JPH08337408A - Separation and recovery method of carbon component and nickel ion from dust - Google Patents

Abstract

(57) [Summary] [Objective] To provide a method for recovering a highly pure carbon component from soot dust and a method for efficiently removing and recovering nickel ions from soot dust. [Structure] Dust such as heavy crude oil ash and EP ash 5 is dispersed in water in a settling separation tank 1 to form a slurry, salts are added to the slurry-like liquid and stirred, and then the heavy metal 5a is allowed to settle, The slurry-like liquid is recovered leaving these sediments,
By applying the collected slurry-like liquid to the centrifugal separator 3, the carbon component is forcibly dehydrated and condensed to be collected.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of recovering carbon components in dust by removing impurities other than carbon from dust generated by burning heavy crude oil and concentrating and purifying the carbon components. The present invention relates to a method for separating and recovering nickel ions adsorbed on a substrate.

[0002]

2. Description of the Related Art Heavy metals, sulfur, and nitrogen components in heavy crude oil are concentrated in the form of salts or oxides in soot and dust produced by burning heavy crude oil. It is mixed in. Soot dust shows sulfuric acid acidity when it absorbs moisture and causes damage due to corrosiveness and pollution due to elution of heavy metals, and is considered to be a hazardous industrial waste.

[0003] In addition, dust contains 26 to 67% of a carbon component. However, if the dust is used as it is, it contains a large amount of impurities other than the carbon component, absorbs moisture, shows strong acidity, and elutes heavy metals.
Due to its great danger to humans, animals and plants, and the environment, it has not been used as a carbon material.

[0004] Therefore, since the dust is a waste, a measure to reduce the amount of dust is preferentially taken, and the carbon component of the dust and salts vaporized at high temperature are incinerated and removed. And 1/20 of the dust
Residue reduced to a volume is regarded as a raw material for recovering some useful metals such as nickel.

[0005]

The removal of carbon components from dust by incineration requires the use of a special incinerator equipped with pollution prevention equipment because harmful gases are generated again by the thermal decomposition of new dust and salts. Costly for incineration. Further, since the combustion residue contains iron rust, the ratio of nickel is reduced, and the cost is increased because acid is dissolved to separate and recover nickel.

[0006] Further, since the soot dust is a porous particle in which a volatile gas is enclosed, it is easily scattered and ignited. If scattered in the air, there is a risk of ignition or explosion due to electrostatic sparks, and care must be taken when handling in a dry state. Furthermore, dust is immediately packaged immediately after it is generated and incinerated at the site where it is generated. However, if it can be handled in a wet state, it can be handled easily and safely, and it can be transported outside the site.

[0007] Therefore, if a method of separating the carbon component in the dust in a wet state into a usable form and recovering nickel at the same time is adopted, an incinerator dedicated to the dust for reducing the weight becomes unnecessary.
It is not necessary to dissolve the acid when recovering nickel.

Therefore, an object of the present invention is to disperse soot dust in water to form a slurry to remove water-soluble salts, to concentrate carbon components by utilizing the difference in specific gravity and to perform coagulation dehydration by centrifugal force, and ultrasonic waves. By providing a method for recovering a high-purity carbon component from soot dust by carrying out a purification operation by, further elution of nickel ions from the soot dust in a state where the soot dust is dispersed in water, by separation, It is intended to provide a method for efficiently removing and recovering nickel ions from soot dust directly without going through the acid dissolution form of the incineration residue.

[0009]

According to the first aspect of the present invention, dust such as heavy crude oil ash or EP ash is dispersed in water to form a slurry, salts are added to the slurry liquid, and the slurry is stirred. After sedimentation of the material, the sediment is left to recover the slurry-like liquid, and the collected slurry-like liquid is centrifuged to forcibly dehydrate and condense the carbon component, thereby separating and recovering. did.

[0010] The invention according to claim 2 is characterized in that heavy crude ash or EP
Soot dust such as ash is dispersed in water to form a slurry, and the carbon component recovered from the slurry liquid is dispersed in water again to form a slurry, and the carbon component is subjected to ultrasonic vibration on the slurry liquid. The nickel ion in the solution was eluted into the liquid to separate and collect the carbon component and the nickel ion.

[0011] Further, the invention according to claim 3 is characterized in that heavy crude ash or E
Dust such as P ash is dispersed in water to form a slurry, and the carbon component recovered from the slurry liquid is dispersed again in water to form a slurry. The slurry liquid has a 5- or 6-membered ring. A sulfonic acid compound was added thereto, and further, ultrasonic vibration was applied to elute and recover nickel ions in the carbon component into the liquid, and the carbon component and nickel ions were separated and recovered.

[0012]

According to the first aspect of the present invention, heavy crude ash or E
Soot dust such as P ash is dispersed in water in the sedimentation separation layer to form a slurry-like liquid, and salts are put into this to be stirred by a stirrer to integrate them. After that, the metal oxide having a large specific gravity settles and is separated from the slurry-like liquid, and the slurry-like liquid is sucked up and recovered by a pump while leaving these sediments, and is then subjected to a centrifugal separator to forcibly dehydrate the carbon component. It can be separated and collected by condensation.

In the invention of claim 2, heavy crude oil ash and E
Dust such as P ash is dispersed in water to form a slurry liquid, and the carbon component recovered from this slurry liquid is dispersed again in water in a cleaning tank having an ultrasonic oscillator to form a slurry. When ultrasonic vibration is applied to the liquid and violent vibration is applied, nickel ions in the carbon component are dissolved in the liquid. After that, these are sucked up by a pump and collected, and when they are applied to a centrifugal separator, they are separated into a carbon component and a liquid in which nickel ions are eluted. The carbon component can be recovered from the centrifugal separator, and the separated liquid is again pumped to the metal removing device to recover nickel ions.

According to the third aspect of the present invention, the operation is basically the same as that of the second aspect of the present invention.
A sulfonic acid compound having a six to six-membered ring is added. Then, the sulfonic acid group bonds to the nickel ion and becomes easily soluble in water. When ultrasonic vibration is further applied to this state, the nickel ion is quickly and efficiently eluted from the carbon component in the slurry liquid, separated and recovered. it can.

[0015]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is an explanatory diagram of an apparatus used in the method of the first embodiment of the present invention. The sedimentation tank 1 is connected to a centrifugal solid-liquid separation / purification device 3 via a pump 2a, and a recovery water tank 4 is connected to the centrifugal solid-liquid separation / purification device 3. The method of the first embodiment will be described with reference to FIGS. 1 and 2. Heavy crude oil ash and EP ash 5 are dry components, and are light and difficult to handle. It is put into a sedimentation separation tank 1 containing water to form a slurry. At this time, the ratio of heavy crude ash and EP ash 5 to water is about 5% to 20%. Then, salts are further added, and the mixture is stirred by a stirrer 1a provided in the sedimentation / separation tank 1, and these are integrated. After a while, 5a of heavy metal iron rust etc. is deposited on the bottom 1b of the sedimentation separation tank 1 by its own weight.
Settles in and then deposits, and is separated into a slurry liquid composed of the carbon component 5b. Thereafter, the slurry-like liquid excluding the deposited iron rust 5a is sucked up by the pump 2b, and is subjected to a centrifugal solid-liquid separation / purification device 3 to remove water, forcibly dehydrate and condense, and recover the remaining carbon component 5b.

Table 1 below shows the recovery rate of the carbon component 5b from soot dust such as heavy crude oil according to the first embodiment of the present invention. According to this, in the state of the dust as it is, the fixed carbon is 82.2% and the ash content is 17.3%. However, when the slurry is recovered in a slurry state and subjected to centrifugal force, the fixed carbon is 87.8% and the ash content is 1
It becomes 2.2%, and it can be seen that the latter can more efficiently collect the carbon component.

[0017]

[Table 1]

Next, FIG. 3 is an explanatory view showing a second embodiment of the present invention. First, the apparatus used in the method of the second embodiment will be described. A washing tank 6 having an ultrasonic oscillator 6a is provided, and a centrifugal solid-liquid separation purification apparatus 8 is connected to the washing tank 6 via a pump 7a. Further, the centrifugal separation type solid-liquid separation purification apparatus 8 is connected with a recovery water tank 9 for collecting the liquid in which the nickel ions separated from the centrifugal separation type solid-liquid separation purification apparatus 8 are eluted. The water tank 9 is connected to the metal removing device 10 via a pump 7b.

The method of the second embodiment is different from that of the first embodiment in that the first tank is charged not with heavy crude ash or EP ash 5, but with carbon recovered from heavy crude ash or EP ash. Component, for example, the carbon component 5b recovered in the first embodiment is dispersed again in a washing tank 6 containing pure water at a ratio of about 5% to 30% to form a slurry. When ultrasonic vibration is applied to the slurry-like liquid by the ultrasonic oscillator 6a provided in the above, nickel ions can be dissolved in the liquid. After the nickel ions are eluted into the liquid in this manner, these slurry-like liquids are sucked up by the pump 7a and applied to the centrifugal solid-liquid separation / purification device 8, whereby the carbon component is removed from the centrifugal solid-liquid separation / purification. The overflow water remaining in the device 8 and from which the nickel ions have been eluted is recovered in the recovery water tank 9. Thereafter, the overflow water is transported from the recovery water tank 9 to the metal removing device 10 by the pump 7b, where nickel ions are recovered. As for the carbon component, the highly accurate carbon component from which nickel ions have been removed as described above is collected from the centrifugal solid-liquid separation / purification device 8.

As shown in Table 2, when ultrasonic waves of 100 KHZ are applied for 5 minutes as the immersion time in the cleaning tank 6, the carbon components separated by the centrifugal solid-liquid separation and purification device 8 are contained. The amount of nickel ions was 36 mg / 1. When the immersion time in the cleaning tank 6 in the liquid is 10 minutes and the ultrasonic vibration is 200 KHZ, the amount of nickel ions contained in the carbon component separated by the centrifugal solid-liquid separation / purification device 8 is 24 mg / l. Diminished. Further, when the immersion time in the washing tank 6 is further increased to 30 minutes and the ultrasonic vibration is set to 100 KHZ, the amount of nickel ions contained in the carbon component separated by the centrifugal separation type solid-liquid separation and purification device 8 is zero. 0.3 mg / l.

Table 2 is a table when the method of the second embodiment was tested at various values of frequency and immersion time. In such a case, the carbon component separated by the centrifugal solid-liquid separation / purification device 8 was used. Shows the amount of nickel ions contained in the sample. The values of the nickel ions are based on the dissolution and shaking test of the Environment Agency Notification No. 13 of 1973. Looking at this, the frequency of the ultrasonic wave is from 100 KHZ to 2
00KHZ, when the immersion time in the liquid is 10 minutes to 30 minutes, the amount of nickel ions contained in the carbon component is small,
This indicates that nickel ions in the carbon component were efficiently eluted into the liquid at the above ultrasonic frequency and immersion time in the liquid. Further, the carbon component recovered by this second embodiment has an extremely high proportion of fixed carbon in an anhydrous state,
It can be seen that the collection efficiency is good.

[0022]

[Table 2]

In addition, in Table 3, the carbon component recovered in the first embodiment contained 2,000 mg / l of nickel ions, whereas the carbon component subjected to ultrasonic vibration in the second embodiment. Contains only 1 mg / l or less of nickel ions, which means that the carbon component recovered in the first example has a low purity as carbon, and the ultrasonic vibration was applied in the second example to obtain nickel. It can be seen that the ions were removed and the carbon component was purified.

[0024]

[Table 3]

In the second embodiment, in addition to the first embodiment, pure water is used as the water in the cleaning tank 6 to reduce impurities in the cleaning tank 6 which are harmful when ultrasonic waves are applied. . In the second embodiment, dust such as heavy crude ash or EP ash was dispersed in water to form a slurry, and the carbon component 5b recovered in the first embodiment was used. The carbon component obtained is not limited to the recovered carbon component of the first embodiment, but may be a carbon component recovered by making dust such as heavy crude ash or EP ash into a slurry by another method. is there.

Finally, the third embodiment of the present invention will be described. The basic structure is the same as that of the second embodiment, but a 5-membered to 6-membered sulfonic acid compound is added when ultrasonic vibration is applied. The reason why the 5-membered to 6-membered sulfonic acid compound is added to the slurry-like liquid is to facilitate the elution of nickel ions from the carbon component into the slurry-like liquid. That is, copper or nickel are those less soluble in the liquid in their native form, those having a sulfonic acid group (-SO ₃ H) in compounds of the 5-membered ring or 6-membered ring is bonded to the copper or nickel slurry It becomes possible to quickly elute in the liquid of.

In Table 2 above, (+ additive) in the column of immersion time in liquid indicates the case where the 5- or 6-membered sulfonic acid compound was added, and the amount of eluted Ni (mg / l)
The numerical value in the column indicates the amount of nickel ions contained in the carbon component recovered from the centrifugal solid-liquid separation purification device 8. For example, the immersion time in the liquid is 10 minutes, and the ultrasonic frequency is 10 minutes.
When it is set to 0 KHZ, the amount of nickel ions in the carbon component separated by the centrifugal separation solid-liquid separation purification device 8 is 12 mg /
1, which is 26 mg / l less than the recovery amount of nickel ions of 38 mg / l when the above additive is not added. When the immersion time in the liquid was 15 minutes and the ultrasonic frequency was 100 KHZ, the recovery amount of nickel ions was 0.2 mg / l, and the recovery amount of nickel ions when the above additive was not added was 0.6 mg / l. 0.4 compared
mg / l is also low. For this reason, it is more efficient to add a 5-membered or 6-membered ring sulfonic acid compound when applying the ultrasonic vibration than to simply apply the ultrasonic vibration to the slurry-like liquid. You can see what you can do.

[0028]

According to the first aspect of the present invention, since the dust is slurried to have wettability, it is easy and safe to recover the carbon component. Moreover, since it does not burn soot and dust, it does not generate harmful gas and does not require expensive equipment.

According to the second aspect of the invention, in the first aspect of the invention, the nickel ions are still contained in the carbon component. However, according to the invention, the nickel ions can be easily recovered. Further, the carbon component can be refined to a higher precision. At the same time, acid dissolution as nickel treatment is not required, and nickel ions separated and recovered can be effectively reused.

According to the invention of claim 3, a 5-membered ring to 6
Since the membered-ring sulfonic acid compound is added to the slurry-like liquid, the carbon component and the nickel ion can be separated and recovered in a shorter time and more efficiently than the invention of claim 2.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a first embodiment of the present invention.

FIG. 2 is a vertical cross-sectional explanatory view of a centrifugal separation type solid-liquid separation purification device according to the first embodiment of the present invention.

FIG. 3 is an explanatory diagram showing a second embodiment of the present invention.

[Explanation of symbols]

1 Settling Separation Tank 3 Centrifugal Solid-Liquid Separation and Purification Device 4 Recovery Water Tank 6 Washing Tank 9 Recovery Water Tank 10 Metal Removal Device

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasunobu Ochiai 2-1 Nakasode, Sodegaura-shi, Chiba Tokyo Electric Power Company Inside the Sodegaura Thermal Power Plant (72) Inventor Kimio Wakatsuki 3-1-5 Sakaemachi, Hamura-shi, Tokyo Stocks Company Kaijo (72) Inventor Mitsu Nishizawa 1136 Hagien, Chigasaki, Kanagawa Japan Surface Chemistry Co., Ltd. (72) Inventor, Koichi Kawase 1 89, Shigeichi, Kasama, Ibaraki Prefecture (72) Inventor, Art Ceramic Co., Ltd. (72) Mamoru Senoh 1 889 Ma, Shimoichi, Kasama City, Ibaraki Prefecture Within Art Ceramic Co., Ltd.

Claims (3)

[Claims] 1. A soot dust such as heavy crude oil ash or EP ash is dispersed in water to form a slurry, salts are added to the slurry-like liquid, and the mixture is stirred. A method for separating and collecting a carbon component from soot dust, characterized in that the slurry-like liquid is recovered and the recovered slurry-like liquid is subjected to a centrifugal separator to forcibly dehydrate and condense the carbon component for recovery. . 2. Dust such as heavy crude ash or EP ash is dispersed in water to form a slurry, and the carbon component recovered from the slurry liquid is dispersed again in water to form a slurry. Separating and recovering the carbon component and the nickel ion from the dust by subjecting the nickel ion in the carbon component to elution into a liquid by applying ultrasonic vibration to the liquid, separating and recovering the carbon component and the nickel ion from the dust. Method. 3. Dust such as heavy crude oil ash or EP ash is dispersed in water to form a slurry, and the carbon component recovered from the slurry liquid is dispersed again in water to form a slurry. , A 5- or 6-membered sulfonic acid compound is added thereto, and ultrasonic vibration is applied thereto to elute nickel ions in the carbon component into the liquid to separate and collect the carbon component and nickel ions. A method for separating and recovering carbon components and nickel ions from dust.