KR20200020518A - Recycle device for wood or lignin and method for producing phenol from wood or lignin using the same - Google Patents

Abstract

In the present invention, disclosed are an apparatus for recycling wood or lignin; and a method for producing phenol from wood or lignin using the same. The apparatus for recycling wood or lignin, an aspect of the present invention thermally decomposes wood or lignin-containing material by using an auger reactor and a fluidized bed reactor, thereby being able to produce a large amount of phenol. Especially, the apparatus conducts primary thermal decomposition of the wood or lignin-containing material at a relatively low temperature to increase molecular activity in the wood or lignin-containing material, followed by conducting secondary thermal decomposition in a high temperature environment, thereby being able to maximize phenol production efficiency.

Description

Recycling apparatus for wood or lignin and a method for producing phenol from wood or lignin using the same {{{RECYCLE DEVICE FOR WOOD OR LIGNIN AND METHOD FOR PRODUCING PHENOL FROM WOOD OR LIGNIN USING THE SAME}}

Disclosed herein is a recycling apparatus for wood or lignin and methods for producing phenol from wood or lignin using the same.

As fossil fuels are depleted, the need for alternative energy continues to increase. Accordingly, biomass, which can be converted into energy, has recently emerged as an important resource. In particular, wood-based biomass can produce useful chemical derivatives, such as phenol, in addition to fuels such as bioethanol, while minimizing carbon dioxide emissions, and have received high attention from related industry workers. However, lignocellulosic contained in the wood-based biomass is difficult to convert into valuable liquid fuel because cellulose and lignin are natural polymers with very strong bonds. Efficient disassembly and separation are difficult, and so much achievements are not achieved.

KR 10-1165073 B

In one aspect, an object of the present invention is to provide a method for recycling waste wood that is discarded.

In one aspect, it is an object of the present invention to provide a method for recycling lignin that is discarded in pulp production.

In one aspect, an object of the present invention is to efficiently produce phenol from waste wood or lignin.

In order to achieve the above object, the present invention in one aspect, the recycling apparatus of wood or lignin, the apparatus, auger reactor; And a fluidized bed reactor, providing a recycling apparatus for wood or lignin.

The present invention also provides, in one aspect, a recycling apparatus for wood or lignin, comprising the auger reactor and fluidized bed reactor of the apparatus connected in order from the auger reactor to the fluidized bed reactor.

The present invention also provides, in one aspect, a recycling apparatus for wood or lignin, comprising the auger reactor and the fluidized bed reactor connected in series.

The present invention also provides, in one aspect, a recycling apparatus for wood or lignin, wherein at least one of the auger reactor and fluidized bed reactor comprises performing pyrolysis.

In another aspect, the present invention provides a recycling apparatus for wood or lignin, the pyrolysis temperature of the pyrolysis is 100 to 900 ℃.

In another aspect, the present invention provides a recycling apparatus for wood or lignin, the pyrolysis temperature of the auger reactor includes 100 ~ 450 ℃, the pyrolysis temperature of the fluidized bed reactor includes 450 ~ 900 ℃.

In another aspect, the present invention provides a recycling apparatus for wood or lignin, comprising at least 10% by weight phenol production capacity, based on the total content of biodegradation product bio oil.

The present invention also provides, in one aspect, a method for producing phenol from wood using the device.

The present invention also provides, in one aspect, a method for producing phenol from wood, wherein the wood comprises waste wood.

In one aspect of the present invention, a wood or lignin recycling apparatus may produce a large amount of phenol by pyrolyzing wood or lignin containing material using an auger reactor and a fluidized bed reactor. In particular, the apparatus can maximize the efficiency of phenol production by first pyrolyzing wood or lignin-containing materials at relatively low temperatures to increase molecular activity in the wood or lignin-containing materials and then secondary pyrolysis in high temperature environments. Can be.

1 shows a system for wood or lignin recycling comprising an apparatus according to one aspect of the invention.
Figure 2 shows the product content (mass balance) in a pyrolysis device consisting of an auger reactor and a fluidized bed reactor.

Hereinafter, the present invention will be described in detail.

The present invention in one aspect, auger reactor; And a fluidized bed reactor.

In the present specification, the lignin is a broad concept including not only lignin itself, but also lignin-containing materials, and may include, for example, residues generated during pulp production, and may include paper produced from wood. .

In one aspect, the auger reactor and fluidized bed reactor of the apparatus may comprise one connected in order from the auger reactor to the fluidized bed reactor.

In one embodiment, the auger reactor and the fluidized bed reactor may comprise a series connection.

In addition, at least one of the auger reactor and the fluidized bed reactor may include performing pyrolysis.

Preferably, the pyrolysis may be performed in both the auger reactor and the fluidized bed reactor.

In the above aspect, the pyrolysis temperature of the pyrolysis may be 100 to 900 ℃. Specifically, the pyrolysis temperature of the auger reactor may include 100 ~ 450 ° C, preferably 200 ~ 400 ° C, more preferably 200 ~ 300 ° C.

When performing the first pyrolysis over the above temperature range of the auger reactor, the high vibration state is activated to activate the molecules in the wood or lignin-containing material to optimize the second pyrolysis in the fluidized bed reactor followed by the bond length of the molecules. May exist.

That is, due to the first pyrolysis, the wood or lignin-containing material may have a long bond length between molecular constituent elements, and as a result, the intermolecular bond strength may be lowered, and thus, the chain chain may be easily broken.

In addition, the pyrolysis temperature of the fluidized bed reactor may include 450 ~ 900 ℃, preferably, may be 500 ~ 800 ℃, more preferably may be 500 ~ 700 ℃.

In the above temperature range, when performing secondary pyrolysis in a fluidized bed reactor, it is possible to maximize the production of phenol.

In this aspect, the device is connected to the auger reactor-> fluidized bed reactor in the order of the wood or lignin input unit, when the pyrolysis is carried out within the temperature range, maximized recycling efficiency of wood or lignin Or phenol production efficiency.

Specifically, the auger reactor serves to activate wood or lignin-containing material, which is a feed material that is fed into the device, which is capable of sufficiently primary pyrolysis while staying in the reactor for a long time in a relatively low temperature environment. Can be. On the other hand, the auger reactor is equipped with a screw in the reactor, so that the activated primary pyrolysate can be immediately delivered to the subsequent reactor as it is activated.

The first pyrolyzed pyrolysis product in the auger reactor is sent to the fluidized bed reactor for second pyrolysis. The fluidized bed reactor is capable of producing a high content of phenol finally from the feed wood or lignin as a result of the high temperature heat being picked up and quickly applied throughout the primary pyrolysate delivered into the reactor.

In one aspect, the device may comprise at least about 10% by weight of phenol production capacity, based on the total content of the biooil as a pyrolysis product. In one embodiment, when recycling the waste wood using the apparatus of the present invention, it is possible to produce more than 10 wt% phenol in the bio oil produced.

On the other hand, the maximum content of phenol in bio-oil during the biodegradation of waste wood known to date is about 0.1 to 3.8% by weight (G.-G. Choi et al., Bioresource Technology 178 (2015), 99-107). It can be seen that the use of the device of the invention can produce a significant amount of phenol.

Referring to FIG. 1, a recycling apparatus for wood or lignin (also referred to as a two-stage pyrolysis device for phenol production) according to one embodiment of the present invention is a two-stage pyrolysis device 100 and a wood or lignin-containing material supply system 400. , Pyrolysis char separation system 500, quenching systems 600, 600 ′, impact separators 700, 700 ′, electrostatic precipitators 800, 800 ′ and gas circulation systems (not shown).

The feed system 400 may include silos 410 in which feed material is stored, one or more screw feed devices 420 and 430 for delivering feed material to the auger reactor 200, the silo 410 and the screw supply device 420 includes a gas injection unit (not shown). The screw supply device can stably supply materials when one or more, for example, two are connected in series.

The pyrolysis char separation system 500 may include one or more filters 510, 520, and may capture pyrolysis char particles having a large particle size of about 1 μm or more or about 1 μm to about 100,000 μm. The filter may be a cyclone filter and / or a ceramic filter.

The quenching system 600, 600 ′ includes one or more condensers 610, 620, the condenser having a Auger reactor at a temperature of about 0 ° C. to about 50 ° C. and / or about 0 ° C. to about −50 ° C. 200) or the gas product withdrawn from the fluidized bed reactor 300 is cooled. In this process, condensation into the liquid proceeds, and the non-condensable gas can be circulated by the gas circulation system.

The impact separators 700, 700 ′ are connected after the quenching system 600, 600 ′ so that a large molecular weight, for example, a weight average molecular weight of at least about 500 g / mole or from about 500 g / mole to about Compound gases of 50,000 g / mole can be captured efficiently.

The electrostatic precipitators 800 and 800 'are installed after the impact separators 700 and 700' to remove aerosols in the gas.

The non-condensable gas may be circulated by the gas circulation system and circulated to the fluidized bed reactor 300 or the like. At this time, a compressor may be used, but is not required.

The two-stage pyrolysis apparatus of the present invention injects some of the product gas into the silos 410 of the biomass feed system 400 to aid in the smooth supply of wood or lignin containing materials.

FIG. 1 shows a thermal infrared sensor (TIR) that detects a physical quantity such as temperature and pressure or a chemical quantity of a compound, an infrared sensor such as a passive infrared sensor (PIR), a motor (M), and components not described above. Such infrared sensors, motors and configurations not described above are not required in a system or apparatus according to one embodiment of the invention. 1 is only illustrated to help understand the present invention, but the present invention is not limited thereto.

In one aspect, the wood may comprise waste wood.

The present invention is also, in one aspect, a process for the production of phenol from wood or lignin using the device.

The method, specifically, the first pyrolysis step, the first pyrolysis of wood or lignin at 100 ~ 450 ℃; And a second pyrolysis step of second pyrolyzing the first pyrolyzed wood or lignin at 450 to 900 ° C.

The first pyrolysis may preferably be carried out in an auger reactor, and the second pyrolysis may be preferably carried out in a fluidized bed reactor.

In one embodiment, the auger reactor and the fluidized bed reactor may comprise a series connection.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Test Examples. However, these examples and test examples are provided only for the purpose of illustration in order to help the understanding of the present invention is not limited to the scope and scope of the present invention by the following examples.

EXAMPLE

1. Preparation of Sample

Waste wood mainly composed of larch was used as a sample.

2. Experimental conditions

In this embodiment, the two stage pyrolysis apparatus includes an auger reactor and a fluidized bed reactor. The auger reactor is connected directly before the fluidized bed reactor. Experiments with a two-stage pyrolysis unit were considered for chlorine removal in the auger reactor. The reaction temperature of the auger reactor was 200-300 ° C. in the example and the fluidized bed reactor temperature was 500-700 ° C.

Specifically, auger reactor 200 ° C. and fluidized bed reactor 500 ° C. (denoted as Run 2), auger reactor 300 ° C. and fluidized bed reactor 500 ° C. (denoted as Run 3), auger reactor 300 ° C. and fluidized bed reactor 600 ° C. (denoted as Run 4). Pyrolysis was carried out at a temperature of 300 ° C., Auger reactor and 700 ° C. (denoted Run 5).

The experiment was started by loading the sample at a rate of about 8 g / min. The total sample weight was 500 g and the run time of the experiment was about 60 minutes. Prior to operation, the pyrolysis unit was purged with nitrogen gas for 1 hour. The reactor was purged and then heated to the reaction temperature determined by the electric furnace. 1.2 kg of silica sand was used as fluidized bed material. As the speed of the fluidized bed reactor, three times the minimum fluidization rate was the flow rate of each experiment. In the Auger reactor, the residence time of the feed material was about 2 minutes 30 seconds.

On the other hand, as a comparative example, except for the Auger reactor in the apparatus, the experiment was also carried out to pyrolyze at 500 ℃ using only a fluidized bed reactor (labeled as Run 1).

3. pyrolysis plant

As shown in FIG. 1, the one-stage pyrolysis apparatus is an auger reactor connected before the fluidized bed reactor. The example was carried out in a two stage pyrolysis apparatus. A nitrogen gas stream was allowed to pass from the silo 410 through the auger reactor to the liquid product collection device.

Auger reactor is acid-resistant 310S tube material. Auger reactors were 23 mm in diameter and 650 mm in length. The fluidized bed reactor was made of 310S tube with a height of 550 mm and an inner diameter of 70 mm. The reactor had three thermocouples and the reaction temperature was defined as the average value calculated from the values measured by the thermocouple. The pyrolysis cyclone, hot filter, quenching system, impact separator, electrostatic precipitator, and gas circulation system were equipped after the fluidized bed reactor. The cyclone was installed to capture pyrolytic shock particles larger than 10 μm and the hot filter was designed to capture particles of 1 μm. The quenching system used two steel condensers, one of which was subjected to continuous cooling in water at 20 ° C. and the other at -20 ° C. in ethanol. The impact separator placed after the condenser captures large weight molecules and the electrostatic precipitator is installed after the impact separator to remove aerosols in the gas. In the gas circulation system, non-condensing gas was circulated to the fluidized bed reactor by compressor (N0150ATE, KNF). The produced gas product was collected using a Teflon gas bag for analysis and the remaining gas was burned in a flare stack. To monitor the temperature of the entire plant, two additional thermocouples were installed in the piping line and the gas vent line. Heating bands and glass wool were used to prevent vapor condensation. A schematic diagram of the two-stage pyrolysis system (plant) is shown in FIG. 1.

4. Analysis of Pyrolysis Products

Analysis of pyrolysis products was carried out through GC-MS and GC-FID and GC-TCD.

5. Result Analysis

Figure 2 shows the product content (mass balance) in the reactor of Run1 ~ Run5, Table 1 shows the concentration of the components in the bio-oil.

As a result, it was found that when the two-stage pyrolysis of the present invention was carried out as compared with the case of pyrolysis only in the fluidized bed reactor, a high phenol content could be produced (see FIG. 2 and Table 1).

TABLE 1

100: two-stage pyrolysis device for phenol production
200: auger reactor heater
300: fluidized bed reactor
400: biomass supply system
410: silo 420: screw feeder
430: auger reactor
500: pyrolysis and separation system
600: quenching system 610, 620: condenser
700: impact separator 800: electrostatic precipitator

Claims (9)

As a recycling device of wood or lignin,
The device,
Auger reactor; And a fluidized bed reactor. The method of claim 1,
Auger reactor and fluidized bed reactor of the device,
Recycling apparatus of wood or lignin, comprising the connection from the auger reactor to the fluidized bed reactor in order. The method of claim 2,
Wherein said auger reactor and fluidized bed reactor comprise serially connected units. The method of claim 1,
At least one of said auger reactor and fluidized bed reactor, comprises pyrolysis. The method of claim 4, wherein
The pyrolysis temperature of the pyrolysis is 100 to 900 ℃, recycling apparatus of wood or lignin. The method of claim 4, wherein
Pyrolysis temperature of the auger reactor includes 100 ~ 450 ℃,
The pyrolysis temperature of the fluidized bed reactor comprises 450 ~ 900 ℃, wood or lignin recycling apparatus. The method of claim 1,
The device,
A recycling apparatus for wood or lignin, comprising at least 25% by weight of phenol production, based on the total content of the biodegradation product bio oil. A process for producing phenol from wood or lignin using the apparatus of any one of claims 1 to 7. The method of claim 8,
Wherein the wood comprises waste wood.

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