DD230549A3 - ADDITIVE MIXTURE - Google Patents

Abstract

Additive mixture for improving the cooling behavior and the emulsifying / dispersing behavior of oil or petroleum fractions. The additive mixture consists of an ethylene-vinyl ester copolymer having a vinyl ester content of from 20 to 50% by weight and a weight average molecular weight of from 500 to 15,000 (component A), a low molecular weight, functional group-containing ethylene polymer having a weight average molecular weight of from 500 to 5 000 (component B) in the ratio of 99: 1 to 50:50 by weight. The vinyl esters used are preferably vinyl acetate and vinyl propionate. and Component B contains the following functional groups: Hydroxyl groups 10 to 85 m Mol / mol CH 2 group g-lactones 2 to 15 m Mol / mol CH 2 groups Ester 5 to 45 m mol / mol CH 2 groups ketones 10 to 70 m mol / mol -CH 2 groups: acid groups 5 to 50 m mol / mol CH 2 groups The additive mixture is added to 0.001 to 0.5 mass% of the petroleum fraction.

Description

Invention claim:

An additive mixture for improving the low-temperature behavior and the emulsifying ZDispergierverhaltens of petroleum or petroleum fractions in boreholes, tanks, pipelines and other means for the handling, transport and storage of such products, characterized in that it consists of an ethylene-vinyl ester copolymer having a vinyl ester content of from 20 to 50% by mass and a weight average molecular weight of from 500 to 15,000 (component A) and a low molecular weight, functional group of hydroxyl type, γ-lactone, ester, ketone and acid group-containing ethylene polymer having a weight-average molecular weight of 500 to 5000 (component B) in the ratio of 99: 1 to 50:50 by weight.

2. additive mixture according to item 1, characterized in that vinyl acetate or vinyl propionate is preferably used as the vinyl ester.

3. additive mixture according to item 1 and 2, characterized in that the low molecular weight, functional group-containing ethylene polymer (component B) is an ethylene-vinyl acetate copolymer.

4. additive mixture according to item 1 and 2, characterized in that the low molecular weight, functional group-containing ethylene polymer (component B) is a polyethylene.

5. additive mixture according to item 3 and 4, characterized in that the low molecular weight ethylene polymer contains as functional groups:

Hydroxyl groups 10 to 85m mole / mole CH ₂ groups

γ-lactones 2 to 15 m mol / mol CH ₂ groups

Esters 5 to 45 m mol / mol CH ₂ groups

Ketones 10 to 70 m mol / mol CH ₂ groups

Acid groups 5 to 50 m mol / mol -CH ₂ groups.

Field of application of the invention

The invention relates to an additive mixture for improving the cold behavior and the emulsifying behavior of crude petroleum and petroleum fractions in boreholes, tanks, pipelines and other facilities for handling, transport and storage.

Characteristic of the known technical solutions

It is known that in crude oil or petroleum fractions such. B. middle distillates, crystallize paraffins contained in the cooling, agglomerate and finally completely prevent the promotion of petroleum or petroleum fractions. It is also known that a number of modifying agents have been proposed which influence the size of the depositing paraffins and their crosslinking rate, thereby keeping the petroleum or the petroleum fraction even at low temperatures still flowable and pumpable.

It is also known (DE-AS 1147799, DE-OS 2227786) that low molecular weight ethylene-vinyl acetate copolymers are effective pour point depressants and flow improvers for crude oil or petroleum fractions.

There are also various terpolymers based on ethylene-vinyl acetate, z. Example, with dialkylvinylcarbinol (US-PS 3915668, US-PS 4015063), have been proposed as flow improvers.

There are also combinations based on ethylene-vinyl acetate copolymers with other materials, eg. B. aromatic copolymers (US-PS 4058371), Laurylacrylsäureestem (DE-OS 1 545287) or a non-nitrogen-containing, oil-soluble additive compound having at least one straight-chain (CH ₂ ) polymethylene section with one of 10 to 30 and larger or space-filling substituents (DE -OS 2156425).

It has also been proposed to use various combinations of EVA copolymers with EVA copolymers (US Pat. No. 3,961,916, DE-OS 2037673), the vinyl acetates or the molecular weights of the two EVA copolymers differing from one another.

From DD-PS 123673 an additive mixture is known, consisting of an ethylene copolymer Gatschprodukt (component A) having a viscosity of 30 to 40OcP at 14O ⁰ C and an ethylene polymer and / or ethylene-vinyl ester copolymer (component B) ) having a viscosity of 20 to 25OcP at 140 ⁰ C, and optionally other known fluidity improvers.

It is also known that the cold splitting of middle distillates (heating oils and diesel fuels) is dependent on the crude oil provenance and on the boiling range of the middle distillate (H.Vogel, Compendium Erdöl / Kohle 1978/79 p.740-778). The added flow or filterability improvers fulfill the following tasks:

1. Lowering the pou points

2. Inhibiting the size growth of paraffin crystals

3. Lowering the CFPP value

Due to the diversity, in particular the climatic influences during production, handling, transport, storage and finally the processing of middle distillates, requirements often have to be met which are not simply guaranteed by complying with the characteristic values cloud point, CFPP and possibly pour-point are. Thus, with appropriate tests of commercial flow improvers and different Emulgieryerhalten been observed for water. An important requirement for handling, transport and storage is z. B. Avoidance of sedimentation of accumulating below the cloud point paraffin crystals in the heating oil tank. The previously known flow improvers are unable or only partially to disperse paraffins in the middle distillate.

Object of the invention

The object of the invention is the development of an additive mixture for the improvement of the refrigeration behavior of petroleum and petroleum mixtures, wherein the disadvantages of previous additives or additive mixtures with respect to the emulsifying / dispersing behavior are canceled.

Explanation of the essence of the invention

The invention has for its object to develop an additive mixture, which acts on petroleum and petroleum fractions so that in addition to the improvement of the low temperature behavior of these products during handling, transportation and storage and the emulsification or dispersing behavior is improved.

This object is achieved by an additive mixture for improving the low-temperature behavior and the emulsifying / dispersing behavior of petroleum fractions in boreholes, tanks, pipelines and other devices for the handling, transport and storage of such products, according to the invention the additive mixture of an ethylene Vinyl ester copolymers having a vinyl ester content of 20 to 50% by mass and a weight average molecular weight of 500 to 15,000.

(Component A) and a low molecular weight, functional groups of the hydroxyl group, γ-lactone, ester, ketone and acid group-containing ethylene polymer having a weight average molecular weight of 500 to 5000 (component B) in the ratio of 99: 1 to 50: 50Ma .-% consists.

Advantageously, the vinyl ester used is vinyl acetate or vinyl propionate.

The low molecular weight, functional group-containing ethylene polymer (component B) is advantageously an ethylene-vinyl acetate copolymer.

The low molecular weight, functional group-containing ethylene polymer (component B) may also be a polyethylene.

Advantageously, the low molecular weight ethylene polymer contains functional groups

Hydroxyl groups 10 to 85 m mol / mol -CH ₂ groups

y-lactones 2 to 15m mol / mol CH ₂ groups

Ester 5 to 45 mmol / mol CH ₂ groups

Ketones 10 to 70m mole / mole CH ₂ groups

Acid groups 5 to 50 m mol / mol CH ₂ groups.

The additive mixture is added in amounts of 0.001 to 0.5 mass%

The products used as component B are prepared analogously to DD-PS 116625 by oxidation of the starting products with oxygen or oxygen-containing gases.

A particular advantage of the invention is that by the use of the additive mixture both an improvement in the low-temperature behavior of petroleum or petroleum fractions such. As diesel fuels, marine diesel fuel or fuel oils, as well as an improvement in the storage of such products is achieved.

It is known that the BPA point (beginning of the paraffin deposition) can not be significantly lowered by the commercial additives, but the pour-point (pour point) and the GTF value (Cold Filter Plugging Point), so that between BPA and pour-point or CTF in the petroleum or petroleum fractions paraffin crystals are present, whose growth in size is prevented by the known additives. If the petroleum or petroleum fraction thus treated is not agitated, e.g. As in tanks, it is due to gravity to settle the existing paraffin crystals. In contrast, this solution is largely eliminated by the solution according to the invention.

Äusführungsbeispiele Examples 1 and 2

A petroleum fraction with a boiling range of 197 to 382 ° C, an n-paraffin content of 16.8Ma .-% at a relative nC ₁₈ H content of 18.4 was additized with the products shown in Table 1 and Table 2. ,

The pour-point (pour point) was determined according to TGL 0-51583, that of the BPA according to TGL 0-51772 and that of the GTF according to TGL 33638.

The concentration of additive in Example 1 was in all cases 0.05% by mass and in Example 2 in all cases 0.02% by mass. As component A, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 29.3 mass% and a weight average molecular weight of 7630 was used.

Component B (oxidized ethylene-vinyl acetate copolymer according to DD-PS 116625) contained the following functional groups:

Hydroxyl groups 18m mol / mol CH ₂ groups

Y-lactones 3.7 m mol / mol CH ₂ groups

Ester 9.3 m mol / mol CH ₂ groups

Ketones 12.0 m mol / mol -CH ₂ groups

Acid groups 11.0m mol / mol CH ₂ groups

and had a weight average molecular weight of 4510.

The petroleum fraction thus added was kept in a climatic chamber between BPA and CTF value and the depositing paraffin cake was examined as a function of the storage time. The petroleum fraction was not moved. The paraffin cake forming on the ground as a result of gravity was separated, freed from the remaining oil and converted in% by mass to the total paraffin content of the petroleum fraction.

Table 1:

characteristic value dimension without Example 2 without Comp. Comp. mixture additive additive A B A = 99% B = 1% BPA K 265 266 264 265 264 pour point K 254 254 237 248 238 GTF K 262 264 243 258 241 settling / Settling Wt .-% 1d 1 1.1 0.1 0.1 0.1 2d 1.5 3.6 0.6 0.3 0.4 3d 4 3.8 1.1 0.5 0.5 7d 9 5.7 2.6 0.9 0.8 14d 15.4 9.5 5.1 2.4 2.0 21d 16.4 20.8 7.3 2.9 2.4 2 months 27 31.1 ι 9.8 6.5 5.7 6 months 78 59.3 23.1 20.0 19.1 Table 2: characteristic value dimension Comp. Comp. mixture A B A = 75% B = 25% BPA K 266 265 265 pour point K 237 248 236 GTF K 256 258 255 settling / Settling Wt .-% 1d 0.5 0.4 0.32 2d 1.2 0.63 0.5 3d 2.0 1.81 1.53 7d 2.3 1.9 1.53 14d 4.3 3.1 2.11 21d 7.4 3.1 2.5 2 months 8.9 4.04 2.9 6 months 15.7   14.9 13.3

Examples 3 and 4

A petroleum fraction with a boiling range of 185 to 402 ⁰ C, an n-paraffin content of 19.7 Ma .-% at a relative nC | _8.6 % of 21.6% was added to the products indicated in Tables 3 and 4.

The determination of the characteristic values was carried out analogously to Example 1. The concentration of total additive in Example 3 was 0.04% by mass and in Example 4 was 0.025% by mass.

As component A, an ethylene-vinyl acetate copolymer was used, which in Example 3, a vinyl acetate content of 22.1 wt .-% and a weight average molecular weight of 786 g / mol and in Example 4, a vinyl acetate content of 48.6Ma .-% and a weight average Molar mass of 14300g / mol had.

Component B (an oxidized polyethylene, according to DD-PS 116625) contained in Example 3 the following functional groups:

Hydroxyl groups 11 m mol / mol CH ₂ groups

γ-lactones 2.4 m mol / mol CH ₂ groups

Ester 6.1 mmol / mol CHj groups

Ketones 12.0 m mol / mol -CH ₂ * groups

Acid groups 6m mol / mol CH ^ groups

and had a weight average molecular weight of 611 g / mole. Component B in Example 4 (an oxidized ethylene-vinyl acetate copolymer, according to DD-PS 116625) contained the following functional groups:

Hydroxyl groups 82m mol / mol CH ₂ groups

γ-lactones 14.6 m mol / mol CH ₂ groups

Esters 43.8m mole / mole CHj groups

Ketones 68 m mol / mol CH ₂ groups

Acid groups 48m moles / mole CH ₂ groups

and had a weight average molecular weight of 4820 g / mole. The numerical values are contained in Tables 3 and 4, respectively.

Table 3: dimension Example 3 without Example 4 without Comp. Comp. mixture additive additive A B A = 50% characteristic value B = 50% K 264 264 264 265 264 K 256 255 236 242 230 BPA K 260 260 241 252 239 pour point GTF Wt .-% settling / 1.7 1.5 0.8 1.4 0.43 Settling 3.6 3.2 2.1 2.8 0.86 1d 5.9 5.6 3.2 5.1 1.7 2d 10.6 11.8 5.4 9.6 2.2 3d 17.5 16.7 8.1 15.4 3.1 7d 22.4 21.8 10.6 20.8 5.4 14d 35.6 33.7 13.8 31.4 8.7 21d 84.1 82.6 21.2 75.9 11.6 2 months 6 months Table 4: dimension Comp. Comp. mixture A B A = 65% characteristic value B = 35% K 264 264 264 K 231 233 231 BPA K 249 246 241 pour point GTF Wt .-% settling / 1.1 1.2 0.2 Settling 2.8 2.2 0.4 1d 3.6 2.8 0.9 2d 8.9 3.2 1.3 3d 11.6 4.1 1.9 7d 17.3 6.1 2.4 14d 23.4 7.1 2.8 21d 28.6 8.5 6.5 2 months 6 months

Examples 5 and 6

A petroleum fraction having a boiling range of 214 to 388 ⁰ C, an n-paraffin content of 18.7 mass% at a relative nC ₁₈₊ content of 19.7%, was composed of 0.015Ma% of an additive mixture of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 7.5 mol% and a melt viscosity at 140 ⁰ C of 156mm ² / s (component A) and an oxidized ethylene-vinyl acetate copolymer (component B, according to DD-PS 116625 ) having a vinyl acetate content of 5.9 mol%, a melt viscosity of 145 mm ² / s, an acid number of 6m moles / mole of -CH ₂ groups, a hydroxyl group content of 11m moles / mole of -CH ₂ groups and a content of ketone groups of 12.1 m mol / mol CH ₂ groups, added. The BPA point was determined according to TGL 0-51772, the pour point according to TGL 0-51583 and the GTF according to TGL 33638.

The thus-enriched petroleum fraction was kept in a climate chamber between BPA and GTF value and examined the depositing paraffin cake as a function of the storage time. The petroleum fraction was not moved. The paraffin cake forming on the ground as a result of gravity was separated, freed from the remaining oil and converted in% by mass to the total amount of paraffin in the petroleum fraction. The values are included in Table 5/6.

Tables 5/6: dimension without Examples 5 and 6 Comp. mixture mixture additive Comp. B A = 75% A = 99% characteristic value A B = 25% B = 1% K 266 266 266 266 K 256 266 242 236 234 BPA K 263 237 255 248 246 pour point 252 GTF Wt .-% settling / 2.1 1.6 0.6 0.4 Settling 4.5 1.3 3.8 0.93 0.65 1d 8.6 3.3 8.2 1.64 0.9 2d 11.4 7.9 10.3 4.2 1.1 3d 17.3 9.5 16.8 6.8 2.8 7d 28.8 15.2 26.2 9.9 4.1 14d 44.2 24.4 37.3 13.4 7.5 21d 76.4 35.1 68.6 17.1 12.6 2 months 65.7 6 months

Example 7

In a test pipeline, attempts were made to transport crude oil. The crude oil was pumped at a pressure of 0.54 MPa. Within 27 days, the pressure had to be increased continuously to 2.4MPa to promote a sufficient amount. The flow was still so low that the experiment was stopped.

After extensive cleaning, individual segments of the Pipline were replaced and replaced by those with a particularly smooth surface.

The repetition of the tests brought an improvement and the test track could be operated for 31 days.

After repeated purification, the crude oil at 314K05.05% by weight of an additive mixture (80% component A and 20% component B, according to DD-PS 116625) was added.

The additive mixture consisted of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 16.3 mol% and a melt viscosity at 140 ° C of 2870 mm ² / s and an oxidized ethylene-vinyl acetate copolymer having a vinyl acetate content of 14.3 mol. %, a melt viscosity of 1,430 mm ² / s, an acid number of 24 m mol / mol CH ₂ groups, a hydroxyl group content of 38m mol / mol CH ₂ groups and a content of ketone groups of 28.6m mol / Mol CH ₂ -Grouppen.

It was started at a pressure of 0.54 MPa. Surprisingly, the required delivery pressure rose in the first 7 days to 1.2 MPa and then dropped again to 0.61 MPa. In the following days, the delivery pressure rose again and reached a pressure of 0.86 MPa after 5 months.

Claims (5)

Invention claim: 1. additive mixture for improving the low-temperature behavior and the emulsifying / dispersing behavior of petroleum or petroleum fractions in boreholes, tanks, pipelines and other devices for the handling, transport and storage of such products, characterized in that it consists of an ethylene-vinyl ester Copolymers having a vinyl ester content of from 20 to 50% by weight and a weight-average molecular weight of from 500 to 15,000 (component A) and a low molecular weight, hydroxyl-type functional groups, γ-lactones, esters, ketones and acid group-containing ethylene polymer having a weight-average molecular weight of 500 to 5000 (component B) in the ratio of 99: 1 to 50:50 Ma .-%. 2. additive mixture according to item 1, characterized in that vinyl acetate or vinyl propionate is preferably used as the vinyl ester. 3. additive mixture according to item 1 and 2, characterized in that the low molecular weight, functional group-containing ethylene polymer (component B) is an ethylene-vinyl acetate copolymer. 4. additive mixture according to item 1 and 2, characterized in that the low molecular weight, functional group-containing ethylene polymer (component B) is a polyethylene. 5. additive mixture according to item 3 and 4, characterized in that the low molecular weight ethylene polymer as functional groups contains: hydroxyl groups 10 bis85mMol / mol CH 2 groups γ-lactones 2 to 15 m mol / mol CH 2 groups ester 5 bis45m mol / mol CH 2 Groups ketones 10 to 70 m mol / mol CH 2 groups acid groups 5 to 50 m mol / mol CH 2 groups.