JPH115987A - Emulsifier for use in treatment of heavy oil and process for treating heavy oil by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To disperse water molecules uniformly in a heavy oil by adding under agitation an oil treating emulsifier containing caustic soda, calcium chloride and water in a specified ratios to a heavy oil mixed with water. SOLUTION: 100 l of water is mixed with 5-50 kg of caustic soda, 5-50 kg of calcium chloride and optionally a suitable amount of calcium carbonate, ammonia or the like to prepare an oil treating emulsifier. Next, a heavy oil such as fuel oil B, fuel oil C, crude oil, oil sand or waste oil is mixed with water in an oil/water weight ratio of 95/5 to 30/70, and the water-containing oil is mixed with the emulsifier in a water-containing oil/emulsifier weight ratio of 1/0.001 to 1/0.1 to obtain a water-containing oil emulsion. Because this emulsion can be perfectly combusted, it can exhibit improved efficiency of combustion, effects cost reduction and is reduced in the formation of pollutants such as sulfur oxides, nitrogen oxides, carbon monoxide, soot and dust.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsifier for treating a heavy oil for forming a water-in-oil type emulsion in which water particles are dispersed in a heavy oil such as heavy oil C or waste oil, and to use the same. Heavy oil processing method.

[0002]

2. Description of the Related Art Heavy oil is produced in the final stage of a petroleum refining process. Generally, heavy oil A (one kind), heavy oil B (two kinds), heavy oil C (3) is used in view of viscosity, pour point and residual carbon content.
Species). The heavy oil is high in calories (approximately 10,000 kcal / kg), relatively inexpensive, and easy to handle, so that, for example, fuels for internal combustion engines such as diesel engines, boilers, various furnaces, etc. The heavy oil consumption accounts for about 70-80% of all petroleum products used in Japan in various industries including large-scale combustion facilities.

The above-mentioned heavy oils, particularly high-viscosity heavy oils such as B-fuel oil and C-fuel oil, generate a large amount of pollutants such as sulfur oxides, nitrogen oxides, carbon monoxide, soot and dust during combustion, and these pollutants Since it pollutes the environment and poses a serious threat to ecosystems, it is necessary to take effective measures to prevent the above pollutants from being polluted. For example, in Japan, various standards regarding the maximum emission of pollutants are set for combustion facilities using heavy oil. as a result,
Generally, in the industry that uses heavy oil as a fuel, large-scale capital investment is made for heavy oil fuel facilities and advanced pollution control equipment is provided.

[0004]

The above pollution control equipment is
In particular, when a low-grade oil such as heavy fuel oil C is used, there is a tendency to be more complicated and expensive. However, C heavy oil is A
Despite emitting more pollutants than heavy oil and heavy oil B, many companies use heavy oil C because it is relatively inexpensive. In this way, companies that use heavy fuel oil C must invest a great deal in pollution control equipment, or use heavy fuel oil A and heavy fuel oil B in heavy fuel oil C in order to reduce emissions of pollutants. It is necessary to mix them, and in any case, the cost of using heavy fuel oil C must be increased.

[0005] When the C heavy oil is actually used as fuel, the C heavy oil is generally atomized and burned by a heavy oil burning burner. At this time, the combustion efficiency of C heavy oil is improved by adjusting the ratio of air and C heavy oil. However, since the operation of adjusting the ratio of air and C heavy oil increases the particle diameter of heavy oil particles, Fuel C burns incompletely, thereby resulting in the emission of large amounts of pollutants. Therefore, it is desired to completely burn C heavy oil without subjecting C heavy oil to any treatment and discharging a large amount of pollutants.

On the other hand, besides the above-mentioned heavy oil, waste oil is one of those for which the measures for its treatment are difficult. For example, in a facility where waste oil is generated in a factory or the like, the waste oil is separated and processed into a reusable portion, a non-reusable portion, water, and the like. In Japan, non-reusable parts are treated by burning them in an incinerator. At that time, the pollutants emitted by the Japanese government are, like the above-mentioned heavy oil C, discharged. Must be controlled below a strict standard value. Further, the water generated by the above separation generally does not contain waste oil, but is contaminated by the waste oil and generates an unpleasant odor. Therefore, the separated water must be filtered and refined in advance before discharging to completely remove the oil component. As a result, in addition to the waste oil treatment separation / combustion equipment, the water filtration Requires refining equipment. Therefore, it is not necessary to separate the waste oil into a reusable portion, a non-reusable portion, and water as described above, and the waste oil does not need to be treated. It is desired to perform the combustion treatment in the state described above.

[0007] The present invention has been made in view of the above circumstances, and an emulsifier for treating heavy oil capable of uniformly dispersing water particles in heavy oil, and a heavy oil treatment emulsifier using the same. Its purpose is to provide a method.

[0008]

In order to achieve the above object, the present invention provides an emulsifier for dispersing water particles in heavy oil to form a water-in-oil type emulsion, comprising: A first gist is a heavy oil processing emulsifier containing calcium chloride and water as main components.

The present invention also provides a process for preparing an oil treatment emulsifier by mixing caustic soda, calcium chloride and water, a process for adding and mixing water to heavy oil to be treated, And a step of adding the above-mentioned heavy oil processing emulsifier to the mixed heavy oil and mixing.

The inventor studied various treatment methods and conducted a series of studies in order to efficiently burn heavy oil such as B heavy oil, C heavy oil, and waste oil. In the course of the research, for example, if the water in the waste oil exists as it is, the water inhibits the combustion, and consequently, using the waste oil as a dispersion medium, disperse the water particles in the dispersion medium. I wondered if I could do that. In other words, it was recalled that a water-in-oil type emulsion was formed, water particles exploded at the time of combustion, and this explosion was used to make the waste oil particles fine and completely burn. Based on this idea, as a result of further research to obtain a completely new emulsifier capable of forming a water-in-oil emulsion, a new heavy oil containing caustic soda, calcium chloride and water as main components was obtained. We have found a processing emulsifier and arrived at the present invention. A so-called water-in-oil type emulsion in which water particles are uniformly dispersed in a dispersion medium composed of the heavy oil by adding and mixing the emulsifier to the heavy oil mixed with water. Was formed. That is, as in the conventional case, the state in which the oil particles are dispersed in the aqueous medium is a phase completely opposite to the state in which the water particles are dispersed in the dispersion medium made of heavy oil, When this water-in-oil emulsion is burned, as described above, the water particles explode during the combustion and the heavy oil particles become fine, and as a result, the central portion of the heavy oil is removed as in the conventional case. Is completely burned without remaining.

The mixing ratio of caustic soda (a), calcium chloride (b), and water (c), which are the main components of the emulsifier, is determined based on the ratio of caustic soda (a) to 100 liters of water (c). 5 to 50 kg, 5 calcium chloride (b)
It is preferable to set the range to 50 kg.

When a water-containing oily emulsion solution is prepared using the above emulsifier, the mixing ratio (X: Y) of the water-containing oil (X) obtained by mixing water with the oil and the oil treatment emulsifier (Y) is used.
X: Y = 1: 0.002 to 1: 0.00 by weight ratio
It is preferable to set the ratio to 3 from the viewpoint of producing the water-in-oil emulsion.

[0013]

Next, an embodiment of the present invention will be described.

The heavy oil processing emulsifier of the present invention (hereinafter abbreviated as "emulsifier") is a water-containing oily emulsion which is an emulsified oil containing a dispersion medium composed of oil and water uniformly dispersed in the dispersion medium. An emulsifier for forming a solution containing caustic soda, calcium chloride and water as main components. Note that, in the present invention, the phrase “constituting a main component” is intended to include the case where only the main component is included.

The heavy oil to be treated using the emulsifier of the present invention is not particularly limited. For example, petroleum heavy hydrocarbon oils, in particular, heavy B oil, heavy C oil, crude oil and oil Sandwich and the like can be mentioned, but in the present invention, in addition to the above, waste oil generated in various industrial facilities is also included as a treatment target.

The emulsifier of the present invention is obtained using caustic soda, calcium chloride and water.

The caustic soda and calcium chloride are not particularly limited, and conventionally known ones are used.

The water is not particularly limited, and ordinary water including tap water or seawater is used.

In the emulsifier of the present invention, the mixing ratio of the above-mentioned caustic soda (a), calcium chloride (b) and water (c) is such that 5 to 50 kg of caustic soda (a) is added to 100 liters of water (c). 5-5 calcium chloride (b)
It is preferably set to a range of 0 kg, more preferably 15 to 25 kg of caustic soda (a) and 15 to 25 k of calcium chloride (b) per 100 liters of water (c).
g, particularly preferably 25 kg of caustic soda (a) and 25 kg of calcium chloride (b) per 100 liters of water (c). That is, in the mixing ratio of the above three, if the mixing amount of water is lower than the above range and is too small, the viscosity of the liquid becomes high and it becomes difficult to flow, and it tends to be difficult to measure and inject. If the mixing amount exceeds the above range and is too large, a large amount of liquid must be added,
This is because there is a tendency for transportation and facilities to take a lot of costs.

The emulsifier of the present invention may optionally contain additives such as calcium carbonate and ammonia in addition to the above-mentioned main components of the above-mentioned caustic soda, calcium chloride and water. The amount of the additive is
There is no particular limitation as long as the action of the emulsifier of the present invention is not impaired, and it is appropriately set.

The emulsifier of the present invention can be obtained, for example, by adding and mixing the above-mentioned caustic soda, calcium chloride and water, and, if necessary, various additives in a desired mixing ratio.

At the time of the mixing, the mixing is not particularly limited, and various conventionally known mixing apparatuses are used.

The treatment of heavy oil using the emulsifier of the present invention comprises:
For example, this is performed as follows. That is, first,
As described above, an emulsifier is prepared by mixing caustic soda, calcium chloride, and water, which are the main components, and other additives as necessary. On the other hand, apart from this,
Water is added to and mixed with the heavy oil to be treated. Next,
The emulsifier is added to and mixed with the water-mixed heavy oil obtained by mixing water with the heavy oil. In this way, the heavy oil is processed to produce a water-in-oil type emulsion.

The mixing conditions for adding and mixing the emulsifier to the water-mixed heavy oil obtained by mixing the heavy oil with water are not particularly limited to the temperature and the like. And can be easily mixed.

The water-in-oil emulsion produced above is in a state in which oil serves as a dispersion medium, and water is dispersed in the oil dispersion medium in a granular state. Moreover, the viscosity is higher than that of the heavy oil to be treated. Due to this high viscosity, the water and heavy oil do not separate due to the difference in specific gravity, and as a result, water particles in a form in which water particles are dispersed in a dispersion medium made of heavy oil even after being left for a long period of time. -An in-oil emulsion is maintained.

In the production of the above-mentioned hydrated oily emulsion solution, the mixing ratio (d: e) of the oil (d) to be treated and the water (e) when they are mixed is represented by weight ratio:
It is preferable to set e = 95: 5 to 30:70. Particularly preferred is d: e = 70: 30 to 75:25 from the viewpoint of solution cost, running cost cost, pollution numerical value, etc. with respect to cost reduction of fuel cost.

Further, when the oil-processing emulsifier (Y) is added to and mixed with the water-containing oil (X) in which water is mixed with the oil, the mixing ratio (X: Y) of the two is expressed by weight ratio: X: Y =
It is preferable to set the ratio to 1: 0.001 to 1: 0.1. Particularly preferably, from the viewpoint of fluidity, ease of measurement, equipment, and transportation cost, X: Y = 1: 0.002-
1: 0.003 ratio.

The hydrated oily emulsion solution thus produced is in a completely opposite phase to the state in which the oil is dispersed in the aqueous medium as in the prior art, that is, as described above, the water is contained in the oil dispersion medium. Because the particles are in a dispersed state, for example,
When the aqueous oily emulsion solution is burned, it is completely burned, so that the combustion efficiency is improved and the cost is reduced. As a result, sulfur oxides, nitrogen oxides, carbon monoxide,
Generation of pollutants such as soot and dust is suppressed, which is a very effective means for environmental pollution and the like.

Next, examples will be described together with comparative examples.

First, an emulsifier was prepared prior to the examples. [Preparation of emulsifier] Each component shown in Table 1 below was blended and mixed at a ratio shown in the table to prepare an emulsifier.

[0031]

[Table 1]

[0032]

Examples 1 to 8, Comparative Example Each of the emulsifiers A to C obtained as described above and a conventional emulsifier (normal surfactant)
Was used to treat heavy fuel oil C as follows. The analysis results of C heavy oil to be treated are shown below.

[Results of Analysis of Fuel Oil C] Moisture 0.22% (according to JIS K-2275) Ash 0.03% (according to JIS K-2272) Sulfur 2.30% (according to JIS K-2541) 86.44% carbon (according to JIS M-8813) Hydrogen 10.38% (according to JIS M-8813) Nitrogen 0.22% (according to JIS K-2609) Total calorific value 10,220 kcal / kg (JIS K Kinematic viscosity 50 ° C 183.5 cSt (based on JIS K-2283) Kinematic viscosity 80 ° C 42.47 cSt (based on JIS K-2283)

[Method of treating heavy fuel oil C] Heavy fuel oil C, water and an emulsifier were blended in the ratios shown in Table 2 below. That is, first, water at 80 ° C. was added to heavy fuel oil C, and then an emulsifier was added and mixed and adjusted by a mixer.

[0035]

[Table 2]

The water-in-oil emulsions and dispersions obtained as described above were subjected to an analytical test for Examples 1-3. The results are shown below. FIG. 1 is a photomicrograph of the water-in-oil emulsion obtained in Example 1.
Shown in From this micrograph, heavy fuel oil C was used as the dispersion medium,
It was confirmed that the water particles were uniformly dispersed in the dispersion medium. In addition, all the other examples were confirmed with a microscope, but as in Example 1, it was confirmed that heavy oil C was used as the dispersion medium and that the water particles were uniformly dispersed in the dispersion medium. In addition, all of the examples had higher viscosities than heavy oil C. On the other hand, a micrograph of the dispersion obtained in the comparative example is shown in FIG. From this micrograph, it was confirmed that the dispersion of the comparative example was a so-called oil-in-water emulsion in which particles of heavy fuel oil C were dispersed in an aqueous medium.

[Analysis Results of Example 1] Moisture 16.76% (according to JIS K-2275) Ash 0.08% (according to JIS K-2272) Sulfur 1.75% (according to JIS K-2541) ) Carbon 69.68% (according to JIS M-8813) Hydrogen 10.39% (according to JIS M-813) Nitrogen 0.19% (according to JIS K-2609) Total calorific value 8,240 kcal / kg (JIS Kinematic viscosity 50 ° C 352.4 cSt (based on JIS K-2283) Kinematic viscosity 80 ° C 72.96 cSt (based on JIS K-2283)

[Analysis Results of Example 2] Water 29.45% (according to JIS K-2275) Ash 0.14% (according to JIS K-2272) Sulfur 1.46% (according to JIS K-2541) ) Carbon 59.98% (according to JIS M-813) Hydrogen 10.61% (according to JIS M-813) Nitrogen 0.12% (according to JIS K-2609) Total heat generation 7,050 kcal / kg (JIS) Kinematic viscosity 50 ° C 473.7 cSt (based on JIS K-2283) Kinematic viscosity 80 ° C 112.2 cSt (based on JIS K-2283)

[Analysis Results of Example 3] Moisture 47.99% (according to JIS K-2275) Ash 0.10% (according to JIS K-2272) Sulfur 1.00% (according to JIS K-2541) ) Carbon 41.09% (according to JIS M-8813) Hydrogen 10.61% (according to JIS M-8813) Nitrogen 0.07% (according to JIS K-2609) Total heat generation 4,770 kcal / kg (JIS) Kinematic viscosity 50 ° C 1394 cSt (based on JIS K-2283) Kinematic viscosity 80 ° C 336.5cSt (based on JIS K-2283)

On the other hand, the water-in-oil type emulsion (Example product) and the dispersion (Comparative example product) obtained as described above were allowed to stand at 25 ° C. for 7 days, and then visually inspected. Was observed. The results are shown in Table 3 below.

[0041]

[Table 3] *: Water and C heavy oil were separated.

[0042]

As described above, the present invention provides an emulsifier for forming a water-in-oil type emulsion comprising water particles dispersed in heavy oil, comprising caustic soda, calcium chloride and water as main components. It is. Then, by adding the above emulsifier to water-mixed heavy oil and mixing, a water-in-oil emulsion in which water particles are dispersed in a dispersion medium composed of the heavy oil is easily prepared. can do. The water-in-oil emulsion obtained by treating heavy oil in this way has a higher viscosity than the heavy oil to be treated, and does not cause separation due to the difference in specific gravity between water and heavy oil. A water-in-oil type emulsion in which water particles are dispersed in a dispersion medium made of heavy oil is maintained even after being left for a long time,
Storage becomes possible. When the water-in-oil emulsion is burned, the water particles dispersed in the heavy oil explode and the heavy oil particles become finer. Completely combusted without remaining. Therefore, it is not necessary to make a large-scale capital investment for treating pollutants generated by incomplete combustion of heavy oil as in the conventional case. For example, the cost of using heavy fuel oil C or treating waste oil is greatly reduced. Is realized.

The main components of the emulsifier of the present invention are sodium hydroxide (a), calcium chloride (b) and water (c).
The mixing ratio is as follows: 100 liters of water (c), 5 to 50 kg of caustic soda (a), calcium chloride (b)
Is preferably set in the range of 5 to 50 kg.

When a water-in-oil type emulsion is prepared using the above-mentioned emulsifier, the mixing ratio (X: X) of the water-containing oil (X) obtained by mixing water with the oil and the oil-processing emulsifier (Y) is used. Y) is a weight ratio, X: Y = 1: 0.002.
It is preferable to set the ratio to １ ： 1: 0.003 from the viewpoint of producing the water-in-oil type emulsion.

[Brief description of the drawings]

FIG. 1 is a micrograph (magnification: × 170) showing the state of a water-in-oil emulsion (Example 1 product) treated with the emulsifier of the present invention.

FIG. 2 is a photomicrograph (magnification: × 170) showing the state of an oil-in-water emulsion (comparative product) treated with a conventional emulsifier.

Claims (9)

[Claims] 1. An emulsifier for dispersing water particles in heavy oil to form a water-in-oil type emulsion, characterized by comprising caustic soda, calcium chloride and water as main components. Emulsifier for treating high quality oil. 2. The mixing ratio of the above-mentioned caustic soda (a), calcium chloride (b) and water (c) is such that 5 to 50 kg of caustic soda (a), calcium chloride (b) 2) The emulsifier for treating heavy oil according to claim 1, wherein the content of the emulsifier is set in the range of 5 to 50 kg. 3. The heavy oil processing emulsifier according to claim 1, wherein the heavy oil is heavy B oil, heavy C oil or waste oil. 4. A step of preparing an emulsifier for oil treatment by mixing caustic soda, calcium chloride, and water; a mixing step of adding and mixing water to heavy oil to be treated; A step of adding and mixing the heavy oil processing emulsifier to the heavy oil. 5. The mixing ratio of the above-mentioned caustic soda (a), calcium chloride (b) and water (c) is such that 5 to 50 kg of caustic soda (a) and calcium chloride (b) are added to 100 liters of water (c). 5) The heavy oil treatment method according to claim 4, wherein (5) is set in a range of 5 to 50 kg. 6. The heavy oil to be treated is B-heavy oil,
The heavy oil processing method according to claim 4 or 5, wherein the method is heavy oil C or waste oil. 7. The mixing ratio (d: e) of the heavy oil (d) and water (e) to be treated is expressed by weight ratio d: e =
A ratio of 95: 5 to 30:70 is set.
The method for treating heavy oil according to any one of claims 6 to 6. 8. The mixing ratio (d: e) of the heavy oil (d) and water (e) to be treated is expressed by weight ratio, d: e =
The heavy oil treatment method according to any one of claims 4 to 6, wherein the ratio is set to 70:30 to 75:25. 9. The mixing ratio (X: Y) of the heavy oil (X) in which the water is mixed and the heavy oil treating emulsifier (Y) is X: Y = 1: 0. The heavy oil treatment method according to any one of claims 4 to 9, wherein the ratio is set to 002 to 1: 0.003.