JPS6329919B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an oil refining and reforming method for removing impurities in oil and adjusting viscosity, flash point, etc., by a hydrogen purification method using water. [Prior Art] Hydrogen refining methods are conventionally known as methods for refining and reforming oil. This method utilizes a hydrogen cracking reaction, in which oil and hydrogen are brought into contact at a pressure of approximately 50 atmospheres and a temperature of 350 to 450 degrees Celsius, hydrogen is added to the unsaturated bonds of the oil, and saturated bonds are broken. Hydrogen is then added to the resulting decomposition products. In addition, as a method for refining and reforming oil by the hydrogen refining method using water, water is injected into oil heated to near its boiling point at atmospheric pressure or slightly higher pressure, and the heat generated by the injection of water is A method is known in which the gas produced as a result of the impact is extracted and cooled, and the liquefied components are separated and obtained (Japanese Patent Application Laid-open No. 139805/1982). [Problems to be Solved by the Invention] However, the above-mentioned conventional hydrogen purification method requires a very high-pressure cooker for bringing oil and hydrogen into contact under heating and pressure, and has the disadvantage that the equipment is expensive. In addition, hydrogen to be brought into contact with oil must be prepared separately, and adding the production of hydrogen adds a great deal of effort, equipment, and expense. In addition, in the conventional hydrogen purification method using water,
Hydrogenation is attempted by injecting water into heated oil, but contact between water and oil in a high-temperature atmosphere, and even contact between hydrogen and oil produced by water decomposition, tends to be insufficient. In addition, the addition of hydrogen to oil is thought to be promoted by creating a high-pressure atmosphere, but since the water and oil are brought into contact at atmospheric pressure or slightly higher pressure, hydrogen addition is likely to be inhibited. There is a problem that carbide tends to be formed and the yield tends to decrease. This can be improved to some extent by bringing water and oil into contact under high pressure, but this requires a high-pressure cooker that can withstand extremely high pressure, which increases the burden on equipment. [Means for Solving the Problems] In order to solve the above problems, the present invention provides 300
The method is to supply oil and water into molten metal at ~800℃, bring the oil and water into contact under heating and pressure by the molten metal, extract the generated gas, cool it, and separate and obtain the liquefied components. It is something. The metals used in a molten state in the present invention include alkaline earth metals, iron group metals, boron group metals, carbon group metals, nitrogen group metals, oxygen group metals, and alloys thereof, and preferably lead, tin, and bismuth. , barium, aluminum, antimony, and alloys containing these. Most suitable are lead, tin, barium, and alloys containing these, which easily combine with oxygen in a molten state. Metals that easily combine with oxygen are a factor that inhibits the resynthesis of carbon and hydrogen. This is because oxygen can be removed from the reaction system in the form of metal oxides and can assist in the production of hydrocarbons. Also,
It is believed that the molten metal also plays a catalytic role during the resynthesis of oxygen and hydrogen, so it is preferable to select a metal that can act most effectively depending on the target oil. The temperature of the molten metal needs to be 300 to 800°C, although it varies depending on the target oil and the metal used. If the temperature is too low, sufficient oil decomposition will not be possible. On the other hand, if the temperature becomes too high, the decomposition progresses and the hydrocarbons produced become too low-grade and cannot be obtained as oil even after cooling. In order to obtain a sufficient amount of refined reformate, the temperature must be between 350℃ and 600℃.
is optimal. In addition, in the present invention, in order to assist the catalytic function of the molten metal, a metal with a melting point higher than the temperature of the molten metal is considered to be able to function as a catalyst for the combination of carbon in oil and hydrogen in water. what you can do,
It can also be interposed within the molten metal. for example,
One possible method is to form a net of nickel, platinum, etc. and install it so that the inside of the molten metal is partitioned into upper and lower parts. The metal for this catalyst is preferably a metal that does not easily oxidize so that it can be used repeatedly. The oil used in the present invention includes crude oil, heavy oil, waste oil, fats and oils, and these can be used alone or in combination. In the present invention, the mixing ratio of oil and water to be supplied into the molten metal varies depending on the oil, but 10 to 100 parts by weight of water to 100 parts by weight of oil, optimally 30 to 100 parts by weight.
Preferably, 60 parts by weight are added. If there is too little water, it will not be possible to recover a sufficient amount of refined reformate;
On the other hand, even if there is an excess amount, the amount of purified reformed oil will not increase much, and instead a large amount of heat will be taken away from the molten metal, resulting in a large heat loss. In order to obtain rapid and reliable reaction, it is preferable that the oil and water mixture is mixed and supplied until it becomes an emulsion. Further, it is preferable that the oil and water to be supplied be preheated to some extent in advance so that the molten metal is not rapidly cooled and solidified by the supply of oil and water. The pressure at which the above mixture reacts in the molten metal can be freely determined depending on the depth within the molten metal to which the mixture is supplied, the specific gravity of the metal used, etc., so it can be adjusted as appropriate depending on the type of target oil, etc. Just adjust it. An injection machine similar to an injection molding machine is preferably used to supply the mixture into the molten metal. [Function] The oil and water supplied into the molten metal are kept in a state where they are shielded from external oxygen within the molten metal, a liquid with an extremely high specific gravity, and are floated up due to the difference in specific gravity, depending on the depth within the molten metal. It will be under pressure and heated at the same time. That is, the supplied oil and water rise within the molten metal while being pressurized and heated by the molten metal while being isolated from the outside air. During this time, the heated and activated oil and water come into contact, and the polymer structure of the oil is decomposed and hydrogenated, producing hydrocarbons.Since both are supplied as a mixture, this contact is ensured. It is. Although the detailed behavior of the oil and water in the molten metal is not necessarily clear, the inventors speculate as follows. In other words, by being exposed to high temperatures in molten metal, the oil chains are broken and the molecules are reduced, and some hydrogen and other atoms that are bonded to carbon and make up the oil are separated. It is thought that carbon and hydrogen are combined preferentially and resynthesized. On the other hand, water is activated at high temperatures and reacts with the carbon produced when oil is exposed to high temperatures, attempting to turn into water gas. It is thought that this acts on the chain of oil, promotes the addition of hydrogen to the resulting decomposition products, and the separation of sulfur, nitrogen, etc. At this time, it is thought that the molten metal also plays a catalytic role during the resynthesis of carbon and hydrogen. Oxygen contained in the composition of oil combines with hydrogen to form water, while oxygen produced by water decomposition combines with carbonic acid in oil to form carbon monoxide and carbon dioxide, both of which result in the regeneration of carbon and hydrogen. It becomes a factor that inhibits synthesis. However, by using the molten metal as a metal that easily binds to oxygen in a molten state, the oxygen can be removed from the reaction system as a metal oxide, and the resynthesis of carbon and hydrogen can be aided. It is also believed that sulfur, nitrogen, and other impurities in the oil are removed by combining with molten metal or becoming various gases. In this way, the oil is reduced in molecular weight in the molten metal and the impurities are removed, and the oil is gasified and taken out together with excess moisture. On the other hand, the carbide is separated by flotation on the molten metal and reduces the molten metal combined with the aforementioned oxygen. When the extracted generated gas is cooled, hydrocarbon oil is recovered as a liquefied component. This liquefied component is roughly divided into water and hydrocarbon oil. Further, the remaining gas component is mainly composed of unliquefied hydrocarbon gas, hydrogen, etc., and is flammable, so it can be used for heating molten metal, etc. [Example] First, the apparatus used in this example will be explained with reference to FIG. In the figure, 1 is a reaction vessel, and inside this reaction vessel 1,
It is filled with molten metal 2. In addition, reaction vessel 1
A heating jacket 3 is attached around the molten metal 2 to maintain the temperature of the molten metal 2 in the reaction vessel 1. At the bottom of reaction vessel 1, oil and water are placed in reaction vessel 1.
A feeder 4 is connected to the lower part of the feeder. At the top of the reaction vessel 1, there are provided a carry-out conveyor 5 for carrying out the generated carbide, etc., and a gas extraction port 6 for taking out the generated gas. The gas extraction port 6 is connected from the oil container 8 to the gas container 9 via the cooler 7, and the liquefied components generated by cooling are collected in the oil container 8, and the remaining gas components that have not been liquefied are The gas is collected into a gas container 9. Example 1 A commercially available engine oil was purified and reformed. The reaction vessel was a cylinder with a diameter of approximately 50 mm, and lead was used as the molten metal, which was filled into the reaction vessel to a depth of 50 cm. Melting the lead and maintaining the temperature was accomplished by a heating jacket of an electric heater wrapped around the reaction vessel. Engine oil with 50% water added is pressurized into the lower part of the reaction vessel with a hydraulic cylinder while the lead is maintained at approximately 550°C, and the generated gas is taken out from the upper part of the reaction vessel and cooled to form a liquefied component. Work was carried out to recover gas components. The liquefied components are broadly divided into water and oil, and this oil is a low-viscosity oil-like liquid that instantly ignites and burns when brought close to the pine flame. The results are shown in Table 1. Example 2 Engine oil was purified and reformed in the same manner as in Example 1, except that the amount of water added was 100% by weight, 429 g was supplied, and the temperature of lead was 600°C. The results are shown in Table 1. Example 3 When engine oil was modified using tin as the molten metal, the same results as in Examples 1 and 2 were obtained. Comparative Example 1 The same commercially available engine oil as in Example 1 with 50% water added was used without adding molten metal.
The oil was purified and reformed by injecting it into a reaction vessel heated to 600°C. The results are shown in Table 1. Comparative Example 2 Oil was purified and reformed in the same manner as in Comparative Example 1, except that the amount of water added was 100% by weight. The results are shown in Table 1.

【table】

[Table] [Effects of the Invention] As is clear from the above description, the main feature of the present invention is that oil mixed with water is supplied into the molten metal, and heating and pressure by the molten metal are utilized. With these, the following benefits can be obtained. (1) Since the molten metal acts as a pressurized catalyst, the pressure can be easily set by simply adjusting the height of the reaction vessel and the filling depth of the molten metal, and the equipment can be extremely simple. (2) Since water is used as the hydrogen source, there is no need to prepare hydrogen separately, and the equipment, labor, and expense for hydrogen production can be saved. (3) Even if there are many impurities such as waste oil, the inclusions can be floated and separated on the molten metal as carbides, so the treatment is extremely easy.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an apparatus used in an embodiment of the present invention. 1: reaction vessel, 2: molten metal, 3: heating jacket, 4: feeder, 5: discharge conveyor, 6: gas extraction port, 7: cooler, 8: oil container, 9: gas container.

Claims (1)

[Claims] 1 A mixture of oil and water is supplied into molten metal at 300 to 800℃, the oil and water are brought into contact under heating and pressure by the molten metal, the generated gas is taken out and cooled, and the liquefied components are separated and obtained. Characteristic oil refining and reforming method.