JPH09137177A - Emulsion thermal modification method - Google Patents

Abstract

(57) Abstract: The heat of an emulsion for modifying an oil-in-water emulsion of a tar-like substance or a heavy oil to remove water and alkali metals or alkaline earth metals contained in the emulsion as much as possible. A reforming method is provided. SOLUTION: A tar-like substance or heavy oil is made into an oil-in-water emulsion, sulfuric acid is added, and a temperature at which a density difference between separated water and heavy oil becomes 0.007 or more and a saturated vapor pressure at that temperature. After standing still under the above pressure, the emulsion is separated into an oil phase and an aqueous alkali or alkaline earth metal sulfate solution, and the water and alkali or alkaline earth metal salt contained in the emulsion are separated into the tar-like substance or the heavy substance. Remove from oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for thermally reforming a heavy oil-water emulsion, and more specifically, to the water and alkali contained in the emulsion by thermally reforming the emulsion. The present invention relates to a method for removing metal salts, alkaline earth metal salts and the like.

[0002]

2. Description of the Related Art When industrially using tar-like substances such as asphalt, coal tar pitch, bitumen or heavy oil, in addition to removing contaminants, it also removes contaminating metal salts. Therefore, various removing means have been proposed conventionally.

For example, the method disclosed in Japanese Patent Application Laid-Open No. 7-34072 discloses a method in which heavy oil is added to acidic water having a pH of 2.5 to 6.5 in a kneader or other high-shear kneading apparatus to obtain high shear. By kneading in a state of spinnability under force, the metal, oxide, and nitrogen components in heavy oil are transferred to acidic water and removed. Orimuljeon (Orinocotal water-in-oil type) An example using an emulsion is shown.

Further, the method disclosed in JP-A-60-106883 relates to a method for removing salt in heavy oil, which comprises adding water to a mixed oil obtained by adding light oil to heavy hydrocarbon oil. Is added by a separator (for example, an electric desalination tank),
The salt-containing water is separated and removed. In addition, Japanese Unexamined Patent Publication No.
The method disclosed in Japanese Patent No. 5-12200 discloses a heavy residual oil,
Asphaltenta tar and the like are solvent-extracted with butyl alcohol / ketone or the like for purification to promote phase separation and removal of impurities.

In the method disclosed in Japanese Patent Publication No. 56-54036, a salt-containing tar-based absorbing oil obtained in a coke oven gas refining process is added with an emulsifying agent to contain an oil phase and water-soluble salts. It is separated into an aqueous phase to continuously and efficiently separate and remove salts from the absorbed oil.

[0006]

By the way, the above-mentioned orinoco tar is a natural asphalt of ultra-heavy oil (hereinafter referred to as orinoco tar) produced in the northern part of the Orinoco River basin of Venezuela, South America, and its enormous reserves have been confirmed. . This orinocotar solidifies at room temperature (however, at 150 ° C., the viscosity drops to 40 cSt and it can be transported), which is difficult to handle. Therefore, the Venezuelan Petroleum Corporation sells as an oil-in-water emulsion (trade name: Orimuljeon) for the purpose of fuel for boilers, and even in Japan, the annual consumption as fuel for boiler power generation exceeds 1 million tons. Therefore, it is considered that the price and supply of all fossil fuels can compete with each other in the long term.

By the way, in Orinoco tar, 400 to 5
It contains 00 ppm of vanadium. This vanadium causes high temperature corrosion due to vanadium attack on the boiler tube when burning it in the boiler,
Since it can be suppressed by adding magnesium salt,
Magnesium salt is added and the standard composition shown in Table 1 is shipped.

[0008]

[Table 1] However, the analysis values of Mg, V, and Na shown in Table 1 are values obtained by elemental analysis. By the way, orinoco tar has various characteristics that can sufficiently oppose C heavy oil, and can be used as fuel for diesel engines for power generation.
Based on the published data, Table 2 shows the characteristics of orinocotar as a fuel in comparison with C heavy oil.

[0009]

[Table 2] However, when Orimulsion is used as a fuel for a diesel engine, there is a problem in that the magnesium salt is precipitated by the combustion of orinocotar, is taken into the lubricating oil, and wears the cylinder wall. Therefore,
In order to use orinocotar as a fuel for diesel engines, magnesium salt is added from orinocotar as a countermeasure against vanadium attack, and once processed as an emulsion (orimulsion) to facilitate handling such as transportation, it is processed again. However, it is necessary to remove magnesium and water.

However, according to the method disclosed in the above publication, it is not possible to efficiently remove Mg and water in orimulsion at a high removal rate, and it is recognized that it is necessary to establish a more effective removal method. The present invention removes water, an alkali metal and an alkaline earth metal contained in an oil-in-water emulsion of a tar-like substance or a heavy oil (hereinafter referred to as a tar-like substance) containing an ultra-heavy oil such as orinocotar, and An object of the present invention is to provide a method for thermally reforming an emulsion, which is a method for recovering tar-like substances.

[0011]

In order to solve the above-mentioned problems, the method for heat-reforming an emulsion of the present invention comprises a water content and an alkali or alkaline earth contained in an oil-in-water emulsion of a tar-like substance or a heavy oil. A method for removing metal salts, which comprises adding sulfuric acid to the emulsion, and allowing the emulsion to stand at a temperature at which a difference in density between separated water and heavy oil is 0.007 or more and at a saturated vapor pressure at that temperature. Then, oil-water separation is performed, and the separated oil phase is taken out.

Examples of the tar-like substance or heavy oil include C
Examples include heavy oil, asphalt, orinoco tar, and tar sands. The means for converting the tar-like substance into an oil-in-water emulsion is not particularly limited, and conventionally used means can be used. The sulfuric acid is not particularly limited, but it is economically preferable to use industrially supplied 98% concentrated sulfuric acid.

The alkali metal and alkaline earth metal to be removed in the present invention include those artificially added such as magnesium in orimulsion. When the oil-water separation occurs, the oil phase is a water-in-oil emulsion, and for orinocotar, the relationship between the density of the oil phase and the water phase and the temperature has the relationship shown in FIG. That is, the relationship between the density of each of the modified orinocotar, the separated water, and the water with a vapor pressure of 6.5 atm and the temperature is as follows. It shows a high value at about 40 ° C, the density difference disappears at around 140 ° C, and the density reverses at higher temperatures, 0.012 and 200 ° C at 180 ° C.
Then, 0.013 shows a high value.

The pressure in the above temperature range is from atmospheric pressure to 15 atmospheric pressure, and it is necessary that all the devices for maintaining the temperature be high-pressure vessels. When oil-water separation is carried out at high temperature and high pressure, when it is allowed to stand for a certain period of time, for example, 1 hour, it is separated into two distinct layers, the oil phase consisting of modified tar as the heavy component, and the metal salt as the light component. It can be separated and recovered as a dissolved aqueous phase.

The removal of water and alkali metal or alkaline earth metal from the emulsion according to the present invention is mainly influenced by the addition amount of sulfuric acid, heating temperature and holding time. Under the condition of providing a density difference of 0.007 or more, preferably 0.01 or more, it is possible to set the water concentration to 1% by weight or less and the Mg concentration to 100 ppm or less, taking modified reformation as an example. .

The amount of sulfuric acid added, the heating and standing temperature, and the standing time are not constant depending on the tar-like substance to be targeted, but the amount of sulfuric acid added is usually 0.05% by weight of the emulsion.
As described above, the stationary time is set to 1 hour or more, and the temperature is set to a temperature at which the density difference is generated. For example, magnesium content 50
0 ppm Orimuljeon (orinocotal equivalent 62
(Corresponding to 0 ppm), if 0.1% by weight or more of sulfuric acid to the orimulsion (corresponding to the theoretical equivalent to Mg) is added, the water concentration in the modified tar is 100% by weight.
Below, it can be seen that about 0.2% by weight can be reduced to 1% by weight or less, and about 0.4% by weight can be reduced to 0.75% by weight or less.

As for the Mg concentration, as long as other conditions are satisfied, if 0.1% by weight or more of sulfuric acid is added to the orimulsion (corresponding to the theoretical equivalent amount to Mg), the concentration in the modified tar will be 300 ppm or less. , About 0.2% by weight, 130p
It can be reduced to pm or less, and to 100 ppm or less at approximately 0.4% by weight. Regarding the temperature conditions, assuming that other conditions are satisfied, the remarkable M at a temperature of approximately 170 ° C. or higher.
g can be removed, the Mg concentration can be 100 ppm or less at 180 ° C. or higher, and the standing time is maintained for at least 1 hour, preferably 3 hours.

It should be noted that when the addition amount of sulfuric acid for orinocotal is 0.4% by weight, the decrease in the concentration of Mg and water is almost saturated, and the addition of more than that causes an increase in post-treatment cost such as neutralization of recovered water. Absent. If the standing time is set to 3 hours, the water-oil separation becomes almost constant, so even if the standing time is further exceeded,
It is uneconomical, such as high temperature maintenance costs. The oil phase separated after the thermal reforming treatment is a water-in-oil emulsion, which is rapidly released into the atmosphere and can be efficiently removed by evaporating the water all at once. Further, the solid content mixed in the reformed tar can be removed by a centrifuge attached to the diesel engine.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to the accompanying drawings. A first embodiment of the present invention by batch processing will be described. To each 800 ml of Orimulsion, add the amount of sulfuric acid shown in Table 3,
After uniformly mixing with a 500 rpm stirrer, FIG.
Samples collected from the container sampling tube 2 after the lapse of time after being placed in the pressure-resistant container 1 shown in Table 1, heated to a temperature rising rate of 4.5 ° C./min, and allowed to stand under the temperature and time conditions shown in Table 3. The results were evaluated for.

[0020]

[Table 3] Based on the data in Table 3, the relationship between the concentration of water and the concentration of Mg contained in the modified tar with respect to the amount of sulfuric acid added is shown in the graph of FIG.

In FIG. 3, the water concentration becomes 100% by weight or less in the modified tar when sulfuric acid is added to the orimulsion in an amount of 0.1% by weight or more, and becomes 1% by weight or less at approximately 0.2% by weight. , And 0.7 if 0.4% by weight
It can be seen that the amount can be reduced to 5% by weight or less. Further, in FIG. 3, the Mg concentration is 0.
If added more than 1% by weight, the concentration in the modified tar will be 300
It can be seen that it can be reduced to below ppm, below about 130 wt% at about 0.2 wt% and below 100 ppm at 0.4 wt%.

Regarding the temperature conditions, as shown in FIG.
It is possible to significantly remove Mg at a temperature around 170 ° C.
It can be seen that the Mg concentration can be 100 ppm or less at 80 ° C. or higher. About the standing time, as shown in FIG.
It can be seen that oil-water separation is carried out by standing for 1 hour.

Therefore, from the above results, in the case of batch processing, 0.1% sulfuric acid was added to orimulsion.
% By weight or more, preferably 0.2% by weight or more, more preferably about 0.4% by weight, and the temperature condition is 170 ° C. or more, preferably about 200 ° C., and the standing time (reaction and oil-water separation time) is It can be seen that the Mg concentration can be reduced to 300 ppm or less, preferably about 50 ppm, and the water content to 1 wt% or less, preferably about 0.5 wt% by setting the time to 1 hour or more.

The mode for carrying out the present invention by industrial implementation will be described below. The emulsion thermal reformer shown in FIG. 6 is a continuous thermal reformer that supplies tar-like substances to a power generation diesel engine (not shown), and the main equipment is an emulsion storage tank 3, a thermal reforming column 4, and a flash column 5. And the tar storage tank 6.

The emulsion in the storage tank 3 is heated to a predetermined temperature by the heater 10 by the transport pump 9 and then fed into the thermal reforming column 4. A predetermined amount of concentrated sulfuric acid in the concentrated sulfuric acid storage tank 7 is mixed into the inlet of the heater 10 by the transport pump 8 and mixed in the heater 10. The thermal reforming column 4 is a cylindrical pressure vessel installed vertically or horizontally, and the emulsion is fed from a predetermined position of the cylindrical vessel. The fed emulsion is slowly moved in the column 4 so as to satisfy the stationary condition. In the column, oil-water separation occurs, and alkali metal or alkaline earth metal reacts with sulfuric acid in the aqueous phase to be dissolved or highly dispersed in the aqueous phase as a sulfate having relatively good thermal stability. The reformed tar is recovered from the bottom of the column and the aqueous sulfate solution is recovered from the top of the column.

The recovered reformed tar contains a small amount of water as described above. After decompressing with the decompression valve, it is jetted into the flash column 5 to remove a small amount of water in the reformed tar. The evaporated and dehydrated reformed tar is recovered from the bottom of the flash column 5 and sent to the centrifugal separator (not shown) attached to the diesel engine through the tar storage tank 6.

The steam recovered from the top of the flash column 5 is accompanied by a light oil component contained in tar. These mixed vapors are condensed in the cooler 15 and sent to the oil / water separator 13 as a liquid. On the other hand, the sulfate aqueous solution recovered from the top of the thermal reforming column 4 is cooled by a cooler.
After being cooled by 12, after depressurization, the entrained oil is separated by an oil / water separation tank 13 and then sent to a water treatment facility 14.

The oil component separated in the oil / water separation tank 13 is sent to the tar storage tank 6. The industrial embodiment shown in FIG.
This is a batch type thermal reformer for supplying tar-like substances to a diesel engine for power generation (not shown), and its main equipment and process are the same as those of the continuous thermal reformer shown in FIG. The difference is that two thermal reforming columns 4a and 4b are installed and the thermal reforming operation of the emulsion is alternately performed in a batch manner.

The batch type heat constitution apparatus shown in FIG. 7 is applied to an emulsion in which the formation of the upper layer sulfate aqueous solution is hindered by a slight disturbance of the downward flow of tar in the continuous thermal reforming column. Is.

[0030]

As described above, according to the method for thermally reforming an emulsion of the present invention, sulfuric acid is added to and mixed with an oil-in-water emulsion of a tar-like substance or a heavy oil, and the mixture is kept under high temperature and high pressure for a certain period of time. The water and the alkali metal or alkaline earth metal contained in the emulsion can be efficiently removed by allowing the solution to stand and separating the oil and water. Therefore,
It can be advantageously used as fuel for diesel engines.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between temperature and oil phase density and water phase density when the emulsion was subjected to thermal reforming with sulfuric acid and oil-water separation.

FIG. 2 is a cross-sectional view of a stationary oil-water separator used in the first embodiment of the batch processing of the present invention.

FIG. 3 is a graph showing the relationship between the amount of added sulfuric acid as a result of the first embodiment and the concentrations of Mg and water remaining in the modified tar-like material.

FIG. 4 is a graph showing the relationship between the resulting thermal reforming temperature according to the first embodiment and the concentrations of Mg and water remaining in the reformed tar-like material.

FIG. 5 is a graph showing the relationship between the stationary time resulting from the first embodiment and the concentrations of Mg and water remaining in the modified tar-like material.

FIG. 6 is a process explanatory diagram according to a second embodiment of the continuous processing of the present invention.

FIG. 7 is a process explanatory diagram according to a third embodiment of the batch type processing of the present invention.

[Explanation of symbols]

1 Pressure-resistant container 2 Sampling tube 3 Emulsion storage tank 4 Thermal reforming column 5 Flash column 6 Tar storage tank 7 Concentrated sulfuric acid storage tank 8 Transport pump 9 Emulsion transfer pump 10 Heater 11 Cooler 12 Cooler 13 Oil water separation tank 14 Water treatment facility

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirohisa Endo 3-1-1 Tam, Tamano-shi, Okayama Mitsui Engineering & Shipbuilding Co., Ltd. Tamano Plant (72) Inventor Hiroshi Kida 3-1-1 Tam, Tamano-shi, Okayama No. Mitsui Shipbuilding Co., Ltd., Tamano Works

Claims (2)

[Claims] 1. A method for removing water and an alkali metal or alkaline earth metal salt contained in an oil-in-water emulsion of a tar-like substance or a heavy oil, wherein sulfuric acid is added to the emulsion to separate water. The density difference with heavy oil is 0.
A method for thermal reforming of an emulsion, which comprises allowing to stand at a temperature of 007 or higher and a saturated vapor pressure at that temperature to cause oil-water separation, and taking out the separated oil phase. 2. The thermal reforming method for an emulsion according to claim 1, wherein the amount of sulfuric acid added to the emulsion is 0.05 to 1.0% by weight, and the standing time is 1 hour or longer. .