JPS6017476B2 - Cold fluidity improver for petroleum products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improving agent for improving the fluidity of petroleum products at low temperatures.

Crab oil and heavy oil such as high quality naphtha, virgin naphtha, kerosene, and diesel oil, as well as the crude oil that is the starting material for these products, may be produced in cold regions, or if oil is refined in the production region, or in pipelines. When transporting oil, the viscosity increases as the temperature drops, reducing transportation capacity, or paraffin contained in the oil precipitates, causing blockages in pipes, valves, and furnace overflow systems. This may lead to problems such as.

- One method to solve these problems is to use ethylene-pinyl acetate copolymer (hereinafter abbreviated as EVA copolymer).

) has been developed and used as an additive resin to the oil neck to lower the pour point. However, the performance of conventionally used EVA copolymers tends to fluctuate depending on their composition. For example, when the ethylene content is low, the effect of improving low temperature furnace permeability for virgin oil decreases, and the solubility at low temperatures decreases. However, there is still room for improvement in the following points: poor performance, formation of precipitates in the lower parts of storage tanks, or loss of the effect of the improving agent itself.

Improved versions include ethylene-vinyl acetate-olefin terpolymer, ethylene monoacetate-pinyl unsaturated ester terpolymer, and EVA copolymer grafted with unsaturated dicarboxylic acid. Copolymers have been proposed, but in either case they are difficult to manufacture due to copolymerization or graft polymerization, and low-temperature fluidization, which is relatively easy to manufacture and has excellent properties such as low-temperature solubility, The reality is that sex-improving agents are desired. However, in view of these problems, the inventors of the present invention have conducted intensive studies and found that the ethylene content is 50 to 9% by weight and the intrinsic viscosity is 0.08 to 0.5 M〆'g (3000
(in benzene) is added to the EVA copolymer with the following formula (where X is hydrogen or a methyl group, or R is an alkyl group having 3 to 21 carbon atoms, and R' is hydrogen or a C 1 group). When a graft copolymer grafted with at least one unsaturated compound represented by (representing an alkyl group of The inventors have discovered that the problem can be solved, and have completed the present invention.

The EVA copolymer serving as the basic skeleton of the graft copolymer used in the present invention has an ethylene content of 50 to 50%.
9% by weight, intrinsic viscosity in benzene at 30°C is 0
．． Females should be ~0.5 MZ/g.

Outside this range, the solubility of the graft copolymer in hydrocarbon oil is insufficient, or the effect of improving low-temperature fluidity is insufficient, making it difficult to put it to practical use. In addition, using a multi-component copolymer in which a small amount of other unsaturated monomers that can be copolymerized with ethylene and vinyl acetate, such as vinyl versatate (manufactured by Shelley B.) (branched higher fatty acid vinyl ester), etc. There is no problem. Next, the unsaturated compound to be grafted onto the EVA copolymer will be specifically explained. Typical examples when Y in the above formula is an acrylic ester or a methacrylic ester include propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate. , (meth)heptyl acrylate, (meth)
Examples include octyl acrylate, decyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, and stearyl (meth)acrylate.

Typical examples include vinyl butyrate, pinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, pinyl stearate, and the like.

Typical examples of Y include styrene, methylstyrene, ethylstyrene, propylstyrene, and butylstyrene, each o-, m, and p-position isomer, Q
- Methylstyrene, etc.

The number of carbon atoms in the alkyl group represented by R in the compound is preferably 3 to 21, preferably 4 to 18; if it is less than 2, the boiling point will be low, making it difficult to perform the graft reaction, or
It is undesirable because it has a problem of insufficient solubility in petroleum and poor persistence of efficacy above 22%. Further, the group represented by R' is hydrogen or an alkyl group having 1 to 4 carbon atoms,
If the number of carbon atoms is 5 or more, the resulting graft copolymer will have insufficient solubility in petroleum, and the sustainability of its efficacy will also deteriorate.

The amount of these unsaturated compounds to be grafted relative to the EVA copolymer is usually selected from a range of 20 to 30% by weight. If it is less than 20% by weight, the solubility at low temperature will be insufficient, and if it is more than 30% by weight, the effect of improving the permeability in a low temperature furnace tends to decrease, which is not preferable.

The method for obtaining the graft copolymer of the present invention is as follows. The Hata VA copolymer is treated in the presence of a radically inert solvent, such as a straight or branched paraffinic hydrocarbon such as octane or decane, or a solvent that has little effect on radical reactions such as tertiary butanol. heating under a nitrogen atmosphere in the absence of nitrogen, and then combining at least one of the unsaturated compounds with a radical catalyst, such as an organic peroxide such as ditertiary butyl peroxide, acetyl peroxide, cumene hydroperoxide, or An azo compound such as azobisisobutyronitrile is added to cause a graft reaction. At this time, the reaction temperature is selected depending on the decomposition temperature of the radical catalyst used, but is preferably 50
-200°C, reaction time is preferably 2 to 1 time, and catalyst amount is preferably 1 to 4% by weight based on the total system, but these are not limited. In the improving agent of the present invention, the graft copolymer often has different characteristics depending on the type of the unsaturated compound to be grafted or the number of carbon atoms in the alkyl group. There is no problem even if the graft copolymers are grafted together or two or more graft copolymers having different grafted unsaturated compounds are mixed.

Depending on the combination, synergistic effects that could not be obtained when used alone for distillate fuel oil may be expected. Specifically, R in Y in the formula of the unsaturated compound may be expected. Alternatively, a graft copolymer obtained by grafting an unsaturated compound having 10 or less carbon atoms in R′ and a graft copolymer obtained by grafting an unsaturated compound having 11 or more carbon atoms in R′ in a ratio of 95:5 to 5:95 ( It is desirable to mix them in a weight ratio). Among the combinations of two types of graft copolymers, combinations of unsaturated compounds that are particularly effective include propyl (meth)acrylate and vinyl stearate, 2-ethylhexyl (meth)acrylate and stearyl (meth)acrylate, and versatate. Examples include pinyl, vinyl stearate, vinyl persate, and stearyl (meth)acrylate.

Incidentally, at the same time as the grafting reaction, some homopolymer of the unsaturated compound used is produced, but it is not necessary to separate and purify it as long as it does not have any particular adverse effect on the intended use. The blending ratio of the graft copolymer to hydrocarbons such as light naphtha, virgin naphtha, kerosene, light oil, heavy oil, and crude oil is 10 to 100,
It is preferably within the range of 50 to 300 peaks, and particularly for light oil, the range of 50 to 20 peaks exhibits excellent pour point depressing properties and low temperature furnace permeability.

If the mixing ratio is less than 1, the effect of the present invention cannot be obtained;
Even if the number of trays exceeds 0.00, the effect will not particularly increase. When adding the graft copolymer, other commonly used additives, antioxidants, other flow depressants, dispersants, viscosity index improvers, etc. may be used in combination depending on the purpose. I can do it.

The present invention will be specifically explained by the following examples.

In the examples, "%" is based on weight. Example 1 Ethylene content is 65%, intrinsic viscosity is 0.1 Koji/g (3
The compounds shown in Table 1 as unsaturated compounds were graft-reacted to the EVA co-domerate (hereinafter the same) in a benzene solution of 000 ml.

(Sample numbers ■ to ■) The reaction conditions were as sea bream soot, ditertiary butyl peroxide was added in an amount of 2% based on the total system, and the reaction was carried out at a reaction temperature of 160° C. for 8 hours under a nitrogen atmosphere. Next, this graft copolymer was added to heating oil 1,0 (1 is the pour point of 000, the filter clogging temperature is 0°C, and 0' is 0°C and 1200, respectively) obtained from Middle Eastern crude oil. 1 for
The pour point PP0 (PourPoint
) was measured according to JIS-K-2269, and the target temperature CFPP (Cold Filter PI Point) of the filter was measured at 1. P. It was measured by the method specified in 309/76.

The results are shown in Table 1. Example 2 Tatylene content is 85%, intrinsic viscosity is 0.1 phantom/
1.0' of fuel oil was added according to Example 1, except that the compounds shown in Table 1 were grafted onto the EVA copolymer of 1.0 g as unsaturated compounds (sample numbers ■ to ■). ,
Performance was evaluated.

The results are shown in Table 1 along with 0. Example 3 A fuel was prepared in accordance with Example 1 in 5, except that the EVA copolymer used in Example 1 was simultaneously reacted with two types of unsaturated compounds as shown in Table 2 to obtain a graft copolymer. The performance was evaluated by adding 1 oil and 150 pieces of Kawako.

The results are shown in Table 2. Example 4 Graft copolymer used in Examples 1 and 2 (sample number ■
- ■) Graft copolymer mixtures in combinations shown in Table 3 were added to 1.0'g of fuel oil in a 15-ounce dish, and the performance was evaluated.

The results are shown in Table 3. Control example 1 EV used in Example 1
A copolymer obtained by grafting dibutyl maleate onto the copolymer A, or the copolymer as it was without grafting was added to fuel oil 1 and 15 times to evaluate its performance.

The results are shown in Table 4. Comparative Example 2 The EVA copolymer used in Example 1 was grafted with dioctyl maleate, or the copolymer was directly mixed with fuel oil 1:0 to 1 without performing the graft reaction.
5Q starvation was added and its performance was evaluated.

The results are also shown in Table 4. Control Examples 3 and 4 As Control Example 3, instead of the graft copolymer in Example 1, an ethylene-vinyl acetate-2-ethylhexyl acrylate terpolymer (composition ratio was 36:20:44, but the weight ratio), and as a control example 4, ethylene-vinyl acetate vinyl chloride: original copolymer (composition ratio was 35:23:
42, but the weight ratio) was evaluated.

The results are shown in Table 5. Explanation of abbreviations in Table 1 (same for Table 2) PAA: Propyl acrylate VVA: Vinyl versatate 28HA: 2-ethylhexyl acrylate VS A: Vinyl stearate SMA: Stearyl methacrylate S t : Styrene VRA:
Pinyl Lawalinate p-BSt:p-Butylstyrene Table 2 Table 3 In the section of graft copolymer mixtures, for example, sample number ■+■ is 3:1, which means that the mixture of this graft reaction product is sample number ■ and ■ It is a mixture of 3 and 3 in weight ratio.
: Indicates that it is 1.

Table 4 Table 5

Claims (1)

[Claims] 1. Ethylene content of 50 to 90% by weight and temperature of 30°C
The intrinsic viscosity in benzene is 0.08 to 0.50 d.
1/g of ethylene-acetic acid-vinyl copolymer has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is hydrogen or methyl group, Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where R is an alkyl group with 3 to 21 carbon atoms, R
'represents hydrogen or an alkyl group having 1 to 4 carbon atoms) A graft copolymer grafted with at least one type of unsaturated compound represented by hydrogen or an alkyl group having 1 to 4 carbon atoms may be used alone or in a mixture of two or more types. Characteristic low-temperature fluidity improver for petroleum products.