JPS6035395B2 - fuel oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a medium-grade fuel oil composition with improved flowability.

When medium grade fuel oils, such as light oil and A heavy oil, are used or stored at low temperatures, wax crystals contained in the oil may grow and clog pipes, or the viscosity of the entire oil may increase dramatically. Eventually, troubles such as the fluid not flowing will occur.

In order to avoid such troubles, an additive called a flow improver (FlowImprover F.1) is generally used. This type of additive is thought to improve the fluidity of oil at low temperatures by changing its crystal structure and morphology through eutectic or adsorption with the wax in the oil.

Currently, this type of additive is attracting attention as being able to cope with the expected future heavier fuel oil, as introduced in numerous documents and patents, and it seems that it has begun to be used in some parts of the country as well. It is.

However, the current situation is that the additives introduced so far still require improvement in terms of performance.

In other words, even if the pour point test used in past performance evaluations shows that the effects of additive use are apparently significant, this may be because the tests do not necessarily correspond to practical performance. Problems such as those mentioned above often occurred. When these items are evaluated by subjecting them to the Cold Filter P1u chick Point CFPP test, which is said to be a more practical test method that has rapidly attracted attention in recent years,
Almost no effect of additives was observed, which indicates that the above-mentioned control of wax crystals was insufficient. For example, a number of fuel oil compositions with improved fluidity have been proposed (for example, British Patent No. 8487) by blending various fuel oils with various ethylene copolymers.
No. 77, No. 993744, No. 1264638, No. 1
486077, U.S. Patent No. 3166387, U.S. Patent No. 3
No. 443917, No. 3499741, No. 350763
No. 6, No. 3524732, Japanese Patent Publication No. 46-32583, Canadian Patent No. 991792, etc.).

According to these proposals, it is said that the fluidity can be improved by combining various fuel oils and various ethylene polymers. It is true that according to the above-mentioned pour point test, it can be said that a considerable improvement has been achieved in many combinations, but according to the above-mentioned CFPP test, most of the combinations do not show an acceptable improvement. Met. The present inventors investigated the relationship between the properties of fuel oil and the properties of ethylene copolymer as an additive in detail in order to obtain a fuel composition with truly improved fluidity despite its high boiling point range. As a result of consideration,
I learned that a purpose can only be achieved by roughly combining things that each have extremely limited properties.

According to the invention, middle distillate fuel oil 1 having a boiling point range of 170 qo to 400 qo and an end point of 360° C. or higher
Ethylene content is 75% and 85% by weight of 0% by weight.
Mol%, number average molecular weight is 2000, 20000,
5. Ethylene/Q-olefin copolymer with a Q value (Mw/Mn) of 3 or less without 0.005. A fuel oil composition is provided in which the fuel oil composition is blended in a proportion of parts by weight of

The fuel oil used in the present invention has boiling point properties as described above.

Even if the boiling point range is between 17,000 and 40,000, if the end point is lower than 360°C, CFPP
In the tests, almost no improvement was observed due to the addition of the ethylene copolymer, and even when the boiling point range and end point were higher than the above ranges, almost no improvement effect was observed. In general, the fuel oil applied to the present invention has a pour point (P·P) of about -12.5 to about -112.500, and a CFPP of about -10 to about 11,000. On the other hand, the ethylene/Q-olefin copolymer used as the fluidity improver of the present invention has an ethylene content of 75
None, 85 mol%, preferably 77 to 83 mol%
The number average molecular weight must be within the range of 20
00 to 20000, preferably 3000 to 1
Must be in the range 5000.

Even if an ethylene copolymer having an ethylene content and/or a molecular weight other than the above is used, the addition effect will be 4.0 and the desired effect will not be obtained. Examples of the Q-olefin constituting the copolymer include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and two or more thereof, with propylene being particularly preferred. More specifically, the copolymers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene copolymer, and ethylene-propylene copolymer.
Examples include 1-hexene copolymer and ethylene-propylene-1-phthene copolymer, and ethylene-propylene copolymer is particularly preferred. These copolymers have a Q value (Mw/Mn) of 3 or less, especially 2
．． 8 or less, and a z value (maximum molecular weight/minimum molecular weight measured by GPC) of 15 or 200, particularly preferably 20 or 190. Please note that GPC measurements are carried out by J.
oumal of Polymer SciencePa
A-2, Vol. 8, pp. 89-103 (1970), and the maximum and minimum molecular weights are the 4th point of the molecular weight at the lowest point in the molecular weight distribution curve, which is 99.5% by weight of the total amount. The molecular weight of the copolymer corresponding to eyes is defined as the maximum molecular weight, and the molecular weight of the copolymer corresponding to 0.5% by weight is defined as the minimum molecular weight. The amount of ethylene copolymer added is 0.005% per 10 parts by weight of fuel oil,
5. parts by weight, preferably no 0.01, and 1. parts by weight. The fuel composition of the present invention may contain corrosion inhibitors, antioxidants, stabilizers, dispersants, and other additives as necessary.

Next, an example will be explained.

Example 1 Using a four-glass reactor equipped with Nada Azusa blades, hexane was added to the top of the reactor twice every hour, a hexane solution of Babudyl trichloride (4 mmol/〆) was added once every hour, and ethylaluminum sesquikirolide was added every hour. Hexane solution (32 mmol/so) 1/hour
The reactor is continuously fed into the reactor, while the reaction liquid is continuously drawn out from the bottom of the reactor so that the reaction liquid in the reactor is always 2 hours.

In addition, a mixed gas of ethylene, propylene, and hydrogen (ethylene 140 m/h, propylene 4 m/h
0 so, hydrogen per hour 120 so). The reaction temperature was controlled at 35° C. by circulating hot water through a jacket attached to the outside of the reactor. A small amount of methanol was added to the reaction liquid taken out from the bottom of the reactor to stop the reaction, and then the reaction liquid was washed three times with water. After that, 30 Yanagi H
The hexane solvent was removed by distillation at a reduced pressure of 10,000 g and a pot temperature of 10,000 g to obtain an ethylene-propylene copolymer. The obtained copolymer (A) had an ethylene content of 79 mol%, a number average molecular weight of 4800, and a Q value of 2. The Z value was 170.
This copolymer was prepared as sample oil (1) (initial boiling point according to JISK2254, 225°C, final boiling point 374°C, pour point (JISK22
69) 2.500, low temperature furnace filter clogging point (C
FPP:Jual of the InSthadate
ofpetrole river m. vol. 52, No. 51
0.02 part by weight was added to 200), and the CFPP and pour point were measured.
Example 2 The same procedure as in Example 1 was carried out except that 0.05 part by weight of the ethylene-propylene copolymer (A) was added to the sample oil (i).

Example 3 In Example 1, instead of sample oil (1), sample oil (B) (initial total point: 180 pm, ending point 380 q0, pour point -10.0°C) was used.
, CFPP-800).

Example 4 In Example 1, sample oil (0) was used instead of sample oil (1).
), and the same procedure was carried out except that the amount of ethylene-propylene copolymer (A) added was 0.035 parts by weight.

Example 5 In Example 1, the concentration of vanadyl trichloride in hexane was 20 mmol/h, the concentration of diethylaluminum sesquichloride in hexane was 160 mmol/h, ethylene was 200 mmol/hour, propylene was 40 mmol/hour, and hydrogen was 20 mmol/hour. The ethylene/propylene copolymer (B) synthesized in the same manner except that 60% of the ethylene was supplied had an ethylene content of 83 mol%,
The number average molecular weight was 3300, the Q value was 2.4, and the Z value was 160.

This copolymer was added to sample oil (1) in an amount of 0.05 parts by weight, and the CFPP and pour point were measured. Example 6 In Example 1, ethylene was 200 m/h and propylene was 70 m/h.
In the evening, the ethylene/propylene copolymer (C) synthesized in the same manner except that hydrogen was supplied at 30 liters per hour.
It had a number average molecular weight of 6 mol %, a number average molecular weight of 10,200, a Q value of 2.5, and a Z value of 175.

This copolymer was added to sample oil (1) in an amount of 0.05 parts by weight, and the CFPP and pour point were measured. Comparative Example 1 In Example 1, ethylene was 117 per hour and propylene was 78 per hour.
Ethylene-propylene copolymer (E) synthesized in the same manner except that hydrogen was supplied at 105 m/hr had an ethylene content of 65 mol%, a number average molecular weight of 4600, a Q value of 2.4, and a Z value of 160.

This copolymer was added to sample (1) in an amount of 0.05 parts by weight, and the CFPP and pour point were measured. Shark example 2 In Example 1, ethylene was 133 per hour and propylene was 17 per hour.
Ethylene was synthesized in the same manner except that hydrogen was supplied at a rate of 150 m/hr.

The pyrene copolymer (F) had an ethylene content of 92 mol%, a number average molecular weight of 5,100, a Q value of 2.5, and a Z value of 165.
When this copolymer was added to sample oil (1) in an amount of 0.05 part by weight, it was hardly dissolved and the solution was cloudy at room temperature. Comparative Example 3 In Example 1, the hexane solution concentration of vanadyl trichloride was 20 mmol/hour, the hexane solution concentration of ethylaluminum sesquichloride was 160 mmol/hour, ethylene was supplied at 115 mmol/hour, propylene was supplied at 35 mmol/hour, hydrogen was supplied at 150 mmol/hour, and so on. is ethylene synthesized in a similar manner.
The propylene copolymer (G) has an ethylene content of 79 mol%
, number average molecular weight 1500, Q value 2. The Z value was 170.

This copolymer was added to sample oil (1) in an amount of 0.05 parts by weight, and the CFPP and pour point were measured. Comparative Example 4 In Example 1, the hexane solution concentration of vanadyl trichloride was 1.2.
Concentration of hexane solution of ethylaluminum sesquichloride: 9.6 mmol/so, ethylene per hour 20
0 evening, supplied 85 Z of propylene per hour and 15 Z of hydrogen per hour.
Ethylene-propylene copolymer (H) synthesized in the same manner as above had an ethylene content of 79 mol% and a number average molecular weight of 30.
000, Q value 2.6, and Z value 180.

This copolymer was added to sample oil (1) in an amount of 0.05 parts by weight, and the CFPP and pour point were measured. Comparative Example 5 In Example 1, the hexane solution concentration of vanadyl trichloride was set to 40
The hexane solution concentration of ethylaluminum sesquichloride is 24 mmol/h, the solvent hexane is 2.9 mmol/h, and the ethylene is 14 mmol/h.
Ethylene-propylene copolymer (J) synthesized in the same manner except that propylene was supplied at 32 m/hr and hydrogen at 120 m/hr on 8 pm had an ethylene content of 82 mol%, a number average molecular weight of 5300, a Q value of 3.8, The Z value was 420.

When this polymer was added to sample oil (1) in an amount of 0.05 part by weight, it was hardly dissolved and the solution was cloudy at room temperature. Comparative Example 6 Using sample oil (dish) (initial boiling point 214oo, final point 333oo, pour point -17.5qo, CFPP-1500) instead of sample oil (1) in Example 1, ethylene-propylene copolymer ( The same procedure was carried out except that the amount of A) added was 0.05 parts by weight.

Comparative Example 7 In Example 1, sample oil (W) (initial boiling point 270°C, final point 410°C, pour point 30.0°C, CFPP) was used instead of sample oil (1).
2800) and ethylene-propylene copolymer (A
) was added in the same manner except that the amount of addition was 0.05 part by weight.

Example 7 Same as Example 1 except that the concentration of vanadyl trichloride in hexane was 8 mmol/hour, the concentration of ethylaluminum sesquichloride in hexane solution was 64 mmol/hour, and 1-butene was supplied at 40 mmol/hour instead of propylene. The ethylene/1-butene copolymer (D) synthesized by the method is
The ethylene content was 80 mol%, the number average molecular weight was 5200, the Q value was 2.3, and the Z value was 165.

Claims (1)

[Claims] 1 Boiling point range is 170℃ to 400℃, 36
Ethylene content is 75 to 85 mol%, number average molecular weight is 2000 to 20000, Q value (Mw/Mn) for 100 parts by weight of middle distillate fuel oil having an end point of 0°C or higher.
0.0 of ethylene/α-olefin copolymer with 3 or less
05 to 5.0 parts by weight of a fuel oil composition.