JP5179038B2 - Method for treating hydrogen-generated oil mud and solid fuel - Google Patents

Description

The present invention relates to a method for treating hydrogen-generated oil mud, and more particularly, to a method for treating hydrogen-generated oil mud that reduces the generation of hydrogen, and a solid fuel obtained by the method.

  Silicon wafers are useful as members for semiconductor devices, solar cells and the like, and their demand is increasing year by year. Such a silicon wafer is manufactured by cutting into a wafer form from a crystal of high-purity silicon, but in recent years, cutting with a wire saw is becoming mainstream from the viewpoint of the performance of a cutting machine.

In cutting with this wire saw, the average particle diameter is usually 10 μm as a cutting medium.
Wire saw oil containing ˜50 μm silicon carbide abrasive grains and mineral oil or aqueous solution is used. The wire saw oil cannot be used because its cutting ability is reduced due to wear of abrasive grains, an increase in silicon scraping, etc. due to repeated use.
And now, most of the waste wire saw oil that can no longer be used is incinerated and treated as industrial waste.

Moreover, in a machining factory, metal processing is performed by operating a large number of cutting, grinding, or polishing apparatuses. In the metal processing process, a large amount of cutting oil and grinding are used to cool and lubricate the workpiece. Oil and polishing oil are used. These cutting oils are also circulated and used, and the deteriorated ones are extracted, and most of them are incinerated as waste cutting oil, waste grinding oil and waste polishing oil.

Here, since oil mud such as the above-described waste wire saw oil and waste cutting oil has high energy, it is expected to be effectively used as fuel without being incinerated as industrial waste.
However, in general, oil mud has a high viscosity, does not flow at room temperature,
Since some solid matter settles and settles, it is difficult to handle as a fuel due to poor handling properties during transportation through a pipeline.

Therefore, in recent years, in Europe, it has been proposed that oil sludge such as crude oil sludge is not used alone, but the oil mud and sawdust are mixed to form a solid fuel and used as an alternative fuel in a cement kiln. Have been proposed (for example, Patent Document 1).
, 2, 3 etc.).

JP-A-54-39401 JP 2002-323213 A JP 2006-169376 A

However, the waste wire saw oil used for cutting silicon wafers contains a large amount of silicon particles and also contains metal particles such as iron resulting from wear of the wire saw. There is a concern that metal particles such as iron react with water and a large amount of hydrogen is generated by the following reaction formula, for example.
Si + 2OH ⁻ + H ₂ O → SiO ₃ ²⁻ + 2H ₂ ↑
Metal + Acid → Metal Compound + Hydrogen ↑
Moreover, since waste cutting oil, waste grinding oil, and waste polishing oil contain a large amount of metal particles such as aluminum particles and iron, there is a concern about the generation of hydrogen.

Oil mud such as waste wire saw oil, waste cutting oil and the like that are concerned about the generation of hydrogen as described above (in the present specification, such oil mud is referred to as “hydrogen generating oil mud”) is ignited to the generated hydrogen, Since there is a risk of explosion, handling such as transportation and storage is particularly difficult, and no effective use method has been found in the past.

The present invention has been made in view of the problems of the background art described above, and its purpose is as follows.
A method for treating hydrogen-generated oil mud, which reduces the amount of hydrogen generated from hydrogen-generated oil mud such as waste wire saw oil and waste cutting oil, and improves handling, such as transportation and storage, and the handling obtained by the treatment method It is to provide a solid fuel with good properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed biomass such as crushed waste tatami into the hydrogen generating oil mud, and the mixed biomass absorbs the liquid content in the hydrogen generating oil mud. As a result, the inventors have found that the handling property is improved and the amount of hydrogen generated can be reduced, and the present invention has been completed.
That is, the present invention provides the following [1] to [6] hydrogen-generating oil mud treatment method and solid fuel.
[1] 40 to 95 parts by mass of biomass having an average particle size of 0.5 mm or more and a maximum particle size of 10 mm or less, and organic powders 60 to 5 having an average particle size of 1/2 or less of the average particle size of the biomass The processing method of the hydrogen generation oil mud which mixes a mass part (however, biomass + organic powder = 100 mass parts) and 30-300 mass parts of hydrogen generation oil mud.
[2] The method of treating a hydrogen-generating oil mud according to [1], wherein the hydrogen-generating oil mud is a liquid or sludge-like oil mud that generates hydrogen by reduction of water or a hydrogen atom-containing compound.
[3] Hydrogen according to [1], wherein the hydrogen-generating oil mud is at least one of waste wire saw oil, waste cutting oil, waste grinding oil, and waste polishing oil containing silicon particles and / or aluminum particles and metal particles. Treatment method of generated oil mud.
[4] The method for treating hydrogen-generated oil mud according to any one of [1] to [3], wherein the biomass is one or more of crushed waste timber, wood chips, wood flour, sawdust, and paper waste.
[5] Any of the above [1] to [4], wherein the organic powder is any one or more of toner, heavy oil ash, pulverized coal, activated carbon powder, meat and bone powder, waste plastic powder, paper powder, and organic distillation residue powder A method for treating such hydrogen-generated oil mud.
[6] A solid fuel obtained by the method for treating hydrogen-producing oil mud according to any one of [1] to [5].

According to the present invention described above, the biomass mixed in the hydrogen-generating oil mud absorbs liquid components (oil and moisture) in the hydrogen-generating oil mud, the handling properties are improved, and the silicon particles present in the oil mud and / or Alternatively, the amount of hydrogen generated by the reaction of metal particles such as iron with water can be reduced, and the hydrogen-generating oil mud can be treated into a mixture having good handling and safety such as transportation and storage.
Therefore, it is possible to effectively use hydrogen-generated oil mud such as waste wire saw oil and waste cutting oil, which has been disposed of in the past, as a resource.

Hereinafter, the method for treating the hydrogen-generated oil mud according to the present invention and the solid fuel obtained by the method will be described in detail.

[Hydrogen generating oil mud]
In the present invention, the hydrogen-generating oil mud refers to a liquid or sludge-like oil mud that generates hydrogen by reducing water or a hydrogen atom-containing compound. Specifically, waste wire saw oil containing silicon particles used for cutting silicon wafers, waste cutting oil containing aluminum particles and metal particles used for cooling and lubrication of workpieces in various metal machine tools, waste Grinding oil, waste polishing oil, etc. can be mentioned. These can be used alone or as a mixture of two or more of these, and also with other oil mud such as recycled heavy oil, waste solvent, crude oil sludge, diesel oil residue, etc. It may be a mixture.
Among the above, waste wire saw oil containing silicon particles has been generated in large quantities due to the recent increase in demand for silicon wafers that are useful as members for semiconductor devices, solar cells, etc., and its treatment has become an urgent task. In addition, since it is an oil mud that is particularly difficult to handle, the generation of hydrogen is concerned in both alkaline and acidic states, it is preferably used as the hydrogen generating oil mud in the present invention.

〔biomass〕
Examples of biomass include crushed tatami (used waste tatami), wood chips (for example, crushed trash from construction waste), wood flour, sawdust, and paper waste.
In the present invention, biomass refers to a generic name of biological organic resources (excluding fossil fuels) that can be used as fuel.

The waste tatami used as the material of the crushed tatami mat may be any material as long as it contains at least a part of plant material. Specifically, not only the main tatami mat that uses rice straw as a tatami floor material, but also polystyrene. Foam board (plate-like molded body formed by adding a foaming agent to a polystyrene resin composition and expanding) and an insulation board (for example, in the wet method, wood is crushed in water, and an adhesive is added. Also included are building material tatami mats, which are made from a soft fiberboard that has been dried after being made, and tatami flooring materials, and paddy sand tatami mats, which are made from rice straw and polystyrene foam plates.
The above-mentioned wood chip refers to a crushed or crushed product of wood having a maximum particle size (mesh size with a sieve residue within 5% by mass) exceeding 5 mm and 10 mm or less.
The above-mentioned wood powder refers to a pulverized product of wood having a maximum particle size (a mesh size with a sieve residue within 5% by mass) of 5 mm or less.
The sawdust usually has a particle size distribution of about 0.5 to 5 mm. As the paper waste, for example, a shredder cut product or the like is used.

The average particle size of the biomass (mesh size residue sieve is within 50 wt%) is assumed to be at 0.5mm or more. This is because when the average particle size is less than 0.5 mm, the entire particle system is miniaturized, so that fluidity and dispersibility are deteriorated, and it becomes difficult to obtain an effect such as improvement in handling properties, and hydrogen generation oil mud. absorption of liquid component (oil and water) is difficult in is because can not be obtained the effect of reducing the amount of hydrogen generation.
Further, the maximum particle size of the biomass (a mesh size in which the remainder of the sieve is within 5% by mass) is 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less. When the maximum particle size exceeds 10 mm, for example, when the mixture obtained by the method for treating hydrogen-generated oil mud according to the present invention is used as a fuel in a cement kiln burner, it is difficult to form a flame (frame), Since the combustion continues even after the fuel has landed, the quality of the cement clinker may be deteriorated. If the maximum particle size is 5 mm or less, the proportion of particles that land and burn is reduced, and the use rate as fuel can be increased, which is preferable.

[Other materials]
In addition to the above-mentioned biomass, organic powder is used as an absorbent material for the liquid in the hydrogen-generating oil mud, and other materials can be blended as long as the quality is not impaired.
Examples of the organic powder include toner, heavy oil ash, pulverized coal, activated carbon powder, meat and bone powder, waste plastic powder, paper powder, and organic distillation residue powder. These organic powders may be used alone or in combination of two or more.

The toner is a dry developer used in office equipment such as a copying machine, a facsimile machine, and a printer, and is a powder having a particle size of about 7 to 11 μm. Usually, waste toner that is waste is used. Since the toner has a very small particle size and a narrow particle size distribution, it can greatly contribute to an increase in the specific gravity of the resulting mixture (solid fuel) and an increase in the throughput of the hydrogen-generated oil mud, which is preferably used. It is done.
The above heavy oil ash is a powder having a particle size of about 1 to 30 μm and has a small particle size. Therefore, it also increases the specific gravity of the resulting mixture (solid fuel) and increases the throughput of the hydrogen generating oil mud. Since it can contribute, it is preferably used.
The pulverized coal is a powder having a particle size of about 10 to 100 μm and is known as a solid fuel in a firing furnace such as a cement kiln.
As said activated carbon powder and meat-and-bone powder, what has an average particle diameter of 1 mm or less is used normally. For example, waste pellets are used as the waste plastic powder. As the paper powder, for example, thunder dust or the like is used. As the organic distillation residue powder,
For example, phthalic acid distillation residue or the like is used.

The average particle size of the organic powder is ½ or less, preferably １ ／ or less of the average particle size of the biomass. If the ratio exceeds 1/2, the difference in particle size between the biomass and the organic powder becomes small, and it is difficult to obtain effects such as an increase in the amount of hydrogen-generated oil mud and an improvement in handling properties. Become.
Among the above organic powders, the average particle size of the activated carbon powder composed of fixed carbon is 300.
If it exceeds μm, the number of particles that land and burn increases, and the quality of the cement clinker may deteriorate. Therefore, the average particle size is preferably 300 μm or less, more preferably 100 μm or less. The lower limit of the particle size of the organic powder is not particularly limited, but is usually 1 μm or more.

[Combination ratio]
The blending ratio of each of the above materials is as follows. First, for the biomass and the organic powder that are absorbents, the mass ratio of the biomass and the organic powder is 40/60 to 95/5, preferably 50/50 to 80 /
20. This is because when the mass ratio is less than 40/60, the blending amount of biomass is small, so that the organic powder fills the gaps between the granules of the biomass, and the fluidity of the mixture (solid fuel) is significantly reduced. is there. On the other hand, when the mass ratio exceeds 95/5, since the blending amount of the organic powder is small, effects such as an increase in the specific gravity of the mixture (solid fuel) cannot be obtained sufficiently.

The blending amount of the hydrogen generating oil mud is 30 to 300 parts by mass, preferably 50 to 200 parts by mass, more preferably 80 to 150 parts by mass, particularly preferably 100 parts by mass of the total amount of the biomass and the organic powder. 100 to 140 parts by mass. When the blending amount is less than 30 parts by mass, the amount of hydrogen-generated oil mud is small and does not meet the gist of the present invention to promote the use of hydrogen-generated oil mud. On the other hand, when the blending amount exceeds 300 parts by mass, it may not be absorbed by the liquid component in the hydrogen-generating oil mud, particularly the biomass mixed with water, and the reduction effect of hydrogen generation may not be obtained. Oil may remain on the particle surface of the solid fuel), resulting in gloss and adhesion on the particle surface, and handling properties may be reduced.

〔mixture〕
Mixing can be performed by putting the above materials into a mixer at the above mixing ratio.
At this time, it is preferable to perform mixing in a state where air is introduced into the mixer and the generated hydrogen is diluted to less than the lower explosion lower limit concentration. This is because when the above-described hydrogen generating oil mud and biomass are mixed, particularly at the initial stage of mixing, that is, at the stage where the mixed biomass or the like has not yet sufficiently absorbed the liquid in the hydrogen generating oil mud. This is because hydrogen is generated from the hydrogen-generating oil mud, and sparks generated in the rotating part of the mixer or the like are ignited and explode.
Therefore, it is preferable to introduce air into the mixer and reliably dilute the generated hydrogen concentration to a concentration that does not cause an explosion, that is, lower than the explosion lower limit concentration of 4%. The specific amount of air introduced into the mixer is appropriately determined depending on the amount of hydrogen generated, the volume of the mixer, the amount of the mixture, etc., but is necessary because it is diluted with free air. A sufficient amount of air may be introduced into the mixer.

Moreover, it is preferable to use a mixer that is not simply provided with stirring blades but also has a structure that rotates the mixing container itself. This is because a highly viscous material such as hydrogen-generating oil mud and a material with low bulk density such as biomass can be mixed well, and the hydrogen generated by the rotation of the container flows and flows into a part of the container. This is because it does not accumulate and can be easily and reliably diluted by the introduced air.
Examples of the mixer having such a structure that also rotates the container itself include an intensive mixer manufactured by Eirich.

In addition, the mixer is equipped with a hydrogen detector that constantly detects the concentration of hydrogen, and if a hydrogen concentration higher than a predetermined level is detected, the mixing operation is immediately stopped and the amount of air introduced into the mixer In order to prevent accidents such as explosions with certainty, it is preferable to further provide a configuration for increasing the flow rate or a configuration for introducing an inert gas such as carbon dioxide into the mixer.

[Mixtures and their use]
Since the mixture obtained by the mixing operation of the hydrogen generating oil mud and the biomass is absorbed by the biomass, etc., particularly the liquid content in the hydrogen generating oil mud, the silicon particles and / or iron in the hydrogen generating oil mud are absorbed. The amount of hydrogen generated due to the reaction of metal particles such as water with water can be reduced, and the safety of transportation, storage, etc. is high.
In addition to the above, since the obtained mixture is a mixture of hydrogen-generating oil mud having high energy and easily combustible biomass, it can be suitably used as a solid fuel with good handleability.

As an example of the method of using the mixture (solid fuel) obtained by the above-described method for treating hydrogen-generating oil mud according to the present invention, the method of using the mixture charged into a firing furnace via a pipe and burning as fuel Is mentioned.
Here, examples of the firing furnace include a cement kiln for producing a clinker and a kiln for firing quick lime and lightweight aggregate.

（２）バイオマス
本畳の破砕物を用いて処理を行った。本畳の破砕物は、次の方法にて調整した。
一軸式破砕機（ロストルの目開き：１５ｍｍ）を用いて本畳を破砕し、平均粒径が０．
５ｍｍ以上であり、かつ、目開き寸法が１０ｍｍである篩の残分が５質量％以下である本
畳の破砕物を調製した。 1. Materials used (1) Hydrogen generating oil mud Various hydrogen generating oil muds (waste wire saw oil A, B, C, D and waste cutting oil A, B) were treated.
Waste wire saw oils A, B, C, and D are hydrogen-generating oil muds containing silicon particles and iron particles, and generally have the component compositions shown in Table 1. Further, the waste cutting oils A and B are hydrogen-generating oil muds containing iron particles and aluminum particles, and generally have the component compositions shown in Table 1.

(2) Biomass Processing was performed using the crushed material of the main tatami mat. The crushed tatami mat was prepared by the following method.
The tatami mat was crushed using a uniaxial crusher (roost opening: 15 mm), and the average particle size was 0.
A crushed material of a main tatami mat having a mesh size of 5 mm or more and an opening size of 10 mm and a residue of 5% by mass or less was prepared.

2. Treatment of hydrogen-generated oil mud 400 g of the above-mentioned various hydrogen-generated oil muds are each charged with 400 g of the above-mentioned crushed material (hydrogen-generated oil mud: mass ratio of crushed material of the main tatami mat 1: 1) in a small intensive mixer and stirred for 2 minutes. As a result, 800 g of a mixture of various hydrogen generating oil muds and biomass was obtained.

3. Measurement of hydrogen generation amount The hydrogen generation amount was measured for each of the obtained hydrogen generation oil mud and biomass and the like. 100 g of the mixture was sealed in a Tedlar bag, and the amount of hydrogen generated from each mixture was measured for 3 days by a method of quantifying the generated hydrogen with a gas chromatograph.
The measurement result is converted into the amount of hydrogen generated from a 400 kg mixture, and listed in Table 2 as an example product.
For comparison, the amount of hydrogen generation was measured in the same manner as described above for each 30 g of hydrogen-generating oil mud that was not mixed with biomass or the like. In order to compare the measurement result with the result of the example product, it was converted into the amount of hydrogen generated from 200 kg of hydrogen generating oil mud, and Table 2
Is also described as hydrogen-generating oil mud.

4). Summary From Table 2, it can be seen that the amount of hydrogen generated can be remarkably reduced by the method for treating hydrogen-generating oil mud according to the present invention. The effect shown in this embodiment is naturally considered to be effective even when scaled up to an actual machine. Therefore, according to the present invention, hydrogen-generated oil mud is treated into a mixture having good safety such as transportation and storage. I found out that I can do it.

Claims (6)

40 to 95 parts by mass of biomass having an average particle size of 0.5 mm or more and a maximum particle size of 10 mm or less, and 60 to 5 parts by mass of organic powder having an average particle size of 1/2 or less of the average particle size of the biomass ( However, biomass + organic powder = 100 parts by mass) and 30 to 300 parts by mass of hydrogen-generating oil mud are mixed. The method for treating a hydrogen-generating oil mud according to claim 1, wherein the hydrogen-generating oil mud is a liquid or sludge-like oil mud that generates hydrogen by reducing water or a hydrogen atom-containing compound. The hydrogen generating oil mud is at least one of waste wire saw oil, waste cutting oil, waste grinding oil, and waste polishing oil containing silicon particles and / or aluminum particles and metal particles. The method for treating hydrogen-producing oil mud according to 1.   The method for treating hydrogen-generated oil mud according to any one of claims 1 to 3, wherein the biomass is at least one of waste crushed material, wood chips, wood flour, sawdust, and paper waste. The organic powder is any one or more of toner, heavy oil ash, pulverized coal, activated carbon powder, meat and bone powder, waste plastic powder, paper powder, and organic distillation residue powder. The processing method of the hydrogen generation oil mud in any one.   The solid fuel obtained by the processing method of the hydrogen generation oil mud in any one of the said Claims 1-5.