DD294967B5 - ADDITIVES FOR REDUCING THE STICK POINT - Google Patents

Description

Field of application of the invention

The invention relates to additives and a process for the preparation and use of additives to reduce the pour point and to prevent settling of excreted below the BPA point paraffins of petroleum fractions (middle oils) whose boiling point is not below 440K and the boiling end not above 665K and at which boil at least 10 mass fractions in% above 575K. It further relates to the application of the additives.

Characteristic of the known state of the art

The trouble-free storage, loading and application of petroleum fractions of the Siedeberelches 440 to 665K, z. B. of diesel oils or extra light Haushultsheizölen, at low temperatures makes u.a. a low pour point (TGL 51583) is required to ensure adequate flowability. Are customary for sufficient low temperatures, depending on the territorial conditions z. B. pour points that are below 263 K and below 258 K. However, in part, much lower pour point temperatures, e.g. 240 K are required. In addition, a trouble-free storage and loading of such petroleum fractions at low temperatures, the prevention of settling of below the BPA point (TGL 51772) exuding paraffins is a prerequisite.

A known measure to ensure low pour points and to prevent the settling of paraffin is the dewaxing of petroleum fractions z. By stereoselective adsorption of the normal paraffins on 5A molecular sieves or by urea inclusion compounds. However, such measures require relatively complicated procedures and are only economical if at the same time the separated normal paraffins can be sold or used profitably. Another way to meet the above requirement is to reduce the boiling point of the petroleum fractions, but this leads to a reduction in the yield. Increasingly, therefore, the use of additives or additive packages to secure so-called winter qualities of petroleum fractions whose boiling point is not below 440K and whose boiling end is not above 665 K, prevails.

Usual is z. As the addition of ethylene-vinyl acetate copolymers of certain sequence and chain length to diesel oils and extralight fuel oils, whereby the pour point and the limit temperature of the filterability (TGL 33638) are lowered. In contrast, these additives promote the settling of the paraffins excreted below the BPA point, which can lead to increased blockages in Behälterablaßstutzen and in pipelines.

It is known to prevent this disadvantage by additional additives based on half esters of alternating propene-maleic anhydride copolymer (DD 253833). However, the effect of these additives is limited to temperatures around the BPA point, which makes this measure only a limited measure of practical concerns where temperatures of 253 K and less are expected.

DD 209649 and DE 2921330 describe an additive package for improving the low-temperature behavior of middle distillate fuel oils, which in addition to so-called flow improvers z. B. on the basis of ethylene-vinyl acetate copolymers or a hydrogenated polybutadiene and another hydrocarbon polymers with unsaturated ester and / or olefin content still containing polar nitrogen compounds, advantageously from dicarboxylic acids or their anhydrides, eg. Example, maleic anhydride, straight-chain secondary alkylamines having up to 30 carbon atoms in the alkyl chain and fatty alcohols at temperatures between 343 and 353K are produced. These additives also delay the settling rate of the excreted paraffins essentially at temperatures just below the BPA point temperature, whereby service lives of 72 hours were not exceeded.

In DD 262 242 is described with the same objective an additive package, one component of which is produced by reacting disulfonic acids, dicarboxylic acids or sulfonic acids at temperatures above 370K with preferably secondary amines having 10 to 12 carbon atoms to form amide ammonium salt mixtures and which also contains »honeycomb polymers«, for example copolymers based on α-olefins and maleic anhydride, such as styrene-dialkylmateate copolymer and ethylene-vinyl acetate copolymers discontinuation of excreted paraffins was not sufficiently prevented or delayed in all cases.

DD 286610 describes ethylene-vinyl acetate-containing middle oils whose increased tendency to settle out at low temperatures paraffins is greatly reduced by a mixture of primary and secondary fatty amines with C) ₂ - to Ci8 alkyl chains and at least 75% and at most 95% primary moiety in the molecule as well as benzoic acid and fatty acids with 1 to 16 carbon atoms. The problem in the application is that the extent of action depends strongly on the middle oil composition and that the handling requires temperatures above 310 K due to the consistency.

Object of the invention

The aim of the invention are additives for reducing the pour point and for preventing settling of the excreted below the BPA point paraffins and the preparation and use of these additives.

Explanation of the essence of the invention The object was to find additives or an additive combination, ie the paraffin sedimentation below the BPA point in petroleum fractions (middle oils) significantly delayed and the pour point is simultaneously further depleted. This object is achieved by additives to reduce the pour point and to prevent settling of the below BPA point excreted paraffins of petroleum fractions (middle oils), whose boiling point above 440K and the end of their boiling

below 665K and in which mass fractions of at least 0.1 kg / kg above 575K boiling, according to the invention solved in that it consists 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 mixtures thereof and B: fatty amines having a primary moiety of at least 75% and an alkyl and / or an alkylene chain having 12 to 22 carbon atoms in a hydrocarbon fraction boiling between 400K and 670K,

optionally in admixture with other additives, such as ethylene-vinyl acetate copolymers, and a hydrocarbon mixture above 675 K, consist.

The additives according to the invention are prepared by A: benzoic acid and formic acid in a molar ratio of 5: 1 to 1: 5 in methanol, ethanol, cyclohexanol or isopropanol or

their mixtures dissolved, B: fatty amines having a primary component of at least 75% and an alkyl and / or an alkylene chain having 12 to 22 carbon atoms with a boiling between 400K and 670 K boiling hydrocarbon fraction

and A and B are combined at temperatures between 290 and 325K, wherein the amounts of A and B are chosen so that the acids and the amine mixture are present in a molar ratio and the resulting solution containing other additives such. For example, ethylene-vinyl acetate copolymers and expediently a above 675 K boiling hydrocarbon mixture can be added.

Surprisingly, the temperature in additive production has a noticeable influence on their effectiveness. 325K should not be exceeded or only for a short time. In contrast, the molar ratio of benzoic acid to formic acid can be varied in a relatively large amount. However, in many applications, it is favorable in view of preventing the settling of the paraffins when the molar ratio of benzoic acid to formic acid is 1: 1.5 to 1: 2.5, preferably 1: 1.75 to 1: 2.

Surprisingly, the use of cyclohexanols, methanol, ethanol or isopropanol in the production of additives is also important. It has been found that additives which were prepared in the absence of these alcohols showed a partly much worse and also poorly reproducible effectiveness in the sense of the task. However, it is expedient to comply with limited amounts of alcohols in the production of additives. A specific 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 mass of benzoic acid. Isopropanol or an alcohol mixture containing such is particularly favorable with regard to a uniform effectiveness with different petroleum fractions.

Furthermore, it is advantageous if the fatty amines have been mixed with a hydrocarbon fraction boiling between 400 and 670 K in a mass ratio of 1: 1 to 1: 3. This limitation has a particular influence on the handling of B, the reaction temperature in the I'zusammengabe of A and B and the required application rate. In addition to this, another specific feature of the present invention is that the fatty amines are mixed with xylene, with a C ₉ -C ₁₂ aromatic mixture or with diesel oil. With regard to the effectiveness, there are no significant differences from the fatty amines claimed according to the invention. However, the production of unsaturated or partially unsaturated amines is particularly fast and smooth. It is therefore advantageous if the fatty amines have an iodine value of at least 15 g J / 100 g.

Above all, petroleum fractions whose boiling point is below 620 K or which have a BPA point below 260 K, can sometimes be insufficiently stabilized with regard to the settling of the precipitated paraffins. Here, it has proved to be beneficial to obtain a stable and homogeneous paraffin suspension, if the additive additionally contains a above 675 K boiling hydrocarbon mixture. In many cases, even very small amounts are effective. On the other hand, it should be noted that this can adversely affect the pour point of the petroleum fractions. Therefore, in another specific embodiment of the invention, the fatty amines are added before or after addition of A to B with a hydrocarbon mixture boiling between 675K and 900K in a mass ratio of 1: 0.01 to 1:30. It is useful in the context of the task if the fatty amines or the mixture of A and B are mixed with a produced by cationic ethylene polymerization hydrocarbon fraction, petroleum vacuum distillate or or with the above 670K boiling residue from the vacuum distillate hydro-cleavage.

Finally, it has been shown that the amount of additive required in the sense of the task has a certain relationship to the boiling curve of the petroleum fraction to be added. It is particularly useful if the amount of additive added to the petroleum fraction boiling between 440K and 665K, based on amine and the above 575K boiling components, 0.01 to 2 parts by mass in%, preferably 0.05 to 0.5 parts by mass in%.

embodiments example 1 The example given production of the additives according to the invention are the following fatty amines {commercial products of VEB DHW Rodleben) based on:

RofaminT20: Mixture of aliphatic amines with a primary content of at least 75%, a total nitrogen content of at least 4.6%, an iodine value of 20 ± 5 g J / kg and a mean molecular mass of the primary component of 258 g / mol. At least 90% of the alkyl radicals have 16 and 18 carbon atoms.

RofaminT: Differs from the Rofamin T20 by the lower iodine number, which is at most 5g / 100g.

RofaminRD: Mixture of aliphatic amines with a primary content of at least 94%, a total nitrogen content of at least 4.6%, an iodine number of at most 5g / 100g and an average molecular mass of the primary component of 275g / mol. At most 80% of the alkyl radicals have 16 and 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 were dissolved in 30 g of methanol at room temperature. Subsequently were

1.75 g of formic acid (85%) was added, which corresponds to a molar ratio of benzoic acid: formic acid = 5: 1. B: In a 200 ml Erlenmeyer flask, 50 g of Rofamin T20 were mixed with 50 g of xylene mixture and the mixture

Rofamin-Xyien cooled to 288 K

Slightly swirling the Erlenmeyer flask was added solution A in B; The temperature rose to 305K, forming a clear, dark yellow colored liquid.

Example 3 A: In a 100 ml beaker, 4 g of benzoic acid were added at room temperature in a mixture of 5 g of methanol and 5 g

Dissolved ethanol and then treated with 8.8 g of formic acid (85%); Molar ratio of benzoic acid: formic acid = 1: 5. B: In a 200 ml Erlenmeyer flask, 50 g of Rofamin T20 were incubated with 150 g of a hydrorefined at room temperature

Petroleum fraction from the boiling range 450 to 668 K and stirred for 10 minutes.

Slightly swirling the Erlenmeyer flask, solution A was added to B. The temperature rose from 294 to 310K to form a clear, transparent, golden liquid.

Example 4 A: 8.25 g of benzoic acid were dissolved in a 100 ml beaker containing 6.75 g of formic acid (85%) and then 165 g

Isopropanol is added. This formed a water-clear solution; Molar ratio of benzoic acid: amic acid = 1: 1.8. B: 50 g of Rofamin T20 were suspended in 50 g of a diisopropylbenzene mixture while stirring in a 200-HnI-Er ¹ semiautomatic flask.

Swirling the Erlenmeyer flask in a cold water bath, A was given in B; the temperature rose from 295 to 297 K to form a transparent, clear, yellow liquid.

Example 5

A: In a 50 ml assay, 7.5 g of benzoic acid were dissolved in 15 g of a mixture of 56 parts by volume in% cyclohexanol, 4 parts by volume in% 1-methylcyclohexanol and 40 parts by volume in% 2-methylcyclohexanol and 3-methylcyclohexanol and then with Added 6.6 g of 85% formic acid; Molar ratio of benzoic acid: formic acid = 1: 2.

B: In a 300 ml Erlenmeyer flask, 50 g of Rofamin RD were slurried in 150 g of a hydrorefined petroleum fraction of boiling range 456 to 4040.

The warm water bath was added with stirring A in B; the temperature rose to give a dark yellow solution

from 308 to 325K.

Example β

A: In a 50 ml beaker, 9.45 g of benzoic acid were treated with 6.3 g of 85% formic acid and 18.5 g of methanol and

solved; Molar ratio of benzoic acid: formic acid = 1: 1.5

 B: In a 300 ml Erlenmeyer flask, 50 g of Rofamin T were charged with 120 g of a petroleum fraction boiling in the range 449 to 618K.

While stirring, A was added to B, with the temperature rising from 293 to 310K to give a clear, dark yellow solution.

Example 7 A: 6.75 g of benzoic acid were dissolved in 15 g of isopropanol in a 50 ml beaker at room temperature and then with '

7.5 g of 85% formic acid added; Molar ratio of benzoic acid: formic acid = 1: 2.5. B: In a 200 ml Erlenmeyer flask, 50 g of Rofamin T were spiked with 80 g of a petroleum fraction boiling in the range of 449 to 618K and then stirred for 15 minutes.

With further stirring, A was added to B. The temperature rose from 290 to 308 K, forming a tan, clear liquid.

Example 8 A: A solution of benzoic acid, formic acid and isopropanol was prepared according to Example 7. B: To the mixture of Rofamin T and petroleum fraction according to Example 7 were added 50 g of a boiling between 690 and about 920K Hydrocarbon fraction from the cationic ethylene polymerization given.

With stirring, A was added to B. A rise in temperature from 292 to 305 K produced a dark yellow, clear liquid.

Example 9 A: According to Example 7, a solution of benzoic acid, formic acid and isopropanol was prepared. B: To the mixture of Rofamin T and petroleum fraction according to Example 7, 0.5g of one boiling between 668 and 883K Added fraction from petroleum vacuum distillation.

With stirring, A was added to B. When the temperature rose from 289 to 306 K, a dark yellow, clear, slightly opalescent liquid was formed after 10 minutes.

Example 10 A: According to Example 7, a solution of benzoic acid, formic acid and isopropanol was prepared. B: In a 300 ml Erlenmeyer flask, 50 g of Rofamin T were mixed with 150 g of hydrorefined petroleum fraction boiling 456

Slurried up to 640K.

With stirring, A was added to B. When the temperature increased from 305 to 325 K in the heated water bath, a dark yellow, clear liquid formed. This liquid was added to 1000 g of a hydrocarbon fraction boiling from 672 to about 800 K from petroleum vacuum distillate in a 2 liter Stutzan. After stirring at room temperature for 15 minutes, a turbid, yellow, phase-stable liquid had formed.

Example 11 A: According to Example 7, a solution of benzoic acid, formic acid and isopropanol was prepared. B: 50g of Rofamin T20 were dissolved in a 300ml Erlenmeyer flask containing 100g of a hydrorefined petroleum fraction from Boiling range 459 to 640 K offset.

With stirring, A was added to B, with the temperature rising from 284 to 292K. To the resulting dark yellow, clear liquid was added ethylene-vinyl acetate copolymeros. This resulted in the formation of a cloudiness; the liquid was phase stable.

Example 12

A: According to Example 7, a solution of benzoic acid, formic acid and isopropanol was prepared.

B: 50g Ro fern in T20 were mixed in a 1-liter nozzle with 100g Xylengemisch.

With stirring, A was added to B. After formation of a clear, yellow solution, with the temperature rising from 296 to 308K, 50Og of a hydrocarbon fraction boiling between 672 and 798K from petroleum vacuum distillate and 9 g of ethylene-vinyl acetate copolymers were added, with further stirring after a few minutes Minutes had formed a yellow, turbid, phase-stable liquid.

Example 13

A: In a 50 ml beaker, at room temperature, 5.9 g of benzoic acid and 7.9 g of 85% formic acid in 15 g of ethanol

solved

 B: 50 g of Rofamin T were mixed in a 200 ml Erlenmeyer flask with 150 g of a hydrorefined petroleum fraction boiling in the range 459 to 640K.

With stirring, A was added to B, with the temperature rising from 295 to 314K. The resulting dark yellow clear solution was placed in a 2 liter glass beaker with constant stirring at room temperature in a mixture of 1500 g of a hydrocarbon fraction of boiling range 690K, 50 g of vacuum distillate and 9 g of ethylene-vinyl acetate copolymer obtained from the cationic ethylene polymers. The final product was a slightly turbid and slightly opalescent yellow liquid.

Example 14

According to Example 4, A and B were prepared and combined. Subsequently, the clear, yellow reaction solution was mixed with 25 g Vaseline and 25 g hot steam cylinder oil, resulting in a clear, slightly darker, slightly fluorescent liquid.

Example 15

To evaluate the additive effect, the petroleum fractions used were determined by the temperature of commencement of paraffin precipitation (BPA) according to TGL 51772, by the pour point according to TGL 51583, by the filterability limit temperature (GTF) according to TGL 33638 and by the settling behavior below the BPA point excreted paraffins characterized. In the latter case, 250 ml of the sample to be examined were placed in a graduated graduated cylinder at 251K over a period of 336 hours in a freezer. The settling behavior of the paraffin precipitations was evaluated with regard to the formation of an upper clear phase and the lower cloudy phase. Since stratification can occur during storage during the cloudy phase, the turbidity phase was again evaluated separately. For the characterization of the settling behavior of the paraffin precipitations under the test conditions mentioned above, a series of three numbers is given, the first of which gives the volume percent clear phase, the second the volume percent turbidity phase and the third, set in Klomerern, the volume percent of paraffin-depleted upper layer within the turbidity phase

 The following application examples were based on the following mineral oil fractions:

sample Siedebeg. Final boiling point Vol .-% BPA floor GTF Absetzver Point hold K K > 575K K K K I 438 613 12 256 239 245 32/68 (0) Il 453 645 35 262 256 258 56/44 (0) III analogously to Il + 0.001% EVA · 261 245 249 95/5 (0) " IV 456 638 20 264 255 257 49/51 (0) V 443 668 43 271 262 265 68/32 (0)

* Ethylene vinyl acetate copolymer ** after 72 hours

Initial boiling point, boiling end and vol .-%> 575K were taken from the boiling analysis according to TGL 21120.

Example 16

To 500g petroleum fraction II were added 0.053 g of additive according to Example 2. This corresponds to an amine content, based on the> 675K boiling components, of 0.01% by mass. The following cold characteristics according to Example 14 were determined:

BPA

pour point

GTF

settling

263 K

251 K

255K

0/100 (45)

Example 17

To 500g petroleum fraction II were added 15.5 g of additive according to Example 3. This corresponds to an amine content, based on the> 575K boiling components, of 2Ma .-%. The following cold characteristics according to Example 14 were determined:

BPA

pour point

GTF

settling

262 K

240K

253K

0/100 (10)

Example 18

50 grams of petroleum fraction II were mixed with 0.6 g of additive according to Example 4. This corresponds to a Aminanteii, based on the

> 575K boiling shares, of 0.06Ma .-%. The following cold keywords were determined:

BPA pour point GTF settling behavior

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

Example 19

500 g of petroleum fraction III were mixed with 1.6 g of additive according to Example 5. This corresponds to a Aminanteii, based on the

> 575K boiling shares, from 0.2Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 20

500 g of petroleum fraction III were mixed with 8.6 g of additive according to Example 10. This corresponds to a Aminanteii, based on the

> 575K boiling shares, from 0.2Ma .-%. The following cold parameters were determined:

BPA pour point GTF AbseL '/ received

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

Example 21

500 g petroleum fraction I were mixed with 1.2 g of additive according to Example 6. This corresponds to a Aminanteii, based on the

> 575K boiling fractions, of 0.5Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 22

500 g of petroleum fraction I were mixed with 0.95 g of additive according to Example 7. This corresponds to an aminantoil, based on the

> 575K boiling fractions, of 0.5Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 23

500g of petroleum fraction V were mixed with 4.5 g of additive according to Example 8. The Aminanteii, based on the> 575K boiling components, this is 0.5Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 24

500g of petroleum fraction V were mixed with 0.7 g of additive according to Example 9. The Aminanteii was, based on the> 575K boiling components, 0.1 wt .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

272K 250K 261K 10/90 (0)

Example 25

500g of petroleum fraction IV were mixed with 1.9 g of additive according to Example 11. In this case, the Aminanteii, based on the> 575K boiling components, 0.5Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Belsplel26

500g of petroleum fraction IV were mixed with 1.6 g of additive according to Example 12. The Aminant6il was, based on the> 575K boiling components, here 0.5Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 27

50 g of petroleum fraction II were mixed with 3.1 g of additive according to Example 13. The amine content was based on the

> 575K boiling fractions, 0.05Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Example 28

500 g of petroleum fraction IV were mixed with 2 g of additive according to Example 14. The amine content was based on the

> 575K boiling fractions, 0.4Ma .-%. The following cold parameters were determined:

BPA pour point GTF settling behavior

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

Claims (11)

-1- 294 967 Claims: 1. Additives to reduce the pour point and to prevent settling of the precipitated below the BPA point paraffins of petroleum fractions (middle oils) whose boiling point above 440K and the boiling end below 665K and in which mass fractions of at least 0.1 kg / kg above 575K, characterized in that it consists of a mixture of A: a solution of benzoic acid and formic acid in a ratio of 5: 1 to 1: 5 in methanol, Ethanol, cyclohexanol or isopropanol or mixtures thereof and B: fatty amines having a primary component of at least 75% and an alkyl and / or an alkylene chain containing 12 to 22 C-atoms in a hydrocarbon fraction boiling between 400K and 670K, optionally in admixture with other additives, such as ethylene-vinyl acetate copolymers, and a hydrocarbon mixture above 675 K, consist. 2. A process for the preparation of additives according to claim 1, characterized in that A: 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: fatty amines having a primary moiety of at least 75% and an alkyl and / or an alkylene chain having 12 to 22 carbon atoms are added to a hydrocarbon fraction boiling between 400 and 670K and A and B are mixed at temperatures between 290 and 325 K, wherein the amounts of A and B are chosen so that the acids and the amine mixture in the molar ratio and optionally further additives, such as ethylene-vinyl acetate copolymers and a above 675 K boiling hydrocarbon mixture can be added. 3. The method according to claim 2, characterized in that the molar ratio of benzoic acid to formic acid 1: 1.5 to 1: 2.5, preferably 1: 1.75 to 1: 2. 4. The method according to claim 2 and 3, characterized in that the amount of methanol, ethanol, cyclohexanol or isopropanol or mixtures thereof is 1.5 to 6 times the mass of benzoic acid. 5. The method according to claim 2 to 4, characterized in that d! E fatty amines with a boiling between 400 and 670K hydrocarbon ^r , raktion in the mass ratio of 1: 1 to 1: 3 are added. 6. The method according to claim 2 to 5, characterized in that the fatty amines are mixed with xylene, with a C ₉ - / C ₁₂ aromatics or with diesel oil. 7. The method according to claim 2 to 6, characterized in that the fatty amines have an iodine value of at least 15 g J / 100g. 8. The method according to claim 2 to 7, characterized in that the fatty amines are added before or after the addition of A to B with a hydrocarbon mixture boiling between 675 and 900 K in a molar ratio of 1: 0.01 to 1:30. 9. The method according to claim 2 to 8, characterized in that the fatty amines or the mixture of A and B with a produced by cationic ethylene polymerization hydrocarbon fraction, with petroleum vacuum distillate or or and with the above 670 K boiling residue from the Vakuumdestillat- Be split back. 10. The method according to claim 2 to 9, characterized in that the petroleum fraction added amount of additive, based on amine and the boiling above 575 K shares, at least 0.0b and at most 0.5Ma .-% is. 11. Use of additives according to claim 1 to 10, characterized in that these additives are added to a boil between 440 K and 665 K petroleum fraction in such an amount that the amount of amine based on the boiling above 575 K shares 0.01 to 2 Ma .-% is.