DD286610A5 - ETHYLENE VINYL ACETATE COPOLYMERS CONTAINING MEDIUM OILS - Google Patents

Abstract

The invention relates to ethylene-vinyl acetate copolymer-containing middle oils whose increased tendency to settle out at low temperatures paraffins without negatively influencing the filterability by a mixture of primary and secondary fatty amines with C12 to C18 alkyl chains and at least 75% and at most 95% Primaeranteil in the molecule and benzoic acid and fatty acids with 1 to 16 carbon atoms, with simultaneous lowering of the pour point, greatly reduced or wholly abolished. {Mitteloel; Paraffin; Kaeltefestigkeit; Pour point; filterability; sedimentation; Ethylene-vinyl acetate copolymers; Fatty amine; Benzoesaeure; Fatty acid}

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 Ethylon-vinyl acetate copolymers in the amount of 0.000025 to 0.00025kg / kg contain and those below the temperature of the beginning of paraffin excretion (BPA Point) formed paraffin crystals keep at the same time largely further lowering of the pour point in the balance. The invention relates in particular to those used as diesel fuel or as extralight fuel oil middle oils 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 even below 252 K wei'estgehend in Levitation be kept at the same time further lowered pour point, what their trouble-free promotion un <. : maintenance even in extreme cold conditions.

Characteristic of the known 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 it is cooled below this temperature of incipient paraffin precipitation (BPA point, cloud point, Cioudpoint), cross-linking of the paraffin crystallites leads to a restriction of the flowability and finally to complete solidification of the middle distillates (pour point). BPA ur.d Stockpunkl of middle distillates (determined according to TGL 0-51772) are independent of their shape on paraffins and doren chain length. In addition, the composition of the other medium oil hydrocarbon content has influence on these temperature points. The same applies to the Gronztemperatur the filterability (GTF point), which is also still dependent on the size and shape of the precipitated paraffin crystals and a relevant utility value size for those middle oils, which are used as diesel fuels (TGL 33638).

Another property that is responsible for the cold behavior of the middle oils vor allen.η when stored in tanks u. a. Of practical importance, results from the tendency of the precipitated at the BPA point and the underlying temperatures Paraffinkristalfo to settle and thus clogged container outflow and pipes. At the same time, the amount and settling velocity of the paraffin precipitates noticeably increase with decreasing temperature. At the same time, the excretion of perfume causes a non-uniform quality distribution of the middle oil when stored in tanks and the like. a. Containers that adversely affect its use.

The limit temperature of the filterability and the pour point can be effectively reduced by additives. Ethylene-vinyl acetate copolymers of specific sequence and chain length have proven particularly useful here. 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. Thus 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 ₆ - to Cie fatty alcohols. However, the effect of this additive combination is limited to temper? .uren around the turbidity trail. In practice, however, in the cold season, temperatures must be expected to fall to 252K and below. DE 2921 330 describes an additive package for improving the low-temperature resistance of fuel oils, the Veizögerung the decoction of the excreted paraffins Umsetzungsprodukie of dicarboxylic acids, in particular derivatives of succinic acid or its anhydrides, with Ci ₇ - to C _M straight-chain alcohols and or or a Ci ₂ - to C »-yeradkottigen primary or secondary alkylamine. These additions also have an effect on the settling behavior of the paraffin precipitates, especially in the cloud point, with a service life of 72 hours not being exceeded.

Analogous restrictions apply to DE 1770011, in which polymers of olefinically unsaturated aromatic compounds and monomers containing hydroxyl, carboxyl, acid anhydride and / or nitrogen groups are proposed as additives.

In order to reduce paraffin settling, DD 200572 and DD 209649 and SU 127137S 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. Even hler limited the effect on temperatures only slightly below the cloud point. Finally, DD 230549 attempts to achieve the same goal by an additive mixture of ethylene-vinyl acetate copolymers and an ethylene polymer having oxygen-containing functional groups. The disadvantage here in addition to the already described limitations of the other proposed solutions, the partial poor solubility of the additive mixture in middle oils.

Object of the invention

The aim of the invention are ethylene-vinyl acetate copolymers containing middle oils containing between 600 and 660 K boiling components and further lowering of the pour point uowie a limit temperature of filterability below 252 K, the excreted paraffins over a period of more than 300 hours largely in limbo hold.

Explanation of the essence of the invention

It is the object to find an additive or an additive combination, v / odurch without adversely affecting the known effect of ethylene-vinyl acetate copolymers on the GTF PUnUi the Paraffinsedimentation significantly delayed in middle oils according to the objective and the pour point is simultaneously lowered further. This object is achieved by ethylene-vinyl acetate copolymers containing middle oils having improved low temperature, according to the invention in that the middle oils a mixture of primary and secondary fatty amines having C ₁₂ - to C _ia 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 mild heating (eg 330 to 340 K). The middle oils of the present invention are used as diesel fuels or heating oils having a boiling range of 440-660K, a boiling end point between 600 and 660K and contents above 600K boiling, of at least 0.15 to 0.25kg / kg and an n-paraffin content of at least 0, 05kg / kg resulting in their final quality 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 0.00025 kg / 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 middle oil limits the amounts of fat-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 benzoic acid to fatty acid should be 1: 1.2 to 1: 1.9

Austührungobelsplele Two samples of middle distillates with the following characteristics are analyzed for their low-temperature behavior

examined. In addition to the characteristics determined for TGL for BPA point and pour point (according to TGL 0-51583) and GTF (acc

TGL 33638), the settling behavior of the paraffins at 251K in the cold chamber over a period of 336 hours

observed.

Add 250ml of the corresponding middle distillate sample in a graduated glass tube of 30cm length and 4cm Diameter stored vertically in a cold chamber and the settling of the paraffins by volume based on the formation of a Clear phase and a sediment detected.

K m ³ / m ^J 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 ^J 0,133 0.145 density kg / kg 0.835 0.829 EVA K K K 0.00015 0.00015 BPA pour point GTF 268 258 268 264 254 261

Absorbed at 251K after 24 hours. Driven 240 hours. 336 hours

in m '/ m ¹ clear phase

0.500 0

0.625 0.116

0,663 0,248

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 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 are at least 90% C ₁₈ - to have C ₁₈ alkyl groups and a primary moiety of 95%, and 0.0006kg / kg of a molar reaction product of formic acid and a mixture of aliphatic, straight-chain amines with 90% Ci ₆ - to Cte-alkyl groups and a share of 25% secondary fatty amines, mixed.

The refrigeration and settling process is considered 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 obtained with 0.0003 kg / kg of a mixture obtained from the molar reaction of a benzoic / formic acid mixture with a mixture of aliphatic, straight chain

Amines with 90% C, _e - added to C, _t -alkyl groups and a proportion of 25% secondary Fcitaminon; The molar ratio of benzoic acid to formic acid used is 1: 1.9 The following passwords were determined on this sample:

K Inventive application without K With 265 BPA K 264 249 pour point mVm ³ 242 249 GTF 24 hours 249 clear phase ? 40Std. 0,008 to J3SStd. 0 0.116 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% Cu to C. , _8- Alkylgruppen and a proportion of 25% secondary fatty amines added.

The following results were achieved:

K Inventive application without K With 263 BPA K 264 244 pour point m '/ rn 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 product of benzoic acid / formic acid in the molar ratio 1: 1.9 and a mixture of aliphatic straight chain amines m ^: t 90% C ₁₄ - to C _{) a} -alkyl groups and e ^! added to a proportion of 25% secondary fatty amines.

The following results were achieved:

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

Example S

0.00015 kg / kg of EVA copolymer-containing middle oil corresponding 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

Example β

0.00015 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 a mixture of aliphatic, gereketteniger amines with 90% C, _e - to cis-alkyl groups and a proportion of 25% secondary fatty amines and a Säuregemi. .ι ,, consisting of benzoic acid and technical Palmitinsäure in the molar ratio 1: 1.7, added.

The following cooling method is achieved:

K Inventive application without K With 264 BPA K 264 245 Punk stock * MVM ' 234 247 GTF 24 hours, 245 clear phase 240 hours 0,450 to 336 hrs 0 0.796 0 0.825 0

Example 7

Each containing 250 ml of oil equivalent to sample 2 and 0.00005 kg / kg of EVA copolymers, are each with. 0.0004 kg / kg of a conversion product of an amine mixture with 90% C ₁₄ - to Cig-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 ratios of the amine mixtures to acid mixtures in the conversion products are 2: 1.1: 1 and 1: 2.

K molar ratio Inventive application 2: 1 1: 1 1: 2 without K With With With 264 K 264 265 266 246 BPA mVm ³ 244 244 244 250 St.ckpunkt 24 hours 241 243 242 GTF 240 hours 0.037 clear phase 336 hrs 0 0 0 0.303 to 0 0 0 0.390 0 0 0

Example 8

A middle distillate according to sample 2 with 0.00015 kg / kg of EVA copolymers 0.0010 kg / kg of a molar reaction product of an amine mixture with 90% C ₁₈ - to Ci "-Aikylgruppen and a share up to 25% of 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 m '/ rn ³ 237 247 GTF 24h. 249 clear phase 240 hours 0.45 to 336 hrs 0 0.796 0 0.825 0

example

A middle distillate according to sample 2 and 0.00015kg / kg EVA copolymers containing, 0.001 kg / kg of a molar reaction product of a amine mixture with 90% C ₁₄ - to C _ta alkyl groups and a share of up to 25% of secondary amines with benzoic acid, and 0.001 kg / kg of a molar conversion product of an amir. mixed with 68% C ₁₂ -alkyl groups, primary portion 95%, added with palmitic acid.

The following cold resistance is achieved:

K Inventive application without K With 264 BPA K 264 245 pour point MVM ' 239 247 GTF 24 hours 240 clear phase 240 hours 0.45 to 336 hrs 0 0.796 0 0.825 0

Claims (4)

1. Ethylene-vinyl acetate copolymers containing middle oils with improved low temperature resistance, characterized
in that the middle oils comprise a mixture of primary and secondary fatty amines having C ₁₂ to C 13 -alkyl chains and at least 75% and at most 96% of 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.