JPH0420593A - Additive for heavy oil/water emulsion fuel - Google Patents

Abstract

PURPOSE:To obtain the title additive which is excellent in emulsifiability, transporting and storing stability, and combustibility by selecting the title additive which contains a specific compound. CONSTITUTION:The title additive which contains 10 to 30C hydroxyalkanesulfonate is selected.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an additive for heavy oil/water emulsion fuel that has excellent emulsifying properties, transportation/storage stability, and combustibility.

[Conventional technology]

Bitumen, heavy petroleum oil, and petroleum alphalt produced in Canada, the Soviet Union, China, the United States, Indonesia, Henesera, etc. are viscous substances with a viscosity of tens of thousands to hundreds of thousands of cps. Currently, these are not widely used as fuel because they are difficult to transport and handle at room temperature. However, due to their vast reserves, the above-mentioned bitumen, petroleum-based heavy oil, and petroleum alphalt are expected to be used as fuels.

It is already known that an emulsion fuel that is easy to handle and has good combustibility can be produced by mixing water and appropriate additives with the above-mentioned heavy oil and stirring the mixture using mechanical force such as a line mixer. Such heavy oil/water emulsion fuel is
Many studies have been conducted on the manufacturing method and additives, such as JP-A-61-247757 and JP-A-63-
No. 54498, JP-A-1-185934, JP-A-1-
No. 203498, JP-A-1247492, JP-A-1-
No. 249892, JP-A No. 1313592, JP-A No. 1-
No. 313593, JP-A-1-313594, JP-A-1
There are various publications such as No.-313595.

(Problem to be solved by the invention) However, although conventional heavy oil/water emulsion fuel additives have a certain effect, they do not have sufficient emulsifying performance during production or stability that can withstand transportation and storage for a certain period of time. However, improvement in the negative layer was desired.

The present invention is aimed at forming a heavy oil/water emulsion fuel that has a low viscosity even at room temperature and a sufficient particle size for combustion, and which does not coarsen or thicken even after a long period of time. The purpose is to develop additives.

[Means for Solving the Problems] According to the present invention, (a) a hydroxyalkanesulfonate having 10 to 30 carbon atoms, or (b) a hydroxyalkanesulfonate having 10 to 30 carbon atoms;
A heavy oil/water emulsion fuel additive is provided comprising a mixture of alkenyl sulfonates.

According to the present invention, by configuring the additive as described above, it is possible to improve the emulsifying property during production, suppress demulsification destruction due to coalescence of particles, and exhibit excellent performance in stability during transportation and storage. Viscosity emulsion fuel can be provided. The present invention is based on the finding that the hydroxyalkanesulfonates contained in these mixtures have good performance as heavy oil/water emulsion additives.

The mixture of (a) a hydroxyalkanesulfonate having 10 to 30 carbon atoms and (b) an alkenyl sulfonate having 10 to 30 carbon atoms used in the present invention is a mixture of -i formula % formula % () (in the formula, R, R' are each hydrogen or a linear or branched saturated hydrocarbon group having 1 or more carbon atoms, and R and R'
The sum of the carbon numbers is 8 to 28).
~30 vinylene monoolefins as woody components,
It can be produced by sulfonating an olefin containing trisubstituted monoolefin in an amount of about 33% by weight or less (about 1/3 of the olefin), neutralizing it with an appropriate base, and hydrolyzing it. Examples of the mixture of (a) and (b) produced in this manner include those shown below.

That is, it is produced by first sulfonating the α-olefin of Funato (1), neutralizing it with an appropriate base, and hydrolyzing it. The α-olefins used in the production of the additives of the present invention are linear and branched vinylidene type. Linear α-f-L, α derived from fins
- Olefin sulfonate is a mixture mainly composed of hydroxyalkanesulfonate, alkenylsulfonate and disulfonates, and generally consists of about 50-20% by weight of hydroxyalkanesulfonate and about 50-80% by weight of alkenylsulfonate, and about 20M
Contains disulfonate in an amount of % or less.

Vinylidene-type α-olefin sulfonate contains alkenyl sulfonate as a main component, and contains hydroxyalkanesulfonate and disulfonates as minor components. Of course, by selecting the sulfonation conditions and the hydrolysis conditions, it is possible to produce an α-olefin sulfonate having a different component ratio from the above-mentioned component ratios.

In order to obtain a heavy oil/water emulsion with good stability, it is preferable to use an α-olefin sulfonate having 10 to 3 carbon atoms. If the number of carbon atoms is less than 10, the emulsifying performance of the emulsion will not be sufficient, and if the number of carbon atoms exceeds 30, the solubility in water will be poor. More preferably, it has 12 to 24 carbon atoms.

The amount of disulfonate is preferably 20% by weight or less, and if it exceeds 20% by weight, the emulsification and stability of the emulsion tend to deteriorate. Since a small amount of disulfonate increases emulsifying power without impairing stability, the content of disulfonate is preferably about 0.5 to 15% by weight, particularly about 1 to 12% by weight.

Examples of α-olefin sulfonates suitable for the present invention include carbon atoms of 12, 14, 16, 18, and 20.
, 21.

22.23.24.26.12-14.14-16.1
4-18.16-18, 16-20, 18-20
, 20-24 and 20-28 α-olefin sulfonates, and mixtures thereof.

The α-olefin sulfonate that is the additive of the present invention is
These include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts of α-olefin sulfonic acid. Preferred countercations are Na, K, Mg,
Ca, NH4 and alkanol ammonium.

Next, the desired additive can also be produced by sulfonating the internal olefin, neutralizing it with an appropriate base, and hydrolyzing it. The invention! The internal olefin used in the production of machining has a vinylene type monoolefin of formula (1) having 10 to 30 carbon atoms, preferably 10 to 26 carbon atoms as an essential component, and may contain about 33% (olefin It is produced by sulfonating an internal olefin containing about 1/3 or less of the trisubstituted monoolefin, neutralizing it with an appropriate base, and hydrolyzing it. The internal olefin sulfonates thus produced typically contain about 10-60% by weight of alkenyl sulfonates with double bonds and about 90-40% by weight of hydroxyalkanesulfonates, while about 80% by weight of monosulfonates. % by weight or more and up to about 20% by weight of disulfonates.

Of course, by selecting the sulfonation conditions and the hydrolysis conditions, it is also possible to produce an internal olefin sulfonate in a proportion different from the above-mentioned component proportions.

Generally, as the number of carbon atoms in the internal olefin increases, the proportion of hydroxyalkanesulfonate tends to decrease, and as the molar ratio of the sulfonating agent during sulfonation increases, the proportion of disulfonate tends to increase.

In order to obtain a heavy oil/water emulsion with good stability, it is preferable to use an internal olefin sulfonate having 10 to 30 carbon atoms. If the number of carbon atoms is less than 10, the emulsifying performance of the emulsion will not be sufficient, and if the number of carbon atoms is more than 30, the solubility in water will be poor. More preferably, it has 10 to 26 carbon atoms. Disulfonate is preferably 20% by weight or less, and if it exceeds 20% by weight,
Emulsification and stability of the emulsion tend to decrease. A small amount of disulfonate increases emulsifying power without impairing stability, so the content of disulfonate should be approximately 0.5 to
Preferably, it is about 1 to 12% by weight to 15% by weight.

Further, in the internal olefin sulfonate of the present invention, in the -Sailor% formula (1), R is a linear or branched alkyl group having 4 to 23 carbon atoms, and R' is a linear or branched alkyl group having 1 to 23 carbon atoms. ~12 linear or branched alkyl groups, the sum of the carbon numbers of R and R' is 8 to 24, and those with R' of 1 to 4 carbon atoms are 5
0% by weight or more, preferably about 60% by weight of an internal olefin with 10 to 26 carbon atoms obtained by sulfonation
So, the content of hydroxyalkanesulfonate is about 40
It is preferred to use an internal olefin sulfonate having a disulfonate content of greater than or equal to 70% by weight, and less than about 20% by weight.

Specific examples of additives suitable for use in the present invention include carbon numbers 10.12, 14.16, 18, 20, 22, 24.2
6.12-16, 13-14, 13-16, 14
~16, 14~18, 14~20°15~18,
15-20, 16-18, 16-20, 17-2
0, 18-20, 18-24, and 20-24 internal olefin sulfonic acids) (IO3), and mixtures thereof.

Internal olefin sulfonates that are additives of the present invention include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts of internal olefin sulfonic acids. Preferred countercations are Na,
K, Mg, Ca, NH4 and alkanol ammonium.

When producing emulsion fuel, the amount of the additive of the present invention to be used varies depending on the oil type, etc., but the amount is 0.
．． 0.01 to 2% by weight, preferably 0.1 to 1% by weight.

The additives according to the present invention may be used alone or in combination of two or more kinds. It can also be used in combination with other conventionally known additives, and the effect becomes even more pronounced when used in combination.

Other additives include nonionic surfactants, anionic surfactants, and the like, with nonionic surfactants being preferred. Furthermore, water-soluble polymers and the like can also be used in combination with these additives.

Examples of nonionic surfactants include the following.

(a) alkylene oxide adducts of compounds having phenolic hydroxyl groups such as phenol, cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol, dinonylphenol, styrenated phenol, styrenated nonylphenol, paracumylphenol, bisphenol A, (b) Alkylene oxide adducts of formalin condensates of compounds with aromatic hydroxyl groups such as phenol, alkylphenols, styrenated phenols, and styrenated nonylphenols, (C) lauryl alcohol, stearyl alcohol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol , aliphatic 1 having a linear or branched carbon number of 2 or more, such as sorbitol
(d) alkylene oxide adducts of amines or amides having one or more active hydrogens, such as laurylamine, stearylamine, stearylamide, ethylenediamine; (e) polyethyleneimine; alkylene oxide adducts, etc.

When the anionic activator in the emulsion fuel of the present invention is used in combination with other additives, the total amount used is 0.01 to 2% by weight, preferably 0.05 to 1% by weight based on the emulsion.
It is. Further, it is suitable to use the nonionic activator to the anionic activator in a weight ratio of 2=98 to 75:25, more preferably 10:9.
0-40:60. Also, the ratio of heavy oil and water that forms the emulsion is 60:40 to 85:
It is 15. Preferably 65:35-75:
It is 25. When heavy oil and water form an o/w emulsion, it is preferable because low-viscosity water becomes a continuous phase and the viscosity is significantly reduced.

As the heavy oil of the mixed fuel component, various types of heavy oil such as bitumen, petroleum heavy oil, petroleum asphalt, and tar are used.

Although a general stirring method is sufficient as a stirring means for producing the emulsion fuel of the present invention, a high shear type stirring device such as a line mixer homomixer is particularly preferred.

The additive of the present invention is (a) a hydroxyalkanesulfonate having 10 to 30 carbon atoms, or (b) a hydroxyalkanesulfonate having 10 carbon atoms.
By using a mixture of ~30 alkenyl sulfonates, it is possible to produce an emulsion fuel that has better emulsifying properties, transport/storage stability, and flammability than conventional ones during the production of heavy oil/water emulsion fuels. can.

The heavy oil/water emulsion fuel of the present invention has low viscosity and excellent long-term transportation and storage stability, so it is useful as an efficient boiler fuel in the fields of electric power and general industry.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

292g of heavy oil, water and specified amount of additives total 400g
The mixture was weighed to give an amount of 1.5 g, heated to 70° C., and then mixed and stirred using a homo mixer (manufactured by Tokushu Kika Kogyo) to prepare an emulsion fuel.

Next, the fluidity and static stability of this emulsion fuel were evaluated. The properties of the heavy oil used are shown in Table 1, the properties of the additives are shown in Tables 2 to 6, and the evaluation results are shown in Tables 7 (Example) and Table 8.
(Example) and Table 9 (Comparative Example).

(1) Evaluation of fluidity The viscosity of the emulsion was measured at 30°C using a Brookfield viscometer after the emulsion reached a constant temperature after preparation.

◎: Very good fluidity ○: Good fluidity △: Insufficient fluidity ×: Poor fluidity (2) Evaluation of standing stability 200 g of the above emulsion was placed in a sealed plastic container with an inner diameter of 6 cm and 250 d, and the temperature was 30° After storage for one month at C, the above evaluation (1) was performed.

6'5, mouth 2, Table 1 - Long-term results

Claims (1)

[Claims] 1. An additive for heavy oil/water emulsion fuel containing a hydroxyalkanesulfonate having 10 to 30 carbon atoms. 2. A heavy oil/water emulsion fuel additive comprising a mixture of (a) a hydroxyalkanesulfonate having 10 to 30 carbon atoms and (b) an alkenyl sulfonate having 10 to 30 carbon atoms. 3. The additive for heavy oil/water emulsion fuel according to claim 2, wherein (a)/(b) = 20/80 to 90/10. 4. Claim 2 obtained by sulfonation of olefin
Additive for heavy oil/water emulsion fuel as described.