KR100896428B1 - Production method of solid acid catalyst from spent oil shale for catalytic cracking of polymeric materials and heavy oil and production method of light oil using thereof - Google Patents

Abstract

The present invention relates to a method for preparing an organic polymer and a solid acid catalyst for heavy oil pyrolysis using oil shale pyrolysis residues, and more particularly, to use in oil shale processes using residues and alkalis remaining after the oil shale retorting process is completed. The present invention relates to a method for preparing an amorphous silica alumina catalyst. The present invention also includes a method of hardening shale oil recovered by oil shale retorting using the catalyst to obtain hard oil and a method of obtaining hard oil from waste plastic.

That is, the present invention uses a low-cost catalyst prepared from the oil shale pyrolysis residue, which is a retorting waste, as the catalyst used in the oil shale process. It can reduce the production cost of the catalyst, and also contribute to the reduction of groundwater and soil pollution due to landfilling of oil shale residues in oil shale development.

Oil shale, residue, alkali, reactant, light oil

Description

Production method of solid acid catalyst from spent oil shale for catalytic cracking of polymeric materials and heavy oil and Production method of light oil using pretty}

The present invention relates to a method for preparing an organic polymer and a solid acid catalyst for heavy oil pyrolysis using oil shale pyrolysis residues, and more particularly, to use in oil shale processes using residues and alkalis remaining after the oil shale retorting process is completed. The present invention relates to a method for preparing an amorphous silica alumina catalyst.

The present invention also includes a method of hardening shale oil recovered by oil shale retorting using the catalyst to obtain hard oil and a method of obtaining hard oil from waste plastic.

Oil Shale is a rock containing an organic substance, keogen, and can recover 5% to 20% of the weight of the oil shale ore as synthetic crude oil through retorting.

Oil shale has a huge amount of more than 2 trillion barrels of oil in the United States, China, Australia, Russia, Brazil, Morocco and Jordan, and has a relatively low exploration risk compared to conventional crude oil.

In order to obtain synthetic crude oil from the oil shale, the oil shale gemstone is heated to 400 ° C. or more in a state where air is blocked, thereby pyrolyzing kerosene in the oil shale. This is called retorting.

On the other hand, after the retorting, a considerable amount of pyrolysis residues are left, and the volume becomes larger than the original raw materials, which makes it difficult to process the oil. It has been pointed out as a major problem of development.

In addition, the quality of the shale oil obtained after the retorting is low, its use is limited to ships or industrial fuels, and the use of the shale oil is restricted worldwide despite the enormous resource value.

Therefore, in order to solve the above problems, a number of methods for efficiently producing synthetic crude oil from oil shale have been developed. For example, a method of increasing the retorting efficiency by pre-treating the oil shale with acid (US Patent 5277796, US Patent 6936159), a method of improving synthetic crude oil quality by removing impurities in shale oil by extraction, etc. (US Publication 2004/0222134, US Publication 2005/0167337), and desulfurization and denitrification catalyst to improve shale oil quality. And the like (US Patent 3948755, US Patent 4086158, US Patent 4153540, US Patent 4716142, US Patent 4948495), and the like.

However, the above conventional methods require an expensive extractant or a commercial catalyst for oil shale pretreatment or refining process, thereby increasing the process cost.

In addition, some techniques for synthesizing mineral raw materials or dry materials from oil shale pyrolysis residues have been developed, for example, a method for obtaining sodium carbonate and sodium bicarbonate (US Pat. No. 6,854,809), and a method for preparing cement raw materials (US Pat. No. 6,835,244). ) And so on. However, the above conventional methods were to use the oil shale pyrolysis residue for a separate use, not the oil shale process.

Literature information of the prior art

1.US Patent 5277796

2.US Patent 6936159

3.US Publication No. 2004/0222134

4.US Publication 2005/0167337

5.US Patent 3948755

6.US Patent 4086158

7.US Patent 4153540

8.US Patent 4716142

9.US Patent 4948495

Accordingly, an object of the present invention is to solve the problems of the prior art as described above, by reacting the oil shale pyrolysis residue and alkali at a high temperature to extract a large amount of silica and alumina source, after coprecipitation at room temperature In addition, the remaining impurities are removed to stably synthesize a solid acid catalyst having excellent catalytic activity.

In addition, the solid acid catalyst of the present invention can be used in the shale oil hardening process and the catalytic pyrolysis oilification process of waste plastic to effectively produce light oil level oil.

That is, the main object of the present invention is to prepare a low-cost solid acid catalyst from oil shale pyrolysis residue, to harden shale oil, and to process waste plastic pyrolysis oilification of the solid acid catalyst prepared by such a method. To provide a process for obtaining light oil pyrolysis oils from these.

In particular, by using a low-cost catalyst prepared from the oil shale pyrolysis residue, a retorting waste, as a catalyst used in the oil shale process, not only can it be directly synthesized at the process site, but it also reduces the production cost of the catalyst for the oil shale hardening process. In addition, the catalyst prepared by the present invention can reduce the retorting waste to prevent environmental pollution such as soil pollution and groundwater pollution caused by the oil shale pyrolysis residue landfill.

In order to achieve the above object, an organic polymer and a method for preparing a solid acid catalyst for heavy oil pyrolysis using an oil shale pyrolysis residue of the present invention are obtained by reacting an oil shale pyrolysis residue with an alkali to obtain an oil shale pyrolysis residue-alkali reactant. It characterized in that it comprises the step of aging by reacting the reactants.

And, a method of obtaining a light oil using the solid acid catalyst,

In the presence of the solid acid catalyst is characterized in that the heavy oil or waste plastic is heated under anoxic conditions.

According to the present invention, solid acid catalysts having excellent catalytic activity can be obtained in large quantities from oil shale pyrolysis residues, and the obtained catalysts can be used to produce light oil level liquid fuel from heavy oil or plastic waste. Useful effects such as widespread use in the process.

In particular, by using a low-cost catalyst prepared from the oil shale pyrolysis residue, a retorting waste, as a catalyst used in the oil shale process, not only can it be directly synthesized in the oil shale process but also the cost of preparing the catalyst for the oil shale hardening process The oil shale development can reduce the groundwater and soil pollution caused by oil shale residue reclamation.

Hereinafter, the present invention will be described in detail.

1 shows a procedure for providing a solid acid catalyst from an oil shale pyrolysis residue according to the present invention.

The main materials used in the preparation of the solid acid catalyst of the present invention are oil shale pyrolysis residues and alkalis.

First, in the present invention, the oil shale pyrolysis residue is reacted with an alkali to obtain an oil shale pyrolysis residue-alkali reactant. The reaction conditions are allowed to react for 0.5 to 2 hours at a temperature of 500 to 700 ° C.

And 70 to 300 parts by weight of the alkali is reacted with respect to 100 parts by weight of the oil shale pyrolysis residue, which is insufficient when the alkali is less than 70 parts by weight, there is a problem in the lack of silica, alumina ions required for the production of a solid acid catalyst, 300 This is because even if the portion is exceeded, the improvement of the characteristics of the catalyst due to the increase in the amount of alkali used is insignificant.

The alkali may be any one or a mixture of two or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and calcium hydroxide, but the present invention does not particularly limit the type of alkali other than those described above. Of course, alkali can be used.

The oil shale pyrolysis residue-alkali reactant reacted as described above has silica and alumina ions, and the reactants are co-precipitated in purified water and then aged to synthesize a solid acid catalyst. At this time, the aging conditions are enough to synthesize a solid acid catalyst from silica and alumina ions, for example, aged for 6 to 36 hours at 20 ~ 30 ℃, if the temperature exceeds 30 ℃ oil shale pyrolysis Residue-Since silica and alumina ions in alkali reactant are transferred to crystalline form, there is a problem that catalyst activity is lowered, and it is difficult to synthesize catalyst when less than 20 ℃, and synthesis is not completed when aging time is less than 6 hours. This is because the synthesis does not proceed any more than time.

Meanwhile, the solid acid catalyst prepared as described above may further include a washing step for increasing purity and a firing step for enhancing strength, wherein the washing step is sufficient if the purity of the solid acid catalyst can be improved. It does not restrict the implementation. In the washing step, for example, the aged solid acid catalyst may be washed 2 to 5 times with purified water at 60 to 80 ° C., and as another example, when a weak acid solution such as an aqueous ammonium chloride solution is used, the washing efficiency may be improved. The activity of can be improved more. In particular, the aqueous solution may be washed with an aqueous ammonium chloride solution of 1.0 to 2.0 molarity, and the aqueous ammonium chloride solution of 1.0 to 2.0 molarity may improve the activity of the solid acid catalyst.

In addition, the small-phase step is also sufficient to improve the strength of the solid acid catalyst, for example, the washed solid acid catalyst may be calcined at 600 ~ 700 ℃ for 4 to 8 hours, the firing temperature And time are conditions that can improve the strength of a solid acid catalyst.

As described above, according to the present invention, a solid acid catalyst is prepared by various conditions using an oil shale pyrolysis residue and an alkali. In order to obtain a solid acid catalyst meeting the object of the present invention, the oil shale pyrolysis residue and It is preferable to make the above-mentioned numerical range on condition of alkali.

And the results of measuring the specific surface area, average pore diameter and physical properties for X-ray diffraction of the solid acid catalyst according to the present invention prepared as described above are shown in Table 1 below.

Measurement results of the solid acid catalyst. Specific surface area Average pore diameter X-ray diffraction 35 to 186㎡ / g 60-100Å Amorphous

On the other hand, the present invention includes a method for hardening heavy oil using the solid acid catalyst described above, the heavy oil can be heated under anoxic conditions in the presence of the solid acid catalyst prepared in the above method to obtain a light oil. .

At this time, as the heavy oil, any one or two or more selected from the group consisting of crude oil distillation residue, bitumen and shale oil obtained from oil shale retorting may be used.

5 to 40 parts by weight of the solid acid catalyst may be used with respect to 100 parts by weight of the heavy oil. When the solid acid catalyst is less than 5 parts by weight, the action of the catalyst becomes insignificant, and even if the amount exceeds 40 parts by weight, no further improved reaction appears. Because it does not.

In addition, if a heavy oil reflux device is additionally installed in the reactor, only light oil is selectively recovered, and only the desired light oil is recovered by refluxing the fraction of the heavy oil discharged through the reflux device by heating it back to pyrolysis. You can do it. As an example of the selective recovery of light oil by the reflux of the heavy oil, the temperature of the heavy oil reflux apparatus is maintained at 150 to 350 ° C., and a fraction having a higher boiling point may be refluxed in the reactor to be pyrolyzed again.

As an example of a method for recovering light oil from the heavy oil, it is heated to 200 to 500 ℃ in the presence of 5 to 40 parts by weight of the solid acid catalyst and anoxic conditions with respect to 100 parts by weight of shale oil recovered from oil shale retorting Hard oil can be recovered.

In addition, the solid acid catalyst of the present invention can also be used in the pyrolysis oilification process of waste plastics. In the presence of the solid acid catalyst prepared in the above method, the waste plastics can be heated under anoxic conditions to recover hard oil. The waste plastic may be an olefin waste plastic, and the olefin waste plastic may be polyethylene, polypropylene, or the like.

In the above, the waste plastic is obtained in the presence of the solid acid catalyst prepared according to the present invention by heating at 350 to 450 ° C. under anoxic conditions to obtain hard oil, and the amount of catalyst used is 100 parts by weight of the waste acid. 5 to 40 parts by weight of catalyst is used, for the same reason as in the method for recovering light oil from the heavy oil described above.

In the present invention, in order to obtain light oil from heavy oil and waste plastic, the heavy oil and waste plastic are pyrolyzed under various conditions. The most preferred light oil level of pyrolysis oil can be obtained.

Hereinafter, the content of the present invention will be described in detail through examples and test examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples and test examples.

(Example 1)

Preparation of solid acid catalyst from oil shale pyrolysis residue.

100 g of the residue generated after the retorting and 120 g of sodium hydroxide were homogeneously mixed with the Colorado oil shale, and heated to a high temperature in a kiln for 1.5 hours to obtain an oil shale pyrolysis residue-sodium hydroxide reactant.

The reaction was dissolved in purified water and then aged at room temperature for 8 hours to coprecipitate the catalyst. In order to remove the unreacted sodium hydroxide contained in the mixture, it was washed several times with 1 molar concentration of ammonium chloride solution and solid-liquid separated by filter paper to separate the impurity solution and the catalyst.

The solid acid catalyst of the present invention was obtained by heating at 600 ° C. for 4 hours in order to enhance the mechanical properties of the catalyst and to remove residual impurities.

2 shows a SEM photograph of the solid acid catalyst prepared above.

Example 2

Physical Characterization of Solid Acid Catalysts Prepared from Oil Shale Pyrolysis Residues

In order to determine the physicochemical properties of the solid acid catalyst obtained in Example 1, physical properties such as X-ray diffraction analysis and BET surface area measurement were performed and shown in FIG. 3.

As can be seen in FIG. 3, XRD diffraction analysis of the catalyst obtained in Example 1 showed that the solid acid catalyst showed a gentle peak and had an amorphous property without showing crystals.

As a result of analyzing the physical properties according to ASTM-related regulations, the amorphous silica alumina catalyst obtained in Example 1 was found to have a surface area of 158 m 2 / g and a pore diameter of 70.8 mm 3.

(Example 3)

 Pyrolysis Activity Analysis of Solid Acid Catalyst Prepared from Oil Shale Pyrolysis Residue

In order to confirm the pyrolysis activity of the solid acid catalyst obtained in Example 1, plastic catalytic pyrolysis was performed using a thermogravimetric analyzer (Rubotherm, Germany). After charging 0.05 g of the low density polyethylene and 0.05 g of the solid acid catalyst obtained in Example 1 into a 0.8 milliliter (ml) alumina container, nitrogen gas was supplied at a flow rate of 60 milliliters per minute to maintain anoxic conditions. The temperature was increased by 5 ℃ per minute to 600 ℃ and the weight loss was measured according to the temperature.

For comparison, a pyrolysis experiment was carried out under the same conditions in the case where only 0.05 g of low density polyethylene was charged without adding a catalyst as a comparative example.

As shown in FIG. 4, when the solid acid catalyst prepared in Example 1 was used, the pyrolysis initiation temperature was lowered by at least 80 ° C. than the noncatalyst, thereby demonstrating excellent activity of the catalyst synthesized by the present invention.

Example 4

Pyrolysis of Shale Oil Catalysts by Solid Acid Catalysts Prepared from Oil Shale Residues

4 g of the catalyst obtained in Example 1 and 40 g of shale oil having a specific gravity of 24.9 ° from the American Petroleum Institute (API) obtained from oil shale retorting were charged into a 1 liter reactor, and the temperature of the reactor was maintained for 40 minutes using an electric furnace. Heat up to 450 ° C. and then maintain reactor temperature at 450 ° C.

Nitrogen gas was fed into the reactor at 60 ml / min for smooth movement of the pyrolysis product and maintenance of anoxic conditions, and cracking was attempted again by refluxing the heavy oil having a boiling point higher than 250 ° C. for efficient cracking.

The non-condensable gas which was not condensed in the pyrolysis product was discharged to the atmosphere, and the condensable gas was condensed with a condenser and collected together with the liquid product.

As a comparative example for comparison, pyrolysis was carried out under the same conditions in the case where only 40 g of the same shale oil having a specific gravity of 24.9 ° of API obtained in oil shale retorting was loaded without a catalyst.

When using the solid acid catalyst prepared in Example 1 showed better pyrolysis results than the simple pyrolysis without the catalyst, the reaction initiation temperature could be lowered by more than 50 ℃ and light oil recovery was also 76.3% to not use the catalyst It was able to improve more than 69.4% obtained from simple pyrolysis.

In addition, the shale oil obtained from the oil shale retorting is difficult to add to the existing oil refining process due to the API specific gravity of 24.9 °, but when the shale oil is thermally decomposed using the solid acid catalyst prepared in Example 1, The oil's API boiling point can be significantly lowered to 32 °, making it harder to synthesize crude oil that can be added to existing refinery processes.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated that it can be changed.

1 is a view showing a procedure for producing a solid acid catalyst according to the present invention.

2 is a SEM photograph of a solid acid catalyst prepared according to an embodiment of the present invention.

Figure 3 is a graph showing the XRD diffraction analysis of the solid acid catalyst prepared according to an embodiment of the present invention.

Figure 4 is a result of measuring the weight loss according to the temperature when the thermal decomposition of low-density polyethylene using a solid acid catalyst prepared according to an embodiment of the present invention and pyrolysis of low-density polyethylene in the non-catalyst state without using a catalyst A graph showing the weight loss measurement results according to temperature.

Claims (15)

The solid for pyrolysis of organic polymers and heavy oils using an oil shale pyrolysis residue, comprising the step of reacting the oil shale pyrolysis residue with an alkali to obtain an oil shale pyrolysis residue-alkali reactant and coprecipitating the reactant. Acid catalyst preparation method. The method of claim 1, A method for producing a solid acid catalyst for pyrolysis of organic polymers and heavy oils using an oil shale pyrolysis residue, wherein the oil shale pyrolysis residue is reacted with an alkali at 500 to 700 ° C. for 0.5 to 2 hours. The method of claim 1, A method for producing a solid acid catalyst for pyrolysis of organic polymers and heavy oils using an oil shale pyrolysis residue, characterized in that 70 to 300 parts by weight of alkali is reacted with respect to 100 parts by weight of the oil shale pyrolysis residue. The method of claim 1, The alkali is a solid acid catalyst for producing organic polymers and heavy oil pyrolysis using oil shale pyrolysis residues, characterized in that any one or a mixture of two or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and calcium hydroxide. The method of claim 1, The oil shale pyrolysis residue-alkali reactant is aged for 6 to 36 hours at 20 ~ 30 ℃, characterized in that the production of solid acid catalyst for organic polymer and heavy oil pyrolysis using oil shale pyrolysis residue. The method of claim 1, After the aging step, The method of preparing a solid acid catalyst for pyrolysis of organic polymers and heavy oils using oil shale pyrolysis residues, further comprising the step of washing the prepared solid acid catalyst and calcining the washed catalyst. The method of claim 6, The washing step is a method for producing a solid acid catalyst for pyrolysis of organic polymers and heavy oils using an oil shale pyrolysis residue, wherein the prepared solid acid catalyst is washed with an aqueous solution of ammonium chloride at a concentration of 0.1 to 2.0 moles. The method of claim 6, The calcining step is a solid acid catalyst for producing organic polymers and heavy oil pyrolysis using oil shale pyrolysis residues, wherein the washed solid acid catalyst is calcined at 600 to 700 ° C. for 4 to 8 hours. In the process for obtaining light oil from heavy oil, A method for obtaining light oil using a solid acid catalyst, characterized in that the heavy oil is heated under anoxic conditions in the presence of the solid acid catalyst prepared by the method of any one of claims 1 to 8. The method of claim 9, A light oil obtaining method using a solid acid catalyst, characterized in that 5 to 40 parts by weight of the solid acid catalyst based on 100 parts by weight of the heavy oil. The method of claim 9, The heavy oil is any one or two or more selected from the group consisting of crude oil distillation residues, bitumen and oil shale retorting from the group consisting of light oil using a solid acid catalyst. The method of claim 9, A method of obtaining light oil using a solid acid catalyst, characterized in that the fraction of the heavy oil discharged using a reflux device is refluxed in a reactor and heated again. In obtaining light oil from waste plastic, A method for obtaining light oil using a solid acid catalyst, characterized in that the waste plastic is heated under anoxic conditions in the presence of a solid acid catalyst prepared by the method of any one of claims 1 to 8. The method of claim 13, A method of obtaining light oil using a solid acid catalyst, characterized in that 5 to 40 parts by weight of the solid acid catalyst is used based on 100 parts by weight of waste plastic. The method of claim 13, The waste plastic is a method for obtaining light oil using a solid acid catalyst, characterized in that the olefin waste plastics.

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