JPS62277492A - Apparatus for recovering rare metal from crude oil or refined oil - Google Patents

Abstract

PURPOSE:To provide a simple and effective means for recovering rare metals contained in crude oil in the form of a porphyrin compound metal complex salt, by arraying plural permanent magnets to each outer wall of a rectangular main cylinder at a specific construction, attaching a blowdown valve to the cylinder and applying a magnetic field to the crude oil, etc. CONSTITUTION:Plural permanent magnets 7, 7... are arranged at regular intervals alternately changing the direction of the pole on each outer wall 1a, 1b, 1c, 1d of a long rectangular main cylinder made of a metal such as stainless steel and having rectangular cross-section. The magnets 7 on the adjacent outer walls are detachably attached in a staggered manner. Blowdown valves 6, 6a are attached to the constricted parts of both ends of the rectangular main cylinder 1 through flanges 4. A crude oil containing rare metals as porphyrin compound metal complex salt is passed through the apparatus to effect the deposition of the rare metals together with the sludge on the inner wall of the main cylinder 1 and the rare metals are recovered therefrom.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an apparatus for recovering rare metals from crude oil or refined oil.

<Prior art> As is well known, refined crude oil (hereinafter referred to as crude oil) contains rare metals such as cobalt, nickel, molybdenum, and vanadium mainly as metal complex salts of porphyrin compounds. During the catalytic cracking reaction when crude oil is produced, it adheres to the catalyst and reduces the catalytic function, or when heavy oil is burned as fuel, it adheres to the boiler or the heating tube of a tube heating furnace, causing the boiler or the This causes various problems such as accelerating the corrosion reaction of the heating tube.

However, although these types of metals cause such problems, on the other hand, many of them are widely used as indispensable metals in cutting-edge technology industries such as semiconductors and optical communications, and are widely used in Japan. It is well known that due to the extremely small amount of reserves, more than 90% of the reserves of Ura-yang have to be imported to importers, which is currently subject to national stockpiling.

In this 1, the present inventor conducted various studies to solve the above points based on the current situation, and found that by applying a magnetic field to crude oil, rare metals can be extracted from crude oil contained as metal complex salts of porphyrin compounds. He was one of the first to propose a simple and effective method for recovering the gas (see Japanese Unexamined Patent Publication No. 162735/1986). Therefore, the need for the most effective equipment to use in carrying out this method has become a pressing issue.

<Problems to be Solved by the Invention> In order to solve the above-mentioned problems, the inventors of the present invention have made various experimental investigations and found the most rational combination of a long metal rectangular tube with a rectangular cross section and a permanent magnet. We have come to the conclusion that meeting these requirements is an important and essential requirement, and have devised a device having the structure described in the claims.

<Means to solve the problem> In a rectangular metal tube with a long rectangular cross section, the rectangular tube is configured to consist of a rectangular tube main body (hereinafter referred to as main body) and a reduced part by squeezing both sides of the rectangular tube. , a plurality of permanent magnets (hereinafter referred to as magnets) are arranged in parallel at equal intervals on each outer wall of the main body with alternating magnetic poles, and the magnets on adjacent outer walls are removably fixed to each other so that the magnets are different from each other, Blow valves are attached to the reduced portions on both sides via flanges, thereby making it possible to rationally recover rare metals from crude oil.

An object of the present invention is to conduct crude oil containing rare metals as a metal complex salt of a porphyrin compound through the main body constructed as described above, thereby rationally decomposing the metal complex salt and effectively producing the desired rare metal. The objective is to provide a device that can be recovered. Another object of the present invention is to provide an apparatus that uses a magnet with minimal demagnetizing force, has a large metal complex decomposition function, is easy to operate, and is extremely advantageous from both a maintenance and economical point of view.

The main body used for this) is made of an oxidation-resistant, non-magnetic metal such as stainless steel (303304) FJ, and a plurality of rectangular bar-shaped magnets are arranged in parallel at equal intervals on each outer wall as described above, and each of the magnets on the adjacent outer walls is These magnets are installed in a staggered manner, but when the magnets are parallel, their bottom surfaces are in close contact with the main external wall surface (see Figures 2 and 4), and the remaining three surfaces (both sides including the top bottom surface) are As shown in the third figure, a plurality of recesses are arranged in parallel at equal intervals, and the protruding hem is fitted into the recess of a one-piece molded body made of a long synthetic resin on the right, and this molded body faces. The magnets are arranged opposite to each other on the outer wall as described later, and the protruding hems of the molded bodies are removably connected to each other by bolts (or may be connected by bolts) as shown in Figure 4, so that the magnet can be attached to and removed from the main body. There is.

The applied magnet has a coercive force of 3000 to 12000.
is preferably 3,400 to 4,500 gauss/piece and preferably has a rectangular bar shape with a rectangular cross section, but in some cases, it may have a semicylindrical cross section (not shown) that has one surface that can be brought into close contact with a flat surface. It's good. However, in the case of the above cross-sectional shape, it goes without saying that the inner surface of the recess of the molded body into which it is fitted is formed in a half-moon shape so that the outer surface excluding the bottom surface matches the inner surface of the recess.

In the above, the coercive force of the magnet is set to 3,000 to 12,000 Gauss/piece. If the coercive force becomes less than 30,000,000 Gauss/piece, rare metals are added to the main body to which the magnet is fixed. When the crude oil contained in the compound (compound) is passed through, the metal complex in the crude oil is not effectively decomposed due to the small coercive force of the magnet. However, most of the metal complex salts adhere to the inner wall of the main body together with the heavy oil in the oil (hereinafter referred to as sludge), making it unsuitable because the desired decomposition effect cannot be obtained.

Also, its coercive force is 12,000 Gauss/Il! It is thought that the above-mentioned drawbacks can be overcome if the magnetic field is greater than i1, but such a high-magnetic-force magnet is not only difficult to manufacture, but also expensive, and thus lacks practicality.

Therefore, in the present invention, the range of coercive force that can effectively eliminate the above-mentioned drawbacks is 3,000 to 12,000 Gauss/piece, preferably 3,400 to 4,500 Gauss, based on the experimental results of multiple methods conducted by the present inventor. Gauss/piece.

However, it is not theoretically clear why the coercive force of the permanent magnet decomposes the complex salts of rare metals contained in the crude oil flowing through the body and releases the desired metal from Ti, and it remains to be clarified in the future. However, according to the inventor's experiments, when crude oil is conducted through a main body in which a plurality of magnets are removably fixed to each outer wall surface of the main body (described later), the crude oil becomes magnetically sensitive. The magnetic field of the magnetized subject is conducted at a constant flow rate (described below), so the angular motion vector of the metal particles in the metal complex starts a two-difference motion in the direction of the magnetic field due to the magnetic field lines, resulting in a total angular motion M. Due to the difference in the number of molecules (4), the free energy splits and there is a continuous transition from ionic bond complexes (high spin complexes) to covalent bond complexes (low spin complexes). An electrostatic field is induced to generate a magnetizing current, and the metal complex salt of porphyrin, which has continuously transferred from the ionic bond mirror to the covalent bond mirror, is decomposed by the magnetizing current generated in the crude oil, and the metal complex salt in the complex salt is decomposed by the magnetizing current generated in the crude oil. It is thought that it liberates rare metals.

The magnetic field in the present invention can be achieved using a known magnet, but a ferrite molded magnet may be used if necessary.

Thus, in the present invention, crude oil is conducted through the main body configured as described above, and it is desirable that the flow rate is 0.577 L/sec or less, and if the flow rate is 0.5 m/sec or more, the It is difficult to avoid turbulent flow of crude oil in the cylinder, which makes the decomposition of metal complexes contained in crude oil uneven and makes it impossible to effectively liberate desired rare metals. When conducting the flow, it is important to adjust in advance the amount of pumping of the crude oil to a desired speed via a flow meter (see FIG. 5) connected to this device.

The structure of the present invention will be explained below with reference to the drawings in which the same parts are given the same reference numerals. In Fig. 1, 1 is a main body made of stainless steel (5US304) consisting of four long outer walls 1a, 1b, 1c, and Id with a rectangular cross section. H. Both sides of the main body are squeezed and reduced 2 as shown in the figure, and T-shaped pipes 3 are welded to each end (crude oil introduction and outlet sides),
A crude oil introduction valve (hereinafter referred to as an inlet valve) 5 is connected via a flange 4 to one extending end 3' of the T conduit 3 on the crude oil introduction side.
Blow valves (hereinafter referred to as first blow valves) 6 are connected to the other extending ends 3'' via flanges 4.Also, as for the crude oil outlet side T-tube 3, one of the extending ends 3''
A crude oil outlet valve (hereinafter referred to as the outlet valve) 5a is connected to the outlet valve ', and a blow valve (hereinafter referred to as the second outlet valve) is connected to the other extending end 3'' via the flange 4.
(referred to as blow valves) 6a are connected to each other.

7 is a bar-shaped magnet with a rectangular cross section (may be semicylindrical), and the magnet 7 has a coercive force of 3000 to 12000.
The length corresponds to the middle of the outer wall of the main body 1 (the first,
(see Figure 2), and a plurality of them are arranged in the axial direction of the main body 1, alternating the magnetic poles (N, S), so that the outer walls 1a, 1 are arranged as shown in Figure 1.
b, 1c, and ld are arranged in parallel at equal intervals. As mentioned above, when these magnets 7 are arranged in parallel, their lower bottom surfaces 7a are in close contact with the surface of the outer wall 1a (see FIG. 2), and the remaining three surfaces (both side surfaces 7b and 7d including the upper bottom surface 7C are the third As shown in the figure, an overhanging hem 10 having a plurality of recesses 9 formed at equal intervals is fitted into the recesses 9 of a long integral molded body 8 made of synthetic resin, for example, Bakelite (see Fig. 3). Subject 1
Two sets of opposing outer walls (1a, 1c) and (lb,
1d) as shown in the fourth figure (this figure shows the former case), and each set is connected with a bottle (or a bolt) 12 through a bottle hole 11. The two sets of molded bodies 8 are located at mutually shifted positions, and the magnets 7 fitted in the recesses 9 are removably fixed together with the molded bodies 8 in a staggered manner (see FIG. 1).

FIG. 5 schematically shows a series of related devices for recovering rare metals contained in crude oil using the device of the present invention having the above-mentioned configuration.

Now, to explain the case of recovering rare metals from crude oil with reference to Fig. 5, first start the pump P1, and operate the flow meter F connected to the conduit 13 in the piping configuration shown in the figure in the usual manner to start the pump. The flow rate of crude oil to be uploaded is constant (0
, 5 m/sec or less). 2nd block〇-
Each of valves 6 and 6a is closed, and inlet valve 5 and outlet valve 5a are opened.

In this way, the crude oil 22 in the crude oil chest 21 is fed into the main body through the conduit 13 at a constant speed via the inlet valve 5 and the squeezing/reducing part 2 of the main body 1, and is diffused throughout the interior wall 1M of the field. Gold complex salts in the class are decomposed by magnetic lines of force,
As a result, the liberated fine particulate metal bottoms (hereinafter referred to as metal particles) adhere to the inner wall of the main body together with the sludge or become encapsulated in the sludge, while the crude oil after demetallization becomes the same as refined oil, resulting in a reduction in the output of the main body. Reduction part 2. The refined oil is stored in the refined oil chest 23 via the outlet valve 5a and the conduit 14.

In this way, the metal particles loosely attached to the inner wall of the main body 1 along with the sludge can be recovered in a timely manner.To this end, the metal particles can be effectively recovered by sequentially performing the following operations.

■After stopping the pump P1 and closing the artificial valve 5 and outlet valve 5a, the first blow valve 6. While opening each of the second blow valves 6a, turn the three-way valve ■1 toward the crude oil chest 21, and
By opening 2 towards the refined oil chest 23,
The first blow valve on the inlet side 6. Conduit 15. At the same time, the second blow valve 6a on the outlet side is discharged to the crude oil chest 21 via the three-way valve V+J'j and the conduit 16.
, conduit 17. The discharge of the crude oil to be treated is completed by discharging it to the refined oil CHEST 23 through the three-way valve V2° conduit 18.

After opening the three-way valves 1 and V2 in the direction of the diesel oil chest 25, the two sets of molded bodies 8 fitted with the magnets 7 are uncoupled from each other, and the magnets 7 and the molded bodies 8 are removed from the outer wall of the main body 1. By separating, the magnetic field within the main body is eliminated, allowing free movement of the metal particles attached to the inner wall.

■Start pump P2. When the pump starts, the light oil 26 in the light oil chest 25 flows into the conduit 20° three-way valve V in the direction of the arrow.
+, conduit 15. Since the sludge in the main body is fed into the main body 1 through the first blow valve 6, it is dissolved in the light oil, while the non-magnetic free metal particles are dispersed in the sludge-dissolved oil and the second blow valve 6a is fed into the main body 1. , conduit 17. The gas is returned to the light oil chest 25 via the three-way valve 2 and the conduit 19.

The metal dispersion oil 26 that has returned to the light oil chest 25 through the series of processes described above, or the dispersion oil 26 that has been repeatedly circulated through the above process as required, stops the pump P2 and transfers the dispersed oil to the light oil chest 25. If you eliminate reflux and leave it still,
Since the metal particles 27 settle and separate at the inner bottom of the chest, a desired amount of the metal particles can be easily recovered by extracting the metal particles after the upper layer of sludge-dissolved oil is led out of the thread by a conventional method at this point.

However, in the above, if you want to further improve the processing capacity of crude oil and the recovery efficiency of metals, you can install multiple units of this device separately (not shown) in advance and pour crude oil into them. Therefore, if you want to improve the yield of recovered metal particles, use metal dispersion oil 2.
6 is satisfied by repeatedly circulating a certain process as described above.

<Effect> The present invention having the above structure operates as follows.

(1) A rectangular tube made of metal (stainless steel) with a long rectangular cross section consists of a main body and reduced parts squeezed out on both sides, and a plurality of magnets are removably fixed to each outer wall of the main body as described above. In this case, L diffuses completely into the main body without interfering with the conduction speed of the crude oil, which passes through the main body at a constant speed (0.5 m/sec or less).
7), the metal complex salts in the crude oil are effectively decomposed and the rare metals are liberated in the form of particles.

(2) The above-mentioned metal particles released in this way become in a state of being encapsulated with the sludge in the crude oil, and adhere to the inner wall of the main body, making it easy to collect rare gold scraps (Example reference).

<Effect of the invention> The present invention exhibits the following unique effects.

■The present invention is a permanent magnet with minimal demagnetizing force (coercive force 3000~
12,000 gauss/piece) are arranged in parallel at equal intervals on each outer wall of the rectangular cylinder main body, but as mentioned above, the bottom surface of this magnet is in close contact with the outer wall of the main body, and the magnet A long molded body made of synthetic resin having an overhanging hem formed integrally with fittable recesses on both sides (see Fig. 3) arranged in parallel at regular intervals. The protruding hems of the main body are removably connected to each other with bolts (see Figure 4), and this structure is set so that the magnets are arranged in a staggered manner between the adjacent outer walls. By passing crude oil through the magnetic field generated by
Metal particles in oil can be attached to the inner wall surface of the main body together with sludge.

(2) Also, as described in detail above, the present invention provides a large mouth valve and a first valve. By operating the second blow valve and the three-way valves V+ and V2 in stages, the piping was designed as shown in the diagram to obtain the following effects. After effectively removing the oil, the discharged oil, which is equivalent to refined oil, can be discharged into the crude oil chest 21 and the refined oil chest 23, respectively. The metal particles are made non-magnetic and their free movement is enabled. (c) Therefore, at this point, light oil chest 2
By feeding light oil from 5 to the main body, this dissolves the sludge in the main body, so that the metal particles are dispersed in the sludge-dissolved oil and return to the light oil chest 25 through a predetermined process. (d) For this reason, by leaving the refluxed metal dispersion oil or the refluxed dispersion oil chest after circulating the above process as necessary, the metal particles can be sedimented and separated at the inner bottom of the chest.

(2) Furthermore, since the present invention requires only the magnets to be detachably fixed to the outer wall of the main body as described above, the device itself can be made compact and easy to operate, making it suitable for mass production of devices with a simple structure.

<Example> Examples 1 to 10 Using this device with the following specifications, C heavy oil (J
Using IS 2205-1960.3 Type No. 2) as a sample, the sample was passed through the apparatus under the following conditions, and the C heavy oil discharged was quantitatively analyzed by a conventional method. The result is the first
- Shown in Table 3. The analysis results of untreated C heavy oil (above) are also listed.

(A) Specifications for kneeling Buddha scolding (1υIXIIXIυ厘×″JlJ familiar)/2
The molded bodies (see FIG. 3) which fit into the recesses of the Bakelite molded bodies formed so that the pieces can be set at intervals of 20M (see FIG. 3) are removably fixed (the same applies hereinafter) as described above.

(B) Processing conditions: When the coercive force and treatment time are kept constant and the flow rate is changed: 10,000 rd sample heated to 80°C is fed at a feeding speed of 0.1 m/sec (flow rate), 0.5 TrL/ seconds, 1
．． The flow rate was 5 TrL/sec, the treatment time was 35 minutes, and conduction was conducted to the main body, and the discharged heavy oil C was sampled according to the flow rate, and each of them was subjected to a constant ω test, and the results shown in Table 1 were obtained.

Part 1: When the coercive force and flow rate are kept constant and the treatment time is varied. Separately collect 10,000 IIi of the test sample heated to 80°C, and set the flow rate to 0.5 m/sec for 15 minutes and 35 minutes.
Minutes.

The treatment time was 75 minutes, and as in (2) above, conduction was conducted to the main body, and the discharged heavy oil C was collected for each treatment time, and each of them was subjected to the above test, and the results shown in Table 2 were obtained.

Table 2 - When the treatment time and flow rate were kept constant and the coercive force was changed, 10,000 d of sample heated to 80°C was taken separately.
The treatment time was 35 minutes, the flow rate was 0.5 m/sec, and the coercive force at the center of the main body was 1350 Gauss and 1600 Gauss.

2,500 gauss and 3,850 gauss, conduction was conducted to the main body as in (2), and discharged heavy oil C was collected according to coercive force, and each of them was subjected to the above test, and the results shown in Table 3 were obtained.

Third! l! However, the numerical values listed in Tables 1 to 3 above indicate the average values of five tests conducted for each example.

As is clear from the above Tables 1 to 3 (Examples 1 to 10), when the C heavy oil is introduced into this device having the above specifications, the conduction conditions (flow rate, processing time, coercive force, etc.) In each of the discharged oils treated by changing the oil as described above, a significant reduction in vanadium (rare gold rira) contained in the untreated sample was observed.

In other words, 221 ppm of vanadium drastically decreased to 17 ppm (7.7% in combination) in Example 1 and 21 ppm (9.5%) in Example 2 due to the change in flow rate, in other words, 92.3% in the former. In the latter case, it was found that an amount equivalent to 90.5X of the metal adhered to the inner wall of the main body, and the flow velocity at this time was 0.
．． It is known that 57 FL/sec or less is optimal (see Table 1). Also, according to Examples 4 to 6, Example 5
Vanadium content in the sample 221 ppm in and 6
The former is 20ppIIl (pairing @ 9.0%) and the latter r91)I)l (4,0%) due to the change of processing time.
The former is 91x and the latter is 96% and 6%.
A considerable amount of metal adheres to the inner wall of the main body, showing good results, but the latter (
In Example 6), the required processing time was 75 minutes, which was more than twice as long as the former, which is not a favorable condition in terms of production efficiency. Therefore, it can be seen that the optimal processing time is around 35 minutes in the former case (see Table 2). Furthermore, Example 7
According to ~10, the vanadium content in the sample is 221 ppm
decreases with changes in coercive force, but especially in Examples 9 and 10, its parent value is 49 ppm (pair m 22
%) and 19 ppm (8.6%), respectively, and it can be seen that in Example 9, an amount equivalent to 91.4% of each metal adhered to the inner wall of the main body in the case of 78 x 1 and 10. However, since the results of Example 9 are not favorable in terms of production efficiency, it is found that the optimum coercive force is 3000 Gauss or more (see Table 3).

For this reason, good effects can be obtained by setting the processing conditions for the crude oil to be conducted through this device to a flow rate of 0.5 m/sec or less, a processing time of 35 minutes, and a coercive force of 3000 Gauss or more, referring to the results of the above examples. This is what happened. However, although such conditions are advantageous in that more than 90% of the vanadium can be deposited on the inner wall of the main body with only one treatment of the sample, it does not mean that all of the vanadium is deposited, so 100% recovery can be achieved in all cases. To contain the oil, the oil discharged during the initial treatment, which is equivalent to refined oil (Refined Oil Diprocess 23 storage), can be returned to the same device (main body), or multiple units of this device can be installed separately (see above). It goes without saying that by conducting the discharged oil one after another, even the smallest amount of remaining metal can be easily recovered, and the desired 100% recovery can be achieved.

Moreover, according to this apparatus, in order to improve the yield of metal obtained under the above processing conditions, in a series of related apparatuses including this apparatus (see FIG. 5), the metal dispersion oil 26 is transferred to the light oil chest By circulating a certain process between the main body 25 and the main body 1, the desired purpose can be easily achieved, so the practical benefits of this device are significant.

[Brief explanation of the drawing]

Fig. 1 is a schematic perspective view of the present invention, Fig. 2 is a perspective view showing a state in which magnets are fixed to the opposing outer wall surfaces of the main body, and Fig. 3 is a recessed part of a resin molded body having a recessed part and an overhanging hem. FIG. 4 is a cross-sectional view of the molded body with the magnet fitted into the concave portion attached to the outer wall of the main body, and FIG. 5 is a series of related devices including the present invention. FIG. 1... Main body, 2... Squeezing reduction part, 3... T-shaped pipe. 4...Flange, 5...Inlet valve, 5a...
・Outlet valve. 6...First blow valve, 6a...Second blow valve. 7... Magnet, 8... Resin molded body, 9... Recessed portion. 10... Overhanging hem portion, 11... Bottle hole, 12... Pin. 13-20... Conduit, 21... Crude oil chest, 23
... Refined oil chest, 25 ... Light oil chest, 26
...Metal dispersion oil, 27... Gold bottom particles, F...
Flowmeter. P+, Pz...pump, V+, V2...
Three-way valve patent applicant Muto - Shinobu Figure 2

Claims (3)

[Claims] (1) A rectangular metal tube with a long rectangular cross section, the rectangular tube consisting of a rectangular tube main body and reduced parts squeezed out on both sides of the rectangular tube main body, and a plurality of permanent magnets with magnetic poles on each outer wall of the rectangular tube main body. The permanent magnets are alternately arranged in parallel at equal intervals, and the permanent magnets on the adjacent outer walls are removably fixed to each other in a staggered manner, and blow valves are attached via flanges to the reduced parts on both sides of the main body of the rectangular tube. An apparatus for recovering rare metals from crude oil or refined oil, characterized by: (2) An apparatus for recovering rare metals from crude oil or refined oil according to claim 1, wherein the permanent magnet has a rectangular or semicylindrical cross section. (3) The apparatus for recovering rare metals from crude oil or refined oil according to claim 1 or 2, wherein the permanent magnet has a holding force of 3,000 to 12,000 Gauss/piece.