JP3250952B2 - Thermochemical modification of emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for thermally reforming a heavy oil-water emulsion, and more particularly, to a method for removing alkali or alkaline earth metal salts contained in the emulsion. Things.

[0002]

2. Description of the Related Art When trying to use tar-like substances such as asphalt, coal tar pitch and bitumen or heavy oil for industrial use, it is necessary to remove such contaminants in addition to removing contaminants. Is required, and various removing means have conventionally been proposed.

For example, a method disclosed in Japanese Patent Application Laid-Open No. 7-34072 discloses a method in which a heavy oil is mixed in a high-shear kneader such as a kneader by adding acidic water having a pH of 2.5 to 6.5, and Metals, oxides and nitrogen in heavy oil are removed by kneading in a state showing spinnability under force by transferring it to acidic water. Orimulsion (water-in-oil type of orinoco tar) (Emulsion) is shown.

Further, the method disclosed in Japanese Patent Application Laid-Open No. 60-106883 relates to a method for removing salt from heavy oil, wherein water is added to a mixed oil obtained by adding light oil to heavy hydrocarbon oil. And a separator (for example, an electric desalination tank)
It separates and removes salt-containing water. In addition, Japanese Unexamined Patent Publication No.
The method disclosed in Japanese Patent Application Laid-Open No. 5-12200 discloses a heavy residual oil,
By extracting and purifying asphaltental and the like with a solvent such as butyl alcohol / ketone, the phase separation is promoted and the removal of impurities is promoted.

The method disclosed in Japanese Patent Publication No. 56-54036 discloses a method in which an emulsifier is added to a salt-containing tar-based absorbing oil obtained in a coke oven gas refining step to contain an oil phase and water-soluble salts. It separates from the aqueous phase and continuously and efficiently separates and removes salts from the absorbed oil.

[0006]

The orinoco tar described in Japanese Patent Application Laid-Open No. 7-34072 is a natural asphalt (hereinafter referred to as orinoco tar) which is an ultra-heavy oil produced in the northern basin of the Orinoco River in Venezuela, South America. ), And huge reserves have been confirmed. This orinoco tar solidifies at room temperature (however, at 150 ° C., its viscosity is reduced to... CSt and it can be transported), and there is a problem in handling. Therefore, Venezuela Petroleum Corporation sells it as an oil-in-water emulsion (trade name: Orimaru John) for the purpose of boiler fuel. In Japan, the annual consumption of boiler power generation fuel exceeds 1 million tons. It is considered that the price and supply of all fossil fuels can compete in the long run.

[0007] By the way, orinoco tar is 400 to 5
Contains 00 ppm vanadium. When this vanadium is burned in a boiler, it is corroded at a high temperature due to a vanadium attack on a boiler tube, but can be suppressed by adding a magnesium salt. By the way, orinoco tar has various properties that can sufficiently compete with heavy fuel oil C, and can be used as a fuel for power generation diesel engines and the like.

However, for example, when orimulsion is used as a fuel for a diesel engine, when the emulsion is destroyed, and water is separated and removed, and the recovered orinoco tar is burned, magnesium salt added for countermeasures against vanadium attack precipitates. However, there is a problem that they are taken in the lubricating oil and wear the cylinder wall. As described above, in order to use ultra-heavy oil as a fuel for a diesel engine, it is necessary to remove water from the emulsion once in order to facilitate handling such as transportation.
In addition, the alkali metal or alkaline earth metal originally contained or mixed during the treatment can be separated.

However, according to the method disclosed in the above publication, water and alkali metals or alkaline earth metals in the super heavy oil cannot be efficiently removed, and the cost of the added agent impairs the economic efficiency. There is a need to establish more effective removal methods. The present invention provides a thermal oil reforming method for removing heavy metals including ultra-heavy oils such as orinoco tar, and alkali metals and alkaline earth metals contained in an oil-in-water emulsion of tar-like substances. It is an issue.

[0010]

In order to achieve the above object, the method of the present invention for thermochemically modifying an emulsion comprises a method for producing water and alkali contained in an oil-in-water emulsion of a tarry substance or heavy oil. Or a method for removing an alkaline earth metal salt, wherein 0.1 to 1.0% by weight of sulfuric acid is added to the emulsion, and at a temperature of 170 to 220 ° C,
The apparatus is allowed to stand for one hour or more to allow oil-water separation, and the separated oil phase is taken out.

The above-mentioned tar-like substances or heavy oils (hereinafter collectively referred to as tar-like substances) include heavy fuel oil C, asphalt, orinoco tar, tar sands, etc., and it is difficult to apply the conventional method for removing metal salts. The present invention can be applied particularly advantageously to heavy oils. The means for converting the tar-like substance into an oil-in-water emulsion is not particularly limited, and means conventionally used can be used.

Although the sulfuric acid is not particularly limited, it is economically preferable to use 98% concentrated sulfuric acid supplied industrially. The metal salts to be removed in the present invention include sodium and potassium as alkali metals, and magnesium and calcium as alkaline earth metals, such as vanadium belonging to Va group of the periodic table of elements, and artificial salts such as orimulsion. Includes those that have been added.

The pressure at the above-mentioned temperature is approximately 13 to 15 atm, and all devices for maintaining the temperature must be high-pressure vessels. When oil-water separation is performed under high temperature and high pressure, the mixture is separated into two distinct phases upon standing for a certain period of time, for example, one hour, and water, alkali metal and alkaline earth metal are easily separated, that is, reformed. A tar or heavy oil can be separated and recovered from the aqueous phase in which the salt of the metal is dissolved.

The oil phase separated from the oil and water after the thermal reforming treatment is:
This is a water-in-oil type emulsion, which can be rapidly released into the atmosphere to evaporate the water at a stretch, thereby removing the water.

[0015]

An embodiment of the present invention will be described below with reference to the accompanying drawings. A first embodiment of the present invention using batch processing will be described. 800 ml of the orimulsion is placed in the pressure vessel 1 shown in FIG.
m, and the mixture was uniformly mixed with a stirrer having a temperature of 4.5 m.
Heat to a temperature of 160 ° C / min.
FIG. 2 shows the result of obtaining the removal rate of Mg in the tar phase of the sample collected from the container sampling tube 2 after the elapse of a predetermined time (holding time).

In FIG. 2, the horizontal axis indicates the amount of sulfuric acid added,
The results are shown graphically for each Mg content in the orimulsion. The retention time was entered for each curve. From this result, it can be seen that as the amount of added sulfuric acid increases, the magnesium removal rate improves, and a value close to 90% can be obtained in any case. Embodiments of the present invention will be described below with reference to industrial embodiments.

The apparatus for thermally reforming an emulsion shown in FIG.
This is a continuous thermal reforming apparatus for supplying tar-like substances to a power-generating diesel engine (not shown). The main equipment includes an emulsion storage tank 3, a thermal reforming column 4, a flash column 5, and a 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 sent to the thermal reforming column 4. Heater 10
A predetermined amount of concentrated sulfuric acid in the concentrated sulfuric acid storage tank 7 is mixed into the heater 10 by the transport pump 8 at the inlet of the heater.

The thermal reforming column 4 has a cylindrical pressure vessel installed vertically or horizontally, and the emulsion is fed from a predetermined position in the cylindrical vessel. The sent emulsion is
The inside of the column 4 is slowly moved to satisfy the stationary condition. In the column, oil-water separation occurs, and at the same time, the 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 relatively thermally stable sulfate. The modified tar is recovered from the bottom of the column, and the aqueous sulfate solution is recovered from the top of the column.

The recovered modified tar contains a small amount of water as described above. After the pressure is reduced by the pressure reducing valve, it is jetted into the flash column 5 to remove the small amount of water in the modified tar. The evaporated and dehydrated modified tar is collected from the bottom of the flash column 5 and sent to a centrifuge (not shown) attached to the diesel engine via 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 the 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 aqueous sulfate solution recovered from the top of the thermal reforming column 4 is cooled
After being cooled by 12 and decompressed, the entrained oil is separated by an oil / water separation tank 13 and then sent to a water treatment facility 14.

The oil 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 heat reformer for supplying a tar-like substance to a diesel engine for power generation (not shown). The main equipment and process are the same as those of the continuous heat reformer shown in FIG. The difference is that two thermal reforming columns 4a and 4b are provided, and the thermal reforming operation of the emulsion is performed alternately in a batch manner.

The batch type thermal constitution apparatus shown in FIG. 7 is applied to an emulsion in which the formation of the upper layer aqueous solution of sulfate is inhibited by the turbulence of the subtle descending flow of tar in the continuous thermal reforming column. It is.

[0023]

As described above, the method for thermochemically modifying an emulsion according to the present invention comprises adding a tar-like substance or heavy oil to an emulsion in oil by adding 0.1 to 1.0% by weight of sulfuric acid to the emulsion.
At a temperature of 0 to 220 ° C., the mixture was allowed to stand for 1 hour or more, and oil-water separation was performed, and the separated oil phase was taken out, so that water and alkali or alkaline earth metal salts could be efficiently removed, For example, it can be used as a fuel for a diesel engine.

[Brief description of the drawings]

FIG. 1 is a sectional view of a stationary oil-water separator used in a first embodiment by a batch process of the present invention.

FIG. 2 is a graph showing the relationship between the amount of sulfuric acid added as a result of the first embodiment and the concentrations of Mg and water remaining in a modified tar-like substance.

FIG. 3 is an explanatory view of a process according to a second embodiment of the continuous processing of the present invention.

FIG. 4 is an explanatory view of a process according to a third embodiment of the present invention by a batch process.

[Explanation of symbols]

DESCRIPTION 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 equipment

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirohisa Endo 3-1-1, Tamano, Tamano-shi, Okayama Prefecture Mitsui Engineering & Shipbuilding Co., Ltd. Tamano Plant (72) Inventor Hiroshi Nagita 3-1-1, Tamano-shi, Tamano-shi, Okayama Prefecture No. 1 Mitsui Engineering & Shipbuilding Co., Ltd. Tamano Works (56) References JP-A-6-41555 (JP, A) JP-A-7-34072 (JP, A) JP-A-6-157015 (JP, A) JP 52-155604 (JP, A) U.S. Patent 5,919,353 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10G 17/06

Claims (1)

(57) [Claims] 1. A method for removing water and an alkali or alkaline earth metal salt contained in an oil-in-water emulsion of a tar-like substance or heavy oil, wherein the emulsion contains 0.1 to 1.0% by weight. 170-220 ° C
A thermochemical reforming method of an emulsion wherein the emulsion is allowed to stand still for one hour or more at a temperature of 1 hour to separate oil and water, and the separated oil phase is taken out.