JP2004337825A - Sulfate pitch detoxification/recycling matter treatment system using pitch treatment agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfate pitch detoxification treatment apparatus for detoxifying sulfate pitch such as sulfate pitch produced when petroleum is refined or waste oil is recycled or after petroleum is refined, waste oil and toxic sludge, and provide a detoxification/recycling matter refining apparatus for recycling liquid pitch which apparatus enables recycling of a refined product produced by detoxification treatment. <P>SOLUTION: In the detoxification/recycling refining apparatus for the sulfate pitch, a first treatment liquid A is mixed with the raw material of the sulfate pitch generated at the petroleum refining or the like, and stirred, then a second treatment agent B is mixed therewith, and stirred. The mixed and stirred refined product is dried to obtain a sand-like refined product. The treatment apparatus is manufactured relatively simply at low costs, thus the apparatus with a size corresponding to the generation amount of waste such as the liquid pitch and sludge can be manufactured. Furthermore, because the refined product is detoxified, the product can be treated in the same manner as river sand or sea sand is. Thus, various reuse applications are possible such as building materials, civil engineering materials and land reclamation. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a detoxification treatment apparatus for sulfuric acid pitch, a waste oil, a harmful sludge or the like as a raw material at the time of petroleum refining, waste oil refining, or after petroleum refining, and a detoxifying apparatus for refining detoxified recycled materials. The present invention relates to a purification technique relating to a detoxifying reclaimed material purification apparatus relating to the circulation and recycling of a liquid pitch, in which a purified product generated by a treatment can be reused.
[0002]
[Prior art]
Japanese Patent Application Laid-Open No. 07-204694 "Method of treating dust and soil mixed with sand" as a first example as a prior art or a similar technology relating to the present invention, and Japanese Patent Application Laid-Open No. 2002-180067 "Method of treating sulfuric acid pitch and sulfuric acid pitch mixed with sand" as a second example Processing method ".
The above-mentioned “dust-mixing method with sand” refers to a method in which raw materials are generated at a site at the time of oil refining, or buried in the ground, or excavated sand-sulfated pitch mixed with sand from the ground, and the sulfuric acid pitch containing the sand Mixed with sand, and mixed and stirred the organic cement-based solidifying agent and treating agent, detoxified by stirring and mixing.The detoxified purified product is separated and refined into lump and oil in the separation process, and the lump is crushed. After crushing in the process, it is refined as a mixture that can be used as a raw material for burning cement, and the refined product with a high oil content refined in the above-mentioned separation process is used as a material for auxiliary combustion material during burning cement. Sulfuric acid pitch treatment technology.
[0003]
Apart from the above, there is a third application filed by the same applicant as the present applicant, Japanese Patent Application No. 2002-361498, "Method of detoxifying sulfuric acid pitch using pitch treatment agent". There is no difference in the detoxification processing method in the basic processing steps in the patent application which is the earlier application of this patent. However, as a problem in the actual treatment process, in the process of detoxifying the sulfuric acid pitch, which is the raw material, the sulfuric acid contained in the raw material reacts with the detoxifying agent, and the sulfur dioxide gas and nitrogen oxides are released into the atmosphere. There is a further problem that serious pollution problems occur.
[0004]
[Problems to be solved by the invention]
Further, in the first example of the prior art, the petroleum refining processing apparatus and processing steps become large-scale, and the purpose is to recycle the sulfuric acid pitch generated at the time of petroleum refining as a material at the time of cement firing. Both lump mass and oil content are limited to use as materials for cement firing.
Furthermore, harmful sulfuric acid pitch, which is industrial waste, is a tar-like pitch that is a by-product of gas oil refining, and it is oil-rich, contains a large amount of sulfuric acid, and contains lead, arsenic, mercury, and sulfuric acid. Contains gas and cadmium and contains harmful substances to humans and livestock.
[0005]
Furthermore, the above-mentioned prior art sulfuric acid pitch is generated in diesel oil refineries all over the country. However, disposal or treatment of the by-product sulfuric acid pitch is limited to industrial waste treatment companies, and inexpensive and effective treatment. Because there is no method, they are packed in drums and stored in warehouses, or are abandoned or discarded in mountains all over the country, or are thrown away, causing pollution and social problems.
In addition, the industrial waste is considered to be responsible for disposal or disposal by the cause of the waste, so that it can be inexpensively and easily treated, and furthermore, it is desired to detoxify the waste at a place close to the place where the industrial waste is generated. There was a request.
[0006]
[Means for Solving the Problems]
In order to solve the above problem, in the invention according to claim 1, sulfuric acid gas odor generated when a sulfuric acid pitch is introduced into a stirring reactor from a container containing a liquid containing sulfuric acid as a raw material is not generated. A refrigeration apparatus for cooling and freezing the whole container, a crushing apparatus for crushing and crushing the frozen and chilled raw material, and mixing the crushed and crushed raw material with the first processing liquid (A) and the second processing agent (B). A liquid pitch detoxifying recycle purifier equipped with a stirring reactor that stirs, the processing process is simple, the processing device is relatively inexpensive, and the size is appropriate for the amount of raw materials generated Can be manufactured. Furthermore, since the purified product treated by the purification apparatus of the present invention is rendered harmless, it can be handled in the same manner as river sand or sea sand, and does not cause pollution. Therefore, it is possible to reuse the purified reusable materials in a wide variety of applications such as building materials, civil engineering materials, and landfills.
[0007]
Further, in the invention of the second claim, in the detoxifying reclaimed material purifying apparatus according to the preceding claim, air is introduced into the stirred reactor in order to treat harmful gas discharged during the purification process in the stirred reactor. And a gas detoxifying device for detoxifying harmful gas discharged from a processing step in the device, which is provided with an intake fan for feeding air into the device and an exhaust fan for discharging air in the device. The liquid pitch detoxifying reclaimed material refining apparatus according to claim 1, wherein the liquid pitch contains a large amount of sulfuric acid in the raw material, so that a clean sulfuric acid pitch detoxifying reclaimed substance refining apparatus having no pollution is used. To provide.
[0008]
Further, in the crushing apparatus according to the third aspect, in the crushing apparatus according to the first aspect, the crushing apparatus for the raw material in the frozen and frozen container is provided with one or a plurality of cutting faces on a circular pedestal, and the pedestal is rotated for cooling. The crushing and crushing apparatus according to claim 1, wherein the crushed raw material is crushed.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a treatment process diagram relating to a refining apparatus for detoxifying and detoxifying sulfuric acid pitch by freeze-pulverization according to the present invention. FIG. 2 is a movement locus diagram (A) and a cross-sectional view (B) of a milling cutter during a milling process of a frozen and frozen material. FIG. 3 is a structural diagram of the stirring paddle in the stirring reactor.
FIG. 4 is a process diagram according to a "sulfuric acid pitch treatment method and a method for treating sulfuric acid pitch mixed with sand" described in Japanese Patent Application Laid-Open No. 2002-180067, which is a second prior art. FIG. 5 is a process diagram of the second prior art, Japanese Patent Application No. 2002-361498, "Method for detoxifying sulfuric acid pitch using pitch processing agent".
[0010]
In FIG. 1, a liquid pitch, which is a raw material 2 containing a large amount of sulfuric acid, is a refined by-product refined in a gas oil refining process, and is usually transported or stored in an inexpensive and simple drum.
Since the liquid pitch contains a large amount of sulfate ion gas harmful to humans and animals, in order to ensure the safety of humans and animals in detoxification and refining, further release the sulfate ion gas to the atmosphere so as not to cause pollution, The liquid pitch, which is the loaded raw material, is frozen and solidified in the refrigerating device 11 while the loaded drum 2 remains.
[0011]
After the drum 2 containing sulfuric acid pitch, which is a frozen and solidified raw material, is turned upside down, the lid is hung downward by the moving crane 12 and moved onto the pulverizer 14.
Next, the lid of the drum 2 moved to the pulverizer 14 is opened, and the frozen and solidified raw material 2 is pulverized and discharged from the drum 2 by the solution adopting cutter 13 provided at the upper part of the pulverizer 14. The raw material 2 that has been pulverized and discharged passes through the inside of the pulverizer 14 by natural fall and is injected into the stirring reactor 15.
Here, as for the pulverization by the solution-adopting cutter 13 provided on the upper part of the pulverizer 14, as shown in FIG. Since the face 31 is provided on the solution adopting cutter 13 on the peripheral edge, the rotating teeth of the solution adopting cutter 13 rotate along the circumference inside the drum 2 containing the raw material by the rotation of the motor. Raw materials can be evenly crushed and taken out.
[0012]
In the stirring reactor 15, a stirring paddle 40 having a structure as shown in FIG. 3 is provided. First, the first processing liquid (A) 22 is mixed, mixed and stirred, and then mixed. The second treating agent (B) 23 is mixed and sufficiently mixed and stirred.
Here, the first treatment liquid (A) 22 is a liquid obtained by ion-separating seawater, in particular, seawater of a deep sea current to remove chlorine, and converting the solution into a strongly acidic and strongly alkaline solution. It is a weakly acidic solution containing green (antioxidant solution), refreshing oil (oil-degrading detergent), and lipolytic enzyme, each of which is about a few percent. The second treating agent (B) 23 is composed of about 40% coal ash, about 20% nitrate lime, zeolite, nanocarbon, aluminum sulfate, magnesium hydroxide, calcium phosphate, and copper from several tens% each. It is a strong alkaline powder containing several percent.
[0013]
The raw material 2, the first processing liquid (A) 22, and the second processing agent (B) 23 are mixed and sufficiently mixed and stirred again with the raw material mixed and stirred up to the previous step.
The second processing agent (B) 23 is mixed with the raw material in the same volume (about 100%) to about 1.2 times (about 120%) in volume ratio, and is mixed and stirred again by the stirring reactor 15. You.
It should be noted that the mixing ratio also has a difference in the ratio of the liquid contained in the raw material, so that the mixing ratio needs to be increased or decreased according to the volume of liquid contained in the raw material. Therefore, the above numerical values are a guide and are not limited to these.
[0014]
When the mixing and stirring are sufficiently performed by the internal stirring paddle 40 in the stirring reactor 15, the raw material after the processing step is almost rendered harmless.
The detoxified raw material becomes granular sand when deodorized and dried in the latter half of the stirring reactor 15, is discharged by the discharging device 16, is put into a flexible container (commonly called flexible container), is loaded on a truck or the like, and is reused. It may be transported to the place where it is needed first, or may be transported on a belt conveyor when the reuse destination is near.
[0015]
In addition, the sulfuric acid pitch released in the mixing and stirring process in the stirring reactor 15 contains a peculiar harmful sulfuric acid gas, and thus is released into the stirring reactor 15. Since the air cannot be discharged as it is, the air is sucked into the agitation reactor 15 by the intake fan 25, and the air is sucked by the exhaust fan 17 through the duct 16 through the interior of the agitation reactor 15. Desulfurization and deodorization are performed in the treated water circulation device 27 of FIG. The deodorization of the gas detoxification device 18 can sufficiently detoxify the sulfuric acid gas by mixing the alkaline water 20 of Hasal liquid as a gas treating agent.
[0016]
The harmless and deodorized sulfuric acid gas is discharged to the atmosphere via the exhaust stack 26. This sulfuric acid gas is rendered harmless and detoxified in the gas detoxification device 18, so that no pollution problem occurs.
The deodorized treated water of sulfuric acid gas is circulated and used by the treated water circulation device 27 below the deodorization device 18.
The raw material detoxified by the stirring reactor 15 becomes a detoxified sandy substance in the same state as river sand or sea sand.
Therefore, the petroleum liquid pitch containing sulfuric acid gas becomes sand detoxified by this device, so cement reinforcement, road pavement, construction material, earth and wood, UL groove material, block material, landfill material, etc. And it can be reused in a wide range.
[0017]
The sulfuric acid pitch, a raw material described above, was detoxified by a sulfuric acid pitch detoxifying device and inspected by inspection laboratories, and found to be harmful substances such as sulfate ion, chloride ion, mercury, cadmium, lead, and arsenic. Almost no carbon was detected, and 11% of water, 64% of ash, and 6% or less of oil and sulfur were detected, but the test result was harmless.
As a result, it is possible to reuse the products of sulfuric acid pitch detoxification in a wide range as cement reinforcing materials, road pavement materials, building materials, earth and wood, UL-shaped groove materials, block materials, landfill materials, etc. Proven.
[0018]
The above is the method for detoxifying sulfuric acid pitch and the like according to the present invention. The above steps are not limited to the above-described method, apparatus or those shown in the figures, but any other apparatus can be used as long as it is an apparatus capable of sequentially mixing and stirring each raw material, a processing agent, and a processing solution. Needless to say, it is possible.
Further, the mixing ratio of the processing agent and the processing liquid is not limited to the numerical values described in the conventional example as described above, and it is natural that the mixing ratio is changed according to the content of various substances contained in the raw material such as sulfuric acid pitch. That is.
[Brief description of the drawings]
FIG. 1 is a treatment process diagram of an apparatus for treating and refining a liquid pitch containing sulfuric acid gas, waste oil, or harmful sludge according to an embodiment of the present invention.
FIG. 2 is an example diagram showing a rotation trajectory of a crushing cutter.
FIG. 3 is a diagram showing an example of a stirring paddle in a stirring reactor.
FIG. 4 is a diagram showing a “procedure for treating sulfuric acid pitch deposited in the ground” which is the first related art.
FIG. 5 is a process diagram of a second prior art “a method for detoxifying sulfuric acid pitch using a pitch treating agent”.
[Explanation of symbols]
1. Raw materials (sulfuric acid pitch, waste oil, toxic sludge, etc.)
11, refrigeration unit 14, crushing unit 15, stirring reaction unit 16, discharge unit 18, gas detoxification unit 20, gas-treated water 21, Hasal liquid alkaline water 22, first treatment liquid (A)
23, the second treating agent (B)
27, treated water circulation device 26, exhaust pipe

Claims (3)

A refrigeration unit that cools and freezes the whole container so as not to generate a sulfuric acid gas odor generated when a sulfuric acid pitch is put into a stirring reactor from a container containing a liquid containing sulfuric acid as a raw material; Device for detoxifying the liquid pitch, comprising: a pulverizing device for pulverizing and pulverizing the mixture; and a stirring reactor for mixing and stirring the pulverized raw material, the first processing liquid (A), and the second processing agent (B). Utilization purification equipment. In the detoxifying purification apparatus according to the preceding paragraph, an intake fan for sending air into the stirred reaction apparatus for processing harmful gas discharged during the purification process in the stirred reaction apparatus, and for discharging air from the apparatus. 2. A liquid pitch detoxifying reclaimed material purification apparatus according to claim 1, further comprising a gas detoxification apparatus for detoxifying harmful gas discharged from the inside of the apparatus. 2. The crushing apparatus according to claim 1, wherein the crushing apparatus is provided with one or a plurality of cutting faces on a circular pedestal, and the pedestal is rotated to pulverize the cooled and frozen material. apparatus

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