentrates preferably contain 3 to 75 and in particular 3 to 60 and usually 10 to 50 wt .-% of the additives, preferably in solution in oil.

Preparation of the compounds example 1

The N, N-dialkylammonium salt of 2-dialkylamidobenzenesulfonate having alkyl radicals of nC₁₆-C₁₈H _{33-37 was} prepared by reacting one mole of the cyclic anhydride of orthosulfobenzoic acid with 2 moles of di (hydrogenated) tallowamine in xylene as solvent with a 50 wt. % concentration was implemented. The reaction mixture was stirred between 100 ° C and reflux temperature keeping the solvent and the compounds as dry as possible to suppress hydrolysis of the anhydride.

The reaction product was analyzed by NMR at 500 MHz to give a spectrum as shown in FIG. 1, which confirmed the following structure.

Example 2

The procedure was analogous to Example 1, but now the Orthosulfobenzonsäure was first reacted with a Moloctadecan-1-ol and 1 mole of di- (hydrogenated) tallow amine. The product was analyzed by NMR at 500 MHz to give the spectrum shown in Fig. 2 and a compound of the following formula:

B. Test method

The effectiveness of the product according to Example 1 and the this product containing additive systems as a filter improver for distillate fuels was as follows certainly.

In one method, the response of the oil was on the additives with the cold filter clogging point for Determination of CFPP value determined by a method as noted in "Journal of the Institute of Petroleum", volume 52, No. 510 pp. 173 to 2285 (June 1966). This test is designed to be consistent with cold flow behavior of a middle distillate in diesel engines in Agreement stands.

This is a 40 ml sample of the examined Oil cooled in a bath, which at a temperature held at about -34 ° C to a non-linear Cooling of about 1 ° C per minute to achieve. The cooled Oil is periodically starting at 1 ° C each from above the cloud point on its fluidity through a fine sieve in a prescribed time examined with a test device, which from a The pipette consists of a reverse one at the lower end Funnel is attached, which is below the surface of the oil to be examined. Across the funnel opening there is a sieve of 12 mm diameter and a mesh of 350. The periodic tests each by attaching a vacuum to the triggered the top of the pipette, taking oil through the Strainer into the pipette and up to a mark is sucked, which corresponds to 20 ml of oil. After every successful Passage, the oil is immediately returned to the CFPP  Tube returned. The test is repeated in each case when the temperature drop is 1 ° C for so long until the oil is no longer able to hold the pipette inside to replenish by 60 seconds. This temperature will referred to as CFPP temperature. The difference between the CFPP value of an oil without additive and the same Oil with an additive is considered CFPP reduction the additive is called. A more effective flow improver gives a greater CFPP reduction at the same Concentration of the additive.

Another determination of the effectiveness of a flow improver is programmed under the conditions of a Cooling tests (PCT) performed, which is a slower Cooling test designed to indicate that whether paraffin in the fuel passes through such filters, which are used in heating oil systems.

In this test, the cold flow properties of the oils containing the content of additives as follows certainly. 300 ml of fuel become linear at 1 ° C each Hour cooled to the test temperature and the temperature is then kept constant. After 2 hours at -9 ° C About 20 ml of the surface layer is removed, and though as abnormally large paraffin crystals, which themselves at the intermediate layer between oil and air during of cooling. The paraffin crystals that are in the vessel have settled by light Stirring is dispersed, and then a CFPP filter assembly used. Thereafter, a vacuum of 500 mm HG applied, which is interrupted when 200 ml Fuel through the filter into a graduated one Vessels have flowed. If 200 ml within 10 Seconds through the given filter with the given Mesh size, the experiment applies  as "passed" if the flow rate too is slow, indicating that the filter is blocking is, the attempt is called "failed".

CFPP filter arrangements with filters are used those of a mesh size of 20, 30, 40, 60, 80, 100, 120, 150, 200, 250 and 350 correspond to the finest filter according to the largest mesh size to be determined at the fuel still goes through. The larger the mesh size is the paraffin-containing fuel goes through, the smaller are the paraffin crystals and the greater the effectiveness of the flow improvers used additives. It must be pointed out that will not even have two different fuel oils exactly the same test results for the same amount give the same flow improver.

In addition, studies on the discontinuation of paraffin crystals before filtration after the PCT test. The extent of the deposited layer was visually in Percentages, based on the total volume of fuel oil, certainly. A strong settling of paraffin crystals gives a low number, while an undeleted fluid propellant or heating oil has a value of 100%. Bad samples with jelled fuel and big ones Paraffin crystals almost always show high values, so that these results are referred to as "gel".

The effectiveness of the additives according to the invention in terms the reduction of the cloud point of distillate fuel or blowing oils was according to the standard method to determine the cloud point according to IP-219 or ASTM-D 2500 determined. Further instructions with regard to the onset of crystallization  the crystallization start point (WAP test) according to ASTM D. 3117-72 and the paraffin excretion temperature (WAT), as measured by differential scanning calorimetry with a Mettler TA 2000B Differential Scanning Calorimeter becomes. In this test, a fuel sample of 25 μl at 2 ° C / min. at a temperature of at least 30 ° C above the expected cloud point of the fuel oil cooled. The observed onset of crystallization is estimated without the lying at about 2 ° C. thermal delay is corrected, though the WAT value from the differential scanning calorimeter is displayed becomes.

The ability of the fuel through a main filter to go through a diesel engine, was in a device determined, that from a usual main filter of a diesel engine which was in a standard housing in the fuel supply line was attached. Suitable for this are Bosch filters like those in the VW Golf Diesel PKW (1980) and in a Cummins FF105 series from Cummins NTC be used. A storage tank and a feed system, with the one half of the fuel of a normal Diesel fuel tank, was fed to a Injection pump, as used in the car Golf VW is used to filter the fuel through the filter the tank at a constant flow rate how to promote in the vehicle. There were also instruments attached to the pressure drop across the filter, the flow rate from the injection pump and the temperatures to measure in unity. There were also receptacles provided to the pumped fuel, namely both the fuel injected and the fuel surplus take.  

In the experiment, the tank was filled with 19 kg of fuel and checked for leaks. Then the temperature became at an air temperature of about 8 ° C above stabilizes the cloud point of the fuel. The Unit was then at 3 ° C per hour to the desired Test temperature cooled and at least 3 hours so held to stabilize the fuel temperature. The tank was shaken vigorously to the existing one Completely disperse wax. It became a rehearsal taken from the tank and 1 liter of fuel at one Test point on the outlet line immediately after removed from the tank and returned to the tank. The pump was then started, with the circulation rate was adjusted so that they are in terms of their pumping power per minute, the driving speed of 110 km / h. corresponded. This value was in the VW Golf in an area from 1900 rpm corresponding to a number of revolutions of the Motors of 3800 rpm. The pressure drop at the filter and the flow rate of fuel from the injection pump were recorded until the last fuel was consumed was what was generally the case after 30 to 35 minutes.

If the fuel supply for injection at 2 ml / s can be held and the additionally supplied fuel at a level of 6.5 to 7 ml / s the test is "passed". A waste in the Fuel supply to the injector is called a "borderline case" assessed, while no fuel at all as "failed" is called. Usually is at a test called "passed" is also an increasing one Determine pressure drop at the filter, which is up to 60 kPa can amount. In general, have significant shares on crystallized paraffin, pass the filter before such a result is achieved. The review "passed" is present if in the experimental procedure  the pressure drop across the filter does not rise above 10 kPa, which is The first indication is that the bulk the paraffins went through the filter, where An excellent result is achieved when the pressure drop is less than 5 kPa.

In addition, fuel samples from the excess fuel and from the fuel supplied to the injector taken, preferably every 4 minutes in the course of the entire experiment. These samples together with the Samples taken from the tank before the test are passed through DSC compared to the proportion of added paraffin determine which has gone through the filter. Samples of the fuel taken before the test also taken and there are SEM samples after the Test taken to the crystal size of the paraffin and its nature under actual conditions of use determine.

The following additives were used:

• (i) The product according to Example 1
• (ii) Additives A

Al is a concentrate of about 50% by weight of a mixture from two ethylene-vinyl acetate copolymers, of which the one composed of ethylene and about 38% by weight of vinyl acetate and an average molecular weight after VPO has 1800, while the other connection of ethylene and about 17% by weight of vinyl acetate with a numerical average molecular weight of about 3000 after VPO which is the additive A2. The Additive A3 was the first single component of A1, the was used alone.  

A4 is a 50/50% mixture of A2 and A3.

A5 consists of a polymer with a content of 13.5% by weight Vinyl acetate and a numerically average Molecular weight of 3500 after VPO.

(iii) Additives B

There were polyethylene glycol esters (PEG) and polypropylene glycol esters (PPG) by mixing one molar portion of the polyethylene or polypropylene glycol with 1 or 2 molar proportions of the carboxylic acids for the mono- or Diester mixed. To the reaction mixture was 0.5 Wt .-% p-toluenesulfonic acid, followed by heated to 150 ° C with stirring and simultaneously with nitrogen the reaction water was driven off. After completion the implementation, assessed by infrared spectrum was the product was poured out in the molten state and gave a waxy solid after cooling.

PEG and PPG usually become along with their molecular weights designated; for example, PEG 600 is on Polyethylene glycol of average molecular weight of 600. Similarly, PEG 600 dibehenate is the obtained one Esters from the reaction of 2 molar portions of behenic acid with 1 mole of PEG 600, which is used as additive B.

(iv) Additives C

This additive is the reaction product of 1 mole of phthalic anhydride with 2 moles of dihydrogenated tallowamine, which forms a half-amide / half-amine salt.

(v) Additives D

This additive D is a copolymer of ethylene and  Propylene with a content of 56 wt .-% of ethylene and a average number molecular weight of 50,000.

(vi) Additives E

The additive E₁ was prepared by esterification of a 1: 1 molar styrene / maleic anhydride copolymers a 1: 1 molar mixture of C₁₂H₂₅OH and C₁₄H₂₉OH per mole of anhydride groups, with a slight excess of about 5% of alcohol was present. The esterification was carried out with p-toluenesulfonic acid as catalyst (1/10 Mol) in xylene as solvent, a product with a molecular weight (Mn) of 50,000 was obtained, which contained 3 wt .-% untreated alcohol.

Polymer E2 was produced by dissolving 2 moles of C₁₄H₂₉OH for esterifying the styrene / maleic anhydride Mixed polymers used, the product an average Had molecular weight of about 50,000 and 3.3% by weight contained free alcohol.

In the other examples, fuels were used with the Then treated at 10 ° C below the paraffin forming temperature (WAT) chilled and the paraffin crystal size with an electronically scanning micrograph and also the ability of the fuel to pass through through a fuel filter of a Cummins FT105 Motors determined. The results are as follows:

Example 3

The fuel used had the following properties:

Cloud Point | -14 ° C CFPP, untreated -16 ° C Crystal formation point -18.6 ° C initial boiling point 178 ° C 20% Sdp 230 ° C 90% Sdp 318 ° C Final Boiling Point 355 ° C Paraffin content at -25 ° C 1.1% by weight

It was an additive combination of 250 ppm each of the Products according to Example 1, the additives A5 and E₁ den Fuels added and tested at -25 ° C. The crystal size of paraffin was 1200 nm in length, and more as 90% by weight of the paraffin went through the Cummins FF105 Filter through.

During the experiment, the passage of paraffin further demonstrated by the pressure drop at the filter, which only increased by 2.2 kPa.

Example 4

Example 3 was repeated, the crystal size of the paraffin at 1300 nm and the maximum pressure drop at the filter was determined at 3.4 kPa.

Example 5

An oil with the following properties was used:

Cloud point | 0 ° C CFPP, untreated -5 ° C Crystal formation point -2.5 ° C initial boiling point 182 ° C 20% Sdp 220 ° C 90% 354 ° C Final Boiling Point 385 ° C Paraffin content at -25 ° C 1.1% by weight

An additive combination of 250 ppm of each product Example 1 and additives A5 and E₂ was the fuel added and the paraffin crystal size with 1500 nm determined to be 75% by weight of Paraffins through a Bosch filter 145 434 106 at a Test temperature of -8.5 ° C went through. The maximum pressure drop at the filter was 6.5 kPa.

Example 6

Example 5 was repeated, with a paraffin crystal size of 2000 nm in length, of which about 50% by weight through the filter at a maximum pressure drop of 35.3 kPa occurred.

Example 7

The fuel according to Example 5 was used with 400 ppm of Product of Example 1 and 100 ppm of A1, wherein the fuel as in Example 5 at -8 ° C examined and at this temperature the paraffin content was 1.4% by weight scam. The paraffin crystal size was 2500 nm and 50% by weight of the paraffin entered through the filter a pressure drop of 67.1 kPa.

When this fuel is used in a pilot plant was, the pressure increase increased relatively quickly and the test was called "failed". It is believed that this is based on how Shown in photographs, the crystals are flat and shallow crystals do not pass through the filter Can and this with a thin impermeable layer cover. Collect cube-shaped or modular crystals on the other hand, if they do not go through the filter, as a relatively loose filter cake through which the fuel can go through until this filter cake  gets so big that the filter is filled and the total strength the paraffin cake is so large that the pressure drop again is excessively large.

Example 8 (Comparative Experiment)

The fuel according to Example 5, with 500 ppm one Mixture of 4 parts of the additive C and 1 part of the additive A5versetzt; this fuel was tested at -8 ° C, where it was found that the paraffin crystal size at 6300 nm and 13 wt .-% of the paraffin through the filter went.

This example is based on one of the best examples of the prior art, in which excellent results were detected without passage of the crystals.

A scanning electron micrograph of the wax crystals which form in the fuels according to Examples 3 to 8 are reproduced in FIGS. 3 to 8. These were obtained by storing fuel samples in bottles of 57 cc in refrigerated containers at about 8 ° C above the cloud point of the fuel for about 1 hour to stabilize the fuel temperature. The container was then cooled at 1 ° C per hour to the test temperature and then left at that temperature. A previously prepared 10 mm diameter sintered ring filter support surrounded by a 1 mm wide circular metal ring held a 200 nm silver membrane filter attached by two vertical pins and placed in a vacuum device , A vacuum of at least 30 kPa was applied and the cooled fuel was dropped from a clean dropper pipette onto the membrane until the membrane was covered by a small pool. The fuel was slowly added dropwise to maintain this oil. After applying about 10 to 20 drops of fuel, the pool was allowed to drain, leaving a thin, non-shiny layer of wet paraffin cake on the membrane. Too thick a paraffin layer will not give acceptable washing and too thin a layer may be washed away. The optimum layer thickness depends on the crystal form, with sheet-like crystals requiring a thinner layer than modular crystals. It is essential that the final filter cake has a dull appearance. A shimmering filter cake indicates too much residual oil and smears the crystals, so this cake should be discarded.

The cake is then mixed with a few drops of methyl ethyl ketone washed, which is allowed to drain completely. This is done several times. When washing ends, it disappears the methyl ethyl ketone very quickly and leaves a shiny matt white surface back when applied another drop of methyl ethyl ketone turns gray. The washed sample is then placed in a cold desiccator given and left there until the coating in the SEM can be done. It may be necessary, this sample leave under cooling to protect the crystals; You can put them in a cooling chamber before the Transition to the SEM with a suitable transport container store to a formation of ice crystals on the surface to avoid the sample.

During coating, the sample must be as cool as possible held to a destruction of the crystals too to decrease. The electrical contact with the stage becomes best with a locking screw that allows the circular ring against the side of a recess  pressed, which is provided so that the surface of the Probe located on the focal plane of the instrument. you can also use electrically conductive paint. If the sample is coated, the photomicrographs can in the usual way with an electronic scanning microscope to be obtained. The microphotographs are analyzed to determine the average crystal size, by putting a transparent film with 88 marks in the form of points at the interfaces of a uniform Grid of 8 rows and 11 rows provides. The Magnification should be chosen so that only some of largest crystals are touched by more than one point, wherein a 4000 to 8000x magnification is suitable. At each grid point, the crystal can be measured when the point touches a crystal dimension whose Form can be clearly defined. It is called distribution scatter the Gaussian standard deviation of the crystal length provided with a correction to Bessel.

Accordingly, Examples 3 to 7 show that when used the oils of the invention the crystals can reliably go through the filter, and the excellent cold temperature behavior can higher paraffin content than previously practicably extended and even at temperatures that are further below the paraffin forming temperature are, as it was so far was feasible without taking into account the fuel system must, like the possibility of fuels from the engine for heating the supplied fuel, which is taken from the fuel tank, to be redirected, and the ratio of fuel supplied to the recirculated fuel, the ratio of the main filter surface to the fuel supplied and the size and position of pre-filters and sieves.

The compounds according to Example 1 were for their effectiveness as an additive for distillate fuels in the following  Investigated fuels, the boiling behavior after ASTM-D86 was determined.

The results in the programmed cooling test, at -12 ° C were obtained with the fuel 1, are like follows:

Further results for fuel 1 were as follows:

The results for fuel 3 were as follows:

Further results for fuel 1 were as follows:

Results in fuel 2 were as follows:

Examples 9 to 15 example 9

Example 2 was repeated with the deviation that decane-1-ol instead of octadecan-1-ol and didecylamine instead of di (hydrogenated) tallowamine was used.

In addition, Example 2 was repeated, with alcohols and amines different alkyl chain length were used. In this way were the C₁₀-, C₁₂-, C₁₄-, C₁₆-, C₁₈-, C₂₀- and C₂₂ derivatives of the compound made from Example 2.

These seven different compounds were subjected to the PCT test (Test with programmed cooling, described in the application) subjected. Very fine filters were used in this test about the optimal acyl chain length for the tested fuel to determine.

The compounds of this example were added to the fuel in Added concentrations of 250 ppm. The fuel contained also 250 ppm of a styrene-n-C₁₄-maleic acid copolymer and 250 ppm of an ethylene-propylene copolymer (56% by weight more effective Component).

There were two series of tests using two different ones Fuel is carried as fuel 191 and fuel 80 012/86 were designated.

In the test series where fuel 191 was used, the filtration was carried out at -8.5 ° C. The results are shown in the following table:  

connection Continuous filter size (μm) in the PCT test C₁₀ derivative <45 C₁₂ derivative <45 C₁₄ derivative <45 C₁₆ derivative <45 C₁₈ derivative 40 C₂₀ derivative 35 C₂₂ derivative 40

In the test in which the fuel 80 012/86 was used, the filtration was carried out at -13 ° C. The results are listed in the following table:

connection In the PCT test swept filter size (μm) C₁₈ derivative 40 C₂₀ derivative 25 C₂₂ derivative <45

They are compounds with different alkyl chain length manufactured and tested. This example shows that in a special fuel an optimal alkyl chain length can be determined. For those tested in this example Fuels is the optimal alkyl chain length C₂₀. In one lighter fuel would make the optimal alkyl chain length shorter his.

example 10

Example 1 was repeated with the deviation, that dihexadecylamine instead of di (hydrogenated) tallowamine  was used. In the following, this compound as C₁₆ / C₁₆- Derivative designated.

The compound of example 1 of the patent application is referred to _below as C _16/18 derivative.

The C _16/17 , C _16/18 , C _17/18 , C _18/18 , C _20/20 and C _20/22 derivatives were prepared in the same manner.

These seven different compounds were used in the PCT test checked. The fuel used was as fuel 80 226/89 designated. This is a commercially available base fuel, treated with an ethylene-vinyl acetate copolymer has been. The filtration in the PCT test was at -14 ° C carried out. At this temperature, base fuel passes through a 180 μm filter.

In addition to the typical filters normally used in PCT Test, the following filters were used:

VW: A Volkswagen Cartridge Filter with openings approximately 40 μm in diameter; LTFT: A filter (40 to 45 μm) used in the US for the "Cryogenic Filtrability Test" -

Compounds with different chain lengths have been made and tested. In this example, the C _16/18 compound was determined to be the optimal chain length derivative for the fuel tested.

example 11

The compound with the following formula

was subjected to the PCT test. The used basic fuel was designated 80 226/89. In addition to the above Compound also contained about 50 ppm of a fuel commercially available middle distillate flow improver from Ethylene-vinyl acetate copolymer type. The filtration became at -14 ° C carried out. At this temperature, the base fuel went through a 180 μm filter.

The PCT test was performed with different amounts of the compound carried out. The results are in the following table summarized.

added amount (ppm) PCT filter (go through) 125 VW 250 100 μm 500 75 μm

example 12

The test described in Example 11 was used a connection with the following formula:

The results are shown in the following table:

added amount (ppm) PCT filter (go through) 125 | 30 μm 250 VW 500 VW

There was another PCT test using the fuel 191 performed. Except the above-mentioned compound contained the fuel 250 ppm of a C₁₄-styrene fumaric acid ester copolymer, 250 ppm of a low ethylene vinyl acetate copolymer Vinyl acetate content and 250 ppm of a commercially available monomeric growth stopper. The filtration became at -9 ° C carried out. At this temperature, the base fuel went through, which did not contain the above-mentioned further additives but the test compound, the LTFT filter.

The PCT test was performed with different amounts of the test compounds carried out. The results are in the following table played.

added amount (ppm) PCT filter (go through) 50 LTFT 125 15 μm 250 15 μm 500 30 μm

example 13

Both test methods from Example 12 were performed using a Test compound carried out with the following formula:

The results of the PCT test in fuel 80 226/89 are in the following table:

added amount (ppm) PCT filter (go through) 125 VW 250 VW 500 125 μm

The results in fuel 191 under the same conditions as in Example 12 are shown in the following table:

added amount (ppm) PCT filter (go through) 50 LTFT 125 30 μm 250 30 μm 500 LTFT

example 14

The test procedure described in Example 11 was repeated, using the following compound:

The results are shown in the following table:

added amount (ppm) PCT filter (go through) 250 | 25 μm 500 15 μm 1000 15 μm

In the formulas of Examples 11 to 14 are the radicals R₁, R₂ and R₃ is a mixture of C₁₆ and C₁₈ alkyl radicals.

Examples 11 to 14 also show that compounds which are different Ring systems as a crystal modifier are useful in fuels. In addition, these examples show that several functional groups in different combinations can be used.  

Claims (5)

1. Petroleum distillate, propellant or heating oil having a boiling range of 120 to 385 ° C and a content of 0.001 to 0.5 wt .-% of a substituted hydrocarbon compound of the general formula in which -Y- has the meaning -SO₃ ^(-) · ⁽⁺⁾ NR³₃-, -SO₂NR³- or -SO₃-,
-X- is either -Y- or -C (O) NR³-, -CO₂ ^(-) · ⁽⁺⁾ NR³₃-, - (CO) O-, -NR³C (O) - or -OC (O) -,
R¹ and R² are alkyl radicals having 10 to 22 carbon atoms in the main chain,
R³ is hydrogen or a straight-chain C₁-C₂₂-alkyl radical, where several R³ may be identical or different to one another, and
in the grouping the carbon-carbon bond and A and B are part of a cyclic structure which is aromatic or polynuclear aromatic. 2. Oil according to claim 1, characterized in that the radical R³ a straight-chain C₁-C₂₂-alkyl radical. 3. Oil according to claim 1 or 2, characterized in that the Radicals R¹, R² and R³ are straight-chain alkyl radicals having 10 to 22 Carbon atoms are. 4. Oil according to claim 1, characterized in that the substituted hydrocarbon compound has the following formula: 5. Oil according to claim 1, characterized in that the substituted hydrocarbon compound has the following formula: