JPS6033870B2 - Low temperature fluidity improver for fuel oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluidity improver for fuel oil characterized by comprising chlorinated ethylene and an ethylenically unsaturated monomer, and the present fluidity improver.

When using fuel oils containing petroleum distillate residues, such as marine diesel fuel oils, heating oils, etc., many problems arise regarding the low-temperature fluidity of these oils.

That is, fuel oil that becomes semi-solid or gelatinous at low temperatures can clog oil pipes and strainers, or make it impossible to supply fuel oil to an internal combustion engine. In order to solve this problem, much research has been carried out to date, and as a result many cold flow improvers have been developed and are in commercial use.

This type of additive controls the crystal growth of the wax in the fuel oil by controlling its crystal growth and improves the fluidity of the fuel oil at low temperatures by keeping it in a fine state. In particular, for fuel oil containing petroleum distillate residue oil, copolymers of relatively high molecular weight ethylene and ethylenically unsaturated monomers are often used, but these copolymers are present in the residue oil. There are many disadvantages in which the effectiveness of the drug is often reduced due to changes in the oil over time due to the interaction between wax and polymeric substances such as resins and asphaldenes.

Furthermore, since the average molecular weight of the copolymer is relatively large, the pour point and viscosity of the fluidity improver concentrate become high, which often causes handling problems.

The present inventors conducted research to solve these drawbacks of fluidity improvers for fuel oils containing petroleum distillate residues, and as a result, they came up with the following invention. In other words, by halogenating (particularly chlorinating) a copolymer of ethylene and an ethylenically unsaturated monomer, the solubility of the polymer in oil increases, making it easy to dissolve in oil even at relatively low temperatures. It has been found that mixing becomes possible and the stability of drug effects over time is also significantly improved. Additionally, chlorination improves handling by lowering the pour point and viscosity of pour point depressant concentrates. These properties are likely to be less limited to the extent that changes in the solubility of copolymers of halogenated ethylene and ethylenically unsaturated monomers in fuel oil facilitate their interaction with waxes and more It is thought that stable fine wax crystals are generated.

The copolymer of chlorinated ethylene and ethylenically unsaturated monomer used in the present invention has a number average molecular weight of 10,000 to 6.
0000 is a copolymer consisting of 60-85% by weight of ethylene and 15-40% by weight of ethylenically unsaturated monomer, and its chlorination rate is about 1-1% by weight. The ethylenically unsaturated monomer to be copolymerized with ethylene has the following general formula [wherein, R is hydrogen or a methyl group, and R2 is -OCO
R4, or a COOR4 group, where R4 is hydrogen or a C, to 4 straight-chain or branched alkyl group.

) and R3 is hydrogen or -COOR. ] are unsaturated mono and/or ethyl. child)
Examples of esters in which R and R3 are hydrogen and R2 is -OCOR4 include vinyl acetate and vinyl isoforthate. Examples of esters in which R2 is -COOR4 include methyl acrylate, methyl methacrylate, and isobutyl acrylate. Since the copolymerization reaction between these compounds and ethylene is generally synthesized commercially by radical reaction under high pressure, a detailed explanation will not be given here. In addition, chlorination of these copolymers is generally carried out using a haloalkane or the like as a solvent.
By blowing chlorine gas into the reaction system at a temperature of 150° C. using ultraviolet rays or visible light as a catalyst, it can be easily carried out in the same way as ordinary alkanes filtration chlorination.

In order to facilitate handling, the fluidity improver of the present invention is generally mixed with a hydrocarbon solvent such as light oil, kerosene, natural oil, etc., and used as a concentrated solution with a purity of 15 to 4% by weight.

The present invention will now be further explained by means of representative examples.

Example 1 As shown in Table 1, the properties of the fuel oils used in the examples are two types of fuel oils including petroleum cannibal residue oil.

Table 1 Table 2 shows the properties of the concentrated solution (30% kerosene solution) of the copolymer and chlorinated copolymer obtained in the present invention.

As is clear from Table 2, the pour point of the concentrated solution of the chlorinated copolymer of the present invention is significantly lowered, and it can be seen that it has extremely advantageous properties in terms of drug handling.

*Table 3 shows the results of measuring the below-pour point temperature and the stability at rising time of the fuel oils shown in Table 1 to which the copolymers and chlorinated copolymers shown in Table 2 were added.

Table-m (△T℃ is above and below the pour point of each oil blank)
From Table 3, it can be seen that the fuel oil to which the concentrated solution of the chlorinated copolymer of the present invention is added exhibits particularly excellent stability over time compared to the fuel oil when the concentrated solution of the copolymer is added.

Therefore, the concentrated solution of chlorinated ethylene and ethylenically unsaturated copolymer according to the present invention has an excellent ability to improve low-temperature fluidity.

Claims (1)

[Claims] 1. Number average molecular weight of about 10.000 to 60.000, 60
~85% by weight of ethylene and 40~15% by weight of the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1
is hydrogen or methyl group, R_2 is -OCOR_4
-COOR_4 group (in the formula, R_4 is hydrogen or C_
R_3 is hydrogen or a -COOR_4 group. ] A fuel oil fluidity improver comprising a chlorinated copolymer (chlorination rate of about 1 to 10% by weight) of an ethylenically unsaturated monomer and an unsaturated mono- and/or diester represented by the following formula.