JP2003089796A - Method for treating waste oil recovered in power station oil separation tank - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating a waste oil, by which the waste oil can simply and efficiently be treated in a simple treating process to give the treated oil capable of being reused as a fuel oil without needing high chemical knowledge, to provide a method for treating a waste oil recovered in a power station oil separation tank, to obtain a combustion improver, and to provide a method for distinguishing the oil type of the waste oil. SOLUTION: The method for treating the waste oil recovered in the power station oil separation tank has the first process for transporting the waste oil into a reaction device, the second process for mixing the waste oil with sodium silicate and then with calcium oxide in the reaction device, and the third process for discharging the mixture after the second process.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for treating waste oil,
The present invention relates to a method for treating waste oil collected in a power plant oil separation tank, a combustion improver, and a method for discriminating the type of waste oil.

[0002]

2. Description of the Related Art A part of the wastewater in a power plant is a wastewater containing a trace amount of oil used for lubrication of auxiliary machinery, etc. After collecting in each pit and passing through the transportation equipment, the oil is collected by the oil separation device. However, since the collected waste oil contains water and contaminants, it is currently being used as industrial waste and outsourced to a processing company without being effectively used.

When waste oil is contained in water, the waste oil contains a large amount of COD and BOD substance-derived components, which are reducing substances,
When the waste oil-containing wastewater is treated, the cost is high, and in the case of high-concentration wastewater such as waste oil-containing wastewater, it has been difficult to treat the wastewater containing waste oil completely within the emission standard value.

[0004] Waste oil belongs to mineral oil under the "Waste Disposal and Cleaning Law", and if it is contained in wastewater,
According to the Water Pollution Control Law, it is a substance regulated by normal hexane extractable substance content, and in the Prime Minister's Ordinance Appendix 2 which sets the drainage standard, it is a substance strictly regulated to 5 milligrams or less per liter. There are problems such as having a great impact. Regarding COD and BOD, 160 milligrams or less per liter (average daily 1
(20 mg or less) and the substance is regulated as strictly as the substance regulated by the normal hexane extract substance.

At present, the treatment technology for the effective use of the recovered waste oil and the treatment / disposal method is not completely established, and the nature of the treated wastewater has many problems from the viewpoint of global environment conservation. Therefore, there is an urgent need for research and development regarding treatment methods.

In recent years, as one of the oil separation techniques contained in wastewater, attention has been paid to treatment using a membrane due to the development of the membrane separation technique. However, due to the nature of oils and fats, the surface of the separation membrane is hydrophilic. Since there is a problem that functional oils and fats adhere to the membrane and reduce the membrane performance, a complete treatment method has not yet been established, such as problems with the material and structure of the membrane. As a conventional waste oil treatment method, there is a method disclosed in Japanese Patent Publication No. 57-43075.

[0007]

[Objective] The present invention solves the above-mentioned problems of the prior art, has a simple processing step, and can be easily processed without advanced chemical knowledge, and is efficiently processed and reused as a combustible material. It is an object of the present invention to provide a method of treating waste oil, a method of treating waste oil collected in an oil separation tank of a power plant, a method of discriminating an oil type of a combustion improver and a waste oil, which is capable of processing.

[0008]

In order to achieve the above object, the method for treating waste oil according to the present invention is characterized by mixing silicates with waste oil and then adding and mixing calcium salts.

The method for treating waste oil collected in the oil separation tank of the power plant according to the present invention is the first method for conveying the waste oil collected in the oil separation tank to the reactor.
A second step of mixing silicates with the oil separation tank recovered waste oil in the reactor and then mixing calcium salts, and a third step of discharging the mixture after the second step. Characteristically, the product is easy to handle and can be efficiently processed by general equipment.

In the method for treating waste oil according to the present invention, it is preferable that the silicates are made of sodium silicate and the calcium salts are made of calcium oxide. The waste oil treatment mechanism in this case is shown in FIG. For waste oil 1,
It is preferable that sodium silicate is mixed in a volume ratio of 1 and calcium oxide is mixed in a weight ratio of 2.

The combustion improver according to the present invention is characterized in that waste oil is mixed with silicates and then with calcium salts.

The method of discriminating the oil type of waste oil according to the present invention is characterized in that after the silicates are mixed with the waste oil, the calcium salts are mixed and the oil type of the waste oil is discriminated by the color of the mixture.

In the present invention, the weight ratio of silicates to calcium salts is 1 silicate to 1 calcium salt.
The above is preferable, and a treatment agent in which silicates and calcium salts are mixed may be used. The processed product of waste oil produced in the present invention is in the form of powder that retains the amount of heat, and can be reused and used as a method for discriminating the oil type of the combustion improver and the waste oil.

The details of the present invention will be described below. The main components used in lubricating oils are mainly fatty acids,
When it is a hydrophilic oil, it is colloidized in water, and the colloids repel each other due to the zeta potential and the electric double layer, and are uniformly dispersed or dispersed by Brownian motion without being affected by gravity (Stokes' law). It is floating.

In addition, depending on the oil and fat component, there is a wastewater in which hydrogen bonds are present between water molecules and the electric double layer maintains a colloidalization due to a large repulsive force, which makes oil separation treatment difficult. In order to change such oils and fats such as hydrophilic fatty acids into hydrophobic ones, it is necessary to convert and form water-soluble oils and fats into insoluble substances such as carboxylates by some method.

On the other hand, in the case of hydrophobic fats and oils, it does not become a problem as much as hydrophilic fats and oils because it floats on the water without being dispersed or colloidal in water, but it is not a problem. There is a problem such as running cost due to the separation equipment.

From the above, when treating hydrophilic or hydrophobic oils and fats, the polarities of water molecules adhering to the colloid are destroyed, the above-mentioned insoluble substances are changed or generated, and the dispersion state is changed. A large force is applied to an object to neutralize charges between particles, and the intermolecular distance is reduced by Van der Waals' law, and at the same time, positive and negative ion exchange
Utilizing interactions such as ionic surface activity, by adding and mixing calcium oxide to waste oil (containing water), hydrogen bonds between water molecules and the electric double layer are destroyed, and a large repulsive force between molecules is used to colloidize the oil. The water molecules that had been difficult to separate are taken up by calcium oxide and changed to calcium hydroxide to lose the repulsive force, and calcium hydroxide and sodium hydroxide react with fatty acids, which are the main components of waste oil, and By changing to a soluble fatty acid ester (fatty acid calcium / sodium), it is changed to a hydrophobic substance (saponification).

Further, by adding sodium silicate having an excellent fat and oil adsorption property, gelation of fatty acid calcium / sodium due to siloxane bond, insoluble silicate metal hydrate due to reaction with polyvalent metal ions, etc. By utilizing the occlusion effect on the treated solid that is produced at the same time as the reaction and promotes pulverization, it is possible to stably remove the normal hexane extract substance, COD, and BOD substance-derived substance, and at the same time, treat the solid substance. The substance changes into a powdery solid substance that retains the amount of heat, and can be efficiently processed, including handling properties, and can be reused as a combustible substance.

[0019]

[Example] [Example 1] After adding silicates 1 (volume ratio) to waste oil 1 (weight ratio), calcium salt treating agent 2
When (weight ratio) was added and mixed, it was pulverized while maintaining the amount of heat.

Example 2 Water-containing waste oil 1 (water content: 10%)
Containing (weight ratio), silicates 1 (volume ratio) were added, and then calcium salt treating agent 2 (weight ratio) was added and mixed. Turned into

[Example 3] To a waste oil 1 (weight ratio), silicates 1 (volume ratio) were added, and then a calcium salt treating agent 2 (weight ratio) was added and mixed to obtain a powdered product. Confirmed that it can be used as a combustion improver because it can be easily processed (pelletized) and the processed product retains heat.

[Example 4] A product obtained by adding silicates 1 (volume ratio) to waste oil 1 (weight ratio) and then adding and mixing calcium salt treating agent 2 (weight ratio) was The characteristics of desulfurization effect and dechlorination effect were shown in the result of co-firing with coal.

[0023]

[Potential of Other Embodiments] In order to achieve the object of the present invention, this embodiment may be modified as follows. The calcium salts and silicates of the treating agent used in the second step are
It is not particularly limited, and the one containing the component can be substituted. In addition, addition as a treatment method
As for the stirring and carrying-out method, it is possible to use a general-purpose device which has been conventionally used or a combination thereof. The present invention can be applied to a wide range of fields such as waste oil treatment that contains water and is difficult to reuse, and simple treatment of waste oil generated during equipment cleaning.

[0024]

As described above, according to the present invention, the waste oil that has been conventionally treated as industrial waste becomes a powder that retains the amount of heat, and it becomes possible to form and process a solid material, which is then solidified by molding. In addition to being easily reusable as an auxiliary combustion material, the handling property is significantly improved, industrial waste can be reduced, the processing time associated therewith can be shortened, and the processing equipment can be used universally. Since it can be done with a product, the processing configuration can be simple, so that the processing cost can be reduced and the industrial effect is remarkable.

The results of each test conducted on the present invention will be described in detail below. The present invention aims to improve the efficiency of waste oil recovery work and reduce the processing cost, because it is a system for easily and inexpensively processing waste oil mixed with water and impurities.

In the present invention, a treatment technology for solidifying waste oil into powder is established, and various characteristic tests of the solidified waste oil are conducted in view of effective utilization from the viewpoint of zero emission.

The waste oil can be solidified by adding and mixing calcium oxide and sodium silicate to solidify the waste oil in powder form, and the treated solid matter is flammable (2,700 to 3,3).
It has a characteristic of 000 kcal / kg) and can be reused. The waste oil solidification processing flow is shown in FIG.

As described above, in the waste oil treatment at the power plant, the waste oil discharged from each system is temporarily accumulated in each pit, and after passing through the transportation facility or the like, the oil separation device recovers the oil content. . However, since the collected waste oil contains water and contaminants, the waste oil is not effectively used and is outsourced to a disposal company. Therefore, the present invention makes waste oil cheap. In addition, we have established a system for easily and easily treating waste oil, aiming to improve the efficiency of waste oil recovery work and reduce processing costs. We have established a treatment technology for powdering and solidifying waste oil, and from the perspective of zero emission, effective utilization. We propose a new oil treatment system by conducting various characteristic tests on the solidified waste oil of.

Outline The present invention proposes a system for treating waste oil mixed with water and impurities at low cost and easily, and aims at improving efficiency of waste oil recovery work and reducing treatment cost.

In the present invention, a processing technique for powdering and solidifying waste oil is established, and regarding solidification processing of waste oil, it is newly added that calcium oxide and sodium silicate are added and mixed to efficiently solidify the waste oil into powder. It is a finding.

At present, from the viewpoint of zero emission, which is a movement in the industrial world aiming at the formation of a recycling society, the present invention aiming at effective utilization conducts characteristic tests on various waste oils in order to confirm each versatility, Flammability (2,700-3,
000 kcal / kg) was evaluated by adding a reproducible and statistical method, and it was confirmed that it could be reused.

Details of implementation (1) Establishing a technology for recovering and processing oil in wastewater Testing lubricants Waste oils Lubricants are used for cooling and abrasion resistance of rotating equipment in power plants, improving cooling and abrasion resistance. To let
Various additives are added to the oil, and the viscosity and additive components are different depending on the purpose of use, and most of them are neutral or weakly alkaline.

Waste oil belongs to mineral oil in the "Waste Disposal and Cleaning Law", and if it is contained in the wastewater,
According to the Water Pollution Control Law, it is a substance regulated by the normal hexane extractable substance content, and it is regulated by Appendix 2 of the Prime Minister's Ordinance that sets the emission standards. (Mineral oil content: 5 milligrams or less per liter, animal and vegetable oil content 30 milligrams or less per liter)

A. Investigation of oil types used and emissions (a) Oil type and quality survey of lubricating oils As for lubricating oil types at power plants, there are many rotating equipments as mentioned above. There are various types. Therefore, we selected oil types with different properties from among the lubricating oils that are used in a relatively large amount, including a survey of the types and quality of oil types currently in use.
A survey of properties etc. was conducted.

(B) Investigation of Emissions from Oil Separation Tanks and Purchases of Lubricating Oils Investigations on the amount of oils discharged from the oil separation tanks and the oils from others and the purchases of each lubricating oil were conducted.

(C) Investigation of oil discharge points at power plants A waste oil discharge points / routes at the power stations and equipment with a large amount of discharge were investigated.

B. Investigation of oil treatment and recovery equipment The oil treatment and recovery equipment in the oil-water separation tank is currently using the rotary drum skimmer system. The rotary drum skimmer system is one of the most popular oil treatment and recovery systems. Therefore, we compared the performance of the oil treatment and recovery equipment currently used in oil-water separation tanks with other equipment and investigated its performance. As a result, the rotary drum skimmer system showed overall superiority.

(A) Rotary drum skimmer system (B) Liquid centrifuge method (C) Pressure floating flotation method (D) Levitation suction method

(2) Establishment test of powder solidification technology of recovered waste oil a. Preliminary test and solidification principle (a) Waste oil treatment Prior art survey and preliminary test A prior art survey was conducted on the waste oil treatment agent, and a preliminary test was conducted on the method of treating waste oil from the power plant. As a result of the preliminary test, the treatment with the addition of sodium silicate and calcium oxide was superior to other applications in terms of simplicity, reactivity, and handling, so further detailed tests should be carried out. And

(B) Consideration of Principle of Waste Oil Treatment In carrying out the detailed test, the treatment principle was considered, and the investigation including the action and effect was conducted. The main components used in lubricating oils are mainly fatty acids,
When it is a hydrophilic oil, it colloids in water, and the colloids repel each other due to the zeta potential and the electric double layer, and they do not spontaneously settle under the influence of gravity (Stokes' law), causing Brownian motion. Are evenly dispersed or suspended by.

Further, depending on the oil and fat component, the hydrogen bond between water molecules and the large repulsive force of the electric double layer maintain colloidation, which makes oil separation from water difficult. In order to change oils and fats such as hydrophilic fatty acids to be hydrophobic, it is necessary to change the water-soluble oils and fats into insoluble substances such as carboxylates.

On the other hand, in the case of hydrophobic fats and oils, it does not become a problem because it floats above water without being dispersed or colloidalized in water, so removing oil from water is not so problematic as with hydrophilic fats and oils. There are problems such as running costs. The present invention solves these problems by the following principle. When treating hydrophilic oils and fats dispersed in a colloidal form, the repulsive force generated by the polarity of the water molecules adhering to them is incorporated by the chemical reaction of the water molecules as calcium hydroxide by the addition of calcium oxide, and the heat generated by water absorption is generated. The action of removing the effect of water molecules by the dehydration action in the reaction.

In order to change an insoluble substance into a hydrophobic substance, by adding sodium silicate and calcium oxide, calcium hydroxide and sodium hydroxide produced in the reaction process are reacted with a fatty acid which is a main component of waste oil to obtain a fatty acid. Generates ester (fatty acid calcium / sodium: hydrophobic) substances. Almost all oil components are occluded in the treated solid by the gelation of fatty acid calcium / sodium by siloxane bond and the formation of insoluble silicate metal hydrate by the reaction with polyvalent metal ion by sodium silicate which has excellent fat and oil adsorption property. To be done. In addition, residual fats and oils are adsorbed to the treated solid matter by a capillary phenomenon or the like when the powdering is promoted.
This is the solidification principle of this waste oil treatment. The waste oil treatment mechanism is shown in FIG.

B. Addition ratio test of solidifying agent (a) Purpose Waste oil and sodium silicate solution (hereinafter referred to as "sodium silicate") (Na2O2SiO2) and calcium oxide (CaO)
Was added to and mixed to cause saponification and siloxane bond to form calcium carboxylate ((RCOO) 2 ・ Ca insoluble salt), and the treatment was performed for the purpose of extracting the optimum addition rate. is there.

(B) Test Method Samples As samples, 5 types of oil types used in large amounts in the above (1) a (b) and 5 types of oil types having different properties and 6 types of collected waste oil were used. -Oil separation tank recovery oil-Oil A-Oil B-Oil C-Oil D-Oil E

Treatment agent ・ Calcium oxide (calcium oxide, CaO, powder) ・ Sodium silicate (sodium silicate, Na2 ・ O ・ 2SiO2,
Solution) A JIS standard No. 3 product diluted to 20% (volume) is used.

Equipment ・ Oil solidification tester ・ Stainless steel balls ・ Medicinal spoon ・ Stopwatch ・ Oil solidification tester

Test procedure: Each sample is weighed on a stainless steel ball, set in a solidification tester, and 100 ml of sodium silicate is added with stirring.・ Start stirring and mix the sample and sodium silicate well. (3 minutes) -Add calcium oxide based on the formulation of the solidification test table,
Record the reaction status.

The test procedure and test were conducted once each, and repeated tests were carried out to confirm reproducibility with respect to the amount of additive determined to be optimum.・ Regarding the sample and sodium silicate, the addition amount is constant,
Find the optimum amount of calcium oxide added.

Evaluation method ・ Proportion of processing agent and waste oil / lubricant ・ Exothermic characteristics depending on waste oil / lubricating oil type ・ Exothermic time ・ Solid state of product

(C) Results As a result of carrying out the above-mentioned test for approximately 100 samples or more in order to find an appropriate addition ratio, the smaller the addition ratio is, the more advantageous it is in terms of cost, and it is possible to cope with various oil types. Sample 1 with complete reaction confirmed at the minimum addition ratio
With respect to (weight ratio), calcium oxide 2 (weight ratio) and sodium silicate 1 (volume ratio) are added appropriately, and
The addition ratio in each test was kept constant.

100 g of oil Calcium oxide 200g Sodium silicate 100 ml

C. Solidification treatment method (a) Purpose To establish the solidification treatment method for each lubricating oil and waste oil and to standardize the operation, establish the method of injecting additives, the timing, the agitation necessary for the reaction, the operating method, and the standing time until completion of the reaction. It is intended for.

(B) Test method and results As a result of a preliminary test conducted in advance, it was found that sodium silicate was added to the additive injection method because the granulation phenomenon due to the addition of calcium oxide occurred and stirring became difficult. Due to the fact that the granulation is prevented by adding it first and the reaction principle, the order of injection of the additives is sodium silicate → calcium oxide.

The rate of saponification reaction between sodium silicate and the sample varies depending on the sample, but is almost 3
The stirring time was set to 3 minutes because the saponification reaction of the sample could be confirmed (in an emulsified state) by stirring for 1 minute. Further, even when mixing with calcium oxide, uniform mixing was possible in about 3 minutes, so that the standardization of stirring time could be confirmed. In addition, powdering is promoted by leaving it to stand for about 20 minutes and complete powdering is completed, so it was decided to leave it so that reaction heat could be fully utilized.

(C) Solidifying method Based on the grounds of item (b), the solidifying method is as follows. 100g of sample is put in a container and sodium silicate solution 10
Add 0 ml and stir slowly. After 3 minutes, 200 g of calcium oxide was further added, and the mixture was stirred at a low speed for 3 minutes, the stirring was stopped, and the mixture was left for 20 minutes.

D. Heat generation characteristic test during processing (a) Purpose Regarding the heat generation characteristics of the treated solids of each lubricating oil and waste oil, it was possible to confirm the approximate heat generation characteristics from the above test results, but this phenomenon may continue to occur. It was carried out for the purpose of reconfirming the reproducibility of things, etc., while giving a statistical evaluation.

(B) Test method sample ・ Oil separation tank recovered oil ・ Oil A ・ Oil B ・ Oil C ・ Oil D ・ Oil E

Treatment agent ・ Calcium oxide (calcium oxide, CaO, powder) ・ Sodium silicate (sodium silicate, Na2 ・ O ・ 2SiO2,
Solution) JIS standard No. 3 product diluted to 20% (volume) is used.

Equipment ・ Oil solidification tester ・ Stainless steel balls ・ Medicinal spoon ・ Stopwatch ·thermometer

Test procedure ・ 100 g of a sample was placed in a container and 100 parts of sodium silicate solution was added.
Add ml and stir slowly.・ After 3 minutes, add 200 g of calcium oxide and add 3
Stir slowly for minutes. Stop stirring and leave for 20 minutes.

(C) As a result, the reproducibility of the exothermic characteristics was confirmed in the collected waste oil and each lubricating oil, and the exothermic temperature was recovered by comparing the exothermic characteristics with the oil A, which occupies the majority of the recovered waste oil. The heat generation time of waste oil was shorter, and the heat generation temperature was 83 ° C on average, which was about 2 ° C lower than that of oil A and oil E on average.

It can be inferred from this result that since the waste oil is composed of various lubricating oils, it tends to have such a heat generation tendency. On the other hand, since the oil B and the oil D exhibit the characteristic of generating heat in a short time of 5 minutes, it is presumed that they are caused by the influence of the constituent components contained in the lubricating oil. In addition, for oil C, the heat generation start time was the longest at 9 minutes, and the reaction tended to proceed slowly. Therefore, the constituents of oil C were formed of difficult-to-react substances, and It is speculated that the onset of fever was prolonged because the reaction gradually decomposed or changed.

E. Handling processability investigation (a) Purpose The purpose is to add chemicals to the waste oil to cause a reaction, and to confirm the reactivity and handleability of the solidified waste oil (the ease of handling in actual equipment).

(B) Test method sample ・ Oil separation tank recovered oil ・ Oil A ・ Oil B ・ Oil C ・ Oil D ・ Oil E

Treatment agent-Calcium oxide (calcium oxide, CaO, powder) -Sodium silicate (sodium silicate, Na2O2SiO2, solution) JIS standard No. 3 product diluted to 20% (volume) is used.

Equipment ・ Oil solidification tester ・ Stainless steel balls ・ Medicinal spoon ・ Stopwatch ·thermometer

Test procedure Repeated tests depending on the type of oil are performed to confirm the ease of processing, reactivity, and handleability.・ Put 100 g of sample in a container and use 100 sodium silicate
Add ml and stir slowly.・ After 3 minutes, add 200 g of calcium oxide and add 3
After stirring at low speed for a minute, stop stirring and let stand for 20 minutes. -Peel off the treated solids from the container.

Evaluation method The following items were evaluated. ・ Peelability from waste oil treatment equipment after treatment ・ Powdered state

(C) Results As all oil types were completely pulverized and peeled from the container well, it was possible to confirm the easiness of treatment, reactivity and handleability. In addition, since reproducibility was confirmed, it is expected that sufficient processing simplicity, reactivity, and handling will be improved even on the actual machine base.

F. Examination of the color in the solidified state (a) Purpose The color after the solidification treatment changes due to the difference in the constituent components of the waste oil and the lubricating oil. Therefore, the color after the treatment is confirmed and the difference in the color after the treatment is confirmed. Verify the possibility of determining the type of waste oil.

(B) Test method sample ・ Oil separation tank recovered oil ・ Oil A ・ Oil B ・ Oil C ・ Oil D ・ Oil E

Treatment agent-Calcium oxide (calcium oxide, CaO, powder) -Sodium silicate (sodium silicate, Na2O2SiO2, solution) JIS standard No. 3 product diluted to 20% (volume) is used.

Equipment ・ Oil solidification tester ・ Stainless steel balls ・ Medicinal spoon ・ Stopwatch ·thermometer

Test procedure: 100 g of a sample was placed in a container, and 100 parts of sodium silicate solution was added.
Add ml and stir slowly.・ After 3 minutes, add 200 g of calcium oxide and add 3
After stirring at low speed for a minute, stop stirring and let stand for 20 minutes.

Evaluation Method The following items were evaluated. -Change in color development (by standard chromaticity plate) depending on the type of oil The color development on the treated solids is caused by the organic compounds exhibiting a color, and the characteristic color changes due to the difference in the constituent components contained in the lubricating oil. To be

(C) Results From the various results of the present invention, the color development of the recovered waste oil is very similar to that of oil A, and it is presumed that the recovery waste oil from the compressor is the main component of the waste oil in the oil fractionation tank. It was Also, from the factual relationship of the waste oil discharge route, compressor type (structure for discharging waste oil), and waste oil discharge amount, it was found that the main component of the collected waste oil is the oil used in the compressor. By being able to identify the type of waste oil by confirming the unique coloration at the time of powder solidification, it can be utilized for identifying the discharge location and maintenance of the equipment, and also contributes to the reduction of waste oil emissions.

(3) Establishment test of effective utilization technology of treated solids a. Solubility of treated solids (a) Purpose The purpose is to confirm the solubility of treated solids in an aqueous solution because the effect of water is concerned depending on the storage state of treated solids from the viewpoint of effective utilization technology. Is.

(B) Test method As a sample sample, 100 g of oil E was used, 100 ml of sodium silicate (20%) and 200 g of calcium oxide were added, and then solidified to obtain a test sample.

Additive Hydrochloric acid (10 wt%)

Equipment ・ Medicinal spoon ·thermometer ・ PH test paper ・ Beaker (500 ml)

Test Method In order to confirm the solubility of the treated solidified product in water and acid, the purpose of the present invention is to investigate the behavior of oil separation when the treated and solidified waste oil is dissolved in water and acid.

The same amount of treated solidified product (20 g)
Weigh. -Add to a beaker containing 100 ml of water and 10% hydrochloric acid and stir.

Evaluation method The following items were evaluated. ・ Comparison of oil separation state in supernatant water ・ Water and acid dissolution state of solidified sample

(C) Results From the test results, when dissolved in water, some suspended matter was present on the surface, but it settled with the passage of time, but at this time no oil separation was observed and the oil was treated with the treating agent. I confirmed that I was holding it. On the other hand, when dissolved in acid, the oil was eluted from the solid and separated into two layers. From this, it was confirmed that it exhibits insolubility in water and dissolves in acid.

H. Property test of powder solidified sample (a) Purpose The purpose is to investigate and confirm the calorific value, sulfur content, water content, etc. of waste oil, lubricating oil and treated solidified product, and to confirm various characteristics of the treated waste oil in flammability. .

(B) Test method sample ・ Waste oil treated solid ・ Oil A and treated solids ・ Oil B and treated solids ・ Oil C and treated solids ・ Oil D and treated solids ・ Oil E and treated solids

Oil separation tank Waste oil collected from the waste oil drum can and treated solids were used as test samples.

Test Method The test method was carried out according to the following test method.・ JIS-M-8814 Coal and coke calorific value measuring method A sample is burned by a thermal laboratory calorimeter, the temperature rise during that period is measured, and the cal number for 1 g of the sample is obtained.
The calorific value was measured. -JIS-M-8813-5-3 Water content measurement method The sample was dried by a constant temperature dryer adjusted to 107 ° C for 1 hour, and evaluated by the mass percentage relative to the weight loss.・
JIS-M-8812 Sulfur content measurement method by high temperature combustion method A sample is heated to about 1350 ° C. in an oxygen stream to oxidize all sulfur content and then gasify it. Titration was carried out with a standard solution of sodium oxide, and the mass percentage for the sample was obtained and evaluated as total sulfur.

(C) Result The amount of heat of the solidified sample is 2680 to 3020 kcal /
Kg and about 1/2 of coal has a water content of 0.3-12.0%
Therefore, it was confirmed that it can be used as a combustion improver.

I. Ignition point of powder solidified sample and characteristic test over time (a) Purpose As one of the evaluations of compatibility of treated solids with boiler fuel, it is necessary to confirm the ignition characteristics by mixing coal with treated solids. To aim.

(B) Test method The treated solids used in the sample test were tested in the following three types.・ Waste oil treated solids ・ Oil A treated solids ・ Oil E treated solids

Measuring Equipment and Equipment-Hot tube type electric furnace (core temperature: 1200 ° C) -Combustion board-Plate balance-Digital thermometer-Hot tube type electric furnace test procedure Prior to testing, temperature distribution in the electric furnace used in advance Surveys were conducted. The thermocouple of the digital thermometer was gradually inserted into the electric furnace toward the core, and the correlation of the relationship between the insertion distance (mm) and temperature was investigated to confirm the characteristics of the electric furnace temperature distribution. After that, the ignition point of each oil type was measured.

(C) Results-Ignition temperature of treated solids-Ignition temperature characteristics of treated solids over time Ignition temperature of each treated solid varies slightly with each oil type, but is different from that of a single oil treated The solids were confirmed to have almost the same ignition temperature. Regarding the ignition temperature for waste oil treated solids, ignition was observed at a furnace temperature of around 220 ° C, and the initial ignition characteristics were 224 ° C.
Ignites at, and the igniting temperature drops once with the passage of time.
After 2 hours, it tended to be constant at 220 ° C, but when the overall temperature was relatively observed, the change in ignition temperature was slight and almost constant. Also, regarding the oil A treated solids,
Ignition temperature of about 20 ℃ higher than the ignition temperature of waste oil was observed, and in contrast to waste oil, the ignition temperature was 234 ℃ in the initial stage, and the ignition temperature increased with time, and peaked at 262 ℃ after 72 hours. After that, the ignition temperature tended to decrease. It was confirmed that the change was relatively small and the temperature was constant. From the above, it was assumed that the ignition temperature of treated solids was constant regardless of changes over time. The ignition point could not be measured for the oil E-treated solids, but it is presumed that this was due to the volatilization of the combustible gas and the lean mixing with the combustion gas, which did not reach the gas concentration in the combustion range. It

J. Calorific value and aging test of powder solidified sample (a) Purpose From the above test results, the smell of the oil volatilized from the treated solid (oil E) was detected. The volatile components are volatilized in accordance with the above, and the change in the calorific value of the treated solid is estimated accordingly. Therefore, the purpose is to confirm the temporal change in the calorific value.

(B) Test method The treated solids used in the sample test were tested in the following three types.・ Waste oil treated solids ・ Oil A treated solids ・ Oil E treated solids

Measuring equipment and instruments-Calimeter-Humidity humidifier for moisture saturation (humidity: 75% constant saturated saline solution for humidification) -Plate, precision balance, thermostat (constant temperature: 25 ° C)

Test Procedure Prior to the test, the water absorption characteristics of calcium oxide used in advance were investigated, and various investigations were also carried out on the water absorption / volatilization characteristics of the treated solid matter. Regarding the volatilization characteristics, they were stored in a thermostat (temperature: 25 ° C constant) for several days, and the amount of volatilization over time was measured for changes in the amount of heat generation. Regarding the water absorption characteristics, in order to confirm the water absorption characteristics of calcium oxide in advance, forcibly absorb the water with a moisture-saturating constant humidity chamber (humidity: 75% constant), and obtain a blank value of the calcium oxide water absorption amount, and then perform oxidation. In addition to confirming the weight increase and adsorption breakthrough point when calcium changed to slaked lime due to water,
The volatile content of treated solids and the amount of moisture absorbed from the air were clarified.

(C) Results The weight of calcium oxide tended to increase with time due to water adsorption. In addition, the reaction-treated solid is
It is presumed that the oil or fat or the treating agent became a factor that hinders the adsorption of water and that the water adsorption amount tended to be low as a whole.

Regarding the oil content volatilization amount, the weight increase amount due to the adsorption of water was largely involved, and the volatile content amount could not be clearly confirmed. However, it can be inferred from the change in the calorific value over time that the waste oil and the oil A As for the oil E, the calorific value decreased by 130 kcal / kg, and for the oil E, the oil content volatilized (odor) in addition to the water adsorption,
It is estimated that the calorific value decreased by 255 kcal / kg over time.

K. Mixed Combustion Test of Coal and Treated Solids (a) Purpose From the above test results, when the treated solids were burned in an oxygen atmosphere, they became glassy by themselves. And whether ash content is confirmed during combustion,
The purpose is to confirm the various characteristics when burned when mixed with coal.

L. Desulfurization effect and corrosiveness confirmation test From the above test results, the product of the treated solids has calcium hydroxide / sodium hydroxide / fatty acid calcium / fatty acid sodium as the main components. Since it is presumed that it contributes, the evaluation and confirmation as a desulfurizing agent in the treated solid matter will be performed by using an S minute meter. Regarding the mixing ratio, as mentioned above, the main components of the treated solids are calcium salts and sodium salts, and the desulfurization effect is expected, while at the same time, the behavior of corrosive substances such as chlorine and sulfur oxides is generated. In order to confirm the above, we confirmed the evaluation as a dechlorinating agent and desulfurizing agent when the mixing ratio of coal and treated solids was changed.

(B) Test method sample ・ Waste oil treated solid ・ Melting point of coal (Daido Coal) (1325 ℃)

Measuring instruments and equipment ・ S minute meter (total sulfur meter) ・ Ion chromatograph

Test Procedure The treated solid matter and coal added at each mixing ratio are burned in an oxygen atmosphere, and a test is performed by each measuring method. -JIS-M-8813 Sulfur content test method (high temperature combustion method) -JIS-K-0102 Sulfate ion measurement method (ion chromatography) -JIS-K-0102 chlorine measurement method (ion chromatography) Test for mixing ratio with coal Was done. (C) Results S content measurement after burning coal and treated solids at each mixing ratio showed a maximum desulfurization rate of 13.6%.
Furthermore, the results obtained by comparing the combustion gas components by ion chromatography of hydrogen peroxide water absorbed in the combustion test by mixing coal 1: 0.5 treated solids with each other showed that chlorine, which is a corrosive gas, was mixed. As for the removal rate of gas, it was confirmed that the removal rate was about 2.0%. Therefore, during combustion, sulfur changed to gypsum or sodium sulfate, and in chlorine, calcium chloride / sodium chloride became a neutralization reaction, resulting in desulfurization.・ It is speculated that the dechlorination phenomenon occurred.

Dissolution test on test residue ash (A) Purpose Confirm the chemical properties of residual ash. (B) Test method sample ・ Waste oil residue ・ Oil A residue ・ Oil E residue Measuring instruments and equipment ・ PH ・ Measuring device (IM-40S) ・ PH ・ Test paper (Advantage ・ 1-12)

Test Method After taking a certain amount of the sample, add 30 mL of distilled water in a beaker.
After soaking for a minute and stirring, measure the pH.

Test Method Distilled water is added to the residual ash to moisten it, and the pH of each residual ash is simply measured with a pH test paper.

(C) Result The treated solid matter cannot be dissolved in water and the pH
Could not be measured. The result was that the pH was similar to that of Daido coal identified as a blank, but the calcium oxide (Ca
O) caused it to be alkaline.

M. Pressurized state test of solidified waste oil (a) Purpose When the solidified waste oil is pressed and crushed, it is confirmed how the taken waste oil behaves, and when the powdery solid is processed into pellets. The purpose is to confirm the effect of.

(B) Pulverization test What kind of particle size distribution characteristic is exhibited in the treated solid matter when the treated oil is pulverized in the same manner as the fuel such as coal.
The behavior of the waste oil component is confirmed.

(C) Test method sample ・ Waste oil treated solid ・ Calcium oxide

Measuring instruments and instruments ・ Hard Glove Grindability Tester (HGI) ・ Vibration mill ・ Particle size analyzer

(D) Test procedure-The particle size distribution of the calcium oxide, which is the main raw material for the treated solid and powder, is measured to confirm the difference.・ Hard globe grindability tester (HGI) for treated solids
Also, pulverize with a vibration mill and measure and confirm the particle size distribution.

(E) Results The treated solid did not change in particle size in the hard glove grinding tester (HGI), but became fine in the vibration mill. It was also found that when the treated solids pulverized by a vibrating mill were mixed with water, a substance considered to be an oil component was separated.

N. Pressurization test (a) When processing the processed oil-treated solid into pellets, it is confirmed under each pressure whether or not the oil is leached by applying pressure. The purpose is to

(B) Test method sample ・ Waste oil treated solid

Measuring equipment and instruments ・ Pressure tester

(C) Test procedure In the pressure test, the treated solid sample was sandwiched between filter papers, and the leaching of the oil component under each pressure was confirmed.
The calorific value of the treated solid after pressurizing the sample at the pressure of ² · was measured.

(D) Results In order to verify whether the liquid oozing on the filter paper is a waste oil component using a pressure tester, the calorific value of the oozing component was measured, and the heat generated during the calorific value characteristic test was measured. Since it was lower than the amount, it is unlikely that the oozing liquid is a waste oil component, and most of it is assumed to be water. From the results, it can be expected that the processed solid matter can be processed into pellets and that the handling property as a product is improved because the calorific value does not change even when pressurized.

O. Solidification test of waste oil with high water content (a) Purpose Usually, waste oil exists as waste oil drainage, and there are many things that contain a large amount of water and are emulsified. Therefore, the objective is to confirm whether the performance of the solidification treatment can be maintained even with waste oil containing a large amount of water.

(B) Test Method Samples Each sample was artificially added with 10% water and mixed, and the prepared samples were used as model drainage.・ Waste oil ・ oil A ・ oil E

Measuring instruments and instruments ・ Solidification tester ・ Stainless steel balls

Test procedure 10 was artificially prepared as a solidification application test of emulsified waste oil.
% Emulsified oil containing water was solidified.

(C) Results As a result of solidifying each emulsified oil, it was confirmed that the reaction was no different from that of the oil before emulsification. By this,
It was confirmed that conventional solidification is possible even for waste oil containing 10% of water or emulsified waste oil. The rotary drum skimmer, which has been optimized as a waste oil recovery technology, has a water content of 10%, confirming its effectiveness as an oil treatment system.

4. Conclusion In the method for treating waste oil recovered from the oil separation tank of the power plant conducted this time, various characteristics in waste oil treatment could be confirmed and effective waste oil was confirmed from the results of the reproducibility confirmation test and the adaptability test result of the present invention regarding the waste oil treatment. It was confirmed that the technology is a treatment technology, and a great result was obtained from the viewpoint of zero emission. Also, the waste oil discharged (including water and foreign substances)
On the other hand, since the waste oil can be treated at low cost by adding and mixing the treating agent with a simple facility, the result of the present invention is that the detour is bypassed in the power plant and all the plants that discharge the waste oil. The technology is adaptable.

Development research on oil treatment system in wastewater (outline) A part of the wastewater at the power plant is a wastewater containing a small amount of oil used for lubrication of auxiliary machinery, etc., and the wastewater discharged from this type of system The oil is once collected in each pit, passed through the transportation facility, and then the oil is collected by the oil separator. However, since the collected waste oil contains water and contaminants, it is currently being used as industrial waste and outsourced to a processing company without being effectively used.

The present invention proposes a system for treating waste oil inexpensively and easily, and aims at improving the efficiency of waste oil recovery work and reducing the treatment cost. In the present invention, a treatment for powdering and solidifying waste oil is carried out. We will establish a technology, and then carry out various characteristic tests of solidified waste oil with a view to effective use from the perspective of zero emissions, and propose a new oil treatment system.

Waste Oil Treatment Technology With reference to the prior art survey on waste oil treatment agents, it was found that waste oil could be powdered and solidified, and a preliminary test was conducted. As a result, we established a technology to solidify the waste oil into powder by adding and mixing calcium oxide and sodium silicate to the waste oil, and the waste oil produced and solidified is flammable (2,7
(0 to 3,000 kca / kg), and there is a possibility of reuse.

Outputs 1. Investigation of oil content treatment and recovery technology in wastewater ● The water content of the recovered oil was about 0.1% in the rotary drum skimmer system used at the power station. ● The rotary drum skimmer system has a water content of less than 10% even with hydrophilic oils such as vegetable oil and animal oil.

2. Establishing powder solidification technology for recovered waste oil <Test sample> The following 6 types were selected for the types of oil that generate a large amount of waste oil at power plants and those with different properties. a. Oil recovered from oil separation tank d. Oil C b. Oil A e. Oil D c. Oil B f. Oil E

(1) Addition ratio test of solidifying agent From the test results, the following addition ratios were appropriate. Oil 100g Calcium oxide 200g (weight ratio) Sodium silicate (20% solution) 100 ml (volume ratio)

(2) Solidification method 100 g of oil was placed in a container and 100 ml of sodium silicate solution was added.
And slowly stir. After 3 minutes, 200 g of calcium oxide was further added, and the mixture was stirred at low speed for 3 minutes. The stirring is stopped and the mixture is allowed to stand for 20 minutes (while standing, powdering is promoted to complete powdering).

(3) Exothermic characteristics during solidification treatment (oil type: waste oil, A to E) ● Exothermic heat is generated by the addition and stirring of the solidification treating agent, but the exothermic start temperature is 4 to 10 minutes later and the exothermic peak temperature is 80 to It was 99 ° C. ● As a result of repeated confirmation of heat generation characteristics, reproducibility was remarkable.

(4) Treatment handling investigation (oil type:
Waste oil, A to E) ● Repeated tests were conducted, and the peelability from the test container after processing and powderization were good.

(5) Investigation of color in solidified state (oil type:
Waste oil ・ AE) ● Depending on the type of oil, there is a distinctive coloration when solidified, and it was confirmed with a standard chromaticity plate. ● Lubricating oil contains unique constituents, which are presumed to be due to its coloring characteristics. ● The unique color of treated solids can be used to identify the type of waste oil.

3. Establishment of effective utilization technology for treated solids (1) Solubility of treated solids (oil type: waste oil) ● When solidified waste oil was immersed in water, oil separation was not observed. ● The solidified waste oil was confirmed to separate when immersed in acid.

(2) Calorific value of powdery solidified sample (oil type: waste oil, A to E) -The calorific value after powdery solidification is 2,680 to 3,020 kca.
It was / kg.

(3) Ignition point of powder solidified sample and characteristics over time (oil type: waste oil, A to E) The ignition point was 224 to 235 ° C., which was the same as the ignition point of the oil alone. ● The ignition point did not change over time.

(4) Time-dependent change in the calorific value of the powdery solidified sample (oil type: waste oil, A, E) ● Oil type: waste oil, A, the calorific value after leaving for 8 days was 130 kca due to the moisture absorption of the solidified sample. / Kg decreased. ● Oil type: E is 255k due to moisture absorption and volatilization of oil components
It decreased by ca / kg.

(5) Results of mixed combustion test of coal and treated solids (oil type: waste oil, A, E) The desulfurization rate was 13.6% at maximum. (Coal burned with 1: 1 solidified waste oil) ● Desalination rate was 2%. (Coal 1: Burned with 0.5 solidified waste oil) ● The surface of the residual ash is vitrified and the elution pH is 12
Met.

(6) Pressurized state test of solidified waste oil (oil type: waste oil) As a result of pressurizing (10 t / cm ² ) with a pressurizing tester, bleeding of water was confirmed. Since the calorific value of the pressed sample is the same as that before pressing, it can be used by forming pellets. ● The separation of oil was confirmed as a result of mixing the solidified waste oil that was crushed under pressure with a vibration mill with water.

(7) Solidification test of waste oil with high water content (oil type:
Waste oil) ● The water content of the waste oil collected at our site is 0.1%, but the solidification process was carried out in the same way as before emulsification, as a result of solidification processing using a sample prepared to waste oil with a water content of 10% assuming emulsified waste oil. Was possible.

4. Integration and practical application of each element ● An integrated system from waste oil recovery to powder solidification equipment was constructed. ● It is possible to reduce the running cost of solidification treatment against the current waste oil treatment cost. ● Utilization of waste oil treatment as a bypass technology (residual oil treatment agent, fuel, etc.)

5. Achievements ● Horizontal deployment is possible at power plants that generate waste oil. ● Treated solids have a calorific value of 2,700 to 3,000 kcal / kg, and zero emission is possible by using them as a combustion improver for boilers. ● The unique coloring during powder solidification can be used to identify the type of waste oil, and can be used for identifying the discharge location and equipment maintenance.

[Brief description of drawings]

FIG. 1 is a flow chart showing a waste oil treatment method according to an embodiment of the present invention.

FIG. 2 shows an example of a waste oil treatment method according to the present invention.
It is explanatory drawing which shows the mechanism of a waste oil processing method.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G01N 33/30 G01N 33/30 (72) Inventor Kazuhiro Imade Maigashima, Daigasakihama, Shichigahama, Miyagi-gun, Miyagi Prefecture No. 1 Tohoku Electric Power Co., Inc. Sendai Thermal Power Station (72) Inventor Toshiki Ujiie Maejima, Daigasakihama, Shichigahama-cho, Shichigahama-cho, Miyagi-gun, Miyagi Prefecture Tohoku Electric Power Co., Inc. Sendai Thermal Power Station (72) Inventor Ono Ikuei Rifu, Miyagi Prefecture 53, Shin-Nakabori, Iimachi, Tohoku, Tohoku Electric Power Co., Ltd., Technology Development Research Center (72) Inventor, Yukiya Konno 1 Maejima, Daigasakihama, Daigasakihama, Shichigahama-cho, Miyagi-gun, Miyagi 1 Tohoku Electric Power Co., Inc. Sendai Branch Office (72) Inventor Shuichi Oshima 1 Maejima No. 1 Maejima, Daigasakihama, Shichigahama-cho, Miyagi-gun, Miyagi Prefecture Tohoku Electric Power Co., Inc. Sendai Branch Office (72) Invention Hiroki Ohara 1 Maejima, No. 1 Maejima, Shimogasaki, Shichigahama-cho, Miyagi-gun, Miyagi Prefecture Tohoku Electric Power Industry Co., Ltd. Sendai Branch Office (72) Inventor Jun Watanabe, 1 Maejima, Maejima, Shichigasaki-cho, Shichigahama-cho, Miyagi-gun, Miyagi Prefecture Power Generation Industry Co., Ltd. Sendai Branch F-term (reference) 2G020 AA08 DA05 DA16 DA62 2G042 AA03 CA10 CB04 DA08 FA19 4D017 AA03 AA05 BA03 BA06 BA09 CA04 CA05 EB09 4H015 AA02 AA25 AA27 AB01 AB04 AB08 BA10 BA12 BB11 CB01

Claims (5)

[Claims] 1. A method for treating waste oil, which comprises mixing silicates with waste oil and then adding and mixing calcium salts. 2. A first step of transporting the oil separation tank recovered waste oil to a reactor, and a second step of mixing silicates with the oil separation tank recovered waste oil in the reactor and then mixing calcium salts. And a third step of discharging the mixture after the second step, the method for treating waste oil recovered from a power plant oil separation tank. 3. The silicates consist of sodium silicate,
The method for treating waste oil according to claim 1, wherein the calcium salts are composed of calcium oxide. 4. A combustion improver, which is obtained by mixing waste oil with silicates and then mixing calcium salts. 5. A method for discriminating the oil type of the waste oil, which comprises mixing silicates with the waste oil, then mixing calcium salts, and discriminating the oil type of the waste oil by the color of the mixture.