KR900003888B1 - A catalyst composition for revival of waste oil and revival method of waste oil thereof - Google Patents

Abstract

A method for reproducing a waste oil comprises (a) producing a slurry by mixing waste oil with white earth in the mixer, (b) heating the slurry at 150-180≰C in the heating furnace, (c) rapidheating the slurry at 300-400≰C, (d) keeping the slurry at 300-400≰C for 5-15 min, and (e) preheating, cooling and filtering the slurry. The catalyst compsn contains aluminium sulphate, magnesium sulphate and sodium chloride.

Description

Catalyst composition for waste oil regeneration and waste oil regeneration method using the same

1 is a block diagram of the present invention.

2 is a process and apparatus diagram as one batch embodiment of the present invention.

* Explanation of symbols for main parts of the drawings

1: preheater 3: purple

4: reversible pump 6: mixer

7 catalyst white soil inlet 9: stirring blade

10: forced circulation reactor 11: heating furnace

12 condenser 13 separator

14 oil tank 15 air preheater

17: strainer

Collecting and regenerating the waste oil of the lubricating oil system generated in various factories, industrial external combustion engines, automobiles, etc. is very desirable in terms of resource utilization and the purpose of expelling pollution. Therefore, in Korea as well as in developed countries, technologies for recycling waste oil have been researched in various ways, and some have achieved commercial success.

It is well-known that the conventional technique of regenerating waste oil is the acid treatment process combining the sulfuric acid treatment process and the clay adsorption process of the waste oil.

The theory of conventional acid treatment process is that paraffinic and naphthenic oils are stable against concentrated sulfuric acid (93%), while aromatic, olefinic, diolefinic, and acetylene oils react with concentrated sulfuric acid to produce acid sulfates, neutral esters, and alcohols. It has been based on the fact that it is polymerized to make a polymer (sludge). Therefore, the acid treatment process itself is relatively simple, and the waste oil is put into a conical tank equipped with a stirrer, and a constant amount of concentrated sulfuric acid is gradually added while stirring the stirrer, and the stirring is continued for 5 to 12 hours. After the rise, the reaction continues, and when the reactants (here aromatic, olefin, etc.) are exhausted, it is usually left overnight to settle acid-sludge, which is removed from the bottom of the conical tank and removed, and then the acid-treated waste oil, which is the upper layer. The clay was added while stirring the stirrer again in situ, and the mixture was stirred for 4 to 5 hours to carry out the clay adsorption process, followed by solid-liquid separation with a filter to regenerate a high purity lubricant base oil.

The most difficult problem in the prior art as described above is a problem of disposing of acid-sludge generated in the sulfuric acid treatment of waste oil.

In other words, incineration of acid-sludge produces sulfur dioxide, which causes secondary pollution more widely, and even if it is landfilled in a certain area, there is no proper disposal method due to its odor and the release of H ₂ SO ₄ . .

On the other hand, the conventional process conditions are relatively simple and convenient, but it is necessary to handle dangerous sulfuric acid, and the anticorrosive device is required, manufacturing facilities are expensive, and the process itself lacks repeatability, which leads to uniform quality control. It was difficult. Another method for purifying waste oil is a combination of distillation and hydrogenation. This is a method for regeneration of waste oil which is followed by distillation followed by hydrogenation, although it has been disclosed in various literatures and some have been industrially carried out, but these have the disadvantage of being expensive in processing and requiring complicated equipment. In addition, it is a big disadvantage that the range of waste oil that can be used as a raw material is very limited.

One example of a process of regenerating lubricating organic oil by main process of distillation and hydrogenation reaction is Korean Laid-Open Patent Publication No. 86-9101. Here, to remove the water and light oil contained in the waste oil, a baffle plate-type tray is installed, followed by a vacuum, a high temperature thin film distillation unit, and a fractional distillation unit to obtain a lubricating organic oil. The method of reclaiming waste oil was disclosed.

However, the above disclosed methods can be said to include the drawbacks of a complicated process and a high purification cost. In addition, a method of producing a lubricant base oil using a solvent is described in detail in Korean Patent Publication No. 84-579.

Here, N-methyl-2- pitolidon is used as a solvent, and a purification method using a conventional extraction column, a low temperature flash, a distillation unit, and an extraction solvent recovery unit is preferable. In terms of efficiency, it is basically a vacuum residue oil (Vacuum). Only gas oil can be used as a raw material and it is not applicable to the recycling of waste oil.

In order to solve the problems of the conventional waste oil regeneration technology, the inventors, as a result of research and development, 1) the invention of high cost and high activity and new and advanced waste oil treatment catalyst, 2) the new and highly advanced catalyst for waste oil treatment of the present application It is invented a new regeneration method for producing a high purity lubricating oil base using 3), and 3) the invention and a process and apparatus capable of performing this regeneration method efficiently.

The present invention can be used as a raw material all the lubricating oil waste oil generated in a wide range of industrial machinery and automobiles, and therefore it is easy to secure the raw material because even a mixture of various kinds of waste oil can be used as raw materials.

The present invention is particularly effective in the regeneration of automotive lubricants. In addition, the catalyst for treating waste oil first invented by the present invention is composed of a ternary composition containing 1 to 98 parts by weight of aluminum sulfate, magnesium sulfate, and sodium chloride, respectively, by weight of each component. As well as obtainable and very inexpensive chemicals, it is a new and advanced invention that such compositions become catalysts for waste oil regeneration.

The present invention relates to a novel process for purifying waste oil in a single process using the above catalyst for wastewater regeneration in combination with conventional clay.

That is, according to the present invention, a waste oil-catalyst slurry is prepared by adding together at least 0.1% of catalyst and at least 10% of catalyst, and at least 10% of clay and at least 40% of clay based on waste oil, and then foaming temperature of the slurry in a forced circulation reactor. The resulting slurry was heated to 150-180 ° C., slowly heated, fully foamed and then rapidly heated to a maximum temperature of 300 ° C. to 400 ° C. and held at this maximum temperature for 5 to 15 minutes to terminate the reaction. Reaction slurry ", followed by a new process for regenerating lubricating oil base oil regenerated via a heat exchanger, a cooler, and a filter.

Therefore, the catalyst of the waste oil according to the present invention and the method of reclaiming the clay can be substantially completed in a single process, which can be said to be a significant improvement over the complicated regeneration method of the conventional sulfuric acid treatment process and the clay treatment process. It is also a completely new regeneration method compared to the conventional distillation and hydrotreating methods.

One of the excellent features of the present invention is that it is a non-polluting regeneration method by producing only solid waste of pollution-free materials, and the solid waste generated by the method of the present invention can be used for land reclamation or the like.

It is another object of the present invention that the flash point highly improved renewable lubricating oil base oil may be carried out simultaneously in a catalyst, a clay treatment process without a separate distillation process. That is, in the present invention, when preheating the waste oil with a preheater, steam-striping method can be applied to remove water 3 to 10% by adding 50 to 400 g of steam based on the waste oil, preferably 125 to 250 g, depending on the type of waste oil. As a result, an improved lubricating oil having a high flash point can be produced without a separate distillation process. The above stripping operation can be performed at any time before or after the addition of the catalyst and the clay.

Another object of the present invention is to connect the reaction of the waste oil, catalyst, and clay in a large single reactor and a direct heating furnace in series to force the circulation of the waste oil, catalyst, and clay slurry to facilitate the process adjustment, increase production, This is to save equipment manufacturing cost and to improve the quality of reclaimed base oil.

In particular, by adopting a forced circulation reactor in the present invention can obtain a strong stirring and shearing effect, it is possible to prevent the precipitation or adhesion of the solid catalyst and the clay in the reactor and refining the resinous material produced during the reaction, coagulation particles Re-separation, etc., to facilitate the reaction.

Still another object of the present invention is to provide an appropriate condenser and oil / water separation facility for directly or condensing volatile gas streams generated from the reaction of waste oil, catalyst, and clay to be used as self-fuel in the process. In the method of the present invention, the non-condensed gas stream in the condenser can also be incinerated as fuel in its own process, thereby serving as a primary pollution prevention treatment of odorous gas.

Moreover, in order to improve the thermal efficiency as a whole process, the preheater which preheats the waste oil which is a raw material to a fixed temperature with high heat quantity (about 350 degreeC) of the produced reaction slurry is provided in a process.

Preheating the waste oil as a preheater first can achieve efficient mixing in the next process, waste oil, catalyst, and clay mixing, in addition to the above-mentioned general purpose of recovering and utilizing the high calorie value (350-400 ° C.) of the reaction slurry. Because there is.

When the waste oil is preheated and mixed with the catalyst and clay of the present invention, the amount of catalyst and clay may be reduced, and the mixing time of the mixing process may be shortened.

The method of the present invention provides a method for solid-liquid separation of the reaction slurry in the temperature range of 150 ℃ to room temperature. That is, in the method of the present invention, the reaction slurry (345-360 ° C.), which has been reacted, is gradually exchanged with raw material oil, cooled to about 150 ° C., collected in a reaction slurry tank, and cooled to room temperature with cooling water, and then filtered at room temperature. Solid-liquid separation may be used, or one of the improved methods is filtering without cooling to room temperature. Therefore, it can be said to filter by adjusting the temperature appropriately within the temperature range of 150 ℃ to room temperature. This is because reaction slurries with high viscosity generally have high filtration resistance (many of pressure type filters are advantageous), and when a vacuum filter is employed, it is better to lower the viscosity by increasing the temperature of the stock solution (reaction sludge). . In addition, if the vacuum is filtered in such a state that the temperature is raised, the volatile gas streams are once again removed, thereby contributing to quality improvement. In addition, the filtrate can be increased while the temperature is raised, and the yield can be increased.

As a filter, all pressurized filters and vacuum filters can be used, and as a pressurized filter, a filter press is typical but the form of a filter which automatically collects a filter is desired.

As the vacuum filter, either batch or continuous type may be used.

The method of the present invention can be carried out continuously or batchwise, and the present invention is to invent a production apparatus suitable for such a production method.

Referring to the drawings the present invention as follows.

1 is a block diagram of the present invention, in which the raw material mixing step, the reaction step, the circulating heating step, the heat exchange (preheating) step, the cooling step, and the filtration step are performed.

2 is a batch process and an apparatus diagram according to one embodiment of the present process. The preheater 1 is provided with a heat exchange jacket 3, which is connected by a source of water vapor 2. In addition, it is possible to condense or discharge the air stream 16 which may be generated during preheating. The preheater receives the high temperature reaction slurry through the valve 1-1 and discharges the low temperature reaction slurry through the valve 1-1. The reversible pump 4 is capable of supplying slurry in any direction, and in the process of the present invention, there is also an advantage in piping design in which the material in all processes is supplied and discharged with only one pump.

The mixer 6 has a multistage agitator blade 9 connected from a power source via a decelerator 8 and an inlet 7 through which the catalyst and the clay can be introduced.

The forced circulation reactor (10) is connected to a valve (10-1) for receiving waste oil, catalyst, and bag slurry. The condenser can be used as a self-process fuel by exhausting or condensing the gas generated during the reaction. The 12 and the separator 13 are connected and the condensed fuel is connected to the fuel tank 14. In addition, the reactor 10 is connected to the reversible pump 4 and the heating furnace 11 to forcibly circulate waste oil, catalyst, and clay slurry.

The heating furnace 11 is a tubular heating furnace structure, and the slurry in the reactor 10 is supplied by the pump 4 to be heated, and then circulated in the reactor 10.

The filter 17 is composed of a discharge section which receives the reaction slurry as a conventional vacuum filter or a pressure filter, performs solid-liquid separation, and sends the regenerated lubricant base oil 18.

As a related facility, the air preheater 15 is installed in the vicinity of the communication of the heating furnace 11, and the necessary process control apparatus, for example, a thermometer, a pressure gauge automatic control system, etc. are provided.

In the above-described process apparatus, the preheater 1 is pumped by the pump 4 through the valve 10-1 and the copper 10-2 to the high temperature reaction slurry in which the reaction is completed in the reactor 10. 10-5), copper (1-2), copper (1-1) through the supply.

Subsequently, the jacket 3 of the preheater carries the waste oil 5 to the valve 6-3, the copper 6-2, the copper 11-3, the copper 10-2, and the copper 10 by the pump 4. Heat exchange is initiated by supply via -3) and the waste oil in the jacket (3) is gradually preheated. During the preheating, a large amount of foam is generated and at the same time, the water and the low boiling fraction contained therein evaporate, which may be sent to the condenser 12 to be recovered as self-fuel or, in some cases, just released to the air.

In the preheater (1), a steam (2) supply system is installed, which supplies steam (2) through the valve (2-2) in the absence of a high temperature heat medium such as a reaction slurry during commissioning or initial operation. 3) It is to preheat waste oil in. During normal operation, water vapor (2) is supplied to the upper end of the jacket (3) with bracket steam to deflate the foam and at the same time block air contact to prevent explosion. It is supplied to the lower end of the jacket (3) to remove the low boiling point material in the waste oil to improve the flash point of the regenerated lubricating oil. The waste oil preheated generally to 110 to 130 ° C. is then pumped back by the pump 4 and enters the mixer 6 through the valve 6-1.

The preheated waste oil entered into the mixer 6 is adjusted to about 50% of the capacity of the mixer 6, and then the stirring motor 8 is operated to stir the stirring blade 9 vigorously, 0.1 to 10 based on the waste oil. Add 10 to 40 parts by weight of clay, based on the weight percent catalyst and waste oil and continue stirring to make a sufficiently uniform slurry.

The uniform slurry is discharged from the stirrer 6 through the valve 6-1 and supplied to the reactor 10 by the pump 4. The waste oil, catalyst, and clay slurry supplied to the reactor 10 have a temperature of 100 to 130 ° C. and occupy about 50% of the reactor capacity (internal volume). Waste oil, catalyst, and clay slurry in the reactor 10 are sent to the furnace 11, heated to 300 to 400 ° C, and circulated to the reactor through the valve 1-2. The circulation of this waste oil, catalyst and clay slurry continues until the desired reaction is completed. At this time, the heating rate is directly related to the circulation rate and controlled in association with the foaming rate.

The foam generated in the reactor 10 controls the temperature and the heating rate so as not to keriobar outside the reactor 10. The steam generated during the reaction in the reactor 10 is sent to the condenser 12, where once condensed, the non-condensed gas, condensed oil and condensed water are separated from the separator 13 and the non-condensed gas 13-1 is directly The fuel is supplied to the heating furnace 11 and the condensed oil is collected in the oil tank 14 and then supplied to the heating furnace 11 as the fuel flow 14-1.

In the reaction process in the reactor 10, a lot of bubbles are generated initially, but when the evaporation of 150 to 150 ℃ is lost. Subsequently, the slurry is continuously circulated in the heating furnace so that the temperature of the slurry is raised (highest temperature) to 300 to 400 ° C., and then kept constant at this highest temperature for about 7 to 15 minutes. The residence time of the slurry in the reactor depends on the heating rate of the circulating rate heating furnace 11 of the slurry, etc., but generally it is preferably 20 to 40 minutes.

The fully treated reaction slurry reacted while being circulated for a period of time in the reactor 10 is transferred to the preheater 1 for heat exchange. The reaction slurry transferred to the preheater 1 is at a high temperature of about 300 to 400 ° C. Here, the waste oil, which is a raw material for the jacket 3, is supplied through the valve 6-3 and the copper 6-2 by the diesel pump 4 to supply the valve 10-2 and the copper 10-3 to the diesel fuel jacket. do. The reaction slurry and the waste oil are gradually heat exchanged in the preheater 1 to cool the reaction slurry to 120 to 180 ° C. If necessary, the reaction slurry once cooled in the preheater 1 may be quenched with cooling water or the like to bring it to room temperature.

Once the reaction sludge which has been heat-recovered in the preheater 1 is solid-liquid separated in the filter 17 via the valves 1-1 and copper 1-2, the reclaimed lubricating oil base oil 18 as a liquid is obtained. Generated by crushing solid waste

Solid wastes can be used as landfills as pollution-free materials and have no difficulty in disposal as with conventional acid slurries.

The above operation is continued in a batchwise manner, but if necessary, a substantially continuous operation may be performed by providing a plurality of preheaters 1, reactors 10 and the like.

[Examples 1-3]

Into a 2-liter three-necked flask equipped with a stirrer, a thermometer, a distillate outlet tube, and a condenser, waste oil, catalyst, and white clay of the type shown in the following Table 1 were added and heated to an indicated temperature using an electric heater. Using a D-type Teflon resin agitator blade, stir sufficiently to thoroughly agitate the catalyst and clay at the bottom of the flask. The stirring speed is rotated at about 60 rpm.

When the waste oil-catalyst slurry reaches 130 ° C., when the water and gasoline components are distilled off, the rate of increase in temperature is controlled in accordance with the foam generated, so that the foam does not flow through the distillate outlet.

If bubbles no longer occur between 150 and 160 ° C., the rate of temperature rise is increased and raised to a temperature between 345 and 360 ° C., the highest temperature. It is held at this maximum temperature for about 10 minutes and then the reaction slurry is slowly cooled in air to lower to 150 ° C. and then cooled to room temperature with cold water. The reaction slurry cooled to room temperature is separated from the catalyst and the clay using Whatman No. 1 cellulose filter paper using a vacuum filter.

The results are shown in Table 2 below.

TABLE 1

Table 2 below is an analysis table comparing the properties of the waste oil used as a raw material in Example 1 and the regenerated lubricant base oil.

TABLE 2

[Examples 4 to 6]

Experiments were carried out in the same manner as in Examples 1 to 3, except that a mixture of base oil and automobile waste oil was used as a raw material, and each component of the catalyst was changed as shown in Table 3.

TABLE 3

Claims (2)

A catalyst composition for waste oil regeneration comprising 1 to 98% of aluminum sulfate, magnesium sulfate and sodium chloride, respectively. Waste oil pre-heated in the preheater and the catalyst composition for waste oil regeneration according to claim 1 are charged with 0.1 to 10% by weight based on the waste oil and 10 to 40% by weight based on the waste oil into the mixer to make waste oil-catalyst and clay slurry. The slurry is transferred to a forced circulation reactor, and then circulated in a series-heated direct heating furnace, which is heated to 150 to 180 ° C. to be sufficiently foamed, and then rapidly heated to the maximum temperature of 300 ° C. to 400 ° C., which is the highest temperature. Remaining for 5 to 15 minutes to terminate the reaction after the heat exchange device, the cooler and the filter regeneration method characterized in that the filter.

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