JPS60162735A - Method for recovering very small amount of metal from petroleum - Google Patents

Abstract

PURPOSE:To separate and recover very small amounts of metals from crude oil in high yields by applying a magnetic field to the crude oil contg. the metals in the form of metallic complex salts of a porphyrin compound to decompose the complex salts. CONSTITUTION:Crude oil and refined petroleum products contain very small amounts of metals such as Co, Ni, Mo and V in the form of metallic complex salts of a porphyrin compound. Plural magnets are arranged in a vessel at fixed intervals, and said crude oil or the like is charged into the vessel. Said metallic complex salts are decomposed in a magnetic field formed by the magnets, and the resulting metals are attracted to the magnets. Metals such as Mo and V as well as ferromagnetic metals such as Co, Ni and Fe are attracted to the magnets in the form of a mixture with ferromagnetic metals such as Co and Ni, and the metals can be recovered from the crude oil or the like.

Description

[Detailed Description of the Invention] The present invention is a method for recovering rare metals from petroleum, comprising:
Its purpose is to provide a method for easily and efficiently recovering rare metals present in petroleum products, and another purpose is to effectively utilize unused rare metals.

As is well known, Go is present in crude oil and refined petroleum products.

There is a surplus of NLMn-VMS metal.

These rare metals are mainly contained in porphyrin compounds to resist metal salts, but these rare metals adhere to catalysts during catalytic cracking reactions in petroleum refining, reducing catalytic function, or when burning heavy oil as fuel. , adheres to boilers or heating tubes of tube heating furnaces, etc., resulting in various problems such as accelerating corrosion of the boiler and heating tubes.

On the other hand, many of these rare metals are widely used as essential metals in cutting-edge technology industrial fields such as semiconductors and optical communications, but the reserves of these rare metals in Japan are extremely small, and 90% of consumption More than 10% of the total amount must be imported, and it is designated as a national stockpile.

In view of the current situation regarding rare metals, the present inventor has conducted various researches and found that by adopting the structure described in the claims, rare metals contained in petroleum products can be easily and efficiently recovered. We were able to make effective use of available resources.

That is, the present invention is characterized in that a magnetic field is applied to crude oil and other petroleum products to decompose the metal salts of porphyrin compounds contained in the petroleum products, thereby liberating and recovering metals from petroleum products. This is a method of recovering rare metals.

The present inventors have discovered that when a magnetic field is applied to a metal salt of a porphyrin compound, it decomposes to liberate the metal, and was able to achieve the present invention.

That is, when a metal salt of a porphyrin compound is placed in a magnetic field, the angular motion vector of the metal particle starts to precess in the direction of the magnetic field, causing splitting of free energy due to the difference in the total angular motion quantum number, and the ionic bond complex ( It is thought that there is a continuous transition from a covalent complex (a high spin complex) to a covalent complex (a low spin complex).

Furthermore, when petroleum is placed in a magnetic field, an electric field is induced inside the petroleum during the fluid motion of the petroleum, producing a magnetizing current. It is thought that the metal salt is decomposed by the magnetizing current generated in the petroleum, and the metal is liberated.

The magnetic field in the present invention may be a known permanent magnet, or may be a ferrite molded magnet if necessary. In order to apply the magnetic field, the magnetic field is applied to the inner surface of a petroleum storage tank at a constant rate in the axial direction of the storage tank. A plurality of rows of magnets are formed at intervals, and if necessary, a plurality of rows of magnets are attached to the inner circumferential surface of the storage tank, and petroleum is injected or stirred therein.

The metal liberated by applying the magnetic field as described above immediately turns into fine metal powder and adheres to the plurality of permanent magnets attached to the inner surface of the storage tank.

The metal attached to the permanent magnet as mentioned above.

In addition to ferromagnetic materials such as Co, Ni, and Fe, Mo, V
, AI, etc., and these mixtures can be collected by adhering to a permanent magnet together with ferromagnetic substances such as Co, Ni, and Fe.

Alternatively, a plurality of permanent magnets may be three-dimensionally assembled to form a cassette at uniform intervals vertically and horizontally, and the plurality of cassettes may be randomly arranged at the bottom of a petroleum storage tank. In this case, the metal salt of the porphyrin compound decomposes under the action of the magnetic field from multiple permanent magnets assembled into the cassette, liberating the metal, and this liberated metal is assembled into the cassette. A method of attaching it to a permanent magnet may also be used.

As mentioned above, the metals that are collected on permanent magnets are mostly a mixture of rare metals, and the content of other impurities is extremely small. It can be easily peeled off with a spatula, etc., and separated and collected as a powder.

The following table shows C heavy oil (JIS K 2205-1980,
A permanent magnet 5 formed into a circular shape with a diameter of 50 mm and a thickness of 10 mm was placed in a glass cylindrical container with a tape heater wrapped around the C heavy oil so that it could be heated. Samples were collected at 20 mm intervals in a cylindrical container, heated to 50°C, and stirred for 4 hours.
This shows an analysis of heavy oil.

As is clear from the results in the table above, by applying a magnetic field to C heavy oil, Fe, Ni, and V in C heavy oil can be
, AI can be removed to almost no trace.

In addition, when applying a magnetic field, the same results can be obtained even if the heavy oil C is not heated and stirred at room temperature (20° C.) for 2 days, or heated to 80° C. and stirred for 3 hours.

On the other hand, the permanent magnets placed in the container were covered with a mixture of various metals produced by the decomposition of the metal salts of the porphyrin compounds, which were removed from each permanent magnet, dried with hot air, and then easily cleaned with a bamboo spatula, etc. It can be peeled off and recovered as a powder.

In addition, these mixed powders were treated with Fe, N
Rare metals can be easily recovered by separating i, Al, V, Mo, etc.

As described above, the present invention separates metals by applying a magnetic field to the metal salts of various porphyrin compounds contained in petroleum products, and then collects the metals by attaching them to a permanent magnet. It is simple and can be made at a low cost. Moreover, it is possible to recover valuable rare metals, so it is possible to effectively utilize unused resources. This has the effect of preventing deterioration in the functionality of the engine and corrosion of the heating tubes of combustion boilers that use petroleum as fuel.

Example: In a magnetic treatment tank with a diameter of 900 mm and a height of 1500 mm, 3750 circular permanent magnets with a diameter of 50 mm and a thickness of l Om m were installed at equal intervals on the inner surface and height of the magnetic treatment tank. death.

This was treated by continuously supplying C heavy oil tooooi.

After completing the magnetic treatment, the permanent magnet was taken out and dried with hot air at 150°C to obtain 1.8'7 kg of metal powder.

Next, this metal powder was heated at 525 ° C. for 5 hours in a Matsufuru path, and after sufficiently cooling, a mixed acid of (t + i) nitric acid and concentrated sulfuric acid at a ratio of 5:1 was added, and heated until white smoke of N 03 was produced. Furthermore, after transferring it to a flask and adding hydrogen peroxide, 15
Dissolved in twice the amount of hydrochloric acid.

By adding N-cinnamoyl-N-phenylhydroxylamine to the hydrochloric acid solution and performing an extraction process to obtain crystals mainly composed of VU05, 99.2% of (1) was recovered.

In addition, after adding iron powder to the hydrochloric acid solution after extraction and sufficiently dissolving it, P) 14~
5 to obtain iron carbonate crystals with an iron purity of 94.7%.

Ammonia carbonate was further added to the hydrochloric acid solution from which the iron carbonate had been removed to adjust the pH to 8 to 9, resulting in Ni of 94.43% and V3.
It was possible to crystallize and recover crystals consisting of 38% Fe and 2.25% Fe. It should be noted that the metal salt in the hydrochloric acid solution after separating these is extremely small.

Patent Applicants Oshiyo Muto, Ritoichi, Osamu Kawa, Tatsuya Yoshito Fuji Procedural Amendment (Voluntary) May 13, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of Case 1980 Patent Application No. 1B572 No. 2, Name of the invention Method for recovering rare metals from petroleum (1) The table on page 7 of the specification is corrected as shown in the attached sheet.

(2) In the first line of page 10 of the same book, "Matsufuru-ro" is corrected to "Matsufuru Furnace."

that's all 〔Attachment〕

Claims (1)

[Claims] A method for recovering rare metals from petroleum products, which comprises applying a magnetic field to crude oil and other petroleum products to decompose the metal salt resistance of porphyrin compounds contained in the petroleum products, thereby liberating and recovering the metals.