DE2327059A1 - CRUDE OIL COMPOSITION - Google Patents

Description

Patent assessor .. Hamburg, 18th quay 1973

Br. Gerhard Schupfner 54-7 / kr

Deutsche Texaco AG

2000 Hamburg 76 Φ 7χ rvui Cd w iw t? \

Sechslingspforte 2 "T 73 O'H CD. 72,132-S ¹ ;

TEXACO DEVELOPMENT COEPOEATION

135 East 42nd Street

New York, N.Y. 10017

UNITED STATES.

Crude oil composition

The invention is directed to improving the flow properties and pour point of crude oils. More precisely The invention relates to crude oil compositions which contain a major amount of a crude oil or crude mixture with high Paraffin and low sulfur content and an additive for Contain lowering of the pour point.

Certain paraffin-containing crude oils, such as the crude oils with a high pour point, have poor flow properties. It is a number of methods have been proposed by which the flow difficulties are to be resolved. For example, the pour point of paraffin-containing crude oils is due to removal Part of the paraffin has been improved by solvent extraction at low temperatures, resulting in significant The expense of solvent recovery, the difficulty of paraflin wax disposal, and the provision of cooling facilities connected is. With recently proposed

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The paraffin wax is made without using any method. Solvent by centrifuging a previously heated Crude oil, that with precisely regulated and low speed. centrifugation temperature of around 1.7 - 12.8 ° C has been cooled, removed.

In another widely practiced procedure, v / ground , Paraffin-containing crude oils with a high stook point with lighter ones Hydrocarbon fractions blended. This method but has several disadvantages; for example, relatively large amounts of expensive hydrocarbon solvents are used used to transport a relatively cheap product. Furthermore, this procedure necessarily requires that the blending hydrocarbons are in sufficient quantities are available, which is troublesome in some cases, and also that there is a receptive market for the solvents am at the other end of the pipeline.

One method of transporting paraffin-containing crude oils with high pour points uses heating devices that are placed along the pipeline at small distances from one another in order to heat the crude oil and reduce its viscosity. Heating devices used for this purpose can run on crude oil as heating oil, that of. is withdrawn from the crude oil to be transported. Amounts of 5 % of the crude oil can be used to generate the heat necessary to lower the crude oil viscosity to a suitable level. In addition, most pipelines are not provided with such heating devices. There is also the added problem of environmental pollution when crude oils are burned because they are difficult to burn completely.

The invention is therefore based on the object of eliminating these disadvantages and creating a crude oil composition,

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the "better flow properties and a lower stick point having*

The task is solved by a raw material composition; that is characterized in that it

a) a large amount of gasol of a high paraffin and a low sulfur content,

b) a small amount of a high asphaltene content Backlog material, and

c) an amount of a copolymer which lowers the pour point sat it of ethylene and a vinyl ester one saturated aliphatic monocarboxylic acid with 2 to 6 carbon atoms with an average molecular weight from about 17,000 to about 30,000 a tinglest erant eil from about 10 to about 45 wt .- ^ and one Melt index from about 7 to about 425

contains or consists of.

The invention thus creates crude oil compositions, which is a mixture of boiled oil with a high pour point as well high paraffin and low Schv / ef el content, a residue material with a high asphaltene content and an oil-soluble copolymer of ethylene and a vinyl ester of a saturated one represent aliphatic monocarboxylic acid. They are characterized by a low pour point and improved flow properties en off.

The mixing of crude oils with a high pour point, high paraffin wax and low sulfur content is essential to the invention with small amounts of highly asphaltene-containing residue materials in order to achieve a large lowering of the pour point,

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4 without the need to use dewaxing processes.

Paraffin-containing crude oils that are suitable for preparing the new crude oil compositions are.-ZvB. High pour point, high wax, low sulfur crude oils having the following properties: An API gravity of about 30 to about 40; a sulfur content between about 0.10 and about 2.0% by weight j a Saybolt viscosity at 37> 8 ° 0 of about 20 to about A 00 SUS; a wax content between about 3 and 20% by weight; and a pour point between about 4.44 and about 37-8 ° G. Ein'Paraffinwachs-containing crude oil with a high pour point and low sulfur content, which has particularly good results in the inventive oil compositions low pour point Revealed is the known as "AMNA" crude \ it has an API gravity of about 36 * 0; a Saybolt viscosity of about 69.8 SUS at 37.8 ⁰ C, a pour point of about + 21.1 ⁰ C, a wax content of about 14.0 wt .-%; and a sulfur content of about 0 wt .-% _t i5. Mixtures of high pour point paraffinic crude oils and low sulfur contents can also be used in preparing the crude oil compositions of the invention if desired.

Residue ^ residue of an Arabian light oil, 566 ° C +), Lake - The high-asphalt containing residue materials that point for the novel oil compositions with low Stocky are suitable, such as Arabian Light (1050 ⁰ +) include a variety of bottoms of residual fuel oil one, medio- (1050 F or above) ^ residue residue of Lake Medio-oil, 566 ⁰ C or above), etc. have the Üückstandsmaterialien, which are preferably used, residue an asphalt content of from about 4 to about 17 wt .-%, a carbon from about 7 to about 25% by weight, and a wax content from about 0 to about 10% by weight. Although the amount of residual material in the low pour point crude oil compositions of the present invention can be varied over a wide range up to a maximum of about 20% by weight,

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are preferably about 2 to about 15 wt .-%, based on the Weight of the finished composition, used.

The physical properties of the typical residue materials used in the compositions of the invention are used, the following table 1 shows:

Table 1

Physical properties of the residue materials

Arabian
Light Lago
Medio
566 ⁰ C + + 57.8 • +57.8 + 57.8 + 57.8 4.0 -. 2.82 5.7 1.02 - 1200 7.0 8.9 * 15.8 14.55

Pour point, ⁰ G
Upper pour point, ⁰ C
Sulfur, wt .-% - paraffin content, wt .-%
Viscosity at 99 ° C, cps
Density at 15.6 ^° C
Pentane-insolubles, vol.%

The pour point-lowering additives which are suitable for carrying out the invention are oil-soluble copolymers of ethylene and esters of saturated monocarboxylic acids, the monocarboxylic acid component of the ester having 2 to 6 carbon atoms. The copolymers have an average molecular weight of about 1700.0 to about 50,000, determined osmometrically, a vinyl ester content of about 10 to about 4-5 % and a melt index of about 7 to about 476.

The preferred copolymers are marketed under the name "Elvax" by EI du Pont de Hemours &Company;"geeignetste- the Type is Elvax 250, which contains 27 to 29% vinyl acetate, an" inherent "viscosity at 57.8 ⁰ C from

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of 0.78 dcl / g in toluene, a softening point determined according to ASTM E-28, of 138 ° C, a cloud point in the paraffin wax of 65 * 6 ° C, a melt index of 12 to 18 and a Has a molecular weight of from about 23,000 to about 27,000. These copolymer additives can be produced by several processes e.g. the method according to US-PS 3,215,678, in which the free radical polymerization of ethylene and a vinyl ester of a saturated aliphatic Monocarboxylic acid is described.

The labeling of the various "Elvax" additives brings the following table 2:

Table 2 Melt Index * 45-70 "Elvax" % Vinyl acetate ί 22-28 in the copolymer 335- ^ 65 40 39-42 125-175 150 32-34 22-28 210 27-29 220 27-29 5- 7 240 27-29 335-465 250 27-29 16 »22 260 27-29 1,6-2 _} 4 310 24-26 - 430-580 350 24-26 2.1-2.9 360 24-26 410 17-19 460 17-19

'*) in g / 10 min, determined according to ASTM 1328, modified

In the preparation of the invention. Crude oil mixture v / ground the crude oil with high paraffin and low sulfur

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and the high asphaltene residue material such as Amna Rohol and the Arabian Light 1050 ° F + residue and the copolymer additive are mixed together at room temperature and the resulting mixture is mixed with constant mixing to a temperature of about 65.6 to about 177 ° C »preferably at about 79-121 ⁰ C, heated to form the composition, which preferably is continued Mischen'etwa 0.2 to 25 hours or longer at a temperature of about 65.6 to about 176.7 ⁰ C. Alternatively, the crude oil and the residue fraction can be heated with mixing to the same temperature as stated above and then the polymer can be added to the heated oil mixture with stirring * The amount of copolymer to be added can vary widely, although it is only necessary to lower the pour point To add amount, this amount depends on the physical properties of the raw materials being mixed and the temperature to which the mixture is brought. The higher the temperature, the less copolymer / lsate is required for the desired effect. Usually about 0.01 to about 0.50% by weight, preferably about 0.01 to about 0.12% by weight, of the copolymer, based on the weight of the finished mixture, is used. If desired, mixtures of suitable copolymers can also be used.

The copolymer can be the crude oil materials mixed with one another can be added directly as granules or in a water-glycol emulsion, such as a water-ethyl englycol egg emulsion or in a hydrocarbon such as toluene, xylene, light return gas oil, hydrocarbon blends, kerosene, a Udex fraction, etc. Suitable emulsions can by Dissolving the copolymer in a hydrocarbon, such as Kerosene, etc., and emulsifying the hydrocarbon polymer solution with a mixture of an alkylene glycol, such as ethylene glycol, propylene glycol, etc., water and a wetting agent

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.Be positioned so that an oil-in-water emulsion is formed. The resulting emulsion has a pour point and viscosity about that of the water-glycol phase. An example of this procedure is the use of a water-ethylene glycol emulsion which contains about 22 % of the copolymer! Sate. This method is particularly suitable when the additive is exposed to cold weather, since an equal concentration of the copolymer in a light hydrocarbon has a pour point at or above room temperature and becomes quite viscous as a result of the thickening effect of the copolymer.

The specific properties of Amna crude oil are in the compiled in Table 3 below:

Table 3

Physical properties of AMMA crude oil

API density (15.6 ° C) 36.0

Flash point (COC) room temp. . -

Viscosity, SUS, at 15.6 ⁰ C -

at 37.8 ⁰ C 69.8

at 65.6 ° C. 4-5.7

Pour point, ⁰ C "+21.1

Paraffin content, wt% 14.0

Sulfur content, wt% 0.15

Salinity (Ib./1000 bbl.) 12.6 (0.0359 kg / m ⁵ )

Ash content, wt% 0.003

In this description, all pour points are determined according to ASTM method D-97.

The following example illustrates an embodiment of the invention is brought, serves to illustrate the invention, which is not limited to this example,

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Example .

; -, ΛΜΝΑ-crude oil,

In this example, a number of mixtures of V Arabian Light (1050 ⁰ I? +) Residue and varying amounts of Elvax 250 were made by first adding the Arabian Light (1050 ° F +) residue to the AMNA crude at 93.3 ° C mixed in, Elvax 25-0 as a 5% solution in toluene in a sufficient amount so that the finished composition contains 0.05% by weight of the copolymer additive, added and the resultant. Mixture stirred at 93.3 ° for 0.5 hours. The pour points and the upper pour points were determined for each of the mixtures. "The synergistic effect achieved is shown by the values in Table 4 below:

. Table 4

Synergistic effect of Elvax 250 and Arabian Light (1050 F +) - residue on the lowering of the pour point of AMNA crude oil

Attempt no. i , 05 2 3 4th Amna crude oil, wt% 100 , 22 98.0 98.0 96.0 1050 ^o F + Arabian Light, Wt% 0 , 22 2.0 2.0 4.0 Elvax 250,% by weight 0 - -0.05 0.05 Pour point, ⁰ C + 7 +21.1 - 3.89 + 1.67 upper pour point, C + 7 +23.9 - 3.89 - 1.11

In experiment no. 1, in which a mixture of Amna crude oil and 0.05% by weight Elvax 250 was prepared, only a moderate reduction in the pour point was achieved. In the case of a mixture of Amna crude oil and 2% by weight _s Arabian Light 1050 ° F + residue, the pour point remained unchanged compared to pure Amna crude oil (Experiment 2). However, when a blend of Amna crude and Arabian Light 1050 ° F + residue was made along with 0.05 wt% Elvax 250, the resulting blend had a stock

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point of - 3t89 ° C, which is a considerable decrease compared to means the pour point of the pure Amna crude oil.

Among other things, the invention includes an improved one Procedure for the pipeline transport of paraffin-containing Crude oils or the use of the inventive crude oil composition in the transport of paraffin-containing crude oils in Pipelines by introducing this composition into the Pipeline;.

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Claims (7)

τ 73 0 * 1 Expectations Crude oil composition, marked thereby e i c h η e t that they a) a large amount of gas oil of a high paraffin and one low sulfur content, b) a small amount of high asphaltene residue material, and c) an amount, which lowers the pour point, of a copolymer of ethylene and a vinyl ester of a saturated one aliphatic monocarboxylic acid with 2 to 6 carbon atoms, with an average molecular weight from about 17,000 to about 3,000,000, a vinyl ester portion from about 10 to about 45 weight percent and a melt index of about 7 "to about 425 contains or consists of. 2) crude oil composition according to claim 1, characterized in that _t it contains the residue material (b) in an amount of from about 2 to about 15 wt .-% " 3) crude oil composition according to any one of the preceding claims, characterized in that · the residue material (b) has an asphalt content of about 4 to about 17% by weight, a carbon residue, of about 7 to about 25 ~ wt% and a paraffin wax content of about Has 0 to about 10 weight percent. . - 12 309883/1261 4-) crude oil composition according to any one of the preceding claims , thereby g e k, ennzeicb.net, that the copolymer! sat (c) in an amount of about 0.01 up to about 0.5% by weight is present in the finished composition. 5) crude oil composition according to any one of the preceding claims ,characterized, that the copolymer (c) is an ethylene-vinyl acetate copolymer is. 6) Oil composition according to address 5? through this geken-n records that the copolymer! sat a average molecular weight from about 2J000 "to about 27,000, a vinyl acetate content of about 27 "to about 29% by weight and has a melt index of about 12-18. 7) Use of the crude oil composition according to one of the preceding Claims in the transportation of crude oils in pipelines by introducing the composition into the pipeline. 309883/1261