JPH01313593A - Ultraheavy oil emulsion fuel - Google Patents

Abstract

PURPOSE:To reduce the viscosity, make it possible to conduct atomization at a low temp. and improve the handleability by mixing an ultraheavy oil with a particular nonionic surfactant and emulsifying the mixture. CONSTITUTION:100 pts.wt. ultraheavy oil (A) heated to 80 deg.C or above is mixed with 30-80 pts.wt. water and 0.05-5 pts.wt. nonionic surfactant having a hydrophile-lipophile balance of 14-19 and selected from ameng an alkylene oxide adduct (a) of a phenolic hydroxyl compd. (provided that the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide or styrene oxide; the same shall apply hereinafter), an alkylene oxide adduct (b) of a formalin condensate of a phenolic hydroxyl compd. having an average degree of condensation of 1.2-100, an alkylene oxide adduct (c) of 2-50C monohydric aliph. alcohol and/or aliph. amine, a block or random addition polymer (d) of ethylene oxide with propylene oxide and/or butylene oxide or styrene oxide, etc., and the mixture is emulsified.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to extra heavy oil emulsion fuel.

[Problems to be solved by conventional techniques and inventions] Petroleum,
As fossil fuel resources that are not included in coal and LNG, oil sands, bicemens (orinocotar, athabascabitumen), etc. are attracting a lot of attention because of their large reserves.

Furthermore, even in petroleum systems, there is a large surplus of asphalt or its heat treatment residues, excluding distillate oils such as naphtha. These extra-heavy oils are usually vacuum distillation residues of 420~
It is an oily substance containing about 60 to 70% or more of a heavy fraction of 450'C or more, and either does not flow as it is or has a high viscosity of centipoise or more. Therefore, in order to use it as fuel, it must be heated to a temperature of 280 to 300°C, otherwise there will be problems with handling and atomization.
It is a very difficult fuel to use as it tends to cause troubles such as clogging of pipes.

[Means to solve the problem]

The present inventors found that using an appropriate surfactant, ultra-heavy oil (0
) is emulsified in water (W) to form ultra-heavy oil droplets in water (
We have discovered that it is possible to produce emulsion fuel (type 0). This emulsion fuel exhibits a viscosity relatively close to that of water,
Sufficient atomization is possible at a temperature of 80 to 90°C, making it a very easy-to-handle fuel. In the convex emulsion fuel, the lower the - (water) content, that is, the higher the 0 (oil) content, the better it is as a fuel and the less fuel loss there will be.

In order for emulsion fuel to be handled like normal liquid fuel oil, it must have long-term stability to withstand transportation and storage. Conventionally, there have been many reports on the use of emulsified oils with good fluidity, such as kerosene, heavy oil, B heavy oil, C heavy oil, etc., but the heavy fraction is very high, and either they do not flow or have a centibois or more. There have been few reports of emulsifying ultra-heavy oil with high viscosity and using it as fuel.

The inventors obtained 100 parts of extra-heavy oil (by weight, the same applies hereinafter)
, 30 to 80 parts of water, and Kita 814 to 19, preferably 15 to 19, selected from the group shown in (i) to (vi) below.
They discovered that a 07W type ultra-heavy oil emulsion fuel with low viscosity can be produced by stirring No. 17 nonionic surfactant with a high-shear stirring device such as a line mixer, and completed the present invention.

(i) Alkylene oxide adducts of compounds containing phenolic hydroxyl s, such as phenol, cresol, butylphenol, nonylphenol, dinonylphenol, dodecylphenol, paracumylphenol, and bisphenol.

However, alkylene oxide is ethylene oxide or/
and propylene oxide, butylene oxide, and styrene oxide.

(11) Alkylene oxide adducts of formalin condensates of compounds having phenolic hydroxyl groups such as alkylphenols, phenols, metacresols, styrenated phenols, and benzylated phenols. The average degree of condensation is 1.
2 to 100, preferably 2 to 20, the alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide.

(iii) A polyalkylene oxide adduct of a monovalent aliphatic alcohol and/or aliphatic amine having 2 to 5 carbon atoms. Alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide.

(iv) ethylene oxide and propylene oxide or/
and block or random addition polymers of butylene oxide and styrene oxide.

(v) Glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin,
Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, or these polyhydric alcohols and carbon atoms 8 to 1
Alkylene oxide adduct of ester with fatty acid of No. 8.

Alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide.

(vi) ethylenediamine, tetraethylenediamine,
An alkylene oxide adduct of a polyvalent amine having multiple active hydrogens such as polyethyleneimine (molecular weight 600 to 10,000). Alkylene oxide is ethylene oxide or/
and propylene oxide, butylene oxide, and styrene oxide.

(vii)) 1 mol of liglyceride-type fat and oil, selected from the group consisting of glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycol with a molecular weight of 1000 or less, propylene glycol, and polypropylene glycol with a molecular weight of 1000 or less. A product obtained by adding an alkylene oxide to a mixture of one or more polyhydric alcohols and/or 0.1 to 5 moles of water. Alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide.

Among the nonionic surfactants selected from the group shown in (i) to (vi) above, the surfactant with the structure (vi) particularly shows excellent performance, and the second one is the surfactant with the structure (i) and (iii). showed excellent performance.

Ultra-heavy oil does not flow as it is, or has a viscosity higher than centiboise, so when producing emulsion fuel, it must be heated to a high temperature of at least 70"C to achieve a certain level of fluidity. After that, it is generally made by adding similarly heated water and a surfactant, or by adding heated extra-heavy oil to hot water containing a surfactant.The surfactant is used to make this emulsion fuel. HLB (hydrophilic-lipophilic balance) most suitable for the temperature when
are selected. The HLB of a nonionic surfactant changes depending on the temperature, and as the temperature of the system increases, the HLB decreases. After producing emulsion fuel, generally 50°C
Emulsion fuels are stored and transported at temperatures below: The temperature during storage and transportation is much lower than the temperature during production, and therefore a surfactant with a small IILB must be used. In the case of the same surfactant, the IILB becomes too large (too hydrophilic) and it becomes unsuitable as a surfactant for that system. Therefore, since the emulsified particles aggregate or coalesce, the viscosity of the emulsion fuel increases with time. In the case of nonionic surfactants, the effect of lowering viscosity is smaller than that of anionic surfactants, and
Due to the above-mentioned reasons, the water content in the emulsion fuel needs to be slightly higher since it thickens over time. Ultra-heavy oil emulsion fuel produced using nonionic surfactants alone is not suitable for long-term storage or transportation, but is suitable for short-term storage and transportation. If the super-heavy oil emulsion fuel using the nonionic surfactant of the present invention is produced within a short period of time during combustion in a boiler or the like, for example within one week, it can be used as an excellent fuel with little unburned content.

11 selected from the group shown in (i) to (vi) above
The action of the nonionic surfactants of LB 14 to 19 is to adsorb to the interface of particles of extra-heavy oil, help reduce the size of the particles, and at the same time prevent re-agglomeration of the particles through a protective effect.

HL selected from the group shown in (i) to (vj) above
A mixture of two or more of the nonionic surfactants B14 to B19 may be used.

Since the viscosity of extra-heavy oil is very high, it is generally emulsified at a high temperature of 80° C. or higher to produce emulsion fuel. Higher viscosity requires higher temperatures. The surfactant is water,
Although it may be added to any oil, it is easier to handle when added to water.

As the mechanical means for producing the emulsion fuel, any efficient stirring means may be used, or a combination of two or more methods may be used. For example, line mixers, fletching turbine blades, propeller blades, pull margin blades, paddle blades, etc.

The oils referred to as extra-heavy oils in the present invention include the following oils that do not flow unless heated to high temperatures.

(1) Petroleum-based asphalts and mixtures of their oils.

(2) Various processed products of petroleum-based asphalt, intermediate products thereof,
residues, and oil mixtures thereof.

(3) High pour point oil or crude oil that does not flow at high temperatures.

(4) Petroleum-based tar pitch and its oil mixture.

(5) Bitumens (orinocotar, athabascabitumen).

It is generally said that naphthenic asphalt is easy to emulsify, while asphalt derived from paraffinic base oils or mixed base oils is difficult to emulsify. In addition, naphthenes also sufficiently distill off volatile components, making it difficult to emulsify in asphalt with a high heavy fraction.

Although many recent asphalts have sufficiently distilled volatile components, the asphalt of the present invention is mainly targeted at asphalts for which it is difficult to produce a stable emulsion for a long period of time using conventional methods.

Bitumen such as orinoco tar is extracted by steam injection, and in this process, the above-mentioned (i) to (
vi) Nonionic surfactants having IL814 to IL819 (selected from the group shown in vi) can be used. Further, after extraction, sand and other solid particles may be removed or desalted, and then the above nonionic surfactant having an HLB of 14 to 19 may be added to produce an emulsion fuel.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited to these Examples.

Example 1 Weigh out predetermined amounts of Middle East petroleum-based asphalt (penetration 60-80) or Athabasca bitumen (softening temperature 12.5°C, produced in Canada), water, and various surfactants for a total amount of 300 g. Place in an 800° centrifuge tube and warm to 75°C. After reaching a certain temperature, stir with a TK homomixer (purchased with low viscosity stirring) manufactured by Tokushu Kikako to prepare an emulsion fuel, put it in a constant temperature bath at 60 ° C, and after reaching a certain temperature, reduce the viscosity. It was measured. A portion of the emulsion fuel was kept warm at 50'C, then taken out and the amount passing through a 100 mesh sieve was measured. The viscosity is Vismetronge 5-AI type manufactured by Shibaura System ■, Na2. The amount passing through the sieve was measured using a rotor of 6 Orpm, and the amount passing through the sieve was calculated by placing about 10 g of the sample on a 100 mesh stainless steel sieve with a diameter of 70 mm in an atmosphere of 50° C., and measuring the amount remaining on the sieve after 10 minutes.

The results are shown in Tables 1 and 2.

The comprehensive evaluation was determined based on the results of both the viscosity of the emulsion and the amount of passage through the sieve. Good in the order of ◎>Q>Δ>×.

Table 1 Back 1 continuation Table 2

Claims (1)

[Scope of Claims] 1 100 parts by weight of extra heavy oil, 30 to 80 parts by weight of water, HLB selected from the group shown in (i) to (vii) below (
An ultra-heavy oil emulsion fuel prepared by mixing and emulsifying 0.05 to 5 parts by weight of nonionic surfactants of hydrophilicity and lipophilicity balance) 14 to 19. (i) Alkylene oxide adducts of compounds having phenolic hydroxyl groups such as phenol, cresol, butylphenol, nonylphenol, dinonylphenol, dodecylphenol, paracumylphenol, and bisphenol A. However, alkylene oxide is ethylene oxide or/
and propylene oxide, butylene oxide, and styrene oxide. (ii) Alkylene oxide adducts of formalin condensates of compounds having phenolic hydroxyl groups, such as alkylphenols, phenols, metacresols, styrenated phenols, and benzylated phenols. The average degree of condensation is 1.2 to 100, and the alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, or styrene oxide. (iii) an alkylene oxide adduct of a monohydric aliphatic alcohol and/or aliphatic amine having 2 to 5 carbon atoms; the alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide; (iv) ethylene oxide and propylene oxide or/
and block or random addition polymers of butylene oxide and styrene oxide. (v) Glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin,
Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, or these polyhydric alcohols and carbon atoms 8 to 1
Alkylene oxide adduct of ester with fatty acid of No. 8. Alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide. (vi) ethylenediamine, tetraethylenediamine,
An alkylene oxide adduct of a polyvalent amine having multiple active hydrogens such as polyethyleneimine (molecular weight 600 to 10,000). Alkylene oxide is ethylene oxide or/
and propylene oxide, butylene oxide, and styrene oxide. (vii) 1 mol of triglyceride fat, glycerin, trimethylolpropane, pentaerythritol,
Sorbitol, sucrose, ethylene glycol, molecular weight 10
Alkylene oxide is added to a mixture with 0.1 to 5 moles of water and/or one or more polyhydric alcohols selected from the group consisting of polyethylene glycol having a molecular weight of 00 or less, propylene glycol, and polypropylene glycol having a molecular weight of 1000 or less. Product of addition reaction. Alkylene oxide is ethylene oxide or/and propylene oxide, butylene oxide, styrene oxide. 2. The extra-heavy oil emulsion fuel according to claim 1, wherein the nonionic surfactant is (vii) according to claim 1. 3. The extra-heavy oil emulsion fuel according to claim 1, wherein the nonionic surfactant is (i) according to claim 1. 4. The ultra-heavy oil emulsion fuel according to claim 1, wherein the amount of the nonionic surfactant added is 0.1 to 1 part by weight per 100 parts by weight of the extra-heavy oil. 5. The super heavy oil emulsion fuel according to claim 1, wherein the nonionic surfactant has an HLB of 15 to 17.