JPS6018577A - Removal of peroxide from degraded oil - Google Patents

Abstract

PURPOSE:To reclaim a degraded oil efficiently, by immersing clay minerals of hydrous silicate in an acidic solution to give clay minerals of hydrous silicate having an amorphous part, bringing a degraded oil into contact with the clay minerals of hydrous silicate having an amorphous part, adsorbing peroxides on them, removing the clay minerals. CONSTITUTION:Clay minerals of hydrous silicate (preferably attapulgite, sepiolite, or talc) are immersed in an acidic solution having 0.01-10 normal acid concentration at normal temperature for 0.05-10hr to give clay minerals of hydrous silicate having an amorphous part, powder of the clay minerals of hydrous silicate having an amorphous part, having 0.01-20mum particle diameters is immersed in a degraded oil (e.g., lubricating oil of car, linseed oil, etc.) for 5min-1hr, brought into contact with it, peroxides in the degraded oil are adsorbed on the clay minerals, and then the clay minerals are removed. 5-20wt% clay minerals of hydrous silicate having an amorphous part are preferably immersed in the degraded oil. EFFECT:The process has improved decoloring properties, and a reclaimed oil having increased transparency is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for regenerating degraded oil by removing peroxides therein using an active adsorbent.

In general, deterioration of oils such as mineral oils and vegetable oils occurs due to the effects of oxidation, thermal decomposition, or mechanical shear stress during use, resulting in the formation of peroxides in the base oil and impurities (organic content such as pigments, solid substances). It is due to the contamination of Peroxides in degraded oils are produced in large amounts in base oils and promote corrosion and wear of metals9.

In the case of lubricating oil for machinery, it degrades the functionality of the machinery due to corrosion, etc. In addition, peroxide is a harmful substance to the human body, and vegetable oil, which is used as edible oil, cannot be used if it contains too much peroxide.

It is being discarded.

Therefore, many methods have been proposed to remove peroxides from degraded oil to produce recycled oil. Methods for regenerating degraded oil can be roughly divided into heating stationary regeneration methods and condensation separation methods. The heating stationary regeneration method involves heating and standing degraded oil, adding chemicals such as acids, alkalis, amines, and urea to the degraded oil, and incinerating moisture, solid content, and low-boiling point content in the oil. The oil is regenerated by removing the sludge and then separating and removing the sludge using a centrifugal separator. But with this method.

Many facilities such as an incinerator, a centrifugal separator, two reaction tanks, etc. are required, the running cost is high, and there are few advantages to regenerating the oil.

On the other hand, in the coagulation separation method, inorganic substances such as clay, alumina gel, and silica gel, ion exchange resins, and surfactants are used as regenerating agents in heated degraded oil.

By adding organic substances such as cross-linked polyvinyl alcohol.

After stirring and mixing for a predetermined period of time to adsorb peroxides in the degraded oil, the recycled oil is separated by static precipitation and compression press. in this way.

It takes a long time to separate the recycled oil and the regenerant, and the substance used as the regenerant has a low ability to absorb peroxide. In particular, clay, which is often used as the regenerating agent, has poor adsorption capacity, and although treatment with sulfuric acid or the like is sometimes carried out to improve the adsorption capacity, the adsorption capacity for peroxides is not sufficient.

The present invention overcomes all of the above-mentioned conventional problems and uses an active adsorbent to enhance the adsorption of peroxides in degraded oil, thereby removing all peroxides easily, efficiently, and at low cost. This is an attempt to regenerate degraded oil.

That is, 1. The method for removing peroxide from deteriorated oil of the present invention is as follows:
An acid treatment step in which a hydrated silicate clay mineral is immersed in an acidic solution to form a hydrated silicate clay material having an amorphous portion, and an oil-containing contact that has deteriorated into a hydrated silicate clay material subjected to the acid treatment. and an adsorption step in which peroxide, which is a deterioration product of oil, is adsorbed onto the hydrated silicate clay material, and a removal step in which the hydrated silicate clay material is removed. be.

The method of the present invention uses an acid-treated adsorbent to adsorb and remove peroxides from degraded oil.

According to the present invention, since the hydrous silicate clay mineral used as an adsorbent has been acid-treated, it has a large surface area, increases adsorption capacity, and adsorbs and removes a large amount of peroxides from degraded oil. At the same time, impurities such as moisture and solid matter other than peroxide can also be adsorbed and removed, and degraded oil can be efficiently regenerated.

Furthermore, peroxides in the oil can be adsorbed and removed simply by bringing the degraded oil into contact with the acid-treated hydrated silicate clay material, so there are very few treatment steps and the degraded oil can be regenerated at low cost. can do.

In the uninvented method, the target oil that can be recycled is:
Either mineral oil or vegetable oil may be used. Examples of the mineral oil include vehicle lubricating oil 1 engine oil, turbine oil, etc., and examples of the vegetable oil include drying oils such as linseed oil and tung oil, and non-drying oils such as olive oil and peanut oil.

There are semi-dry oils such as bean oil and rapeseed oil.

The hydrated silicate clay mineral has a large specific surface area of 260 to 91260 d/1/r, and has a hollow fiber-like structure with long tunnel-like pores. The reason why the effects of the present invention can be obtained by performing acid treatment by immersing the hydrated silicate clay mineral in an acidic solution is thought to be due to the following phenomenon occurring. That is, part of the metal such as Aβ or Mf on the surface of the mineral is dissolved by acid, and part of the silica is also detached from the crystal structure, resulting in a hydrous silicate clay material with a large surface area. , the adsorptivity is further increased. Furthermore, since the hydrated silicate clay material is negatively charged as a whole, it selectively physically and chemically adsorbs all cations and functional groups, but it has poor adsorption properties for hydrocarbon materials. Naphthenic hydrocarbons, which are the main component of the oil, are not adsorbed by the clay material because of the lack of oil. Due to this property.

It selectively adsorbs all impurities such as peroxides that cause deterioration in deteriorated oil, and removes a large amount of these impurities.

Can regenerate degraded oil.

Examples of such hydrous silicate clay minerals include attapulgite and seviolite.
pilolite), talc (Trzlc), etc. are used. The particle size of the mineral is preferably made as small as possible in order to increase the surface area and improve the reactivity.

The acid treatment step in the present invention is a step in which the clay mineral is immersed in an acidic solution and left to stand for a certain period of time to obtain a hydrous silicate clay material having an amorphous portion. By nucleic acid treatment,
The silicate component on the surface of the clay mineral is separated into the acidic solution, increasing the surface area, and part of the crystals collapses to form an amorphous part. Thereafter, the hydrated silicate clay material is removed from the acidic solution by a method such as filtration, and the adhering acidic solution is removed by washing with water or the like.
A hydrated silicate clay material having an amorphous portion is obtained. The hydrated silicate clay material (hereinafter referred to as the core material) has a large surface area and contains a non-madder metal, so it is very active and can adsorb a large amount of peroxides in degraded oil.

In order to add the substance to degraded oil and efficiently adsorb the degraded oil, it is preferable to crush it into powder. The particle size of the substance powder increases the surface area by 9.

In order to improve grain layer properties, it is recommended to make the grain size as small as possible (preferably in the range of 0.01 to 20 μm).

The substance may also be formed into granules or plates.

Examples of the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid;
Alternatively, an aqueous solution of an organic acid such as formic acid or acetic acid is used. The acid concentration of the acidic solution is preferably in the range of 0.01 to 10 normal. When the acid concentration is less than 0.01 normal, the action of the acid is weak and one reaction does not proceed sufficiently, so that the treatment takes a long time. On the other hand, when the acid concentration is 10N or more, the reaction is accelerated, making it difficult to control the amount of the silicate component released into the acidic solution, and requiring neutralization treatment after the acid treatment. Also.

Even if the acid concentration is within the above range, the 9 reaction is promoted if the amount of silica and acid salt components released is small.

After the hydrated silicate clay mineral is immersed in the acidic solution, the acidic solution may be stirred, and the acidic solution may be further heated.

The immersion time is not determined in part by the concentration and temperature of the acidic solution, but is preferably in the range of about 0.05 to 10 hours at room temperature, for example. If immersed for less than 0.05 hours, the 9 reaction will not proceed sufficiently, and if immersed for more than 10 hours, the mineral will dissolve.

Silica-only precipitates may contain gold.

Further, after removing the acidic solution adhering to the acid-treated hydrated silicate clay material by washing with water or the like.

Adhering water is removed by drying.

Since this drying process only removes adhering water in the clay material, it should be heated and held in a room rM to 650°C for 3 to 120 hours in an atmosphere of pregnant air or inert gas. is preferred.

Next, the degraded oil is brought into contact with the hydrated silicate clay material to adsorb peroxides in the degraded oil. The method for bringing the substance into contact with the degraded oil is preferably a method of immersing and holding powder or granules of the substance in the degraded oil, or a method of passing the degraded oil through a plate-shaped body made of the substance. Through this step, the peroxide in the degraded oil is adsorbed by the substance, and the degraded oil can be purified.

In the method of immersing the substance, after the substance is completely immersed in degraded oil, the adsorption of peroxide is promoted.

May be stirred. Furthermore, by heating the degraded oil to lower its viscosity, the agitation of the adsorbed substance is increased and the adsorption time is shortened. This seems to be because the probability of contact between the deteriorated oil and the substance increases.

The proportion of the substance to be immersed in the degraded oil is preferably 5 to 20% by weight (hereinafter referred to as wt%). When the immersion ratio is 5wt% without vortex.

Adsorption power of peroxide in deteriorated oil is insufficient. on the other hand.

If it exceeds 20 wt%, a large amount of the substance will be mixed into the oil and the overall viscosity will increase, resulting in a decrease in the recovery rate of recycled oil.

The above immersion time varies depending on the immersion ratio.

For example, it is generally desirable for 5 minutes to 1 hour. If the soaking time is less than 5 minutes, the amount of peroxide adsorbed is small, and if the soaking time exceeds 1 hour, a commensurate adsorption effect cannot be obtained.

Next, after allowing the substance to sufficiently adsorb the peroxide in the oil,
A step is performed to separate and remove the substance from the oil and obtain recycled oil. Through this step, the recycled oil, which does not contain impurities such as peroxides that cause deterioration, is separated from the substance. The obtained recycled oil not only contains less peroxide, but also has other impurities adsorbed and removed, is decolored and transparent, and can be used again for various purposes.

The method for removing this material from oil is qualitative - paper based.

Or a filtration method such as by vacuum filtration.

Alternatively, the substance may be separated by centrifugation. In addition, when using the plate-shaped body made of the acid-treated substance as a filter plate, by passing the deteriorated oil through this filter, the peroxides in the deteriorated oil can be adsorbed and the recycled oil can be separated at the same time. can be done.

Hereinafter, nine aspects of the present invention will be described in detail.

Example Attapulgite powder (particle size 1.0 to 20 μm) was used as a hydrated silicate clay mineral, and the powder (i) was immersed in a 0.1N aqueous solution of hydrochloric acid (HCl) and held for 30 minutes.
After filtering to remove the hydrated silicate clay mineral and washing with water,
After drying at 0°C for 2 hours, a hydrated silicate clay mineral gold having an amorphous portion was obtained. The substance 5y was immersed in the degraded oil 40y, stirred and mixed for 10 minutes, and then filtered through qualitative paper to obtain recycled oil. Also.

For comparison, all recycled oil was prepared in the same manner as above, using the conventionally used white clay as an adsorbent, and immersing the same attapulgite powder as above in degraded oil without acid treatment. .

Infrared analysis of the above three types of recycled oil.

The absorbance of the residual peroxide spectrum was calculated. The results are shown in FIG. The absorbance of peroxide in degraded oil is 4.1X1
0-2, and the conventional clay treated one is 58
10"2, while that treated with non-acid-treated attapulgite was 2.3x io"-2;
It can be seen that peroxide is adsorbed and reduced. Furthermore, the adsorbent according to the present invention showed a low value of 1.8 x io''-2, indicating that the adsorbent treated with the acid of the present invention has excellent peroxide adsorption properties.

In addition, the light transmittance of the recycled oil was measured using a spectrophotometer to measure the decolorization property of the degraded oil. The results are shown in Figure 2. From Figure 2, the transmittance of the recycled oil treated with clay was 54%, and that of the oil treated with attapulgite, which was not treated with acid, was 80%, whereas the transmittance of the recycled oil treated with the present invention was 80%. It shows a high value of 94%, indicating that the method of the present invention can adsorb and remove a large amount of impurities such as dyes, and is also highly effective in terms of decolorization.

[Brief explanation of drawings]

Figure 9 shows the measurement results of peroxide absorbance and light transmittance of recycled oil in Examples of the present invention. Figure 1 shows the measurement results of peroxide absorbance, and Figure 2 shows the light transmittance of recycled oil. It is a figure which shows the measurement result of a rate. Applicant Corporation Toyota Central Research Institute Figure 1 Figure 2

Claims (3)

[Claims] (1) An acid treatment step in which a hydrated silicate clay mineral is immersed in an acidic solution to form a hydrated silicate clay material having an amorphous portion, and a degraded oil is converted into a hydrated silicate clay material treated with a nucleic acid. Deterioration characterized by comprising an adsorption step of contacting the hydrated silicate clay material to adsorb peroxide, which is a degradation product of oil, and a removal step of removing the hydrated silicate clay material. How to remove peroxide from oil. (2) The above-mentioned hydrated silicate clay mineral is attapulgite,
The method for removing peroxide from deteriorated oil according to claim (1), which is at least one of Seviolite and talc. (3) The method for removing peroxides from deteriorated oil according to claim (1), wherein the acidic solution is an aqueous solution having an acid concentration of 0.01 to 10N.