JPS62172092A - Process for improving low-temperature fluidity of fuel oil - Google Patents

Abstract

PURPOSE:To obtain a fuel oil rich in paraffin wax and having relatively high boiling point an improved low-temperature fluidity during storage or transportation, by adding a specific amount of a specific fluidity-improving assistant in combination with a low-temperture fluidity improver to a fuel oil. CONSTITUTION:A fuel oil is added with (A) a low-temperature fluidity improver and (B) 0.01-50pts.wt. (based on the component A) of one or more fluidity improving assistants selected from (i) an aliphatic saturated monohydric alcohol f formula I (n is 1-8), (ii) an aliphatic saturated dihydric alcohol of formula II (n is 3-8), (iii) an oxyalkylene glycol of formula III (A is 2-4C alkylene; x is 1-7) and (iv) an oxyalkylene glycol monoalkyl ether of formula IV (A is 2-4C alkylene; Y is 1-5; R is 1-4C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for improving the cold flow properties of fuel oils prepared from medium and heavy S1 fractions of petroleum.

According to Kawaishi, when fuel oils such as light oil and heavy oil, which are medium and heavy fractions of petroleum oil, are exposed to low temperatures, their fluidity decreases significantly due to the precipitation of paraffin wax contained therein, resulting in serious problems. Ifil ffl may occur.

For example, when the temperature drops in winter, the paraffin wax contained in diesel oil precipitates, causing blockages in oil pipes 111 and 1 block in filters installed in the combustion 1 supply line of internal combustion engines. There are many cases of engine 1+JI failure.

In addition, 'jlj iyu' also loses zeta-activity (due to the precipitation of rosefinwa and nox when heated) and becomes unable to be transported, or when burned in a burner (B becomes difficult).

On the other hand, in recent years, although there has been a tendency for imported Ji:F oil to become more or less The demand/demand ratio for distillate fuels such as I'l oil is on the rise.

Therefore, in order to obtain as much fuel oil as possible from ili (1+I oil) by distillation fractionation, which contains a large amount of paraffin wax with a large molecular Jij, it is necessary to extract the high-boiling fraction from ili (1+I oil). It becomes necessary to cut (cut), and the content of paraffin wax with a large molecule II1. ), there is a lack of a method for directing the low-temperature flow η:bn using the jj method of H.

(bC powder technology) Many fluidity-property two-agents have been disclosed to solve such in1 problems J-i, and the representative ones include ethylene ^[flJi vinyl]t! Bath swimming (
US INl 11 Permit No. 3.0.1B, No. 1179), ethylene-acrylic acid ester (PolymerizationﾾKUSII!i
2゛1 No. 2.6 +34.453 'f''r, alkyl (meth)acrylate) / [[L rootstock (US 11' + j Mochi21 No. 2.091.627), chlorine 1 Hibara fin and naphthalene Condensation with 1-(US 11,1 Patent No. 1.815.
(122)) Nitrogen-containing derivatives of alkenylsuccinic acids (Non Ill 1'IWI IN3, 144. (No. 182)
, copolymerization of ethylenically unsaturated dicarboxylic acid and α-olefin (!1.￥Kaikai No. 511-157106)
Copolymer of 2 ethylene and α-olefin
-4202 Publication) and more! ) can be lost.

(Problem to be solved) These fluid bamboo clay preparations were tested by pour point test (JISK-226
9), all of them show a good pour point lowering effect, but the cold filter plugging boiler h (ColtJFiRer lol
There are many cases where the uBiru I'ainL) test is not sufficiently effective.

In particular, there are few that are effective against fuel oils that contain a large amount of paraffin wax in the polymer base.

In the pour point test, it is not possible to predict the blockage of the filter to the fuel supply system W by the crystal particles precipitated at a temperature considerably higher than the pour point, but the cold filter bragging boil (hereinafter referred to as , (: I' i)P is abbreviated, and the measurement method is CI? l)
The I) test, which will be described later as the I) method, is a test method that is used to predict such phenomena and is currently widely used.

(Means for solving ln1 problem) Main statement - As mentioned in h et al. 1i, 1iii (;
As a result of extensive research in order to improve the drawbacks of the present invention, the present invention was achieved.

In other words, the uniform amount of the present invention is to add 1 or more of 1 or 2 of θ (overflow 4111 property improvement (A)) to the fuel oil to obtain low temperature fluidization. When improving the properties, add λ1 to the low-temperature fluidity direction cutting (△) and add λ1 to (T1-11) (1, (-4)).
1 or 2 or more of 1-1, 001 to 5n l'+
: A method for improving the low-temperature fluidity of fuel Ti oil, the special feature of which is addition of a stopping point.

(+1-1) Fat-11ji group saturated -1-al:!-ru represented by the general formula C1" 2110 If, where n; number of 1 to 8 (Tl-2) -1ff1 Formula C. II 2. ( OII
) aliphatic saturated dihydric alcohols represented by 2, where n: 3 to 8 (B-31 general formula + 1 DI A l, oxyalkylene glycols represented by 011, where A: C2 to C4 alkyl 1/n group.

×21-7 number + 11- = 1) -m formula 11. (OA)yol
Oxyalkylene glycol monoalkyl ethers represented by +, where A: C2-C4 alkyl 1/n group.

Y: number of 1 to 5, I't: C, to C51 alkyl group It is.

According to the present invention, the residue obtained for Fumikawa (J + tt improvement 11 J + Δ
II (+1), the fatty 111i saturated 1+l -ta als selected from l+Y of (B'-1) include methanol, ethanol, 11-bu1]panol, isop17banol, 1 ■-Butanol, imbutanol, 1st-butanol, tert-butanol, 11-amyl alcohol, isoamyl alcohol, n-hexanol, 2-ethylbutanol, r+ -he7tanol, n-
Examples include octatool, 2-ethylhexanol, etc., but preferably 03 to C5 alcohols and mixtures thereof are used.

Examples of aliphatic saturated dihydric alcohols selected from Ij'l of fit-2) include trimethylene glycol, butanediol, 1°5-bentanediol, hexylene glycol, octylene glycol, etc. ,
Preferably C3 to C6 dihydric alcohols 1 and these lli f! It is jfk.

Examples of the oxyalkylene glycols in 1-31 include ethylene glycol, diethylene glycol, I-diethylene glycol, 1-lyoxyethylene glycol (average molecular ja300 or less), propylene glycol, and diethylene glycol; Propylene glycol, tripropylene glyco1-
Polyoxymole, Polyoxymbu 1 Fubilene glycol (co V homogeneous molecular weight h
) 300 or less), polyoxyethylene polyoxy 11
7 Birenlanda! , Gri=! -L (average molecule jL30Q
), and their il1 compounds.

A high molecular weight of 300 or more is not preferable because it becomes difficult to dissolve in fuel oil.

Examples of the oxyalkylene glycol monoalkyl ether of ([4l-4)] include cellosolve necks such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol motsubutyl ether. carpitols such as triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, toss (oxyethylene/oxypropylene 1:1 random copolymerization) Examples include glycol monobutyl needle, ditetraethylene glycol monobutyl ether, and mixtures thereof.

That is, the fluidity improving aid (B) of the present invention has 1 or more and 2 or less water molecules in the molecule! selected from alcohols, glycols and ethers having groups.

([1-1) to (B-41, preferably ([]-2
), (B-31, (n -4), with (B-43 being most preferably used).

Regarding the conventionally used fluidity improver (A), which is another factor of the present invention, for example, the following are used, but the examples are not limited to these.

The ethylene-vinyl acetate copolymer has a molecular structure of 10,
000 or less, which has a relatively low molecular weight.

The vinyl acetate-containing material can be used in a wide range from 5 to 60%, but preferably has a molecular Jt of 1.000 to 5%.
,000 and contains vinyl acetate J120-50%.

Examples of the ethylene-acrylic ester copolymer include those having a molecular f of 30.000 or less, and a wide range of ethylene-acrylic ester copolymers having a molecular f of 10 to 80% can be used. Furthermore, the acrylic esters can range from relatively lower alkyl esters such as methyl acrylate and ethyl acrylate to higher alkyl esters such as octyl acrylate and octadecyl acrylate.

The preferred one is molecular ml, 000-6,000. Acrylic acid ester containing ff130-60111 [M%, acrylic esters include methyl acrylate,
Lower (Cl'' C4) alkyl acrylates such as ethyl acrylate.

01 as a 7°lkyl (meth)acrylate polymer
Examples include methacrylates or acrylates having a wide range of alkyl groups from CI2 to CI8 or (B combinations (molecules ht1.ooo~l, 000, 000), preferred are CI2 to CI8 alkyl U
methacrylate-1 or acrylate with large 1
It is a polymer containing 21 polymers (for example, 80I "9g or more"), and the molecule'i is 5.000 to 200.000.
NoRI/If.

Condensation 111 of accumulated paraffin and naphthalene is as follows:
[:8 and above, 114 compounds of R & element 1 arsenic compound of l-paraffin and naphthalene are mentioned. 1 tl of 51 children is usually less than 20,000 5 preferably 2,000 to 8,00
It is 0.

As a nitrogen-containing derivative of alkenylsuccinic acid, C4 to C2
B. An alkenylsuccinic acid or anhydride containing an alkenyl group and a mono- or dialkylamine.

It is obtained by reacting polyalkylene triamine with alkenylsuccine #1 containing a C10 to C22 alkenyl group or its anhydride and '1
It is a reaction product with a dialkylamine containing a 2-C22 alkyl group 21I11.

A copolymer of an ethylenically unsaturated dicarboxylic acid and an α-olefin is produced by reacting maleic anhydride with an α-olefin containing 20 to 60 carbon atoms per molecule.
+) is a copolymer of molecules 111s, ooo to 50,000, preferably 7.000 to 20.000.

In addition, as a copolymer of ethylene and α-olefin, a molecule M 1 obtained by reacting 1 mole of a 2-linear chain CIO to C22 α-olefin with 1.1 to 30 moles of ethylene is used.
．． It is a copolymer of OO[1 to 50,000, preferably a copolymer of molecules M2.000 to 3.000 obtained by reacting 11 moles of dodecene with 3 to 20 moles of ethylene.

These fluidity improvers (A) are contained in fuel oil at a concentration of 1, usually 0,
[101~lOj[j M% 6'f'J, shi<
1. It is added to have a small M%* of tO,01~O,1, and can also be used as 111, 6, or il&compound.

See you again! <1l-1)~(B-41 to crawl 1z
The fluidity improver (b) is a fluidity improver (41
It is added in an amount of 1 to 50 parts by weight, preferably 0.1 to 10 parts by weight, and can be used either in 11 parts or as a mixture.

Addition of fluidity improving aid 1111, lil 0. ONu welfare department xylem error less than the addition effect within fiVII Itll
Moreover, even if more than 50 parts by weight is added, the effect will not be further improved and it will be economically disadvantageous, which is not preferable.

The fuel oil in the present invention is one of petroleum products that is used as a fuel.

! Examples of L1 include distillate fuel oil, residual oil, and mixed fuel oil, with distillate fuel oil being most preferred.

Distillate fuel oils include gasoline (automobile gasoline, aviation gasoline), kerosene (No. 1, 2S), diesel oil (1) No. 1, 1
No., No. 2, No. 3 and No. 3> and heavy oil (heavy oil, B
heavy oil).

Among these, preferred are light oil and A heavy oil.

(Effect of the invention) The pour point of 5 fuel oil is lowered by adding the fluidity improving aid (+3) of the present invention and the conventionally used fluidity improver (A) to fuel t1 oil. As well as C
Since F P 13 can be greatly reduced, the relatively high boiling point fuel f1 that burns a lot of rose fin wax
This makes it possible to solve various problems related to low-temperature fluidity during storage and transportation of oil.

Since even high boiling point fractions can be utilized, it is possible to increase the production amount of high quality fuel oil by 1.

Effect of the fluidity improvement effect according to the present invention II! Although the side effects are not clear, the effects of the decline in CF OII are particularly important.
Therefore, in the process of precipitation of paraffin wax in fuel F1 oil due to temperature decrease and J(J), when flowability improver (A) and flowability improving aid II ([13] are not used, crystal particles 11 and 14 each other to form a three-dimensional net [1
It forms a paraffin wax and loses fluidity by absorbing wax oil, but by adding a fluidity improver (Δ), these precipitate as crystal nuclei of paraffin wax and form a large number of nuclei. Although the flow JJ point test @ (JISK2269) shows good JJ point depression due to the presence of wax crystals and fineness, the crystal particles are strong and the pore size of the filter is 350 mesh < 4471). No matter how big it is, one item has m holes and 1゛ worth of CFr'P is 711.

In addition to this, by using the fluidity improving aid (b) of the present invention in combination, the paraffin wax crystal particles are further reduced, and the strength of the mu crystal particles is weakened and added to the filter passing through the filter. It is thought that the crystals are destroyed by the stress and the filter passability is improved, thereby significantly improving CFPP.

In addition, the fluidity improving aid of the present invention (by using Bl as C heavily, it is absorbed into the fuel oil or absorbed from the outside).
Let's scatter the moisture in the city into the oil, and burn it.''
(Removal by combustion is i + I Ik, and it also solves the problem of metal materials i1 such as fuel T1 tanks and iA 1111 pipes due to moisture accumulation, and the problem of clogging of oil pipes and filters due to freezing of water). Are there any effects that can be avoided?

In the flow + J + bamboo improvement Jj method of the present invention, the Ji method in which the fluidity improving aid (I) and the conventionally used fluidity improving paris (A) are included in the fuel T1 oil is particularly limited. Not done.

For example, fluidity improving aid (II) 86L and Ryusenchiku+M
1. A method of adding directly to fuel oil, a method of adding fluidity improvement agent 61 (n) and TfL Chih Takemukai-1 fil+ (
The J' method, etc., in which Δ) is diluted and added is F+.

In addition, the Fluid I/Improved Jr" method of the present invention can be applied to fuel oil.
i+'+'Added 1lJj Rust removal, acid (HiIsu7 +
1st cut and still 1st + I: / I'l It can be used with the additive of 01 river, or if necessary, it can be used in combination with the agent for pond flow / DH.

1. Below, the present invention will be further explained with reference to Example 6, but the present invention is not limited thereto.

Implementation IN and Hichu as an example e @ stone i1+, commercially available No. 1 light oil, No. 2 light oil Ill
Fluidity improver (A) and abbreviation a%, which have been used since No. f1313 and heavy oil since C;
Table 1.2 shows the results of examining the low-temperature fluidity by adding the fluidity improving aid ([I) indicated by i. Shown in Table 3.

In addition, among the low-temperature fluidity, flow 9 points were measured according to JISK-2269 (hereinafter abbreviated as pp), and CFI)P was measured according to the following.

<CFPP method> Using the method developed by FSO to evaluate the low-temperature fluidity of oil, when the oil is cooled, the fluidity decreases due to precipitated paraffin wax, which is used as an index for filterability. 1
The temperature of the oil when it takes 1 fl + at a given time to pass through the w4th point i) In this method, a glass test tube heated with stainless steel was shallowly placed in dry ice kept at -34℃. , put ticM45@e in it and cool it, 35
A glass pipette with a stainless steel mesh (filter) of 0 mesh (pore diameter 44μ) at the tip was inserted into bCf-1, and the sample was aspirated into the pipette under reduced pressure of 200 mm If 20 tl. ) is Bibe 1
This CFPr' is expressed as cr:pp value by the oil temperature until the rising time reaches a specified scale of 60 seconds.
The lower the fii (temperature), the lower the temperature at which filter clogging occurs, that is, the better the low-temperature kinetics is.

In the present invention, measurements were carried out using a commercially available device (manufacturer: Old Il+ 14 Gakken e) as "Filter Me! I Cloudy Dot @ Instrument".

Fluidity -71) (A) A; Ethylene-61 acid vinyl
: 2, 500 1'i) Vinyl acid, containing J1:, ; 35 % b:
Ethylene-acrylic acid ester copolymer molecule ffi;
3,000 Acrylic acid ester content i: 4011! ffi% C; Mono I = m (Molecular weight of condensate of hibarafine and naphthalene; 5,000 2]Alkenylsuccinic acid amide ■-detradecenyl = reaction product of dihataic acid and di(n-octadecyl)amine; Copolymerization of ethylene unsaturated dicarboxylic acid and α-olefin. [Combined 17 moles of dodecene and 10 moles of ethylene!1 (combined molecular weight of 1 bottle, 2,500 [Q] is not shown).

The fluidity improving aids (b) are indicated by the following abbreviations a to i.

ii: l・lyethylene glycol=1-l monomenal ether l); ethylene' glycol (:hexylene glycol (1: iso-10 panol) (.琶2Qfl) "2 methanol g, n~oct7-l h, diethyl 1/ngly 1-l monoethyl ether i
; :l? Rioquin ethylene glycol OV-uniform molecular weight 1
i1200) In addition, abbreviations, ) to (l) were added for comparison.

, 1. Nonyl alcohol kin-dodecyl alcohol I, allyl carbinol ln: benzyl alcohol 11: 3-butene-1,2-diol O, glycol p; diethylene glycol diethyl ether [I From the results of diethylene glycol acetate-1-Wl, conventional By using the fluidity improving agent (I3) of the present invention in combination with the fluidity improvement agent II (A) used from
It can be seen that the fluidity of the oil, in particular, CFl) 1) decreases when 2'L<2'L.

J! In addition, as a result of k2, the fluidity improving agent of the present invention (
B) iF+J+j is i that has been used since LC.
It can be seen that 0.01 to 50 parts by weight of the fluidity improver (A) is hydrating.

On the other hand, from the results in Table 3, it can be seen that the fluidity improving agent (B) of the present invention
It can be seen that anything other than this has almost no effect on improving fluidity.

Claims (1)

[Claims] A low-temperature fluidity improver (
When adding one or more of A) to improve low temperature fluidity, (B-
1) to (B-4).
1. A method for improving the low-temperature fluidity of fuel oil, which comprises adding 0.01 to 50 parts by weight of one or more of the following. (B-1) Aliphatic saturated monohydric alcohols represented by the general formula C_nH_2_n_+_1OH, provided that n is the number from 1 to 8 (B-2) Aliphatic saturated dihydric alcohols represented by the general formula C_nH_2_n(OH)_2, provided that , n; number of 3 to 8 (B-3) oxyalkylene glycols represented by the general formula H(OA)_xOH, where A; alkylene group of C_2 to C_4, x; 1 to
Number of 7 (B-4) Oxyalkylene glycol monoalkyl ethers represented by the general formula R(OA)_YOH, where A: alkylene group of C_2 to C_4, Y: 1 to
Number of 5, R; alkyl group of C_1 to C_4