JPS60388B2 - Surfactant for emulsion fuel - Google Patents

Description

[Detailed description of the invention] The present invention relates to a surfactant for emulsion fuel.

The purpose of the present invention is to reduce the concentration of nitrogen oxides (N○x) emitted during combustion of fuel oil in boilers, heating furnaces, etc. The present invention relates to a water-in-oil type surfactant for emulsion fuel that can reduce N○× when added together with water.

It is well known that NOx, etc. produced by the combustion of various fuel oils is one of the causes of air pollution.
To solve this problem, N
Numerous studies have been conducted on ways to reduce the amount of ○×.

This method is a method for suppressing the occurrence of N○× and a method for suppressing the occurrence of N○×.
There are two methods for removing x (a method called denitrification). In the former case, methods to suppress the generation of N○× include improving the structure of the burner and combustion chamber, improving the combustor itself such as circulating combustion exhaust gas, and changing the type of fuel oil. There is also a method of improving the fuel, such as adding water or other additives to fuel oil in advance or during combustion. The present invention relates to a method for suppressing the generation of N0x. N○x is generally NO and N02
It is said that approximately 95% of the NOx in the boiler exhaust gas is NO. N0 in exhaust gas
x is N○× (fuel N0×) generated by nitrogen components (pyridine, pyrrole, quinoline, etc.) in fuel oil.
It can be divided into two types: N○× generated when N2 in the air reacts with 02 during combustion (called thennaIN○×). fuelN○× and therma
Both lN○× increase at high temperatures, but especially th
It is known that ermal N○x increases rapidly in a temperature range of 1500 to 1600 qo or higher. It is said that the following three principles are responsible for suppressing the amount of N○x produced by a water-in-oil type emulsion fuel in which water is emulsified in fuel oil using a surfactant.

(i) The generation of N○× is greatly influenced by the combustion temperature, and can be suppressed by lowering the combustion temperature.

In emulsion fuel, the latent heat of vaporization of water in the fuel lowers the combustion temperature and suppresses the generation of NOx. (ii)
Due to rapid volumetric expansion due to evaporation of water droplets dispersed during combustion, fuel particles become more atomized. Therefore, the contact area between oil droplets and air increases, and the air/fuel oil (kerosene or heavy oil) ratio can be reduced (low excess air combustion is possible).
can suppress the occurrence of In general, as the air/fuel oil ratio approaches 1.0, the concentration of excess N2 and 02 during combustion becomes diluted, so the rate of N0x production (especially the
) is delayed, and as a result, the occurrence of N○× is suppressed.

(iiD Water is uniformly dispersed (emulsified) in the fuel, but the latent heat of water during evaporation lowers the temperature of the flame surface and prevents local high temperatures from occurring.

In particular, as mentioned in (ii) above, in the case of emulsion fuel, the fuel particles are atomized, thereby preventing local high temperatures from occurring. In order to prevent local high temperatures from occurring, the generation of N○× is suppressed. When water is added to fuel oil, the resulting fuel includes, in addition to emulsion fuel, fuel in which water vapor is injected into fuel oil, or fuel in which water is injected into combustion oil. However, with these fuels (or combustion methods), the water droplets are not uniformly dispersed (emulsified) in the fuel oil, or the particle size of the water droplets is large.
The effect of suppressing x generation is considerably smaller than that of emulsion fuel, and there are also problems in terms of combustion stability. in general,
When preparing emulsion fuels, both the ease of emulsification and the stability of the resulting emulsion are considered.

Moreover, in the case of emulsion fuel, in most cases it is burned immediately after the emulsion is prepared, so ease of emulsion formation is important, and the stability of the prepared emulsion is 5.
~10 minutes, or at most 3 minutes, is enough. ``This level of stability is sufficient for normal use.Generally, when preparing an emulsion, a surfactant (active agent)
is used in an amount of LI~10% based on the entire system (oil and water).

A suitable commercially available activator such as polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan laurate, etc.
Even if 10% (based on the whole system) is used, when emulsion fuel prepared from fuel oil and water is used as boiler fuel, the generated N○× concentration is significantly lower than when fuel oil itself is used as fuel. However, emulsion fuel prepared using such a large amount of activator is expensive and has problems from an economical point of view, making it difficult to put it into practical use. The present inventors used a specific surfactant composition (active agent) for kerosene at a rate of 0.05 to 0 for the entire system (10% fuel oil).

5% "preferably 0.2-0.4%, for heavy oil 0.01-0.5% for the whole system, preferably 0.05-0
．． It has been found that when the emulsion fuel prepared in addition to the NOII concentration is combusted by 3%, the NOII concentration generated decreases by 4.

That is, 0.1 to 5 moles of water or polyhydric alcohol, preferably 0.2 moles per mole of L-triglyceride oil or fat.
A mixture of 2.0 mol to 2.0 mol of ethylene oxide is used as a raw material, and 0.5 mol to 40 mol, preferably 1.0 mol to 20 mol, of ethylene oxide is added to this, per 1 mol of the total polyhydric alcohol in the raw material. The obtained surfactant composition is added to the entire system (100% of fuel oil) in the amount mentioned above to prepare emulsion fuel. It was found that by using each of the activators alone, the amount of N○× generated was significantly suppressed compared to combustion of an emulsion fuel prepared by adding the same amount of the activator of the present invention. By using the activator of the invention, an emulsion can be prepared in a much smaller amount than when using a general activator, so there is an advantage that the N○× suppression effect can be increased even with a small amount of activator used. The activator of the invention is a triglyceride-based fat such as 0.1 to 5 moles of a polyhydric alcohol per mole of animal oil or fish oil such as coconut oil, balm oil, beef tallow, or whale oil, or a mixture thereof. It is characterized in that it is produced using a mixture of 0.0 mol, preferably 0.2 mol to 2.0 mol as a raw material, and 0.45 mol is added to the above raw material per 1 mol of the total polyhydric alcohol in the raw material. mole to 4
It is a surfactant composition obtained by adding 0 mol, preferably 1.0 mol to 20 mol of ethylene oxide by a known general method. The above-mentioned ethylene oxide addition reaction in the present invention uses a catalyst of 0.1 to 5% by weight of the total weight of alcohol and ester in the raw materials, and a reaction temperature of 100 to 200q.
o, The reaction pressure may be carried out at normal pressure or below 5k9/g.

As a catalyst, an alkali metal, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal alcoholate, an alkali metal organic acid salt, etc. are used. The total polyhydric alcohol in the raw material is the sum of the glycerin in the fat and oil and the added polyhydric alcohol, and the polyhydric alcohols include, for example, glycerin, trimethylolpropane, bentaerythritol, sorbitol, futo sugar, Ethylene glycol "Polyethylene glycol (molecular weight 1000
(below), propylene glycol, polypropylene glycol (molecular weight 1000 or less), etc. In the present invention, a mixture formed by mixing 0.1 to 5 moles of water to 1 mole of oil or fat can be used as the above raw material, and the present invention is a product obtained by subjecting the raw material to an addition reaction with ethylene oxide. The present invention provides a surfactant comprising: The main components of the active agent of the present invention are ethylene oxide adducts such as transesterification products and raw materials, and contain soap and other by-products.

The transesterification products include monoglycerides, diglycerides, triglycerides, fatty acids and esters of polyhydric alcohols. In this case, oil and fat acids refer to the fatty acids that make up oils and fats. When preparing emulsion fuel using the surfactant of the present invention, any type of activator may be used as long as it has an excellent cross-country effect; the better the activator, the more effective the activator will be with a small amount. be.

For example, a propeller type flying machine, a mixer, a homogenizer, etc. are used as the crossing machine. Next, examples of the present invention will be shown.

Example 1 Three parts were prepared: 100 parts (wt%) of heavy oil of Type 1 standard specified in the Japanese Industrial Standards (A heavy oil, N: 0.08%), 2 parts (wt%) of water, and a predetermined amount of activator. An emulsion (W/O type) was prepared using a line mixer at room temperature using an emulsion, and the emulsion was used as fuel for a boiler.

N0x amount and 0 in boiler exhaust gas using this fuel
In measuring the two amounts, a Yanagimoto exhaust gas nitrogen oxide concentration measuring device (ECL-77 model) and a Yanagimoto exhaust gas oxygen measuring device (EMG-77 model) manufactured by Yanagimoto Seisakusho were used, respectively. N○×
The amount was evaluated using a 4%02 conversion value. Comparing the N○× amount (value) of emulsion fuel combustion and heavy oil pre-burning when the boiler load and air/heavy oil ratio are almost the same, how much N○ It was calculated whether the x amount decreased. Table 1 shows the emulsion particle size, emulsification state, reduction rate of N○× amount, amount of activator used to prepare emulsion fuel, etc. of emulsion fuel prepared using the present invention sample and comparative sample as activator. show. Table 1 Note 1 Average molecular weight of beef tallow 861) and glycerin 92 (beef tallow/glycerin = 1/1 (molar ratio))
A reaction product obtained by reacting 132 ml of ethylene oxide at 140 to 160° C. under pressure of 2 to 3 k9/gauge pressure using 2 minutes of caustic soda as a catalyst.

The analytical values of the reaction product are: acid value 0.05, hydroxyl dynamic surface 190
．． 9, saponification value 152-0, iodine value 37.6, moisture 0.0
45*, soap 1.5%. Note 2 Beef tallow: 861 mm and glycerin: 27.6 mm (beef tallow/glycerin (molar ratio): 1
/0.3) in an autoclave with 2 and 2 to 3
A reaction product obtained by reacting 440 ml of ethylene oxide under pressure with a gauge pressure of k9/. The analytical values of the reaction product are saddle value 0.04, hydroxyl value 70.4, and saponification value 124.5.
, iodine value 30.0, moisture 0.028 grand, soap 0.99%
It is. *1 The average particle size of the emulsified water droplets was calculated by microscopic photograph observation and divided into 5 grades from 5 to 1. 5: Particle size 1-5, 4: Particle size 5-10, 3: Particle size 10
~20 pay, 2: particle size 20-50 pay, 1: particle size 50 pay or more.

*2 The degree of whiteness of the emulsion was observed with the naked eye and evaluated on a scale of 4 to 1. The larger the number, the better the emulsification state. 1 is the same color as fuel oil.

*3 Air/fuel oil 31.2, boiler load is N for fuel oil only and emulsion fuel combustion under almost the same conditions.
○× Generation weight (4%02 equivalent value) was compared to determine the reduction rate for fuel oil only.

Example 2 10 groups (weight %) of heavy oil type 3 type 2 standard stipulated by Japanese Industrial Standards (C heavy oil, N: 0.21%)
An emulsion fuel was prepared in the same manner as in Example 1 using 20 parts (wt%) of water and a predetermined amount of activator at a temperature of 80-90 pm, and used as fuel for a boiler.

The amount of N○x and the amount of Q in the boiler exhaust gas were measured using the same method as in Example 1, and how much N○x compared to C heavy oil and bran.
We calculated whether the amount would decrease. The results are shown in Table 2.
Tables *1, *2, and *3 are all the same as in Example 1.

Example 3 Example at room temperature using kerosene (N; 0.015%, manufactured by Cygnus Oil Co., Ltd.) 8 parts (weight %), water 2 parts (weight %), and a predetermined amount of activator. Emulsion fuel was prepared in the same manner as in Example 1 and used as boiler fuel.

In the same manner as in Example 1, the amount of N0x and the amount of 02 in the boiler exhaust gas was measured, and the amount of N
It was calculated whether the amount of ○× was reduced. Table 3 shows the results.
Table 3 *1, *2, and *3 are all the same as in Example 1.

Example 4 Three types of fuel oil: A heavy oil, C heavy oil, and kerosene
For 100 parts (weight%) of this fuel oil, 5
Emulsion fuels were prepared and used as boiler fuels in the same manner as Examples 1-3 with addition of ~30% water and activator.

The amount of N0x and the amount of 02 in the boiler exhaust gas were measured in the same manner as in Example 1, and the extent to which the amount of N○x was reduced was calculated. The activator was added at 0.2% to the total system. The results are shown in Table 4. Table 4 *1, *2. *3 is the same as in Example 1.

Claims (1)

[Scope of Claims] 1. From the group consisting of 1 mol of triglyceride oil and fat, 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 For a mixture of 0.1 to 5 moles of one or more selected polyhydric alcohols or water, 0.1 to 1 mole of the total polyhydric alcohol in the mixture including glycerin in the oil finger. A water-in-oil emulsion fuel surfactant prepared from water and a fuel oil consisting of a product obtained by addition reaction of 5 to 40 moles of ethylene oxide. 2. The surfactant according to claim 1, wherein the addition reaction is carried out at a temperature of 100 to 200°C in the presence of a catalyst. 3. The surfactant according to claim 2, wherein the catalyst is an alkali metal, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal alcoholate, or an alkali metal organic acid salt.