JP2006061753A - Agent and method for treating strong acid waste material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agent for treating a strong acidic waste material which can obtain a treated material having the quantity of heat to the extent capable of reutilizing as fuel while maintaining a liquid state without emitting a toxic gas such as sulfur dioxide during neutralization treatment, and a method for treating it. <P>SOLUTION: The agent for treating the strong acidic waste material comprises compositions 1 to 3 including the following composition. The method for treating the strong acidic waste material loads the strong acidic waste material with the compositions 1 to 3 having the following composition. The composition 1 comprises an alkaline metal compound and/or an alkaline earth metal compound, or its aqueous solution. The composition 2 comprises an alcohol derivative having a molar equivalent ratio of carbon atoms to oxygen atoms ranging from 1:1 to 4:1 and at least one hydroxy group or more in a molecule, and the alkaline metal compound and/or the alkaline earth metal compound. The composition 3 comprises fatty acid or its derivative. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a treating agent and a treating method for appropriately neutralizing strongly acidic wastes such as sulfuric acid pitch and sulfuric acid sludge generated in a sulfuric acid washing process of petroleum products such as lubricants and heavy oils.

  Since sulfuric acid pitch, sulfuric acid sludge, etc. generated in the sulfuric acid washing process of petroleum products such as lubricants and heavy oil are strongly acidic industrial wastes, it is necessary to appropriately disinfect them and dispose of them.

  Conventionally, strongly acidic waste generated after separating the oil was incinerated, but this method requires an intermediate process of collecting the oil and a final process of incineration. There is a drawback that the processing time becomes longer as the scale becomes larger. In addition, in the conventional method, since incineration was performed without performing neutralization, a large amount of harmful gas such as sulfurous acid gas was generated, causing a great danger to the human body.

  Therefore, before incineration of strongly acidic waste, a method of incineration after being neutralized with a basic compound such as slaked lime has been adopted as pretreatment. However, if an alkaline substance is added directly to a strongly acidic waste such as sulfuric acid pitch, which is a strong acid, it will be partly heated by the heat of neutralization, and a large amount of toxic sulfurous acid gas and hydrogen sulfide will be generated, and the working environment will be significantly deteriorated. There was a problem that the situation was dangerous for the human body. Moreover, since the viscosity and the solid concentration are too high even after neutralization, problems such as difficulty in continuous charging into the incinerator and damage to the incinerator have occurred.

In order to solve the above problems, several methods have been proposed for detoxifying strongly acidic waste using a cement-based solidifying agent to obtain a cement raw material (for example, Patent Documents 1 to 3). These methods are relatively safe because neutralization and solidification are performed simultaneously. Furthermore, a treatment method for reusing sulfuric acid in strongly acidic waste has been proposed (Patent Document 4).
JP-A-6-165999 JP 2000-42594 A Japanese Patent Laid-Open No. 2002-180067 JP 2002-1399 A

  However, the method of using the above-mentioned sulfuric acid pitch as a cement raw material does not originally focus on the use of the sulfuric acid pitch as a potential fuel. In addition, the treatment method for reusing the sulfuric acid content in the strongly acidic waste requires a special sulfuric acid treatment facility, and is difficult to say as a simple method.

  Since strongly acidic wastes such as sulfuric acid pitch are extremely acidic, it is necessary to carry out a neutralization treatment when attempting to use them as fuel. However, in the conventional neutralization treatment, the treatment work itself is dangerous as described above. In addition, there is a neutralization method using alkaline powder in order to avoid the above-mentioned danger, but since the obtained processed product is solidified, it can only be used as a cement material and can be reused as a valuable fuel. Have difficulty. There is also a method of simply neutralizing strongly acidic waste with an aqueous solution of an alkaline substance such as sodium hydroxide, but there is a problem that a large amount of toxic gas such as sulfurous acid gas is generated during the neutralization treatment. Furthermore, after neutralization, it cannot be used as fuel unless it is dehydrated. In general, when such a treatment is performed, the viscosity of the solution extremely increases and becomes semi-solid, so that it is not practical.

  Therefore, the present invention provides a strongly acidic product capable of obtaining a treated product having a calorific value that can be reused as fuel while maintaining a liquid state without generating toxic gas such as sulfurous acid gas during neutralization treatment. It aims at providing the processing agent and processing method of a waste.

  In order to solve the above-mentioned problems, the present invention provides a strongly acidic waste treatment agent comprising Compositions 1 to 3 having the following compositions.

(Composition 1) Alkali metal compound and / or alkaline earth metal compound, or an aqueous solution thereof (Composition 2) The molar equivalent ratio of carbon atoms to oxygen atoms is in the range of 1: 1 to 4: 1, and , Alcohol derivatives having at least one hydroxy group in the molecule, and alkali metal compounds and / or alkaline earth metal compounds (Composition 3) fatty acids or derivatives thereof

  With such a configuration, it is possible to obtain a processed product having a calorific value that can be reused as fuel while maintaining a liquid state without generating a toxic gas such as sulfurous acid gas during the neutralization process.

  According to the preferable aspect of the said invention, it is as follows. The weight ratio of the alkali metal to the alkaline earth metal is preferably 7: 3 to 9: 1. The aqueous solution preferably contains glycerin. The composition 2 preferably further contains an alcohol. The fatty acid or derivative thereof is preferably an oleic acid derivative. The fatty acid or derivative thereof is preferably a fatty acid or derivative thereof represented by the following formula (1).

RCOOR 'formula (1)
(Wherein R represents alkyl, alkenyl, alkynyl, hydroxyalkyl or alkoxyalkyl, and R ′ represents hydrogen, lithium, sodium, potassium, calcium, magnesium, barium, alkyl, hydroxyalkyl, alkenyl, alkynyl. Further, the blending amount of each of the compositions 1 to 3 is preferably 1% by weight or more.

  Moreover, this invention provides the processing method of a strongly acidic waste which adds the compositions 1-3 which have the following compositions to a strongly acidic waste.

(Composition 1) Alkali metal compound and / or alkaline earth metal compound, or an aqueous solution thereof (Composition 2) The molar equivalent ratio of carbon atoms to oxygen atoms is in the range of 1: 1 to 4: 1, and , Alcohol derivatives having at least one hydroxy group in the molecule, and alkali metal compounds and / or alkaline earth metal compounds (Composition 3) fatty acids or derivatives thereof

  With such a configuration, it is possible to obtain a processed product having a calorific value that can be reused as fuel while maintaining a liquid state without generating a toxic gas such as sulfurous acid gas during the neutralization process.

  Preferred embodiments of the invention are as follows. The compositions 1 to 3 are preferably added to the strongly acidic waste in the order of the composition 1, the composition 2, and the composition 3. The composition 1 is added until the pH of the strongly acidic waste is 1.0 or more, the composition 2 is added until the pH of the strongly acidic waste is 6.0 or more, and the composition 3 Is preferably added until the pH of the strongly acidic waste is 6.5 or more.

  The neutralization treatment agent such as sulfuric acid pitch of the present invention suppresses the intense generation of toxic gas such as sulfurous acid gas during the treatment of organic waste such as strongly acidic sulfuric acid pitch, and the produced treatment is used as fuel. It can be used. Furthermore, it is possible to cope with the strongly acidic sulfuric acid pitch only by adjusting the amount of the neutralizing agent, and since the obtained treated product can be used as a fuel, the amount of waste does not increase. .

  Hereinafter, the present invention will be described in more detail. As described above, the present invention is a strongly acidic waste treatment agent comprising the compositions 1 to 3 having the following compositions.

(Composition 1) Alkali metal compound and / or alkaline earth metal compound, or an aqueous solution thereof (Composition 2) The molar equivalent ratio of carbon atoms to oxygen atoms is in the range of 1: 1 to 4: 1, and , Alcohol derivatives having at least one hydroxy group in the molecule, and alkali metal compounds and / or alkaline earth metal compounds (Composition 3) fatty acids or derivatives thereof

  First, the composition 1 will be described. The composition 1 is mainly used for neutralizing sulfuric acid protons contained in strongly acidic waste. The pH is preferably 14.

  Examples of the alkali metal compound include lithium, sodium, potassium, rubidium, cesium, francium, and hydroxides thereof. These may be used alone or in combination of two or more. Moreover, you may use together with the alkaline-earth metal compound mentioned later.

  Although the compounding quantity of the said alkali metal compound is suitably set according to the acidity of a strongly acidic waste, when using independently, it is 10-60 weight part generally. Moreover, when using together with the alkaline-earth metal compound mentioned later, it sets suitably in relation to the compounding quantity of an alkaline-earth metal compound.

  Examples of the alkaline earth metal compound include calcium, strontium, barium, radium, and hydroxides thereof. These alkaline earth metal compounds may be used alone or in combination of two or more. Moreover, you may use together with beryllium and magnesium or these hydroxides, and the above-mentioned alkali metal compound.

  The blending amount of the alkaline earth metal compound is appropriately set according to the acidity of the strongly acidic waste, but is generally 10 to 60 parts by weight when used alone. When used in combination with the above-mentioned alkali metal compound, it is appropriately set in relation to the blending amount of the alkali metal compound.

  When the alkali metal compound and the alkaline earth metal compound are used in combination, the weight ratio is preferably 7: 3 to 9: 1 from the viewpoint of liquefaction after the treatment.

  The water used in the aqueous solution is preferably pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water.

  The aqueous solution preferably contains a polyhydric alcohol from the viewpoint of solubility in strongly acidic waste and heat capacity. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, and triglyceride. And methylolpropane. In particular, glycerin is preferable from the viewpoint of economy.

  Next, the composition 2 will be described. Composition 2 is primarily used to promote uniform mixing of the alkali metal compound and / or alkaline earth metal compound of composition 1 with strongly acidic waste. Moreover, the calorie | heat amount which can be utilized as a fuel is provided to a processed material by making the content rate of the carbon atom of the alcohol derivative which has at least 1 or more hydroxy group in a molecule | numerator into the range of 1: 1-4: 1. be able to. The pH of the composition 2 is preferably 12 to 14 from the viewpoint of accurate neutralization.

  Examples of the alcohol derivative include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, glycerin monostearic acid ester, and the like, and one or more of these are used.

  Although the compounding quantity of the said alcohol derivative is suitably set according to the acidity of a strongly acidic waste, it is 2-15 weight part.

  The composition 2 can also contain an alcohol. Examples of the alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butanol, tert-butanol, isobutanol, glycerin and the like. These alcohols or derivatives thereof may be used alone or in admixture of two or more.

  The blending amount of the alcohol is appropriately set according to the acidity of the strongly acidic waste, but is 40 to 90 parts by weight.

  Specific examples of the alkali metal compound and the alkaline earth metal compound are the same as the alkali metal compound and the alkaline earth metal compound described for the composition 1, and thus the description thereof is omitted here. The blending amount of the alkali metal compound and the alkaline earth metal compound is 4 to 8 parts by weight.

  Next, the composition 3 will be described. Composition 3 acts as a surfactant. That is, since strongly acidic waste is hydrophobic, the solutions of Compositions 1 and 2 containing basic substances (alkali metal compounds, alkaline earth metal compounds) are rapidly and uniformly dissolved in strongly acidic substances. .

The fatty acid or derivative thereof used in the composition 3 is preferably a fatty acid or derivative thereof represented by the following formula (1).
RCOOR 'formula (1)
(Wherein R represents alkyl, alkenyl, alkynyl, hydroxyalkyl or alkoxyalkyl, and R ′ represents hydrogen, lithium, sodium, potassium, calcium, magnesium, barium, alkyl, hydroxyalkyl, alkenyl, alkynyl. )

  The pH of the composition 3 is preferably 6.5 to 8.0 from the viewpoint of the buffer effect.

  The fatty acid or derivative thereof is preferably an oleic acid derivative, and particularly preferably oleic acid methyl ester. The fatty acid or derivative thereof may be used alone or in combination of two or more.

  The treatment agent for strongly acidic waste according to an embodiment of the present invention is a mixture containing at least 1% by weight of each of the above compositions 1 to 3 when the total weight of the treatment agent is used as a reference (100% by weight). Although it can be used, it is preferable to add the compositions 1 to 3 to the strongly acidic waste separately in the order of the composition 1, the composition 2, and the composition 3.

  If the compositions 1 to 3 are added to the strongly acidic waste in the order of the composition 1, the composition 2 and the composition 3, heat generation due to a rapid reaction and generation of toxic gas can be more effectively prevented. . In this case, the composition 1 is added until the pH of the strongly acidic waste is 1.0 or higher, and the composition 2 is added until the pH of the strongly acidic waste is 6.0 or higher, The composition 3 is preferably added until the pH of the strongly acidic waste is 6.5 or higher. Moreover, it is preferable to add the processing agent of a strongly acidic waste gradually and to perform sufficient stirring at the same time.

  The treated product thus obtained is not only neutralized and detoxified, but also can be used as a fuel, and is excellent in handling because it is liquid.

  A sulfuric acid pitch treating agent comprising the following compositions 1 to 3 was prepared. The alkali metal hydroxide is a mixture of potassium hydroxide (KOH) and sodium hydroxide (NaOH) at a ratio of 8: 2.

Composition 1
Alkali metal hydroxide (K: Na = 8: 2) 50 parts by weight
40 parts by weight of water
Glycerin 10 parts by weight Composition 2
44 parts by weight of glycerin
10 parts by weight of glycerin monostearate
40 parts by weight of methanol
Alkali metal hydroxide (K: Na = 8: 2) 6 parts by weight Composition 3
95 parts by weight of oleic acid methyl ester
5 parts by weight of alkali metal oleate

  Under good ventilation conditions, 5.2 liters of Composition 1 was dropped over about 1 hour while stirring 100 liters of sulfuric acid pitch pH 0.0. After completion of the dropping, stirring was continued for 1 hour. It was pH 1.24 when pH of the obtained processed material was measured.

  Next, 26 liters of Composition 26 was added dropwise over about 1 hour while stirring the treated product. After completion of the dropping, stirring was continued for 1 hour. It was pH 6.50 when pH of the obtained processed material was measured.

  Further, 10 liters of Composition 3 was added dropwise over about 10 minutes while stirring the treated product. Stir until Compositions 1 and 2 are uniformly dissolved in the treated product. It was pH 6.7 when pH of the obtained processed material was measured.

  During the treatment process, rapid temperature rise and generation of toxic gases such as sulfurous acid gas and hydrogen sulfide gas were hardly observed.

  Under good ventilation conditions, 17.0 liters of Composition 1 was added dropwise over about 1 hour while stirring 100 liters of sulfuric acid pitch of pH 0.5. After completion of the dropping, stirring was continued for 1 hour. It was pH1.07 when pH of the obtained processed material was measured.

  Next, 10.0 liters of composition 2 was added dropwise over about 1 hour while stirring the treated product. Even after the dropping was completed, stirring was continued for 1 hour. It was pH 6.60 when pH of the obtained processed material was measured.

  Further, 16.7 liters of Composition 3 was added dropwise over about 10 minutes while stirring the treated product. Stir until Compositions 1 and 2 are uniformly dissolved in the treated product. It was pH 6.72 when pH of the obtained processed material was measured.

During the treatment process, rapid temperature rise and generation of toxic gases such as sulfurous acid gas and hydrogen sulfide gas were hardly observed.
[Comparative Example 1]

Under good ventilation conditions, 5.5 liters of Composition 1 was added dropwise over about 1 hour while stirring 100 liters of sulfuric acid pitch pH 0.0. After completion of the dropping, stirring was continued for 1 hour. It was pH 5.0 when pH of the obtained processed material was measured.
[Comparative Example 2]

Under good ventilation conditions, Composition 2 was added to 100 liters of sulfuric acid pitch pH 0.0 until pH 5.0 or higher. At this time, since the required amount of the composition 2 reached 100 liters, it was found that such a treatment method was not practical.
[Examination of combustibility]

  In order to examine the utility as a boiler fuel, the processed products obtained in Examples 2 and 3 and Comparative Example 1 were burned in a boiler corresponding to a high salt concentration (high ash content). As a result, it was found that the processed products obtained in Examples 2 and 3 burned without problems and recovered a desired amount of heat, so that they were useful as boiler fuel. Moreover, since the processed products obtained in Examples 2 and 3 were in a liquid state, the processed products could be smoothly charged.

  On the other hand, the processed product obtained in Comparative Example 1 was not able to obtain a desired amount of heat, and further auxiliary fuel was required for sufficient combustion, so that it proved to be impractical as a boiler fuel. did.

Claims (10)

The processing agent of strongly acidic waste which consists of the compositions 1-3 which have the following compositions.
(Composition 1) Alkali metal compound and / or alkaline earth metal compound, or an aqueous solution thereof (Composition 2) The molar equivalent ratio of carbon atoms to oxygen atoms is 1: 1 to 4: 1, and molecules An alcohol derivative having at least one hydroxy group therein, and an alkali metal compound and / or alkaline earth metal compound (Composition 3) fatty acid or derivative thereof   The treating agent for strongly acidic waste according to claim 1, wherein the weight ratio of the alkali metal to the alkaline earth metal is 7: 3 to 9: 1.   The processing agent of the strongly acidic waste of Claim 1 or 2 which contains glycerol in the said aqueous solution.   The processing agent of the strongly acidic waste of any one of Claims 1-3 in which the said composition 2 contains alcohol further. The processing agent for strongly acidic waste according to any one of claims 1 to 4, wherein the fatty acid or a derivative thereof is a fatty acid or a derivative thereof represented by the following formula (1).
RCOOR 'formula (1)
(Wherein R represents alkyl, alkenyl, alkynyl, hydroxyalkyl or alkoxyalkyl, and R ′ represents hydrogen, lithium, sodium, potassium, calcium, magnesium, barium, alkyl, hydroxyalkyl, alkenyl, alkynyl. )   The treatment agent for strongly acidic waste according to any one of claims 1 to 5, wherein the fatty acid or a derivative thereof is an oleic acid derivative.   The processing agent of the strongly acidic waste of any one of Claims 1-6 whose compounding quantity of each of the said compositions 1-3 is 1 weight% or more. The processing method of strongly acidic waste which adds the compositions 1-3 which have the following compositions to a strongly acidic waste.
(Composition 1) Alkali metal compound and / or alkaline earth metal compound, or an aqueous solution thereof (Composition 2) The molar equivalent ratio of carbon atoms to oxygen atoms is 1: 1 to 4: 1, and molecules An alcohol derivative having at least one hydroxy group therein, and an alkali metal compound and / or alkaline earth metal compound (Composition 3) fatty acid or derivative thereof   The method for treating strongly acidic waste according to claim 8, wherein the compositions 1 to 3 are added to the strongly acidic waste in the order of composition 1, composition 2, and composition 3. The composition 1 is added until the pH of the strongly acidic waste is 1.0 or more,
The composition 2 is added until the pH of the strongly acidic waste is 6.0 or more,
The method for treating strongly acidic waste according to claim 9, wherein the composition 3 is added until the pH of the strongly acidic waste becomes 6.5 or more.