FR2649407A1 - ADDITIVES FOR LOWERING THE FLOW POINT AND PREVENTING THE DEPOSITION OF SEPARATE PARAFFINS BELOW THE TROUBLE POINT - Google Patents

Abstract

a) Additives to lower the pour point and to prevent deposition of separated paraffins below the cloud point. b) Characterized in that they consist of a mixture: A: of a solution of benzoque acid and formic acid in molar proportion 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof; B: fatty amines with a proportion of primary amides of at least 75% and an alkyl and / or alkylene chain of 12 to 22 carbon atoms in a fraction of hydrocarbons entering boiling between 127 degree (s) C (400 K) and 397 degree (s) C (670 K); where appropriate in admixture with other additives, such as ethylene-vinyl acetate copolymers, as well as a mixture of hydrocarbon entering a boiling point above 402degre (s) C (675 K). c) The invention relates to additives for lowering the pour point and for preventing deposition of the separated paraffins below the cloud point.

Description

"Additives to lower the pour point and prevent the deposit

  separate paraffins underneath

of the cloud point ".

  The invention relates to additives and a process for the preparation and the use of pour point depressant additives and to prevent the deposition of separated paraffins below the cloud point of petroleum fractions (medium oils). , whose boiling point is above 167 * C (440 K) and whose boiling point is less than 392'C (665 K) and for which at least% by weight boils above 302 'C. It concerns the use of additives, especially in diesel fuels or in medium oils

used as heating oil.

  The safe storage, transfer and use of petroleum fractions in the 167 C (440 K) to 392 ° C (665 K) boiling range, for example low temperature diesel or heating oil, low pour point (TGL 51 583) to ensure sufficient fluidity. Are customary for a sufficient cold resistance according to the local particularities, for example pour points lower than -10 ° C (263 K) or lower than -5 ° C (258 K). In some cases, however, much lower flow temperatures are required, for example -33 ° C (240 K). In addition, the problem-free storage and transfer of such petroleum fractions at low temperatures assumes that the deposition of paraffins which separate below the cloud point (TGL 51,772) is prevented. An arrangement known to ensure low pour points and to prevent the deposition of paraffins is to deparaffinize the petroleum fractions, for example by sterile adsorption of normal paraffins on 5x10 -mole molecular sieves, or by inclusion of urea. Such provisions, however, require. These processes are relatively expensive and are only economical if at the same time the normal paraffins can be sold at a good price or if they can be used. Another possibility of fulfilling the requirements mentioned is to reduce the boiling point of the petroleum fractions, which nevertheless leads to a decrease in yield. That is why more and more, to guarantee the so-called winter qualities of oil fractions whose boiling point is not lower than 167'C (440 K) and whose end boiling does not exceed 392'C (665 K), is required

  the use of additives or additive mixtures.

  It is customary, for example, to add ethylene-vinyl acetate copolymers of sequence and chain length determined for gas oils and light fuel oils, which lowers the pour point and

  the filterability limit temperature (TGL 33 636).

  On the other hand, thanks to these additives, the deposition of the separated paraffins below the cloud point is accelerated, which reinforces the risk of clogging the

  outlet ports of tanks and tubings.

  It is known to prevent this disadvantage by other additives based on hemiesters of copolymers

  alternate propene-maleic anhydride (PD 253 833).

  The effectiveness of these additives is however limited to temperatures close to the cloud point, which reduces the practical interest of these provisions, because it is necessary to count with temperatures of -20 * C (253 K) and less. Documents DD 209 649 and DE 2 921 330 describe a mixture of additives for improving the cold behavior of medium fuel oils which in addition to plasticizers for example based on copolymers of ethylene-vinyl acetate or a hydrogenated polybutadiene contains another hydrocarbon polymer with a concentration of unsaturated ester and / or olefin, as well as polar nitrogen compounds, which can advantageously be prepared from dicarboxylic acids or anhydrides thereof, for example anhydride maleic, straight-chain secondary alkylamines with up to 30 carbon atoms in the alkyl chain and fatty alcohols at temperatures between 70 and 80-C (343 and 353 K). These additives also slow down the deposition rate of the separated paraffins, essentially at temperatures below the cloud point,

  not exceeding rest periods of 72 hours.

  In the document DD 262 242 there is described with the same objective a mixture of additives of which a component is prepared by reaction of dicarboxylic acids, disulfonic acids or carboxylic sulphonic acids at temperatures higher than 97 ° C. (370 K. ) with preferably 12-carbon secondary amines forming mixtures of amides and ammonium salts and which further contains in addition "honeycomb polymers", for example alpha-based copolymers. -olefins and

  of maleic anhydride, such as styrene

  dialkyl maleate and the ethylene-copolymers

  vinyl acetate. This relatively expensive additive mixture significantly lowers the filterability temperature, whereas the deposition of the separated paraffins has not been sufficiently prevented, or delayed,

in all cases.

  In addition it is known to add to medium oils to reduce the deposition of paraffins a mixture of homo and copolymers of ethylene polar compounds soluble in oil, primarily based on succinic acid, and another polymer of hydrocarbon (PD 200,572 and SU 1,271,375). Here too

  efficiency is limited to temperatures a little

below the cloud point.

  The object of the invention is constituted by additives for lowering the pour point and for preventing the deposition of the separate paraffins below the cloud point, as well as the preparation and the use of these additives, also also additives for medium oils containing copolymers of ethylene-vinyl acetate, which include boiling fractions between

327 ° C (600 K) and 387 ° C (660 K).

  There is a need to find additives or a combination of additives which significantly slows down the deposition of paraffins below the cloud point in the petroleum fractions (medium oils) and at the same time lowers the pour point. This goal is achieved by additives to lower the pour point and to prevent the deposition of paraffins separated from petroleum fractions (medium oils) below the cloud point, whose onset of boiling is greater than 167 ° C. (440 K) and whose boiling point is less than 392 ° C (665 K) and a mass proportion of not less than 0.1 kg / kg boiling above 302 C (575 K), characterized in that they consist of a mixture A: of a solution of benzoic acid and formic acid in molar ratio of 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof and B: fatty amines with a primary amine content of at least 75% and an alkyl and / or alkylene chain of 12 to 22 carbon atoms in a hydrocarbon fraction boiling between

127 ° C (400 K) and 397 ° C (670 K).

  If necessary mixed with other additives, such as ethylene-vinyl acetate copolymers as well as with a hydrocarbon mixture entering into

  boiling above 402 ° C (675 K).

  The additives of the invention are prepared by: A: dissolving benzoic acid and formic acid in a molar ratio of 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof, B: adding fatty amines with a primary proportion of at least 75% and an alkyl and / or alkylene chain of 12 to 22 carbon atoms to a hydrocarbon fraction boiling between 127 ° C (400 K) and 397 C (670 K), and A and B are combined at temperatures between 17 ° C (290 K) and 52 ° C (325 K), choosing the amounts of A and B in such a way that the acids and the The amine mixture is in a molar proportion and, to the solution thus formed, other additives can be added, for example ethylene-vinyl acetate copolymers and, as appropriate, a mixture of hydrocarbons entering. boiling above 402 ° C (675 K). Surprisingly, the temperature during the preparation of

  the additive has a notable influence on its effectiveness.

  It should not exceed 52 ° C (325 K) or only briefly. On the other hand, it is possible to vary the molar proportion of benzoic acid with acid.

  in a relatively important field.

  However, in many cases of application, it is beneficial to prevent the deposition of paraffins, to have the molar proportion of benzoic acid to formic acid of 1: 1.5 to 1: 2.5, preference

1: 1.75 to 1: 2.

  Surprisingly, the use of cyclohexanols, methanol, ethanol or isopropanol is also important in the preparation of the additive. It has been found that additives prepared in the absence of these alcohols have an efficiency that is partly poorer and also less reproducible in the sense of the specification required. However, it is appropriate to limit the amounts of alcohol during the preparation of the additive. A preferred embodiment of the present invention is therefore characterized in that the amount of methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof is 1.5 to 6 times the weight of benzoic acid. Isopropanol or a mixture of alcohols containing it is particularly suitable for having a regular effectiveness for different

petroleum fractions.

  In addition, it is advantageous to mix the fatty amine with a boiling hydrocarbon fraction between 127 ° C (400 K) and 397 ° C (670 K) in a weight ratio of 1: 1 to 1: 3. This limitation has a particular influence on the handling ability of B, on the reaction temperature in the meeting of A and B, and the quantities required, In addition to this, another special feature of the present invention is that a mixture of C9 to C12 aromatics or gas oil is added to the fatty amines of xylene.In terms of efficiency, there are no significant differences between the fatty amines claimed according to the invention. However, preparation takes place particularly quickly and without problems with the unsaturated or partially unsaturated amines, which is why it is advantageous for the fatty amines

  have an iodine value of at least 15 g / 100 g.

  Above all, petroleum fractions whose boiling point is below 347-C (620 K) or the cloud point is below -13C (260 K) can not be sufficiently stabilized from the point of view of separate paraffins. In order to obtain a stable and homogeneous paraffin suspension, it has been found necessary here that the additive also contains a boiling hydrocarbon mixture above 402 ° C (675 K). In this case very small additions are already very effective. On the other hand, it must be taken into account that in this way the pour point of the petroleum fractions can be adversely affected. Therefore, in another special embodiment of the invention, the fatty amines are mixed before or after the addition of A to B to a boiling hydrocarbon mixture between 402C (675K) and 627C. (900 K) in mass proportion 1: 0.01 to 1:30. Thus, in the sense of the problem posed, it is appropriate to mix the fatty amines or the mixture of A and B with a hydrocarbon fraction produced by cationic polymerization of ethylene with petroleum distillate or with the remaining boiling above 397 C (670K). cracked fraction of distillate under hydrocracking vacuum. Finally, it turned out that, in the sense of the problem posed, the necessary quantity of additive is in a certain ratio of the behavior to

  the boiling of the petroleum fraction to be added.

  It is particularly suitable when the amount of additive added to the boiling petroleum fraction between 1670C (440 K) and 392 C (665 K) comprises, relative to amine and boiling fractions above 302C ( 575 K), 0.01 to 2%

  by weight, preferably 0.05 to 0.5% by weight.

  The object of the invention is furthermore the use of additives for improving the cold resistance of medium oils containing copolymers of ethylene-vinyl acetate, by adding to the medium oils as additive a mixture of fatty amines primary and secondary with alkyl chains of C-2 to Ce6 and not less than 75 and not more than 95 per cent of primary amine in the molecule, and benzoic acid and fatty acid with a number of C's inclusive between 1 and 16, for a total quantity

  compared to the average oil of 0.0003 to 0.003 kg / kg.

  Mixtures of primary and secondary fatty amines as well as benzoic acid and / or fatty acids are prepared by mixing the amino components with the acidic components with stirring and usually under moderate heating, for example 57-C (330 K). ) at 67 ° C (340 K). The average oils added according to the invention are used as diesel or domestic oil, with a boiling range of 167 ° C. (440 ° C.) at 38 ° C. (660 ° C.), a final boiling point of between 32 ° C. (600 ° C.). ) and 387 ° C (660 K) and boiling fractions above 327 ° C (600 K), at least 0.15 to 0.25 kg / kg, and a n-paraffin content of at least 0.05 kg / kg resulting in the final quality of the processing transformation technologies

primary and secondary oil.

  Such medium oils contain ethylene-vinyl acetate copolymers with weight average molar masses of 3000 to 10,000 and a vinyl acetate content of 0.25 kg / kg, 0.000025 to 0.00025 kg. kg based on average oil

to improve filterability.

  It has been found that the average oils which preferably fulfill the conditions set in all respects are those in which the mass ratio of the ethylene-vinyl acetate copolymers to the fatty amine-acid mixture is from 1 to 40 to 1. Finally, it has been found that from the point of view of a long-term action of the stabilization of the suspension of paraffins separated at low temperature and still suspended in the medium oil, it is advantageous to have a ratio of mass of fat amine and benzoic fatty amine of 1: 2 to 2: 1. This molar ratio of benzoic acid to fatty acid must be

from 1: 1.2 to 1: 1.9.

Modes of realization

Example 1

  For the preparation given by way of example of the additives of the invention, starting from the following fatty amines (products marketed by VEB DHW Rodleben): Rofamin T 20: mixture of aliphatic amines with a content of primary amines of at least 75%, a total nitrogen content of at least 4.6%, an iodine value of 20-5 gJ / kg and an average molar mass of the primary amine content of 258 g / mol. At least 90% of the alkyl residues have 16 to 18 carbon atoms, Rofamin T: differs from Rofamin T 20 by the lower iodine value, which is at most 5 gJ / 100 g, Rofamin RD: mixture of aliphatic amines with a primary amine content of at least 94%, a total nitrogen content of not less than 4,6%, an iodine value of not more than 5 gJ / 100 g and a molar mass of primary amines of 275 g / mole. Not more than 80% of the alkyl radicals have 16 to 18 carbon atoms and at least 15% of the alkyl radicals

  have 20 and 22 carbon atoms.

Example 2

  A) In a 100 ml beaker, 19.7 g of benzoic acid was dissolved in 30 g of

ambient temperature.

  Then, 1.75 g of formic acid (85%), which corresponds to a molar proportion, was added.

  of benzoic acid: formic acid = 5: 1.

  B) In a 200 ml Erlenmeyer flask, Rofamin T 20 was mixed with 50 g of xylene mixture and the Rofamin-xylene mixture was cooled to 15 ° C (288 K). By gently bending the Erlenmeyer flask, Solution A was added to Solution B; after which the temperature is raised to 32 ° C (305 K) giving a clear liquid,

  transparent, dark yellow color.

Example 3

  A) In a 100 ml beaker, 4 g of benzoic acid was dissolved in a mixture of 5 g of methanol and 5 g of ethanol at room temperature and then 8.8 g of formic acid (at 85%); proportion

  molar benzoic acid: formic acid = 1: 5.

  BA) In a 200 ml Erlenmeyer flask, 50 g of Rofamin T 20 was added to 150 g of a hydrorefined oil fraction boiling between 177 ° C (450 g).

  K) and 395 ° C (668 K) and stirred for 10 minutes.

  By gently tilting the Erlenmeyer flask, Solution A was added to Solution B. After that, the temperature rose from 21 ° C (294 K) to 37 ° C (310 K)

  forming a clear liquid, transparent golden yellow.

Example 4

  A) In a 100 ml beaker, 6.75 g of formic acid (85%) was added to 8.25 g of benzoic acid, and then 165 g of isopropanol was added. There was thus obtained a clear colorless solution; proportion

  molar benzoic acid: formic acid = 1: 1.8.

  B) In a 200 ml Erlenmeyer flask, Rofamin T 20 was slurried in 50 g of

diisopropylbenzene with stirring.

  By gently leaning the Erlenmeyer flask into a cold water bath, A was added to B; the temperature is then raised from 22-C (295 K) to 24 ° C

  (297 K) forming a transparent clear yellow liquid.

Example 5

  A) In a 50 ml beaker, 7.5 g of benzoic acid was dissolved in 15 g of a mixture of 56%

  volume of cyclohexanol, 5% by volume of

  methylcyclohexanol and 40% by volume of 2-

  methylcyclohexanol and 3-methylcyclohexanol and then 6.6 g of 85% formic acid; proportion

  molar benzoic acid: formic acid = 1: 2.

  B) In a 300-ml Erlenmeyer flask, 50 g of Rofamin RD was slurried with 150 g of a hydrorefined oil fraction of boiling range 183 ° C (456 K).

at 367 ° C (640 K).

  In a hot water bath, A was added to B with stirring; the temperature is rising by forming a

  dark yellow solution, 35C (308 K) at 52 ° C (325 K).

Example 6

  A) In a 50 ml beaker, 9.45 g of benzoic acid was mixed with 6.3 g of 85% formic acid and dissolved in 18.5 g of methanol; proportion

  molar benzoic acid: formic acid = 1: 1.5.

  B) In a 300 ml Erlenmeyer flask, 50 g of Rofamin T was added to 120 g of a petroleum fraction of boiling range 176 ° C (449 K) at 345 ° C (618 K). With stirring, A was added to B, which raised the temperature from 20 ° C (293 K) to 37 ° C.

  (310 K) and gave a clear, dark yellow solution.

Example 7

  A) In a 50 ml beaker, 6.75 g of benzoic acid was dissolved in 15 g of isopropanol and then 7.5 g of formic acid (85%) was added; molar proportion of benzoic acid: formic acid

= 1: 2.5.

  B) In a 200 ml Erlenmeyer flask, 50 g of Rofamin T were added to 80 g of a petroleum fraction boiling between 449 and 618 K and then

stirred for 15 minutes.

  While stirring, A was added to B. The temperature rose from 290 to 308 K and

  a limpid, yellow-brown liquid has formed.

Example 8

  A) A benzoic acid solution was prepared,

  of formic acid and isopropanol according to Example 7.

  B) To this mixture of Rofamin T and petroleum fraction according to Example 7 was added 50 g of a boiling hydrocarbon fraction between 690 and about 920 K from the polymerization.

cationic ethylene.

  With stirring, A was added to B. With a temperature increase of 292 K to 305 K, it was

  formed a clear, dark yellow liquid.

Example 9

  A) A benzoic acid solution was prepared,

  of formic acid and isopropanol according to Example 7.

  B) To the mixture of Rofamin T and petroleum fraction according to Example 7 was added 0.5 g of a boiling fraction between 668 and 883 K from the boiling under vacuum of petroleum. With stirring, A was added to B. With a temperature rise of 289 to 306 K, it formed after

  minutes a dark yellow light opalescent liquid.

Example 10

  A) According to Example 7, a solution was prepared

  benzoic acid, formic acid and isopropanol.

  B) In a 300-ml Erlenmeyer flask, 50 g of Rofamin T were slurried with 150 g of hydrorefined oil fraction boiling range 183 ° C. (456 K)

at 367 C (640 K).

  With stirring, A was poured into B. With a temperature increase from 32 ° C (305 K) to 52 ° C (325 K) in a warm water bath, a clear, dark yellow liquid was formed. This liquid was placed in a 2 liter flask with 1000 g of boiling hydrocarbon fraction between 399C (672 K) and about. 527'C (800 K) from

  distillate hydrocracking under vacuum of oil.

  After stirring for 15 minutes at room temperature,

  a stable, cloudy yellow liquid was obtained.

Example 11

  A) According to Example 7, a solution was prepared

  benzoic acid, formic acid and isopropanol.

  B) 50 g of Rofamin T 20 were added to a 300 ml Erlenmeyer flask to 100 g of hydroformed petroleum fraction boiling between 186 ° C (459 ° F).

K) and 367 ° C (640 K).

  With stirring, A was added to B, which raised the temperature from 11 ° C (284 K) to 19 ° C (292 K). In the clear, dark yellow liquid formed, we have

  added 9 g of ethylene-vinyl acetate copolymer.

  Then there was trouble; the liquid was in

stable phase.

Example 12

  A) According to Example 7, a solution was prepared

  benzoic acid, formic acid and isopropanol.

  B) 50 g of Rofamin T 20 were added in a

  1 "flask containing 100 ml of xylenes mixture.

  While stirring, A was poured into B. After formation of a clear yellow solution, with a temperature rise of 23 C (296 K) at 35 ° C (308 K), 500 g of a boiling hydrocarbon between 399 ° C (672 K) and 525 (798 K), from petroleum distillate hydrocracking and 9 g of ethylene-vinyl acetate copolymer, which after stirring resulted in a few

  minutes a yellow liquid, stable phase disorder.

Example 13

  A) In a 50 ml beaker, 5.9 g of benzoic acid was dissolved at room temperature, and 7.9 g

  85% formic acid in 15 g of ethanol.

  B) 50 g of Rofamin T were added in a 200 ml flask to 150 g of a hydrorefined oil fraction of boiling range 186 ° C (459 K)

at 367 ° C (640 K).

  While stirring, A to B was added, which raised the temperature from 22 ° C (295 K) to 41 ° C (314 K). The clear, deep yellow solution was poured into a 2 liter beaker with continuous stirring at room temperature, in a mixture of 1500 g of a hydrocarbon fraction obtained by cationic polymerization of ethylene and boiling at 417 ° C. (690 K), 50 g of vacuum distillate and 9 g of ethyleneacetate copolymer. The final product was a slightly cloudy yellow liquid and

weakly opalising.

Example 14

  A) and B) according to Example 4 and 10 were prepared and mixed. Then, the yellow clear reaction solution was added to 25 g of petrolatum and superheated steam cylinder oil, which gave a clear, slightly dark liquid.

slightly fluorescent.

Example 15

  To evaluate the effectiveness of the additive, the petroleum fractions used were characterized by the paraffin separation start temperature (BPA = cloud point) according to TGL 51 772, by the filterability limit temperature (GTF) according to TGL 33. 638, by the pour point according to TGL 51 583 and by

  the deposition behavior of the separate paraffins

  below the cloud point. In the latter case, 250 ml of the test sample were placed in a graduated cylinder at -22 ° C (251 K) for 336 hours in a freezer. The deposition behavior of paraffin separations was evaluated from the point of view of the formation of an upper clear phase and a lower turbid phase. As in the cloudy phase, a layer may be formed during storage, the haze phase in particular has been tested. To characterize the tendency to deposit paraffin separations under the test conditions mentioned, a succession of three numbers has been indicated, the first of which is the volume percentage of the clear phase, the second of which is the volume percentage of the phase. turbid, and the third, in parentheses, is the volume percent of the upper layer in the paraffin-enriched turbid phase.

  The application examples presented below

  above are composed of petroleum fractions

following: -

  Echan- Start Dis Fin Dis Vol .-% BPA Item GTF Contains-

  tillation tillation> 302 ° C (> 575K) deposit

I 165 C 340'C -17'C -34C -28'C

  438 K 613 K 12 256 K 239 K 245K 32/68 (0)

II 180 C 372-C-11 C-17'C-15 C

  453 K 645 K 35 262 K 256 K 258 K 56/44 (0)

III -12 * C -28'C -24'C

  analogue II + 0.001 Z EVA * 261 K 245 K 249 K 95/5 (0) **

IV 183 C 365 C -9 'C -18'C -16'C

  456 K 638 K 20 264 K 255 K 257 K 49/51 (0)

V 170 C 395'C -2 C -11'C -8 'C

  443 K 668 K 43 271 K 262 K 265 K 68/32 (0)

  ________________________________________________________________

  *: ethylene-vinyl acetate copolymer

**: after 72 hours.

  Start of boiling, boiling and% by volume> 302 ° C (> 575 K) were determined according to

  the boiling analysis according to TGL 21 120.

Example 16:

  To 500 g of petroleum fraction II, 0.053 g of additive according to Example 2 was added. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0.01. % by weight The following cold-holding characteristics were determined according to Example 14: BPA Pour point GTF Deposition behavior

(263 K) (251 K) (255 K) 0/100 (45)

-10 C -22'C -18 C

Example 17

  To 500 g of petroleum fraction II was added 15.5 g of additive according to Example 3. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 2 % by mass. The following cold-holding characteristics were determined according to Example 14: BPA Pour Point GTF Depot Behavior

(262 K) (240 K) (253 K) 0/100 (10)

-11 C -33 C -20 C

Example 18

  To 500 g of petroleum fraction II was added 0.6 g of additive according to Example 4. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C (> 575 K) of 0. , 06% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(261 K) (244 K) (252 K) 0/100 (0)

-12 ° C -29'C -21'C

Example 19

  To 500 g of petroleum fraction III was added 1.6 g of additive according to Example 5. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0, 2% by mass. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(260 K) (237 K) (244 K) 10/90 (35)

-13 C -30 C -29 C

Example 20

  To 500 g of petroleum fraction III, 8.6 g of additive according to Example 10 was added. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0. , 2% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(265 K) (241 K) (246 K) 0/100 (0)

-8'32'C -27'C

Example 21

  To 500 g of petroleum fraction I, 1.2 g of additive according to Example 6 was added. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C (> 575 K) of 0. , 5% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(255 K) (231 K) (241 K) 0/100 (25)

-18 C -42'C -32'C

Example 22

  To 500 g of petroleum fraction I was added 0.95 g of additive according to Example 7. This corresponds to an amine content, relative to the fractions boiling at> 30 ° C. (> 575 K) of 0.5 % by mass. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(253 K) (229 K) (238 K) 0/100 (0)

-20'C -44 "C -35 C

Example 23

  To 500 g of petroleum fraction V was added 4.5 g of additive according to Example 8. This corresponds to an amine content, relative to the fractions boiling at> 30 ° C. (> 575 K) of 0.5 % by mass. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(271 K) (253 K) (263 K) 0/100 (30)

-2'C -20'C -10'C

Example 24:

  To 500 g of petroleum fraction V was added 0.7 g of additive according to Example 9. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0. , 1% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(272 K) (250 K) (260 K) 10/90 (0)

-1C -23C -12'C

Example 25

  To 500 g of petroleum fraction IV, 1.9 g of additive according to Example 11 were added. This corresponds to an amine content, relative to the fractions boiling at> 302 ° C. (> 575 K) of 0. , 5% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(264 K) (243 K) (248 K) 8/92 (75)

-9'C -30'C -25'C

Example 26:

  To 500 g of petroleum fraction IV was added 1.6 g of additive according to Example 12. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C (> 575 K) of 0. , 5% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(262 K) (245 K) (248 K) 0/100 (0)

-11'C - 28-C -25 * C

Example 27:

  To 500 g of petroleum fraction II, was added 3.1 g of additive according to Example 13. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0. , 05% by weight. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(264 K) (247 K) (251 K) 0/100 (0)

-9'C -26'C -22'C

Example 28

  To 500 g of petroleum fraction IV was added 2 g of additive according to Example 14. This corresponds to an amine content, relative to the boiling fractions at> 302 ° C. (> 575 K) of 0.4 % by mass. The following cold-holding characteristics were determined: BPA Pour point GTF Deposition behavior

(265 K) (241 K) (246 K) 0/100 (0)

-8'C -32'C -27'C

  Example 29 (comparison): Two samples of middle distillates were studied with the following characteristics in terms of their cold behavior. In addition to the characteristics determined by TGL for cloud point (BPA) and pour point (according to TGL 0-51 583) or GTF (filterability) (according to TGL 33 638), the deposition behavior of paraffins at

  -22 C (251 K) in the freezer for 336 hours.

  Next, a graduated 250 ml sample of the middle distillate sample, 30 cm high and 4 cm in diameter, was placed vertically in a freezer and the paraffin deposit was evaluated in volume using the formation. a clear phase and a

deposit at the bottom.

  Sample 1 Sample 2 Range C 182-367 168-367 Boiling K (456) - (640) (441) - (640) Fraction above 327 C (600 K) m3 / m3 0.25 0, 15

Content in n

  paraffin kg / kg 0.133 0.145 Density g / cm 0.835 0.829 EVA kg / kg 0.00015 0, 00015

___________

BPA C -5 -4 -9 -9

K (268) (269) (264) (264)

Point of contact

C -15 -32 -19 -28

K (258) (241) (254) (245)

GTF C -5 -21 -12 -26

K (268) (252) (261) (247)

  Deposition behavior at -22 ° C (251 k) m3 / m3 clear phase after 24 hours storage 0.500 0 0.450 after 240 hours storage 0.625 0.116 0.800 after 336 hours storage 0.663 0.248 0.825

* Example 30:

  Medium oil containing 0.00015 kg / kg of EVA copolymers corresponding to Sample 1 was mixed to improve cold performance and, to decrease paraffinic sedimentation, 0.0006 kg / kg of molar reaction product prepared at 67 ° C (340 K), from benzoic acid and a mixture of linear amines of high molecular weight, the alkyl radicals of which have at least 90% of C16 to C18 alkyl residues and a primary amine content of 95%, as well as 0.0006 kg / kg of a molar reaction product of formic acid and a mixture of linear aliphatic amines with 90% of C16 to C18 alkyl groups and a content of 25% secondary fatty amines. The cold behavior and the deposit becomes the following: Application according to the invention with without

BPA C -3 -4

K (270) (269)

Pour point C -41 -26

K (232) (247)

GTF C -25 -21

K (248) (252)

  Clear phase m3 / m3 after 24 O 0.458

240 "0 0.625

336 "0 0.663

Example 31:

  To medium oil containing 0.000025 kg / kg of EVA copolymers according to Sample 2 of Example 29 was added 0.0003 kg / kg of a mixture obtained by molar reaction of a mixture benzoic acid / formic acid with a mixture of linear aliphatic amines with 90% of C16 to C18 alkyl groups and a content of 25% of fatty amines

secondary.

  The molar ratio used of benzoic acid to formic acid is 1: 1.9. On these samples, the following characteristic values were determined: Application according to the invention with without

BPA C -9 -8

K (264) (265)

Pour point C -31 -24

K (242) (249)

GTF C -24 -24

K (249) (249)

  Clear phase m3 / m3 after 24 hours 0 0.008 240 hours 0 0.116 336 hours 0 0.153

Example 32

  To medium oil containing 0.00025 kg / kg of EVA copolymers according to Sample 2 of Example 29 was added 0.001 kg / kg of a molar reaction product of benzoic acid and formic acid, in molar ratio 1: 1.2, and a mixture of linear aliphatic amines with 90% of C16 to C18 alkyl groups and a content of 25% of secondary fatty amines. The following results were obtained: Application according to the invention with without

BPA C -9-10

K (264) (263)

Pour point C -36 -29

K (237) (244)

GTF C -27 -29

K (246) (244)

  Clear phase m3 / m3 after 24 hours 0 0.383 240 hours 0 0.813 336 hours 0 0.833

Example-33:

  To medium oil containing 0.0001 kg / kg of EVA copolymers according to Sample 2 of Example 29 was added 0.0006 kg / kg of a molar reaction product of benzoic acid and of formic acid, in molar ratio 1: 1.9 and a mixture of linear aliphatic amines with 90% of C16 to C18 alkyl groups and a content of 25% of secondary fatty amines. The following results were obtained: Application according to the invention with without

BPA C -9 -8

K (264) (265)

Pour point OC -34 -28

K (239) (245)

GTF C -28-27

K (245) (246)

  Clear phase m3 / m3 after 24 hours 0 0.300 240 hours 0 0.770 336 hours 0 0.804

Example 34

  To medium oil containing 0.00015 kg / kg of EVA copolymers according to Sample 2 of Example 29 was added 0.0006 kg / kg reaction product of a mixture of amines with formic acid (according to Example 30) and -0.0006 kg / kg of the reaction product of a mixture of amines with benzoic acid (according to Example 30). The following cold behavior was obtained: Application according to the invention with without

BPA C -4 -9

K (269) (264)

Pour point 'C -35 -28

K (238) (245)

GTF C -28 -26

K (245) (247)

  Clear phase m3 / m3 after 24 hours 0 0.450 240 hours 0 0.800 336 hours 0 0.825

Example 35

  Medium oil containing 0.00015 kg / kg of EVA copolymers according to Sample 2 of Example 29 was added to 0.001 kg / kg of a reaction product of a mixture of linear amines. aliphatics with 90% C16 to C18 alkyl groups and 25% secondary fatty amine content and a mixture of acids consisting of benzoic acid and technical palmitic acid,

molar ratio 1: 1.7.

  The following cold behavior was obtained: Application according to the invention with without

BPA C -9 -9

K - (264) (264)

Pour point C -39 -28

K (234) (245)

GTF C -28 -26

  Clear phase m3 / m3 after 24 hours 0 0.450 240 hours 0 0.796 336 hours 0 0.825

Example 36

  To 250 ml of medium oil according to Sample 2 of Example 29 and containing 0.00005 kg / kg of EVA copolymers, 0.0004 kg / kg of reaction product of a mixture was added. of amine with 90% C16 to C18 alkyl groups and with a content up to% of secondary amines and a mixture of benzoic acid and formic acid in a proportion

molar 1: 1.9.

  The molar proportion of amine mixtures

264,940?

  to acid mixtures in reaction products

are 2: 1, 1: 1 and 1: 2.

  Application according to the invention Molar ratio 2: 1 1: 1 1: 2 with with without

BPA C -9 -8 -7 -9

K (264) (265) (266) (264)

  Pour point OC -29 -29 -29 -27

K (244) (244) (244) (246)

GTF C -32 -30 -31 -23

K (241) (243) (242) (250)

  Clear phase m3 / m3 after 24 hours 0 0 0 0.037 240 hours 0 0 0 0.303 336 hours 0 0 0 0.390

Example 37

  To an average distillate according to Sample 2 of Example 29 with 0.00015 kg / kg of EVA copolymers, 0.0010 kg / kg of a molar reaction product of a mixture of amines was added. with 90% of C16 to C18 alkyl groups and with a content up to% of secondary amine with formic acid as well as 0.001 kg / kg of a molar reaction product of

  same mixture of amine with benzoic acid.

  On these samples, the following cold behavior was determined: Application according to the invention with without

BPA C -9 -9

K (264) (264)

Pour point OC -36 -28

K (237) (245)

GTF C -24 -26

K (249) (247)

  Clear phase m3 / m3 after 24 hours 0 0.45 240 hours 0 0.796 336 hours 0 0.825

Example 38

  To an average distillate according to sample 2 of Example 29 and containing 0.00015 kg / kg of EVA copolymers, 0.001 kg / kg of a molar reaction product of a mixture of amines with 90% C, 6 to C 8 alkyl groups and up to 25% content of secondary amines with benzoic acid, as well as 0.001 Kg / Kg of an amine mixture mole reaction product with 68% of C12 alkyl groups, a primary amine content of 95%, with palmitic acid. The following cold resistance was obtained: Application according to the invention with without

BPA C -9 -9

K (264) (264)

Pour point * C -34 -28

K (239) (245)

GTF C -33 -26

K (240) (247)

  Clear phase m3 / m3 after 24 hours 0 0.45 240 hours 0 0.796 336 hours 0 0.825

Claims (2)

1) Additives for lowering the pour point and for preventing the deposition of paraffins separated from petroleum fractions (medium oils) below the cloud point, the onset of boiling is greater than 167 ° C (440 K ) and whose boiling point is less than 392 ° C (665 K) and a mass proportion of not less than 0.1 kg / kg distils above 302 C (575 K), characterized in that those These consist of a mixture of: A: a solution of benzoic acid and formic acid in a molar ratio of 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or their mixtures and; B) fatty amines with a primary amine content of at least 75% and an alkyl and / or alkylene chain of 12 to 22 carbon atoms in a hydrocarbon fraction boiling between 127 C (400 K) and 397 C (670 K). If necessary mixed with other additives, such as ethylene-vinyl acetate copolymers, as well as a boiling hydrocarbon mixture above 402 ° C (675 K). 2 ') Process for the preparation of additives according to claim 1, characterized in that: A) benzoic acid and formic acid are dissolved in a molar ratio of 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof, B) fatty amines with a primary amine content of at least 75% and an alkyl and / or alkylene chain of 12 to 22 carbon atoms, at a fraction of boiling hydrocarbons between 127 ° C (400 K) and 397 ° C (670 K); and A and B are mixed at temperatures between 17 ° C (290 K) and 52 ° C (325 K), selecting the amounts of A and B, so that the acids and the amine mixture are in a molar proportion and further additives may be added, such as ethylene-vinyl acetate copolymers and a boiling hydrocarbon mixture above 402 ° C (675 K). ).   3) Process according to claim 2, characterized in that the molar proportion of benzoic acid to formic acid ranges from 1: 1.5 to 1: 2.5, preferably 1: 1.75 to 1: 2.   4 *) Process according to claims 2 and 3,   characterized in that the amount of methanol, ethanol, cyclohexanol or isopropanol or mixture thereof is 1.5 to 6 times the weight of the benzoic acid.   Method according to claims 2 to 4,   characterized in that the fatty amines are added to a boiling hydrocarbon fraction between 127C (400 K) and 397 ° C (670 K) in a ratio mass of 1: 1 to 1: 3.   6 '*) Process according to claims 2 to 5,   characterized in that the fatty amines are added to   xylene, with an aromatic Cg- / C, 2 or with gas oil.   7) Method according to claims 2 to. 6   characterized in that the fatty amines have a   iodine number of at least 15 gI / 100 g.   8 ') Process according to claims 2 to 7,   characterized in that the fatty amines, before or after addition of A to B, are added to a boiling hydrocarbon mixture between 402 ° C (675 K) and 627 ° C (900 K) in a molar proportion of 1 : 0.01 to 1:30.   9 ') Process according to claims 2 to 8,   characterized in that the fatty amines or the mixture of A and B are added to a hydrocarbon fraction produced by cationic polymerization of ethylene, petroleum distillate or the remainder boiling above 397C. (670 K) cracked distillate fraction under a hydrocracking vacuum.   Method according to claims 2 to 6,   characterized in that the amount of additive added to the petroleum fraction, based on amine and boiling fractions above 302 ° C   (575 K) is at least 0.05 and not more than 0.5% by weight. ) Use of additives according to   Claims 1 to 10, characterized in that   these additives to a petroleum fraction boiling between 167 C (440 K) and 392 C (665 K) in proportion such as the amount of amine, based on boiling fractions above 302 C   (575 K) represents 0.01 to 2% by weight.