DD286610B5 - ETHYLENE VINYL ACETATE COPOLYMERS CONTAINING MEDIUM OILS - Google Patents

Description

Field of application of the invention

The invention relates to middle oils which boil in the temperature range between 440 and 660K, to lower the limit temperature of filterability ethylene-vinyl acetate copolymers in the amount of 0.000025 to 0.00025kg / kg contain and below the temperature of the beginning of Paraffinausicheidung (BPA Point) paraffin crystals keep at the same time further lowering of the pour point weitestgohond in the balance. The invention relates to insbesondsre such as diesel fuel or as extraleichtcs fuel oil used middle oil whose boiling point is between 600 and 660K and in which excreted at temperatures below the BPA point during storage in tanks or other storage containers paraffins are still kept below 252K largely in limbo at the same time further lowered pour point, which ensures their trouble-free promotion and handling even in extreme cold.

Characteristic of bekannton state of the art

The paraffins present in medium oils form crystal bodies at low temperatures, which initially appear on decay in an incipient haze. If the temperature of the beginning paraffin precipitation (BPA point, cloud point, cloud point) is cooled, cross-linking of the paraffin crystals leads to a restriction of the flowability and finally to complete solidification of the middle distillates (pour point) BPA and pour point of the middle distillates (determined according to TGL 0). 51772) are independent of their shape of paraffins and their chain length. In addition, the composition of the other medium oil hydrocarbon content has influence on these Temperaturpunk'o. The same applies to the limit temperature of the Fütierbarkeit (GTF point), which is also still dependent on the size and shape of the excreted paraffin crystals and a relevant use word size for such middle oils, which are used as diesel fuels (TGL 33638).

Another characteristic that is responsible for the cold behavior of the middle oils, especially when stored in tanks u.a. Of practical importance, it follows from the tendency of the paraffin crystals excreted at the BPA point and the underlying temperatures to settle and thereby clog Bohälterabgangsstutzen and piping. At the same time, the amount and rate of settling of the paraffin formations noticeably increase with decreasing temperature. At the same time, the paraffin excretion causes a non-uniform quality distribution of the middle oil when stored in tanks and the like. Containers that adversely affect its use.

The limit temperature of the filterability and pour point can be effectively herabsetzer by additives herabsetzer .. Here, in particular ethylene-vinyl acetate copolymero certain sequence and chain length have proven. In contrast, the settling speed of the excreted paraffins is not significantly improved by these additives, but on the contrary increased.

It has been attempted to avoid this unfavorable effect of the ethylene-vinyl acetate copolymers by additional additives and moreover to markedly reduce the settling speed of the paraffins. For example, DD 253833 proposes an additive combination which, in addition to ethylene-vinyl acetate copolymers, also contains the half-ester of propane / maleic anhydride copolymers with C ₁₆ - to C ₁₈ -fatty alcohols. However, the effect of this combination of additives is limited to temperatures around the cloud point. In practice, however, temperatures must be expected in the cold season, which may fall below this level. DE 292 ¹ 330 describes an additive package for improving the low-temperature resistance of fuel oils, which is used to delay the settling of the precipitated paraffins reaction products of dicarboxylic acids, in particular derivatives of succinic acid or their anhydrides, with C _{) 2} to C ₃₀ straight-chain alcohols and / or or a C ₁₂ to C ₃ g straight-chain primary or secondary alkylamine. These additives also have an effect on the settling behavior of the paraffin precipitates, above all in the cloud point, with a service life of 72 hours not being exceeded.

Analogous restrictions apply to Dt '1 770011, which proposes as an additive polymers of olefinically unsaturated aromatic compounds and monomers containing hydroxyl, carboxyl, acid anhydride and / or nitrogen groups.

-2- 288 610

To reduce paraffin settling, DD 200572 and DD 209649 and SU 1 271375 describe adding to the middle oils a mixture of an ethylene homo- or copolymers, a hydrocarbon polymer and polar oil-soluble compounds, mainly based on succinic acid. Again, the effect is limited to temperatures only slightly below the cloud point. The DD 230549 finally tries to achieve the same goal by an additive mixture of ethylene-vinyl acetate copolymer. ¹ . in and an ethylene polymer having acid-functional groups. The disadvantage here in addition to the already described limitations of the other proposed solutions, the partial Schwe'löslichkeit the Additivgomisches in middle oils.

Ziol of egg-making

The aim of the invention are ethylene-vinyl acetate Copolymcre containing middle oils which contain boiling between 600 and 660K shares and keep the deposited paraffins over a period of more than 300 hours largely in the balance with further lowering of the pour point and a limit temperature of filterability below 252 K. ,

Explanation of the essence of the invention

The object is to find an additive or an additive combination, which significantly delays the paraffin sedimentation in middle oils according to the target position and simultaneously reduces the pour point without adversely affecting the known effect of ethylene-vinyl acetate copolymers on the GTF point. This object is achieved by ethylene-vinyl acetate copolymers containing middle oils with improved low temperature, erfindungsgomäß in that the middle oils a mixture of primary and secondary fatty amines having C ₁₂ - to Cia-alkyl chains and at least 75% and at most 95% primary moiety in the molecule and benzoic acid and fatty acid having a C number of 1 to 16 in a total oil-based amount of 0.0003 to 0.003 kg / kg. The said mixtures of primary and secondary fatty amines and benzoic acid and / or fatty acids are prepared by simply mixing the amine component with the acid component with stirring and usually with gentle heating (eg 330 to 340K). The middle oils of the present invention are used as diesel fuels or heating oils having a boiling range of 440-660 K, a boiling end point between 600 and 660K and contents above 600K boiling, at least 0.15 to 0.25Kg / kg and an n-paraffin content of at least C , 05kg / kg, which in their final quality result from processing technologies of primary and secondary petroleum processing.

Such middle oils contain according to the invention ethylene-vinyl acetate copolymers having weight average molecular weights of 3000 to 10,000 and a vinyl acetate content of 0.25 kg / kg in amounts of 0.000025 to 0.00025kg / kg, based on the middle oil, to improve the filterability.

It has been found that the amount of ethylene-vinyl acetate copolymer contained in the medium oil limits the amounts of the fatty acid mixture up and down. It has thus been found that preferably such middle oils fulfill the objective in all respects, in which the mass ratio of ethylene-vinyl acetate copolymers to fatty amine-acid mixture is from 1: 40 to 1: 4.

Finally, it has been found that it is with regard to a long-term effect of suspension stabilization excreted at low temperatures and initially floating in the middle oil paraffin advantageous if the mass ratio of fatty amine to benzoic and fatty acid 1 to 2 to 2 to 1. The molar ratio of Qemeosäure to fatty acid should be 1: 1.2 to 1: 1.9.

Ausführungsbeisplolo

Two samples of middle distillates with the following characteristics are examined for their low-temperature behavior. In addition to the determined according to TGL Konnwerte for BPA point and pour point (according to TGL 0-51 583) and GTF (according to TGL 33638), the settling behavior of paraffins at 251 K in the cold chamber over a period of 336 hours

observed.

For this purpose, 25 ml of the corresponding middle distillate sample are stored vertically in a cold chamber in a graduated glass tube of 30 cm in length and 4 cm in diameter, and the settling of the paraffins is determined by volume based on the formation of a clear phase and a sediment.

K mVm ³ Sample 1 269 241 252 Sample 2 264 245 247 Boiling range shares above 600K kg / kg 456-640 0.25 441-640 0.15 n-Paraffingeh. g / cm ³ 0,133 0.145 density kg / kg 0.835 0.829 EVA K K K 0.00015 0.00015 BPA pour point GTF 268 2Ü8 268 264 251 261

Depositing behavior at 251 K after 24 hours stocked 240 hours stocked 33G hours

in m '/ m ³ clear phase 0 0,450 0,500 0.116 0,800 0.625 0,248 0.825 0.663

-3- 236 610

example 1

0.00015 kg / kg of EVA copolymer-containing middle oil according to sample 1 are used to improve the cold behavior and to reduce the paraffin sedimentation 0.0006 kg / kg of a molar product of benzoic acid prepared at 340K and a mixture of high molecular weight straight-chain amines whose alkyl radicals have at least 90% C ₁₆ to C ₁₈ alkyl groups and a primary moiety of 95%, and 0.0006 kg / kg of a molar product of formic acid and a mixture of aliphatic, straight-chain amines with 90% C ₁₆ to Cie alkylgrcopen and a share of 25% secondary fatty amines, mixed.

The cold and settling process is influenced as follows:

K Inventive application without K With 269 BPA K 270 247 pour point mVm ³ 232 252 GTF 24h. 248 clear phase 240 hours 0.458 to 336 hrs 0 0.625 0 0.663 0

Example 2

0.000025 kg / kg of EVA copolymer-containing middle oil corresponding to Sample 2 is mixed with 0.0003 kg / kg of a mixture obtained from the molar reaction of a benzoic acid / formic acid mixture with a mixture of aliphatic straight chain amines with 90% C ₁₆ - C _he alkyl added and a proportion of 25% secondary fatty amines; The molar ratio of benzoic acid to formic acid used is 1: 1.9

The following parameters were determined on this sample:

K Inventive application without K With 265 BPA K 264 249 pour point mVm ¹ 242 249 GTF 24 hours 249 clear phase 240 hours 0,008 to 336 hrs 0 0.113 0 0.153 0

Example 3

0.00025 kg / kg of EVA copolymer-containing middle oil corresponding to sample 2 is mixed with 0.001 kg / kg of a molar reaction product of benzoic acid and formic acid in the molar ratio 1: 1.2 and a mixture of aliphatic, straight-chain amines with 90% C _{) 6} -bis C _{) 8-} alkyl groups and an Anilil of 25% secondary fatty amines.

The following results were achieved:

K Inventive application without K With 263 BPA K 264 244 pour point m ³ / m ³ 237 244 GTF 24 hours 246 clear phase 240 hours 0,383 to 336 hrs 0 0.813 0 0,833 0

Example 4

0.0001 kg / kg of EVA copolymer-containing middle oil corresponding to sample 2 is mixed with 0.0006 kg / kg of a molar conversion product of benzoic acid / formic acid mixture in the molar ratio 1: 1.9 and a mixture of aliphatic straight chain amines with 90% C _{) 6} - added to C, _B alkyl groups and a proportion of 25% secondary feitamines.

The following results were achieved:

K Inventive application without K With 265 BPA K 264 245 pour point m '/ m ³ 239 246 GTF 24h. 245 clear phase 240 hours 0,300 to 336 hrs 0 0,770 0 0.804 0

example

0.00015 kg / kg of EVA copolymer-containing middle oil according to sample 2 are mixed with 0.0006 kg / kg of product of an amine mixture with formic acid (corresponding to Example 1) and 0.0006 kg / kg of product of an amine mixture with benzoic acid (corresponding to Example 1).

The following cooling procedure was achieved:

K Inventive application without K With 264 BPA K 269 245 pour point mVm ³ 238 247 GTF 24 hours 245 clear phase 240 hours 0,450 to 336 hrs 0 0,800 0 0.825 0

Examples

0.00015 kg / kg of EVA copolymer containing middle oil corresponding to sample 2 is added with 0.001 kg / kg of a molar reaction product of a mixture of aliphatic, straight-chain amines with 90% Cie to Cia alkyl group and a proportion of 25% secondary fatty amines and an acid mixture from benzoic acid and technical Palmitinsäuro in a molar ratio 1: 1.7, added.

The following cooling method is achieved:

K Inventive application without K With 264 BPA K 264 245 pour point mVm ³ 234 247 GTF 24 hours 245 clear phase 240 hours 0,450 to 336 hrs 0 0.796 0 0.825 0

Boispiel7

Each containing 250 ml of medium oil ontsprechond sample 2 and 0.00005kg / kg EVA Copolymei e, each with 0.0004 kg / kg of a product of the reaction of an amine mixture with 90% Cu- to C | _S- alkyl groups and a proportion of up to 25% of secondary amines and an acid mixture of benzoic acid and formic acid in a molar ratio 1: 1.9 added.

The molar ^«1 ratios of amine mixtures to acid mixtures in the sales products are 2: 1,1: 1 and 1: 2.

Inventive application

Molar ratio 2: 1 1: 1 1: 2

with with

without

BPA K pour point K GTF K clear phase mVm ³ to 24 hours 240 hours 336 hrs

264 265 266 264 244 244 244 246 241 243 242 250 0 0 0 0.037 0 0 0 0.303 0 0 0 0.390

Examples

A middle distillate according to sample 2 with 0.00015 kg / kg of EVA copolymers becomes 0.0010 kg / kg of a molar reaction product of an amine mixture with 90% Cu to C, _B alkyl groups and up to 25% secondary amine with formic acid and 0.001 kg / kg of a molar conversion product of the same amine mixture with benzoic acid added.

The following cooling method was determined on this sample:

K Inventive application without K With 264 BPA K 264 245 pour point mVm ³ 237 247 GTF 24 hours 249 clear phase 240Stci. 0.45 to 336 hrs 0 0.796 0 0.825 0

Example 9

A middle distillate corresponding to sample 2 and containing 0.00015 kg / kg of EVA copolymers, 0.001 kg / kg of a molar reaction product of an amine mixture with 90% C ₁₈ - to C, ₈ alkyl groups and a share of up to 25% of sfakundär amines with bonzoic acid , and 0.001 kg / kg einos molar conversion product of an amine mixture with 60% C _{) 2} -Alky! groups, primary part 95%, gesgesotzt with palmitic acid.

The following cold resistance is achieved:

K Inventive application without K With 264 BPA K 264 245 pour point mVm ³ 239 247 GTF 24 hours 240 clear phase 240 hours 0.45 to 336 hrs O 0.796 0.825

Claims (4)

1. Ethylene-vinyl acetate copolymers containing middle oils with improved low temperature resistance, characterized
characterized in that the middle oil is a mixture of primary and secondary fatty amines having C _{12 to} C ₁₈ alkyl chains and at least 75% and at most 95% primary amine content in the molecule and
Benzoic acid and fatty acid having a C number of 1 to 16 in one based on the middle oil
Total amount of 0.0003 to 0.003kg / kg included. 2. ethylene-vinyl acetate copolymers containing middle oils according to claim 1, characterized
characterized in that the mass ratio of ethylene-vinyl acetate copolymers to fatty amine-acid mixture is 1: 4 to 1: 40. 3. ethylene-vinyl acetate copolymers containing middle oils according to claim 1 and 2, characterized
characterized in that the molar ratio of fatty amine to benzoic and fatty acid is 1 to 2 to 2 to 1
is. 4. ethylene-vinyl acetate copolymers containing middle oils according to claim 1 to 3, characterized
characterized in that the molar ratio of benzoic acid to fatty acid is 1: 1.2 to 1: 1.9.