USE OF AN ADDITIVE FOR IMPROVING THE COLD FLOW PROPERTIES OF A PETROLEUM OIL, PETROLEUM COMPOSITIONS CONTAINING THIS ADDITIVE AND MASTERBATCHES CONTAINING THIS ADDITIVE

Abstract: Copolymers of ethylene with vinyl acetate for which the expression VA/6 + B/2.3 - log (MFI) is less than 6.2 are used as a cold-flow improver especially in crude oils. (In the expression B represents methyl groups per 1000 C-atoms as measured by defined nmr method and VA represents % weight of vinyl acetate). Wax containing petroleum oil composition containing such a copolymer and a master batch for forming this composition.

Description: USE OF AN ADDITIVE FOR IMPROVING THE COLD FLOW PROPERTIES OF A PETROLEUM OILt PETROLE31 COMPOSITIONS CONTAINING THIS ADDITIVE AND MASTERBATCHES CONTAINING THIS ADDITIVE. This invention relates to additives for improving the cold flow properties of petroleum oil especially crude oils and fuel oils which contain distillation residues. The use of copolymers of ethylene with vinyl acetate (known as EVA) to improve the flow properties of petroleum oils at low temperature has bee known for many years. This subject matter is described in US patent specifications 4 087 255; 3 981 850; 3 947 368; 3 862 825; 3 792 984; 3 709 359 and 3 669 189 as well as UK patent specifications 1 263 151; 1 147 904 and 900 202. We have now found that certain special EVA's are particularly effective. Accordingly this invention includes the use of a copolymer of ethylene with vinyl acetate, which copolymer (a) contains V% by weight of vinyl acetate where V is 5 to 50, preferably 15 to 40; (b) has a melt flow index of M g/10 minutes as measured according to British Standard 2782: Part 1/105C of 1976 using a 2.16 kg load where M is 1 to 100, preferably 1 to 50, and (c) has a B parameter as hereinafter defined where B is 1 to 10 to improve the cold flow properties of a petroleum oil, especially a crude oil, characterised in that the copolymer is such that the algebraic expression (V/6) + (B/2.3) - log M is less than 6.2. (Throughout this specification logarithms are to base 10.) The invention includes a wax containing petroleum oil composition which includes 10 to 10000 ppm, preferably 10 to 1000 ppm (e.g. 20 to 250 ppm), by weight, based on the total composition, of a copolymer as specified above. Suitable compositions include crude oils; e.g. residual fuel oil compositions and waxy distillates, e.g. waxy diesel fuels. One method of preparing the copolymers mentioned above comprises feeding the comonomers together with a peroxide initiator and a non-reactive chain terminator,- e.g. propane, to a stirred autoclave which has been previously purged with nitrogen. The polymerisation is preferably carried out at 1000 to 2700 atmospheres and 100"C to 3000C, especially 1500C to 2504C. The copolymers can also be applied down oil wells to inhibit the formation of waxy deposits or to dissolve existing deposits on the sides of the well casing. Similarly the copolymers can also be used to inhibit deposition, or to assist in the removal of, waxy deposits from the walls of pipelines, tanks and storage vessels. The blending of the above-mentioned copolymers with petroleum oils can by facilitated by first forming masterbatches, i.e. concentrated solutions of the EVA in suitable hydrocarbon solvents, e.g. aromatic hydrocarbons such as toluene, xylene or aromatic extracts from petroleum fractions. Suitable concentrations of the EVA in the masterbatch are 0.5 to 50%, preferably 1 to 30% by weight based on the total masterbatch. These masterbatches form part of the invention. The methods used to measure the vinyl acetate content and the B parameters will now be described. Vinyl acetate content All the vinyl acetate contents given in this specification were obtained by infrared spectroscopy using an absorbance ratio method. The method was applied to specimens in the form of hot pressed sheet approximately 3 to 4 mm thick. (The exact thickness does not matter since an absorbance ratio method is used.) The absorption bands at 2.133 Am and 1.429 Mm are measured. The absorbance at 2.133 pm, hereinafter AVA, arises from carbonyl groups and hence it is a measurement of the vinyl acetate content of an EVA. The absorbance, hereinafter AE, at 1.429 Sm is related to carbon-hydrogen. vibration. The vinyl acetate makes a small contribution to and is corrected by AE = AE - O.1AVA Aye is then proportional to the ethylene content of an EVA and hence the ratio AVA/AE is proportional to the ratio of vinyl acetate:ethylene in - the copolymer. It is necessary to standardise the method against an EVA of known composition but once standardised the-method gives the vinyl acetate content of an EVA as weight ratio of vinyl acetate:ethylene. The weight per centage and the mole ratio can be calculated from this. B Parameter The B parameter is obtained by nuclear magnetic resonance spectroscopy, hereinafter called "nmr". It is believed to correspond to the amount of chain branching but we do not intend to be bound by the interpretation of the B parameter. The method is carried out as follows. About 1 g of the EVA is dissolved in about 5 ml of a mixture of ortho and/or para dichlorobenzene. A small amount of this solution in a 5 mm diameter nmr tube is used in the nmr probe. The sample was maintained at 1400C during the scan which is taken at an operating frequency of 220 MHz. The resonance positions are defined as chemical shifts (in ppm of magnetic field) from the resonance position of hexamethyl disiloxane (which is arbitrarily assigned the position of zero ppm). The scan is carried out over a shift range of 0 to 5 ppm. The following resonances are noticed in this range: Shift (ppm) Assignment 0.85 C-OX3 or CH2CX3 1.25 (cX2)n 1.45 -CX2-CHO-CX2- 1.87 -CO-CX3 4.85 -CX(OOC-)- Figure 1 shows this portion of the spectrum: the resonance at 0 ppm is caused by hexamethyl siloxane as standard. This nmr method responds to hydrogen atoms in certain environments. The environments are given in the "assignment" in which X represents the hydrogen atoms responsible for the resonance. The resonance at 0.85 ppm arises from the (three) hydrogen atoms of methyl groups attached to a CH2 group at the end of linear branches or at the ends of the main chain or attached to a CH2 group inside a chain. The area of this resonance, hereinafter called A1 is,therefore, a measure of the amount of branching. The resonance at 4.85 ppm, arises from one of the hydrogen atoms of the vinyl acetate groups (i.e. X in the formula -CXOOCCH3). Its area, hereinafter called A2, is a measure of the amount of vinyl acetate in the copolymer. The ratio R1"A1/3A2 gives the molar ratio of "branches:VA in the copolymer. It is emphasised that it is necessary to use a frequency of 22MHz (or higher) in order to resolve the required resonances adequately. Figure 2 shows the methyl resonance (A1) and Figure 3 the vinyl acetate resonance (A2) both on the same enlarged scale. These resonances should be measured from the plot (instead of using the integrating circuitry of the spectrograph) by measuring the shaded areas in Figures 2 and 3. The results of the infrared method described above can be used to obtain the mole ratio R2=(VA groups): (-CH2-groups) in the copolymer. The parameter B is given by 1000R1R2. We interpret the parameter B as the number of branches per 1000 carbon atoms of the copolymer. Even if the interpretation is wrong, the B parameter, in conjunction with VA content and the MFI, defines and determines which EVAs give particularly good performance as pour point additives. Four compositions according to the invention will now be described by way of example. These four compositions illustrate the use of the ethylene/vinyl acetate copolymers prepared using profane as chain terminator. These copolymers, commercially available as "Evatane" 33-25, "Evatane" 28-05, "Evatane" 24-20 and "Evatane" 18-02, are defined in Table 1 as EVA 1, EVA 2, EVA 3 and EVA 4 respectively. TABLE 1 EMI6.1 <tb> <SEP> CODE <SEP> EVA1 <SEP> EVA2 <SEP> EVA3 <SEP> EVA4 <tb> Vinyl <SEP> acetate <SEP> content <SEP> (%)(=V) <SEP> 33 <SEP> 28 <SEP> 24 <SEP> 18 <tb> V/6 <SEP> 5.50 <SEP> 4.66 <SEP> 4.00 <SEP> 3.00 <tb> MFI <SEP> (= <SEP> M) <SEP> 25 <SEP> 5.5 <SEP> 20 <SEP> 2 <tb> log <SEP> M <SEP> 1.40 <SEP> 0.74 <SEP> 1.30 <SEP> 0.30 <tb> B <SEP> parameter <SEP> 4.7 <SEP> 5.0 <SEP> 7.1 <SEP> 6.0 <tb> B/2.3 <SEP> 2.04 <SEP> 2.17 <SEP> 3.08 <SEP> 2.60 <tb> (V/6)+(B/2.3)-log <SEP> M <SEP> 6.14 <SEP> 6.09 <SEP> 5.78 <SEP> 5.30 <tb> The B parameter was obtained using nuclear magnetic resonance as described above. The value of (V/6)+(B/2,3)-log M will be called the "discriminant of the EVA. The use of each copolymer specified in Table 1 is in accordance with the invention because each discriminant is less than 6.2. Five comparative tests were carried out on five other copolymers as defined in Table 2. TABLE 2 EMI6.2 <tb> <SEP> CODE <SEP> C1 <SEP> C2.l <SEP> C2.2 <SEP> C3 <SEP> j <SEP> C4 <tb> Vinyl <SEP> acetate <SEP> F(=V) <SEP> 33 <SEP> 28 <SEP> 28 <SEP> 24 <SEP> 18 <tb> V/6 <SEP> 5.50 <SEP> 4.66 <SEP> 4.66 <SEP> 4.00 <SEP> 3.00 <tb> MFI <SEP> (=M) <SEP> 43 <SEP> 6 <SEP> 3 <SEP> 20 <SEP> 2.5 <tb> log <SEP> M <SEP> 1.63 <SEP> 0.28 <SEP> 0.48 <SEP> 1.30 <SEP> 0.40 <tb> B <SEP> parameter <SEP> (=B) <SEP> 8.5 <SEP> 5.5 <SEP> 5.3 <SEP> 11 <SEP> 31 <SEP> 10.2 <tb> B/23 <SEP> 3.82 <SEP> 2.39 <SEP> 2.30 <SEP> 4.91 <SEP> 4.43 <tb> (V/6)+(B/2.3)-log <SEP> M <SEP> 7.69 <SEP> 6.27 <SEP> 6.48 <SEP> 7.61 <SEP> 7.03 <tb> These copolymers have discriminants above 6.20 and their use is, therefore, not in accordance with the invention. Four compositions according to the invention will now be described by way of Example. For ease of handling the EVA copolymer was added as a masterbatch in the form of a solution in toluene at concentration of 5 g per 100 mls of solution. EXAMPLE 1 30 g of a North Sea Crude oil, hereinafter called oil l, were placed in a beaker at room temperature and EVA 1, in the form of masterbatch in toluene (5 g per 100 mls solution) was added with stirring. 0.015 mls of the solution were added to the 30 g of crude, i.e. 0.75 mg of EVA 1, or an addition rate of 25 ppm. Pour points were measured by ASTM D97-57. The crude oil had a pour point of 8"C; with 25 ppm of EVA 1 the pour point was reduced to -23 C. EXAMPLE 2 25 ppm of EVA 2 were added to a second sample of Oil 1 using the method described in Example 1. The pour point was reduced from8"C to below -26 C. EXAMPLE 3 30 g of a different North Sea Crude, hereinafter called oil 2, were placed in a beaker and heated to between 500C and 60"C and EVA 3, in the form of masterbatch in toluene (5 g per 100 mls solution), was added with stirring. 0.06 mls of the solution were added to the crude1 i.e. 3 mg of EVA 3, or an addition rate of 100 ppm. The pour point was reduced from 27"C to 70C. EXAMPLE 4 200 ppm of EVA 4 was added to a 'Chilean' crude by the method described in Example 3. The pour point was reduced from 21"C to 11.50C. COMPARATIVE TESTS To provide a basis for comparison, blends resembling the compositions of Examples 1, 2, 3 and 4 were prepared using C1 instead of EVA1, C2.1 and C2.2 instead of EVA 2, C3 instead of EVA 3 and C4 instead of EVA 4. The pour points of these compositions are given in Table 3. For ease of comparison results of Examples 1 to 4 are included in Table 3. TABLE 3 EMI8.1 <tb> Crude <SEP> Additive <SEP> Discriminant <SEP> Addition <SEP> Pour <tb> <SEP> Oil <SEP> Rate <SEP> Point <tb> <SEP> (ppm) <tb> <SEP> NONE <SEP> - <SEP> - <SEP> + <SEP> 80C <tb> Oil <SEP> 1 <SEP> EVA <SEP> 1 <SEP> 6.14 <SEP> 25 <SEP> -23 C <SEP> <tb> <SEP> C1 <SEP> 7.69 <SEP> 25 <SEP> -130C <tb> <SEP> EVA <SEP> 2 <SEP> 6.09 <SEP> 25 <SEP> -26 C <SEP> <tb> <SEP> C2.l <SEP> 6.27 <SEP> 25 <SEP> - <SEP> 60C <tb> <SEP> C2.2 <SEP> 6.48 <SEP> 25 <SEP> -11 C <SEP> <tb> <SEP> NONE <SEP> - <SEP> <SEP> - <SEP> <SEP> +27 C <SEP> <tb> Oil <SEP> 2 <SEP> EVA <SEP> 3 <SEP> 5.78 <SEP> 100 <SEP> + <SEP> 70C <tb> <SEP> C3 <SEP> 7.61 <SEP> 100 <SEP> +14 C <SEP> <tb> 'Chilean' <SEP> NONE <SEP> - <SEP> - <SEP> <SEP> +21 C <SEP> <tb> <SEP> EVA <SEP> 4 <SEP> 5.30 <SEP> 200 <SEP> +11.5 C <SEP> <tb> <SEP> C4 <SEP> 7.03 <SEP> 200 <SEP> +21 C <SEP> <tb> Table 3 clearly shows that the use of ethylene/vinyl acetate copolymers in accordance with the invention i.e. with discriminants below 6.2, gives a greater depression of the pour point than the use of similar copolymers but with an discriminants above 6.2.

Claims: CLAIMS 1. The use, to improve the cold flow properties of a petroleum oil, of a copolymer of ethylene with vinyl acetate, which copolymer (a) contains V% by weight of vinyl acetate where V is 5 to 50, (b) has a melt flow index of M g/10 minutes as measured according to British Standard 2782: Part 1/105C of 1976 using a 2.16 kg load where M is 1 to 100, and (c) has a B parameter between 1 and 10, characterised in that the copolymer is such that the algebraic expression (V/6) + (B/2.3) - log M is less than 6.2. 2. The use according to Claim 1, characterised in that V is 15 to 40 and M is l'to 50. 3. A wax containing petroleum oil composition which includes 10 to 10000 ppm, based on the total composition, of a copolymer of ethylene with vinyl acetate, which copolymer (a) contains V% by weight of vinyl acetate where V is 5 to 50, (b) has a melt flow index of M g/10 minutes as measured according to British Standard 2782: Part 1/105C of 1976 using a 2.16 kg load where M is 1 to 100, and (c) has a B parameter between 1 and 10 characterised in that the copolymer is such that the algebraic expression (V/6) + (B/2.3) - log M is less than 6.2. 4. A composition according to Claim 3, characterised in that V is 15 to 40 and Mis 1 to 50. 5. A composition according to either Claim 3 or Claim 4, characterised in that it contains 10 to 1000 ppm of the copolymer. 6. A composition according to Claim 5, characterised in that it contains 20 to 250 ppm of the copolymer. 7. A composition according to any one of Claims 3 to 6, characterised in that the oil is a crude oil. 8. A masterbatch for forming compositions according to any one of Claims 3 to 7, wherein the masterbatch consists of a solution of 0.5 to 50% by weight, based on the total masterbatch, of a copolymer of ethylene and vinyl acetate dissolved in a hydrocarbon solvent wherein the copolymer (a) contains V% by weight of vinyl acetate where V is 5 to 50, (b) has a melt flow index of M g/10 minutes as measured according to British Standard 2782: Part 1/105C of 1976 using a 2.16 kg load where M is 1 to 100, and (c) has a B parameter between 1 and 10, characterised in that the copolymer is such that the algebraic expression (V/6) + (B/2.3) - log M is less than 6.2. 9. A masterbatch according to Claim 8, which consists of 1 to 30% by weight of the copolymer dissolved in toluene, xylene or an aromatic extract from a petroleum oil.

Inventors: GILBY, GORDON WILLIAM
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1980
Main classification: C10L1
IPC codes: C08F210, C10L10, C10L1, C09K8