JP2007185644A - Sulfate pitch sludge by-produced upon petroleum refining and reprocessing for reprocessed sulfate pitch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for processing and effectively utilizing sulfate pitch sludge by-produced during petroleum refining characterized in that the sulfate pitch sludge causing air pollution when being burnt is charged and masticated with lime or the like upon desulfurization, thus the obtained briquette is used as solid fuel, and pollution is eliminated. <P>SOLUTION: The sulfate pitch sludge is used as solid fuel in thermal power generation or the like, thus sulfide is reacted with lime or the like and is changed into the form of gypsum silicate and hydrocarbon. When the same is burnt, there is no generation of SOx, and gypsum silicate ash is effectively utilized as the raw material for building materials or the like, and, when kitchen garbage and the briquette are mixed, the mixture is utilized as fuel. Further, when pulp fiber is recovered from the kitchen garbage, and is made into a cellulose ether, the sulfate pitch sludge can be made into a solid agent as well, and, when the briquette is burnt, there occurs no air pollution of SOx. Further, by utilizing the incinerated ash of the briquette for the adsorption of sulfate pitch sludge as gypsum, cost can be reduced. Moreover, the same can be utilized as fuel with the other industrial waste, thus is useful for reducing pollution. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

Sulfuric acid pitch sludge is generated when neutralizing the sulfuric acid treatment that is always performed in oil refining, and this causes marine pollution, and steelworks, power plants, and cement factories that use this as fuel become a major factor in air pollution. An industrial waste supplier who purchased sulfuric acid pitch sludge as a raw material was contaminated with soil because it refilled the retreated sulfuric acid pitch sludge without permission, and in particular, the latter was reworked.

Therefore, when treating this sulfuric acid pitch sludge, that is, petroleum crude oil with sulfuric acid, desulfurization and unsaturated hydrocarbons are agglomerated and neutralized with an alkali solution, and then filtered to separate paste-like sulfuric acid pit sludge, Briquette is made by mixing succinate soda and aluminate so as to form a solid from a paste in which lime and lime succinate are mixed.
This improves the inconvenience of handling due to the paste formation of sulfuric acid pitch sludge and improves the pollution of transport and drainage.
However, when this briquette is subsequently placed in a sealed kettle and is distilled at around 300 ° C., some of the hydrocarbons and coumarone are fractionated. In addition, when this is baked in a heating furnace at around 480 ° C., hydrogen gas is decarburized and can be reused as a hydrogen source for fuel cells. When this is fired at a higher temperature, calcium gypsum oxalate remains as burned ash. Similarly, sulfuric acid pitch sludge desulfurized by sulfuric acid pitch sludge also recovers the same hydrocarbons when briquette formed by mixing lime carbonate, lime and oxalate and mixing binder is subjected to the above heat treatment. Residue is made in the form of lime and gypsum succinate, and if this is used for building materials, added value can be increased and pollution can be prevented.
The present invention seeks to make this development.

When sulfuric acid pitch sludge is analyzed, the sulfuric acid pitch sludge contains 50% hydrocarbons, 18-25% sulfated hydrocarbons, and 2-3% coumarone. When this is immediately put into an incinerator and used as fuel, a large amount of Sox is mixed in the exhaust gas and diffuses, so that it remains as a serious result of air pollution.
However, this is pressure-molded with lime carbonate, lime, oxalate and bonding agent to make briquettes.
When incinerating briquettes made as solid fuel, the process proceeded with this method because there was almost no contamination of the exhaust gas of Sox gas.

Sulfuric acid pitch sludge is usually treated with sulfuric acid first, then neutralized with caustic, and filtered to remove the paste.
Therefore, it is necessary to solidify it when it is transported from the factory and reprocessed. Similarly, re-processed sulfuric acid pitch sludge is processed by molding a mixture of lime carbonate, lime, oxalate and bonding agent under pressure, but if it is sun-dried, it contains hydrocarbons in the middle of drying. It is a problem to determine how much the dry state is to be lost.
The temperature at which this molded briquette is heated and fired is important, but the amount of oil-containing fuel is a problem when it is used as a fuel in cement, steelworks, power plants and other factories.
Moreover, the expansion of productivity by mixing natural tribute oil rock powder (3-5% containing oil) becomes a problem.

Means to solve the problem

When the amount of oil contained in the sulfuric acid pitch sludge is 50% or more, the amount of lime carbonate or the amount of lime added becomes a problem. One of the problems is whether or not sufficient desulfurization is performed quickly when mixed ash is mixed.
If there is a lot of oil, the bonding ability of the bonding agent will decrease, so it is necessary to adjust the viscosity, but when mixing with lime carbonate, lime or lime succinate, the aging time is sufficient for the reaction with calcium carbonate sulfate Usually 12 hours.
In order to further shorten the time, it is a problem how much the additive other than oil should be made.
Also, if the molded briquette is left as it is, some of the hydrocarbons will scatter, so how to prevent this.
Another problem is how much oil content can be increased by adding natural tribute oil powder.

Effects of the present invention

When sulfuric acid pitch sludge is transported from an oil refining factory, it becomes paste-like and difficult to carry, and it is offensive odor.
Therefore, when this is adsorbed with lime carbonate and the sulfate radical is reacted with lime, it is gradually solidified and further solidified when an adhesive is added, so that it becomes easy to convey and the generation of malodorous gas is suppressed.
Next, this solid briquette can be handled in the same manner as coal because the treatment method differs depending on whether it is hydrogen gasified or fueled even with hydrocarbons. Further, even if only hydrocarbon-containing hydrocarbons are separated and recovered as in the conventional sulfuric acid pitch sludge treatment, sulfated hydrocarbons and sulfurized hydrocarbons remain indefinitely, resulting in secondary contamination.
In the present invention, if incinerated, it becomes gypsum, so there is no secondary contamination, and it is also used for building materials. Using natural tribute oil powder as an adsorbent increases the oil content.
Further, since it is fluid like conventional sulfuric acid pitch sludge, it causes marine pollution, but the method of the present invention has no pollution.
In addition, solid fuel that has been mixed with industrial wastes and bonded with a bonding agent does not cause air pollution, nor is it dumped into the ocean, so it does not cause secondary pollution.
Also, when collecting the fiber fibers of industrial waste of fiber ether and making it into alkaline pulp with caustic, heat reaction with methyl halide or ethyl halide to make fiber ether, When the price is reduced and this fibrous ether is mixed as a solidifying agent with sulfuric acid pizza sludge, there is little transportation effort and it is effective as a solid fuel.
In addition, when oil shale powder and sulfuric acid pitch sludge are mixed, the oil content is increased and the fuel price of oil sale is increased.

Sulfuric acid pitch sludge is a paste liquid and is offensive odor. A container is required to convey this, and when the container is used, the paste liquid adheres to the container surface and is washed to become waterpox contamination, giving off a foul odor and solidifying it to prevent the container from becoming dirty.
For this purpose, a briquette paste molding process that keeps the surface dry by mixing and molding a binder that solidifies lime carbonate, lime and oxalate paste liquid to produce solidified dry cotton. did.

An example of blending sulfuric acid pitch sludge and sulfuric acid pitch sludge regenerated soot is as follows.
Example 1 Sulfuric acid pitch sludge 100
Lime carbonate powder 500
Lime powder regenerated gypsum mixture 500
Sodium oxalate or
Aluminum aluminate 30
Example 2 Sulfuric acid pitch sludge 100
Lime carbonate powder 500
Oil of natural tribute oil 3-5% oil 500
Bentonite acid clay powder 300
Recycled gypsum powder 100
Sodium oxalate 30
Example 3 Sulfuric acid pitch sludge reprocessing tank 100
Lime carbonate 300
Lime 300
Oxalate powder 10
Recycled gypsum powder 100
Binder Soda oxalate 100
These blended examples are put into a mixer and mixed. Finally, a binder is added and kneaded to form a briquette by solidifying with a molding machine.
Example 4 Sulfuric acid pitch sludge solution 100
Fibrin ether 10
Lime carbonate lime 500
Succinate 100
Recycled gypsum powder 50
Example 5 Pitch sludge solution of sulfuric acid 100
Rice bran, Husma, Okara rice bowl,
Momiji-an 300
Lime carbonate 100
Sodium oxalate 300
Example 6 Sulfuric acid pitch sludge solution 100
Fibrin ether 50
Rice bran flour / Okara flour 100
Lime carbonate 100
Oxalate water 50
Waste wood powder 100
Examples 4 to 5 are similarly mixed and solidified, and then molded to form briquettes.
In Example 6, the sulfuric acid pitch sludge is heated to 80 ° C. and fiber ether is added and dissolved, and this is mixed with rice bran powder and okara powder and then heated and heated to mold a briquette. Fibrin ether collects paper pulp in raw garbage, soaks it in caustic water, dries and drains the alkali fiber, and puts it in a reaction tube, which is ethyl bromide at 180 ° C. Alternatively, fiber ether having a degree of ether of 2 by blowing butyl bromide was used after drying. We used rice bran and okara powder because most of them were dumped into the ocean.
Also, when mixing using garbage as an adsorbent for sulfuric acid pitch sludge, the sulfate radicals are plastered by mixing lime, lime carbonate and oxalate to prevent air pollution.

Fig. 1 shows the transport of sulfuric acid pitch sludge liquid in a tank lorry before putting it into the mixer (1). Is conveyed to the mixer by the conveyor (3), put into the hopper (1 ') and mixed (5), and then the sulfuric acid pitch sludge (4a) contained in the hopper (4) is introduced and stirred by the stirrer (1c). Then, it is introduced into the carriage from the outlet (1d) and allowed to stand, and the bonding agent (P) is put into the mixer (1a), and the mixture is poured from the hopper (6) and masticated to convey the conveyor (7 ) Under pressure and heat molding with a molding machine (8). Then, the mold (7 ′) to briquette solid fuel taken out is transported by the carriage (10) and the contour (9), dried and packed in a bag (11) to produce solid fuel. This solid fuel is introduced into the hall from the rotary kiln (11 ′) hopper (12), heated to a heater (12 ′) (12 ″) at 280 ° C., and dry-distilled. The volatilized gas is sucked by the pump (13). Then, the tank (15) stores the distillate liquid.
The dry distiller is loaded and conveyed from the rotary kiln outlet (16) by the conveyor (17), cooled in the cooling chamber (18), conveyed by the conveyor (19), and pulverized by the pulverizer (20). In this dry distillation device, 50% of the sulfuric acid pitch sludge liquid is recovered as hydrocarbons, but in the case of containing a large amount of sulfurized hydrocarbons, lime peroxide is oxidized using sodium percarbonate so as to react with lime. To desulfate. The desulfurization temperature is a heating temperature of 300 ° C. or higher.

Most industrial waste has been burned or disposed of by ocean dumping, but since last year it has been banned in accordance with international treaties, and the dumping of sulfuric acid pits sludge liquid has also been banned. A large amount of non-hydrocarbon soot that has already been processed and removed from the sulfuric acid pitch sludge solution is buried in the landfill, which becomes secondary pollution, and in order to eliminate this pollution by incineration alone, it becomes air pollution. Waste oil causes water tank pollution and its amount is enormous.
In order to purify this, it is not possible to incinerate or desulfurize, and it is necessary to desulfurize it for landfill or block incineration.
However, in order to treat sulfuric acid pitch sludge with inexpensive and simple equipment, it is necessary to suppress volatilization by a mixed reaction of lime and lime carbonate, dolomide, oxalate, and peroxide, and the present invention is more excellent as a means for that. Inexpensive.
Especially when incinerating other garbage, incinerating lime, carbonated lime, dolomide, and oxalate in advance to give enough time to react with sulfuric acid will promote harmless plastering. Is done. The gypsum is useful as a raw material or building material for cement, and when this gypsum is used for adsorption of sulfuric acid pitch sludge, the production cost can be reduced by 20% or more. Also, mixing tribute oil powder increases oil content and enables effective use of oil shale rock powder.
In addition, when garbage is separated and paper fiber is made and converted into a cellulose ether, it has the advantage of absorbing and solidifying sulfuric acid pitch sludge as an adsorbent, and desulfurized briquettes using sulfuric acid pitch sludge mixture are combusted together when garbage is incinerated. Even so, since the generation of Sox is low, it is possible to prevent pollution and use hydrocarbons in sulfuric acid pitch sludge as fuel, so high temperature incineration is possible. By briquetting, Sox can also be used in thermal power generation, iron making, and cement incineration. Because there is almost no outbreak, the fuel which becomes pollution prevention is made.

  Process chart of sulfuric acid pitch sludge liquid by-produced during petroleum refining and reprocessing of dredged pollutants extracted by desulfurizing this liquid.   Characteristic diagram of lime, carbonated carbonate, oxalate and time mixed with sulfuric acid pitch sludge.

Claims (4)

Desulfurization reaction was performed by mixing sulfuric acid pitch sludge liquid and by-product sulfuric acid pitch sludge generated during petroleum refining with lime, lime carbonate, dolomide, oxalate, oil shale powder, fiber ether and raw garbage and other additives. Add a bonding agent to change the material from a liquid to a powdered solid, mix and knead, make a solid briquette fuel by pressure and heating molding, mix this with fuel for thermal power generation, iron making or cement raw material, incinerate or greenhouse Recycled gypsum succinate incineration ash obtained for heating of buildings is reused as an adsorbent for sulfuric acid pitch sludge. Effective use of sulfuric acid pitch sludge, which is characterized by pollution-free by mixing and reaction. Mixing lime, carbonated lime, dolomide, and oxalate with desulfurized sulfuric acid pitch sludge solution and mixing it with raw garbage powder, separated garbage powder, rice bran, bran, okara powder, and waste wood powder Add to kneaded briquette fuel. Briquette fuel in which oil shale rock powder and lime, carbonated lime, dolomide, basic sludge powder, and oxalate are mixed with sulfuric acid pitch sludge liquid, and then kneaded with oxalic acid soda and aluminate soda. Solid fuel obtained by mixing pulp ether fibers, which are separated and recycled from raw garbage, as an adsorbent for sulfuric acid pitch sludge.

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