JP2013170224A - Method for producing petroleum alternative liquid fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a petroleum alternative liquid fuel from a woody biomass, etc., in higher efficiency compared with conventional methods and to provide a petroleum alternative liquid fuel produced by the method.SOLUTION: A petroleum alternative liquid fuel having high fuel properties is produced at a low temperature in higher efficiency compared with conventional methods by using a method including a step of performing co-pyrolysis of a woody biomass and a plastic material. There is also provided a petroleum alternative liquid fuel produced by the method.

Description

  The present invention relates to a method for producing petroleum-substitute liquid fuel. More specifically, the present invention relates to a method for producing petroleum alternative liquid fuel, including a step of co-pyrolysis of woody biomass and plastic.

In recent years, as a fuel that can be changed to fossil fuels such as petroleum, petroleum-substitute liquid fuels using woody biomass such as waste materials and wood chips as raw materials have been manufactured. However, in the conventional manufacturing method, only woody biomass is heated and thermally decomposed in the presence of a solvent, so that undecomposed products and decomposed products are polycondensed during the decomposition reaction to form a residue, resulting in a low yield. However, there was a problem that liquid fuel alternative to petroleum could not be produced.
In addition, since the obtained petroleum substitute fuel contains a large amount of aromatic compounds and oxygen-containing compounds, it has low physical properties as a fuel and also contains a lot of highly polar compounds, so it can be used by mixing with existing petroleum-derived fuels. There was also a problem that only the department. Therefore, it is desired to provide a method capable of producing petroleum alternative liquid fuel with higher efficiency using woody biomass as a raw material.

In view of such a problem, the present inventors studied to produce petroleum alternative liquid fuel by co-pyrolysis of woody biomass and plastic in the present invention.
As a technology for producing a petroleum alternative liquid fuel using plastics and components such as polyethylene, polystyrene, and polypropylene as raw materials, for example, in Patent Document 1, plastic is cited as one of hydrocarbon-containing residues, and alkali metals A method of producing diesel oil by catalytic cracking at a temperature of 300 to 400 ° C. using aluminum silicate doped with bismuth as a catalyst is disclosed.
Moreover, in patent document 2, as a method of liquefying waste plastic mixed with oily inadequate materials such as paper, wood chips, and raw garbage, first, water is added at a temperature lower than the decomposition reaction temperature of the plastic to start from the waste plastic. There has been disclosed a technique for removing foreign substances (unsuitable for oil formation) and then processing a plastic suitable for oil formation remaining in a molten state at a decomposition temperature suitable for recovering oil.
However, these methods are only for the purpose of liquefying plastics and the components that form plastics, and are intended to obtain petroleum alternative liquid fuels by co-pyrolysis of woody biomass and waste plastics. It was not something to do.

  As a method of using a combination of woody biomass and plastic, for example, in Patent Document 3, in a fuel made of a foamed plastic molded product mainly composed of foamed polystyrene, a good fuel can be obtained by mixing wood chips with this. It is also disclosed what can be done. However, this document does not suggest or examine the use of these as raw materials to obtain petroleum substitute liquid fuel.

JP 2005-163013 A JP-A-9-78072 JP-A-6-1987

  An object of the present invention is to provide a method for producing a petroleum-substitute liquid fuel from woody biomass or the like with higher efficiency than conventional methods.

The inventors of the present invention have made extensive studies to solve the above-described problems. As a result, by co-pyrolysis of woody biomass and plastic, a low-temperature petroleum alternative liquid fuel can be obtained at a lower temperature than conventional methods. The present inventors have found that it can be produced with higher efficiency and have completed the present invention.
In the manufacturing method completed in the present invention, the wood decomposition product and the plastic decomposition product are combined by co-pyrolysis of woody biomass and plastic, so that the wood decomposition products and undecomposed products are polycondensed. As a result, the formation of residues is suppressed and the yield of petroleum alternative liquid fuel is improved. In addition, the physical properties of the resulting fuel are improved, since there are few aromatic compounds and oxygen-containing compounds, the aliphaticity is increased and the polarity is lowered, so even when mixed with petroleum-derived fuel, phase separation does not occur. There is an advantage that can be used.
Moreover, since the decomposition of waste plastics is promoted by radicals generated from the wood decomposition products, it becomes possible to produce petroleum substitute liquid fuel at a temperature lower than the liquefaction temperature of plastics that have been studied conventionally. Furthermore, since the production method of the present invention does not require a catalyst, there is an advantage that a mechanism for recovery is unnecessary.

That is, the present invention relates to a method for producing petroleum alternative liquid fuel, etc., as shown in the following (1) to (5).
(1) A method for producing petroleum-substitute liquid fuel comprising a step of co-pyrolysis of woody biomass and plastic at 300 ° C. or higher and 450 ° C. or lower.
(2) The method for producing a petroleum alternative liquid fuel according to the above (1), wherein the woody biomass and the plastic are mixed at a weight ratio of 2: 8 to 8: 2.
(3) The method for producing a petroleum alternative liquid fuel according to the above (1) or (2), wherein the plastic is a plastic containing any one or more of polyethylene, polystyrene or polypropylene as a raw material.
(4) The petroleum alternative liquid fuel according to any one of the above (1) to (3), wherein the woody biomass is a woody biomass containing any one or more of cedar, red pine, yellow poplar, cypress, white pine or red oak. Production method.
(5) A petroleum alternative liquid fuel produced by the production method according to any one of (1) to (4) above.

  According to the production method of the present invention, it is possible to efficiently produce high-quality petroleum alternative liquid fuel using thinned wood, building waste, waste plastic, and mixed waste thereof as main raw materials. In the production method of the present invention, it is not necessary to recover the solvent and catalyst, and the reaction can be carried out at a low temperature. Therefore, a dedicated factory is not required, and these raw materials are directly processed in the discharged place. By doing so, it is possible to easily manufacture an alternative liquid fuel for petroleum.

It is the figure which showed the change (reaction conditions: 350 [degreeC] / 60 [min.] / No catalyst) of the product yield by the mixing ratio of woody biomass and a plastic (Test Example 1). It is the figure which showed the change of the product yield (reaction conditions: 350 [degreeC] / 60 [min.] / With a catalyst) by the mixing ratio of woody biomass and a plastic (Test Example 1). It is the figure which showed the change of the product yield (reaction conditions: 400 [degreeC] / 0 [min.] / No catalyst) by the mixing ratio of woody biomass and a plastic (Test Example 1). It is the figure which showed the change of IR spectrum of HI (reaction conditions: 400 [degreeC] / 0 [min.] / No catalyst) (Test Example 1). It is the figure which showed the change (reaction conditions: 400 [degreeC] / 60 [min.] / No catalyst) of the product yield by the mixing ratio of woody biomass and a plastic (Test Example 1). It is the figure which showed the change of IR spectrum of HI (reaction conditions: 400 [degreeC] / 60 [min.] / No catalyst) (Test Example 1). It is the figure which showed the change of the boiling point distribution of HS (Reaction condition: 400 [degreeC] / 60 [min.] / No catalyst) (Test Example 1). It is the figure which showed the change of the product yield (reaction condition: 400 [degreeC] / 60 [min.] / With a catalyst) by the mixing ratio of woody biomass and a plastic (Test Example 2). It is the figure which showed the change of GC-MS TIC of the light oil fraction (reaction conditions: 400 [degreeC] / 0 [min.] / With catalyst) (Test Example 2). It is the figure which showed the change of IR spectrum of a heavy oil fraction (reaction conditions: 400 [degreeC] / 0 [min.] / With catalyst) (Test Example 2).

The “petroleum substitute liquid fuel” of the present invention refers to a liquid fuel that can be used as it is in an internal combustion engine using existing petroleum as fuel and can be used for applications equivalent to petroleum and can be used in place of petroleum.
The “petroleum substitute liquid fuel” of the present invention includes any “petroleum substitute liquid fuel” as long as it is obtained by pyrolyzing a mixture of woody biomass and plastic. The “petroleum alternative liquid fuel” of the present invention may be obtained from a raw material containing other components as long as the main raw material is woody biomass or plastic. The other components are preferably substances that do not inhibit the production of the “petroleum substitute liquid fuel” of the present invention.

The “method for producing petroleum-substitute liquid fuel” according to the present invention can produce wood biomass and plastic at a temperature lower than the conventionally known liquefaction temperature of plastic, and can produce the “oil-substitute liquid fuel” according to the present invention. Any manufacturing method including a step of co-pyrolysis at temperature may be used.
The temperature lower than the conventionally known plastic liquefaction temperature, and the temperature at which the “petroleum substitute liquid fuel” of the present invention can be produced may be, for example, 300 ° C. or more and 450 ° C. or less, more preferably 300 ° C. The temperature may be not lower than 400 ° C., more preferably not lower than 350 ° C. and not higher than 400 ° C. The lower the temperature, the less heat is used in the production of the “petroleum substitute liquid fuel” of the present invention, and the production cost can be reduced.
In addition, the co-pyrolysis of the present invention can be performed with an electromagnetic induction stirring type autoclave (manufactured by Suzuki Rikagaku Co., Ltd.) or the like, but after enclosing necessary materials and filling with nitrogen gas, for liquefaction. It can be performed by heating to a predetermined temperature and maintaining the temperature for a certain period of time. The holding time at the predetermined temperature may be a time during which co-pyrolysis can be performed, and is sufficient if it is within 60 minutes. If co-pyrolysis is performed at the stage of heating to a predetermined temperature, the holding time may be 0 minutes.

In the “method for producing petroleum-substitute liquid fuel” according to the present invention, wood biomass or plastic is used as a main raw material, and the wood biomass and plastic are mixed so that the weight ratio of wood biomass to plastic is 2: 8 to 8: 2. It is preferable. The weight ratio between the woody biomass and the plastic may be appropriately selected according to the reaction conditions, and may be, for example, 2: 8, 5: 5, or 8: 2.
The woody biomass used in the “method for producing a petroleum alternative liquid fuel” of the present invention may be any wood biomass that can produce the “oil alternative liquid fuel” of the present invention. Examples include thinned wood, building waste, and waste obtained in agriculture such as straw and bacas. Moreover, woody biomass containing at least one of cedar, red pine, yellow poplar, cypress, white pine or red oak can be used as the woody biomass of the present invention.
For these woody biomass, the material obtained as a raw material may be introduced as it is into a machine for co-pyrolysis, or may be used by appropriately adjusting the size of the woody biomass according to the machine. Any machine or tool may be used to adjust the size of the woody biomass, for example, a tower mill or the like.

  The plastic used in the “method for producing petroleum alternative liquid fuel” of the present invention may be any plastic as long as it can produce the “petroleum alternative liquid fuel” of the present invention, such as polyethylene, polystyrene or Among plastics including one or more types of polypropylene, waste plastics can be used.

  EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention in detail, this invention is not limited to it.

Production method of petroleum alternative liquid fuel Woody biomass and plastic were mixed and subjected to co-pyrolysis at 300 ° C to 450 ° C to produce petroleum alternative liquid fuel.

[Test Example 1]
According to the production method of Example 1, a petroleum alternative liquid fuel was produced.
1. Preparation of test material 1) Woody biomass Sugi was crushed by a tower mill to a particle size of 150 μm or less.
2) Plastics Based on the discharge ratio of general-purpose plastics (discharge ratio: ratio of each component contained in plastic discharged as waste plastic), the weight ratio is 20.8 for polyethylene, 8.9 for polypropylene, and 9. for polystyrene. What was mixed so that it might become 1 (it may be shown as 3P below) was used.
3) Test material A mixture of 1) and 2) above so that the weight ratio of the woody biomass of 1) above and the plastic of 2) above is 8: 2, 5: 5, or 2: 8. Was used as a test material. Also, wood biomass only (weight ratio 10: 0) or plastic only (weight ratio 0:10) was used as a comparison.

2. Thermal decomposition reaction The following steps 1) to 4) were performed for thermal decomposition reaction, separation and analysis of the product obtained after the reaction.
1) 20 g of each of the above test materials 1 and 3) and 60 g of a non-polar mineral oil that is considered not to be involved in the reaction as a solvent were sealed in an electromagnetic induction stirring autoclave (manufactured by Suzuki Riken Co., Ltd.) having an internal volume of 200 ml. . Further, 4 g of NaY type zeolite was enclosed as a catalyst as required. Thereafter, nitrogen gas was charged at 0.5 MPa.
2) The contents filled in 1) above were heated to a predetermined temperature by an external electric furnace while performing horizontal stirring at 200 rpm, and the reaction was carried out while maintaining the temperature for a predetermined holding time. Tables 1 and 2 show reaction conditions (predetermined temperature, holding time, and presence / absence of catalyst) of each reaction.
3) Immediately after the completion of the reaction in 2) above, the mixture was air-cooled to room temperature. A total amount of gas (Gas) generated by the thermal decomposition reaction was collected in a Tedlar bag and subjected to composition analysis by gas chromatography (GC-TCD). Further, after the contents were directly recovered, an extraction operation using hexane was performed to separate the contents into a hexane-soluble component (hereinafter sometimes referred to as HS) and a hexane-insoluble component (hereinafter sometimes referred to as HI). The HS obtained in this way corresponds to the “petroleum substitute liquid fuel” of the present invention.
4) With respect to HS and HI obtained in the above 3), functional group analysis using Fourier transform infrared spectroscopy (FT-IR) and elemental composition analysis using CHN coder were performed. For HS, further, qualitative analysis of compounds using gas chromatography mass spectrometry (GC-MS) and boiling point distribution measurement using distillation gas chromatography (DGC-FID) were also performed.

3. Result 1) The reaction conditions are a reaction temperature of 350 ° C., a holding time of 60 minutes, and there is a catalyst (reaction conditions: 350 [° C.] / 60 [min.] / There may be indicated as a catalyst). In the case of holding time 60 minutes, no catalyst (reaction conditions: 350 [° C.] / 60 [min.] / No catalyst may be indicated) reaction conditions: 350 [° C.] / 60 [min. ] / No catalyst is shown in Table 1 and FIG. Reaction conditions: 350 [° C.] / 60 [min. ] / With catalyst, the yield is shown in Table 1 and FIG. As shown in these figures, regardless of the presence or absence of a catalyst, the yield of HS is improved compared to the predicted calculated value when wood biomass and plastic are mixed and reacted under any reaction conditions. Was confirmed.
In addition, the calculated value is that of each component (Gas, HS, HI) when the wood biomass only (weight ratio 10: 0) or the plastic only (weight ratio 0:10) is reacted under the same reaction conditions. Assuming that the additive rule holds, the yield is a value obtained by taking an arithmetic average at each addition ratio.
Compared to this calculated value, the yield of HS when wood biomass and plastic are mixed and reacted is improved. By mixing wood biomass and plastic, in the production of petroleum alternative liquid fuel, It was suggested that a synergistic effect was obtained rather than additive.

2) When the reaction conditions are a reaction temperature of 400 ° C., a holding time of 0 minutes, and no catalyst (reaction conditions: 400 [° C.] / 0 [min.] / No catalyst may be indicated) Reaction conditions: 400 [° C. ] / 0 [min. ] / No catalyst is shown in Table 2 and FIG. As shown in these figures, when wood biomass and plastic are mixed and reacted, even when they are mixed so that the weight ratio is 8: 2, even when they are mixed so that the weight ratio is 5: 5, In either case, it was confirmed that the yield of HS was improved as compared with the predicted calculated value. Therefore, it was suggested from this result that a synergistic effect can be obtained in the production of petroleum alternative liquid fuel by mixing woody biomass and plastic.

The results of functional group analysis are shown in FIG. As a result, the peak of HI when wood biomass and plastic are mixed and reacted (weight ratio 8: 2) is similar to that when wood biomass alone (weight ratio 10: 0) is reacted. I was able to confirm. On the other hand, there is almost no HI peak when plastic alone (weight ratio 0:10) is reacted, and this result suggests that woody biomass promotes the decomposition of plastic. It was.
Therefore, from this result, it was suggested that by mixing woody biomass and plastic, liquefaction of plastic progressed and petroleum alternative liquid fuel could be produced more efficiently.

3) When the reaction conditions are a reaction temperature of 400 ° C., a holding time of 60 minutes, and no catalyst (reaction conditions: 400 [° C.] / 60 [min.] / No catalyst may be indicated) Reaction conditions: 400 [° C. ] / 60 [min. ] / No catalyst is shown in FIG. As shown in FIG. 5, when wood biomass and plastic are mixed and reacted, even when mixed so that the weight ratio becomes 8: 2, even when mixed so that the weight ratio becomes 5: 5 In any case, it was confirmed that the yield of HS was improved compared to the predicted calculated value. Therefore, it was suggested from this result that a synergistic effect can be obtained in the production of petroleum alternative liquid fuel by mixing woody biomass and plastic.

  The results of functional group analysis are shown in FIG. As a result, the peak of HI when wood biomass and plastic are mixed and reacted (weight ratio 8: 2 or 5: 5) is the same as when wood biomass only (weight ratio 10: 0) is reacted. It was confirmed that they were similar. On the other hand, there is almost no HI peak when plastic alone (weight ratio 0:10) is reacted, and this result suggests that woody biomass promotes the decomposition of plastic. It was.

Furthermore, the result of the boiling point distribution measurement by gas chromatography (DGC-FID) is shown in FIG. As a result, HS when wood biomass and plastic are mixed and reacted (weight ratio 8: 2 or 5: 5) is HS when wood biomass only (weight ratio 10: 0) is reacted. It was confirmed that the high-boiling fraction slightly increased as compared with HS when the plastic alone (weight ratio 0:10) was reacted.
Therefore, from this result, by mixing and reacting woody biomass and plastic, the woody biomass degradation product and the degradation product of the plastic degradation product react with each other, suppressing HI generation due to condensation between the woody biomass degradation products, It was suggested that a component with a high boiling point was newly formed.

[Test Example 2]
According to the manufacturing method of Example 1, petroleum substitute liquid fuel was manufactured using the test material prepared in the same manner as in Test Example 1.

1. Thermal decomposition reaction Each test material mixed in the weight ratio shown in Table 3 has a reaction condition of a reaction temperature of 400 ° C., a holding time of 60 minutes, and a catalyst (reaction condition: 400 [° C.] / 60 [min.] / Catalyst. 2) and 2) above. In the same manner as in Steps 1) and 2), the thermal decomposition reaction was carried out. A total amount of gas (Gas) generated by the thermal decomposition reaction was collected in a Tedlar bag and subjected to composition analysis by gas chromatography (GC-TCD).
The contents other than the obtained gas (Gas) were directly recovered by the reaction, and then separated by the following procedure.

1) Preparation of simple distillation apparatus A separable flask (internal volume 300 ml) was covered with a two-neck separable cover. A glass apparatus used for the thermocouple cover for measuring the liquid phase temperature in the kettle with a modified capillary tube was attached to the upper opening (small diameter) of the two-port separable cover. A Claisen tube was connected to the upper opening (large diameter) of the separable cover, and the upper opening (large diameter) of the Claisen pipe was sealed with a stopper. A glass apparatus used for a thermocouple cover for gas phase temperature measurement with a modified capillary tube was attached to the upper opening (small diameter) of the Claisen tube. A 50 cm cooling pipe was connected to the lateral outlet of the Claisen pipe. A trifurcated branch pipe was connected to the tip of the cooling pipe. A glass device for condensate component recovery and a glass device for sealing the system were connected to each lower outlet of the trifurcated branch pipe. The upper outlet of the trifurcated branch pipe was connected to a liquid recovery trap using a rubber pipe. The trap during the distillation operation was cooled using dry ice. The trap was connected to a position type manometer to which a vacuum pump and a needle valve were connected using a branched rubber tube. Any connecting portion was sealed with vacuum grease. The temperature in the kettle and the gas phase was measured using a thermocouple. This was used as a simple distillation apparatus.

2) Separation The contents obtained by the reaction were charged into the above simple distillation apparatus, and the simple distillation apparatus was heated using a mantle heater and a ribbon heater. For each temperature distillate, the condenser was cooled using water and dry ice and condensed. I. B. Pb. p. The 180 ° C. fraction was collected at normal pressure. b. p. About the 180-350 degreeC fraction, the vacuum distillation operation based on JIS-K2254 (petroleum product-distillation test method) was performed, temperature and pressure were operated, and it collect | recovered. Specifically, distillate condensate from a temperature of 180 ° C. and a pressure of 760 mmHg to a temperature of 230 ° C. and a pressure of 30 mmHg is b. p. A 180-350 ° C. fraction (light oil fraction) was used. The residue from the kettle was subjected to hexane extraction, and the hexane soluble component was used as the heavy oil fraction and the hexane insoluble component was used as the residue.
I. B. Pb. p. The 180 ° C. fraction was subjected to stationary separation and separated into a water-soluble component and a gasoline fraction. The yield of each fraction thus separated is shown in Table 3. The heavy oil fraction, light oil fraction, gasoline fraction, and the like thus obtained correspond to the “petroleum alternative liquid fuel” of the present invention.
In addition, as a calculated value, each fraction (residue, heavy oil fraction, when wood biomass only (weight ratio 10: 0) or plastic only (weight ratio 0:10) is reacted under the same reaction conditions, Table 3 also shows the values obtained by calculating the arithmetic mean at the respective addition ratios, assuming that the additive law holds for the yield of light oil fraction, gasoline fraction, Gas).

2. Result Reaction conditions: 400 [° C.] / 60 [min. ] / Yield with catalyst is shown in Table 3 and FIG.
As a result, when wood biomass only (weight ratio 10: 0) was reacted, a heavy oil fraction was not obtained, but when wood biomass and plastic were mixed and reacted (weight ratio 2: 8). ), A heavy oil fraction was obtained in the same manner as in the case of reacting only plastic (weight ratio 0:10).
In addition, even when wood biomass and plastic are mixed and reacted (weight ratio 2: 8), even when wood biomass and plastic are mixed and reacted (weight ratio 5: 5), compared with the calculated values. It was confirmed that the residue was clearly reduced and the yield of the light oil fraction, gasoline fraction, etc. was improved. Therefore, it was suggested from this result that a synergistic effect can be obtained in the production of petroleum alternative liquid fuel by mixing woody biomass and plastic.

  The gas oil fraction was qualitatively analyzed using gas chromatograph mass spectrometry (GC-MS). As a result, as shown in FIG. 9, when wood biomass and plastic are mixed and reacted (weight ratio 2: 8, 5: 5), only wood biomass (weight ratio 0:10) is reacted. It was confirmed that the respective peak intensities were higher than those in the case of reacting with plastic alone (weight ratio 0:10). Therefore, from this result, it was suggested that decomposition proceeded by the interaction between woody biomass and plastic.

  Moreover, the functional group analysis which used the Fourier transform type | mold infrared spectroscopy (FT-IR) was performed about the heavy oil fraction and the residue. As a result, as shown in FIG. 10, when wood biomass and plastic are mixed and reacted (weight ratio 2: 8), only wood biomass (weight ratio 0:10) is reacted, and In any case where only plastic (weight ratio 0:10) is reacted, the peak of the heavy oil fraction considered to contain mineral oil as the solvent does not change, so the solvent is inactive. It was confirmed that it acts only as a heat medium without being involved in the reaction.

  According to the production method of the present invention, it is possible to efficiently produce high-quality petroleum alternative liquid fuel using thinned wood, building waste, waste plastic, and mixed waste thereof as main raw materials. The high-quality petroleum substitute liquid fuel obtained by the present invention can be widely used in fields such as the manufacturing industry.

Claims (5)

A method for producing petroleum-substitute liquid fuel, comprising a step of co-pyrolysis of woody biomass and plastic at 300 ° C or higher and 450 ° C or lower. The method for producing an alternative petroleum liquid fuel according to claim 1, wherein the woody biomass and the plastic are mixed at a weight ratio of 2: 8 to 8: 2. The manufacturing method of the petroleum alternative liquid fuel of Claim 1 or 2 whose plastic is a plastic which contains any one or more of polyethylene, a polystyrene, or a polypropylene as a raw material. The method for producing a petroleum alternative liquid fuel according to any one of claims 1 to 3, wherein the woody biomass is a woody biomass containing any one or more of cedar, red pine, yellow poplar, cypress, white pine and red oak. A petroleum alternative liquid fuel produced by the production method according to claim 1.