WO2011096444A1 - 油乃至ガス吸着材の製造方法及び油乃至ガス吸着材 - Google Patents
油乃至ガス吸着材の製造方法及び油乃至ガス吸着材 Download PDFInfo
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- WO2011096444A1 WO2011096444A1 PCT/JP2011/052170 JP2011052170W WO2011096444A1 WO 2011096444 A1 WO2011096444 A1 WO 2011096444A1 JP 2011052170 W JP2011052170 W JP 2011052170W WO 2011096444 A1 WO2011096444 A1 WO 2011096444A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Definitions
- the present invention relates to a method for producing an oil or gas adsorbent and an oil or gas adsorbent, and more particularly, organic waste derived from plants or animals (for example, rice husks which are waste abundant in Japan)
- the present invention relates to a method for producing an oil or gas adsorbent using sawdust or the like, and an oil or gas adsorbent.
- rice husk which is a waste material abundant in Japan, can be used as an oil adsorbent by carbonization.
- This rice husk charcoal is carbonized (activated carbon) through an activation process (activation) in which heat treatment is performed in an environment of 800 to 1000 ° C. using an oxidizing gas such as water vapor, carbon dioxide, or oxygen in order to develop pores.
- activation activation process in which heat treatment is performed in an environment of 800 to 1000 ° C. using an oxidizing gas such as water vapor, carbon dioxide, or oxygen in order to develop pores.
- Non-Patent Document 1 a method for producing a highly functional oil adsorbent by performing carbonization in a reducing atmosphere has also been proposed (see Non-Patent Document 1).
- Non-Patent Document 1 Since the technique disclosed in Non-Patent Document 1 described above is simply carbonized in a reducing atmosphere, it is not suitable for continuous production, and it is difficult to produce a large amount of rice husk charcoal. The fact was not made.
- the carbonization equipment is as follows.
- a carbonization pipe with a screw conveyor inside is installed in the combustion furnace, and the carbonization furnace is configured with the front stage of the carbonization pipe as the drying zone, the middle stage as the carbonization zone, and the latter stage as the activation zone.
- the carbonized raw material supplied from the raw material supply device is indirectly heated in the carbonization tube, so that drying and water vapor in the previous stage are performed.
- an apparatus for producing activated carbide that generates activated carbide by generation of carbon, generation of carbonization and pyrolysis gas in the middle stage, activation and activation by steam and pyrolysis gas in the latter stage (see, for example, Patent Document 4). ).
- the fly ash containing dioxins in the activation / activation process decomposes and detoxifies the dioxins by heat treatment via a dechlorination pipe provided with a screw conveyor inside separately from the carbonization pipe.
- the atmosphere gas is reduced or a low oxygen atmosphere as a condition for detoxifying (dechlorinating) the ash (dioxin decomposition condition).
- Patent Document 5 is provided as a carbonization apparatus and a carbonization method that improve this point. That is, in Patent Document 5, the porous structure is not lost even after the carbonization reaction, and a high-quality carbide having a high carbon fixation rate can be obtained. That is, it is possible to obtain a carbide having a large specific surface area that maintains the porosity of the material without going through an activation process.
- Patent Document 5 is pending on the priority date of the present application, it is still unpublished in general. The technique according to Patent Document 5 has the structure shown in FIG.
- one kiln 2 having an inlet 2in and an outlet 2out and drying, pyrolyzing (carbonizing) and storing heat in this order in a series of internal spaces 2c, and a large amount of rice husk P as a raw material are stored.
- This device can produce high energy regenerated coal.
- An object of the present invention is to provide an oil or gas adsorbent that can produce organic substances such as rice husk and sawdust by continuous carbonization and has excellent oil adsorbability and gas adsorbability.
- the invention according to claim 1 has an inlet and an outlet and supplies the carbonized raw material to the internal space of one kiln that performs drying, pyrolysis (carbonization), and heat storage of the carbonized raw material in this order in a series of internal spaces.
- the carbonized raw material supplied to the internal space is indirectly heated in a reducing atmosphere without introducing oxygen from the outside, while storing heat in the carbonized raw material to reduce the moisture content,
- This is a method for producing an oil or gas adsorbent made of charcoal that has been carbonized by indirect thermal decomposition.
- an organic material is used, and either a plant-derived material or an animal-derived material may be used.
- a plant-derived material or an animal-derived material include coffee bean residue, plum seed, okara, cow dung, pig dung, sludge, rice husk, paulownia, cedar thinned wood, sawdust, and other organic materials.
- a material having a high degree of porosity is preferable.
- Plant-derived is preferable, and rice husk, paulownia and cedar are more preferable among plants.
- the invention according to claim 2 is characterized in that the carbonized raw material is rice husk or paulownia.
- the invention according to claim 3 is the method for producing an oil or gas adsorbent according to claim 1 or 2, wherein the carbonization temperature is 250 to 800 ° C.
- the carbonization temperature is 300 to 700 ° C
- the carbonization temperature is 300 to 700 ° C
- the invention according to claim 5 is the method for producing an oil or gas adsorbent according to any one of claims 1 to 4, wherein the gas is ethylene gas.
- the carbonization temperature is 500 ° C or higher, and when the gas adsorbent is made of paulownia charcoal, the carbonization temperature is 300 ° C or higher. 5.
- the invention according to claim 7 is the method for producing an adsorbent for oil or gas according to any one of claims 1 to 4, wherein the gas is ammonia gas.
- the invention according to claim 8 is the method for producing an oil or gas adsorbent according to claim 7, wherein the carbonization temperature is 300 to 400 ° C.
- the invention according to claim 9 is the method for producing an oil or gas adsorbent according to any one of claims 1 to 4, wherein the gas is acetic acid gas.
- the carbonization temperature is 600 ° C or higher
- the carbonization temperature is 300 ° C or higher.
- the invention according to claim 11 is the oil or gas according to any one of claims 1 to 10, wherein the rice husk having a high water content is carbonized while the residence time in the kiln is longer than that of the rice husk having a low water content. It is a manufacturing method of this adsorbent.
- the invention according to claim 12 is characterized in that the residence time of rice husks in the internal space is increased as it goes downstream in the transport direction.
- the oil or gas adsorbent according to any one of claims 1 to 11 It is a manufacturing method.
- the invention according to claim 13 is the method for producing an adsorbent for oil or gas according to any one of claims 1 to 12, wherein the organic matter containing water of a predetermined amount or more is conveyed while being repeatedly advanced and returned. is there.
- the invention according to claim 14 is characterized in that the inner peripheral surface of the kiln has spiral blades extending spirally along the longitudinal direction of the kiln and has at least one stirring blade protruding inward.
- Item 14 The method for producing an oil or gas adsorbent according to any one of Items 1 to 13.
- the invention according to claim 15 is the method for producing an adsorbent for oil or gas according to claim 14, characterized in that the longitudinal interval between the stirring blades is larger on the upstream side than on the downstream side.
- the invention according to claim 16 is characterized in that the staying time is performed by changing the height of the stirring blade provided on the inner peripheral surface of the kiln and the interval in the longitudinal direction in accordance with the water content and the input amount of the organic matter.
- the invention according to claim 17 is characterized in that dry distillation gas generated by decomposition of the rice husk in the kiln is combusted in a recovery chamber, and the rice husk in the kiln is heated from the outside of the kiln by heat generated by the combustion. 17.
- the invention according to claim 18 is characterized in that the combustion in the recovery chamber is performed by introducing air into the recovery chamber without using an external burner. This is a method for producing a gas adsorbent.
- the invention according to claim 19 is the method for producing an oil or gas adsorbent according to any one of claims 1 to 18, wherein drying is performed by setting the inside of the kiln to 180 ° C or lower.
- Pyrolysis starts from a state where the inside of the kiln is 180 ° C. or higher, but drying in a reducing atmosphere is realized when drying is performed at a temperature lower than that.
- the only gas that is generated is water vapor and odor gas emitted from organic substances containing moisture. Therefore, the volume of generated gas can be minimized. Therefore, since the volume of the target gas to be deodorized is small, it can be deodorized at a low running cost by other drying methods.
- the amount of generated gas will increase, a volume will increase, and the process of odor gas will become large.
- the invention according to claim 20 is an oil or gas adsorbent produced by the method for producing an oil or gas adsorbent according to any one of claims 1 to 19.
- the present invention is a method for producing an oil or gas adsorbent capable of producing an organic substance by continuous carbonization and capable of producing an oil or gas adsorbent having excellent oil adsorbability and gas adsorbability.
- an oil or gas adsorbent can be obtained.
- (A) is a chart of the oil adsorption test (volume) of rice husk charcoal
- (B) is rice husk charcoal. It is a graph of an oil adsorption test (volume).
- the characteristics of the rice husk charcoal carbonized at each temperature using the reductive carbonization apparatus concerning one embodiment of the present invention are shown, (A) is a chart of simple elemental analysis (weight) of rice husk charcoal, and (B) is rice husk charcoal. It is a graph of the simple elemental analysis (weight).
- (A) is a simple elemental analysis (atomic weight) chart of rice husk charcoal
- (B) is rice husk charcoal. It is a graph of the simple elemental analysis (atom). It is a graph which concerns on Example 2 of this invention and shows adsorption
- Example 3 of this invention It is a graph which concerns on Example 3 of this invention, and shows adsorption
- Example 6 of this invention It is a graph which concerns on Example 6 of this invention, and shows the relationship between the carbonization temperature about a rice husk charcoal, and a specific surface area. It is a graph which concerns on Example 6 of this invention and shows the relationship between the carbonization temperature about a rice husk charcoal, and a specific surface area and pore distribution. It is a graph which concerns on Example 6 of this invention, and shows the relationship between the carbonization temperature about a paulownia charcoal, and a specific surface area. It is a graph which concerns on Example 6 of this invention and shows the relationship between the carbonization temperature about a paulownia charcoal, and a specific surface area and pore distribution.
- FIG. 1 is an explanatory view of a reduction carbonization processing system according to an embodiment of the present invention
- FIG. 2 is a cross-sectional view of a kiln in the reduction carbonization processing system according to an embodiment of the present invention.
- a reduction carbonization apparatus 1 applied to a reduction carbonization system is a method for drying input material (rice husk P) inside one substantially cylindrical kiln 2.
- -It is configured to perform each process of pyrolysis (carbonization) and heat storage.
- the reduction carbonization apparatus applied to the reduction carbonization system has an inlet 2in and an outlet 2out, and drying, pyrolysis (carbonization), and heat storage of rice husk P in a series of internal spaces 2c. 1 in this order, a supply unit for storing a large amount of rice husk P as a raw material and supplying the rice husk P sequentially from the inlet 2in to the internal space 2c, and heating the internal space 2c from the outside of the kiln 2.
- the combustion chamber 3, the exhaust part 5 for exhausting the air contained in the rice husk P supplied from the supply part to the inlet 2in, and the carbonized rice husk charcoal Q discharged from the outlet 2out are recovered and the outside air to the outlet 2out is recovered.
- the supply unit includes a hopper 14 storing rice husk P as an input material to be carbonized, a supply pipe 15 connected to the hopper 14 and having an elbow shape so that one end faces the internal space 2c from the inlet 2in, And a supply screw 16 arranged along the horizontal axis direction of the pipe 15 to maintain an oxygen-free atmosphere (including a low oxygen atmosphere) in the vicinity of the inlet 2in side of the internal space 2c.
- a supply screw 16 arranged along the horizontal axis direction of the pipe 15 to maintain an oxygen-free atmosphere (including a low oxygen atmosphere) in the vicinity of the inlet 2in side of the internal space 2c.
- the combustion part has a casing-like main body that forms a combustion chamber 3 that surrounds the whole except for the inlet 2in and the outlet 2out formed at both ends of the kiln 2, and the vicinity of the upper portion of the outlet 2out so as to communicate with the combustion chamber 3.
- An exhaust pipe 3a having one end connected to the exhaust pipe 3a, a chimney 23 connected to the other end of the exhaust pipe 3a and communicating with the outside, a combustion chamber in the vicinity of the upper end of the inlet 2in with one end connected to the chimney 23 and the other end 3, a circulation pipe 24 connected to the main body so as to communicate with the main body 3, a heating source 4 such as a burner facing the combustion chamber, and a fan 13 for promoting exhaust.
- the combustion unit can store heat in the rice husk P while indirectly heating the rice husk P supplied to the internal space 2c in a reduced state in an oxygen-free atmosphere, and supply heat to the entire one internal space 2c.
- the exhaust unit 5 includes a water vapor exhaust pipe 12 for draining water vapor generated inside the kiln 2 and a fan 13 for promoting exhaust so that the moisture content of the rice husk P is lowered early.
- the exhaust part 5 can reduce the moisture content of the rice husk P at an early stage by cooperation with the steam exhaust pipe 12 disposed below and the exhaust promoting fan 13 disposed inside the main body. It can contribute to shortening drying and carbonization time and promoting self-combustion.
- a cooling device such as a cooling pipe is disposed around the recovery unit 60, and the rice husk P can be generated (recovered) as regenerated charcoal by this cooling.
- the outlet 2out of the kiln 2 and the recovery unit 60 are connected so as to maintain an oxygen-free atmosphere (including a low oxygen atmosphere) in the internal space 2c.
- the collection unit 60 is disposed below the outlet 2out of the kiln 2, is connected so as to collect the rice husk charcoal Q by falling under its own weight, and is piped in the depth direction of FIG.
- the kiln 2 is installed horizontally on the left and right side walls of the combustion chamber 3 at both ends.
- the kiln 2 is a metal tubular rotating body disposed in the combustion chamber 3, and a sprocket around which a chain extending from the drive device is wound is provided on the inlet 2in side, although not shown. It can be rotated by driving the drive device.
- the inlet 2in side of the kiln 2 is covered with an exhaust part 5 for evacuating air contained in the rice husk P supplied from the supply part 30 to the inlet 2in, and at the same time, releasing steam generated by the carbonization treatment from the steam vent pipe 22. It has been broken.
- outlet 2out side of the kiln 2 is a discharge section (connection) for discharging rice husk charcoal Q that has been heated and carbonized and discharging primary combustion gas (combustible gas containing CO) from the degassing pipe 25. Tube) 19.
- the drying process and the carbonization process can be continuously performed inside one kiln 2, and the rice husk P introduced into one kiln 2 is indirectly heated in a reduced state in an oxygen-free atmosphere.
- the self-combustion associated with the indirect thermal decomposition of the rice husk P can be promoted, and the high-energy rice husk charcoal Q having a wide use purpose can be generated.
- a reduction carbonization apparatus includes a rotating kiln 2 in which a spiral blade and a stirring blade 1 are disposed, and an inside of the one kiln 2.
- a heating unit 4 a drying unit 2 a having an area set inside the kiln 2 so as to evaporate water contained in the organic matter or the like introduced into the kiln 2 by indirect heating of the combustion chamber 3, and a drying unit 2 a
- a carbonized portion 2b having an area set inside the kiln 2 so as to be carbonized by indirectly heating and decomposing the dried organic matter or the like.
- the inner space 2 c of the kiln 2 has a spiral blade 1 a and a stirring blade 1 b that is located between the spiral blade 1 a and protrudes inward from the inner wall of the kiln 2. And are provided.
- sections 2a, 2b, and 2d for performing drying, pyrolysis (carbonization), and heat storage steps from the upstream side to the downstream side in the transport direction from the inlet 2in to the outlet 2out are set. .
- the pitch interval of the spiral wing 1a is made different in each of the sections 2a, 2b, 2d, and the pitch interval is narrowed toward the downstream side in the transport direction, whereby the residence time of the rice husk P in the internal space 2c is downstream in the transport direction. The longer it goes to the side.
- the pitch interval of the spiral blade 1a is set so that the residence time is increased stepwise in units of the sections 2a, 2b, and 2d in the order of the processes of drying, pyrolysis (carbonization), and heat storage.
- the drying unit 2a is a drying section that performs a drying process that evaporates moisture contained in the rice husk P by indirect heating of the combustion chamber 3 and reduces the water content to a state where it can be carbonized.
- the carbonization part 2b is a carbonization section that performs a carbonization process in which the chaff P after the drying process is carbonized (thermally decomposed) in an oxygen-free atmosphere by indirect heating of the combustion chamber 3.
- the heat storage section 2d is a heat storage section in which heat energy is accumulated in the husk charcoal Q after carbonization by indirect heating of the combustion section 4 and a heat storage process is performed to increase the thermal efficiency of drying and carbonization inside the kiln 2.
- Fig. 2 shows the basic operation of each process performed in the kiln.
- the first process is a drying process.
- the water content is reduced to a state where water contained in the input material is evaporated by indirect heating and can be carbonized.
- the next process is a carbonization process.
- the dried material is carbonized (thermally decomposed) in an oxygen-free atmosphere by indirect heating.
- the next process is a heat storage process.
- This step is a step for accumulating indirectly heated thermal energy in the carbide and increasing the thermal efficiency of drying and carbonization inside the kiln.
- the carbonization processing system of the present example uses a difference between the specific gravity of the steam generated inside the kiln 2 and the connected two or more connected to separate the gas having a lower specific gravity or a higher specific gravity. It is preferable to provide a triple piping section.
- such pipe portions are provided as a downstream exhaust gas pipe 19 and an upstream exhaust gas pipe 22 on the upstream side (carbonized material inlet port side) and the downstream side (carbide outlet port side).
- the downstream exhaust gas pipe 19 is divided into a downstream exhaust gas pipe upper pipe 19a and a downstream exhaust gas pipe lower pipe 19b. Water vapor / odor gas flows through the downstream exhaust gas pipe upper pipe 19a, and the downstream exhaust gas pipe lower pipe 19b Mainly dry distillation gas flows.
- exhaust gas pipes are provided not only on the downstream side but also on the upstream side.
- the upstream exhaust gas pipe 22 is divided into an upstream exhaust gas pipe upper pipe 22a and an upstream exhaust gas pipe lower pipe 22b. Steam and odor gas flow through the upstream exhaust gas pipe upper pipe 22a, and the upstream exhaust gas pipe lower pipe 22b Mainly dry distillation gas flows.
- the downstream side exhaust pipe upper pipe 19a and the upstream side exhaust pipe upper pipe 22a merge, Deodorization is performed in the combustion furnace through the steam cooling tank. Further, the downstream side exhaust pipe lower pipe 19b and the upstream side exhaust pipe lower pipe 22b join together, and after combustion in the dry distillation gas combustion furnace, the waste heat is reused as a heat source for carbonization.
- the gas to be deodorized mainly contains water vapor and odor gas. That is, it contains almost no carbonization gas. Therefore, it is possible to perform the deodorizing process with the minimum volume. As a result, the deodorizing process can be performed at low cost.
- hydrogen gas lighter than water vapor, carbon monoxide, methane gas, hydrocarbon gas, etc. heavier than water vapor can be separated from water vapor.
- the cooling part 6 which isolate
- a deodorizing unit 7 for deodorizing.
- the steam generated in the kiln 2 is cooled by the cooling unit 6 to separate the steam generated in the kiln 2 into odor gas and water, thereby deodorizing the odor gas. It can be performed in the deodorizing unit 7.
- a dry distillation gas recovery unit 8 that recovers dry distillation gas generated inside the kiln 2 by pyrolysis accompanying carbonization in the carbonization unit 2 b is provided, and the fuel energy recovered by the dry distillation gas recovery unit 8 is used as a heat source for the combustion chamber 3. Reuse as.
- the fuel recovered by the dry distillation gas recovery unit 8 is recovered by recovering the dry distillation gas generated in the kiln 2 by the pyrolysis accompanying carbonization in the carbonization unit 2b by the dry distillation gas recovery unit 8.
- the energy can be reused as a heat source for the combustion chamber 3.
- an auxiliary heating source 9 is provided inside the dry distillation gas recovery unit 8 so as to heat the dry distillation gas recovered in the dry distillation gas recovery unit 8 when the amount of heat is insufficient.
- the amount of heat when the amount of heat of the dry distillation gas recovered in the dry distillation gas recovery unit 8 is insufficient can be supplemented by the auxiliary heating source 9 provided in the dry distillation gas recovery unit 8.
- route 10 which collect
- the oily unit 11 collects the smoke. Smoke can be cooled and oiled to produce recycled oil.
- the cooling unit 6 includes an air distribution pipe 12 that exhausts water vapor generated inside the kiln 2 and an exhaust promotion fan 13 so as to quickly reduce the moisture content of organic substances and the like.
- the cooling unit 6 includes the air distribution pipe 12 that exhausts the water vapor generated inside the kiln 2 and the exhaust promotion fan 13. It can be reduced early, and can contribute to shortening drying and carbonization time and promoting self-combustion.
- the following structure may be used for an organic substance having a high moisture content in order to make the residence time in the kiln 2 longer than that of an organic substance having a low moisture content.
- Fig. 5 shows an example of this.
- the inner peripheral surface of the kiln 2 has spiral blades 1 a extending spirally along the longitudinal direction of the kiln 2 and one or more stirring blades 1 b protruding inward.
- the kiln 2 is rotated counterclockwise.
- the spiral wing 1a is formed by attaching a strip-shaped thin plate to the inner peripheral surface of the kiln 2 in a spiral. It is preferable that the protruding amount h of the spiral feather 1a from the inner peripheral surface of the kiln 2 is larger than the protruding amount in the carbonized portion 2b than the protruding amount in the drying portion 2a. In the drying part 2a, 0.5 to 0.7 is preferable. The same applies to the protruding amount of the stirring blade 1b. In addition, you may enlarge gradually toward the decomposition
- a plurality of stirring blades 1b may be provided.
- an inclination ⁇ is provided.
- ⁇ is an angle between the tangent line 8 and FIG. 6).
- the return amount becomes a constant value regardless of the moisture content.
- the carbonized material that does not need to be dried is returned, the drying is performed more than necessary.
- the return amount can be controlled to an arbitrary amount.
- ⁇ should be large. Note that ⁇ is not limited to an acute angle and may be an obtuse angle. Set ⁇ corresponding to the return amount. The relationship between the return amount and ⁇ may be obtained in advance by experiments or the like.
- the distance between the pitches of the spiral wings 1a is made larger on the upstream side than on the downstream side. Thereby, the supply amount of the organic substance into the kiln can be maximized.
- the amount of protrusion of the spiral feather 1a from the inner surface of the kiln is preferably set so as to decrease from upstream to downstream.
- the conveyance amount of organic matter can be increased on the upstream side.
- the amount of organic matter gradually decreases, the amount of protrusion of the spiral wing 1a may be small. If the amount of protrusion is reduced, the hollow area increases. Also, the gas inside the kiln
- the stirring blade 1b may be provided continuously in the longitudinal direction of the kiln 2 or may be provided intermittently. What is necessary is just to select suitably in consideration of the ease of manufacture.
- An organic substance having a high water content is an organic substance having a high adhesiveness
- an organic substance having a low water content is an organic substance having a low adhesiveness
- FIG. 6A shows the case where the water content is high
- FIG. 6B shows the case where the water content is low.
- the organic matter falls after being lifted to a high position.
- the organic substance falls at a low position.
- the time spent in the drying process becomes longer.
- the time spent in the drying process is shortened.
- the difference in the staying time can be further increased if the distance between the stirring blades in the longitudinal direction is larger on the upstream side than on the downstream side.
- FIG. 7 shows an apparatus according to another embodiment.
- the upstream opening end of the kiln 2 is covered so as to be blocked from the outside, and the water vapor / dry distillation gas from the upstream opening end is caused to flow through the connection pipe 27 to the gas recovery unit 29 of the heat recovery facility.
- a line is provided, and an intake blower capable of arbitrarily adjusting the intake air amount is provided in the middle of the connection pipe 27.
- downstream opening end of the kiln 2 is covered so as to be blocked from the outside, and gas (mainly dry distillation gas) from the downstream opening end is supplied to the gas recovery section 29 of the heat recovery section via the connection pipe 27.
- gas mainly dry distillation gas
- connection pipe 27 and the gas recovery unit 29 are a parallel line, and a damper capable of adjusting the displacement is provided in the middle of each parallel line.
- the problem is the volume of a large amount of water vapor. Under atmospheric pressure, 1 liter of water is 100 ° C. and the volume of water vapor is about 1,700 liters. At 373 ° C., the volume of water vapor is about 3,400 liters.
- the intake air amount can be arbitrarily adjusted, an intake blower is installed, an exhaust pipe that leads the dry distillation gas to the heat recovery combustion facility, It is effective to install exhaust pipes that lead to the heat recovery combustion equipment in parallel, and to install dampers that can adjust the amount of each exhaust.
- a water jacket is provided outside the second exhaust pipe 19 in the recovery unit 60, and a water jacket is also provided around the heat recovery combustion facility to prevent overheating.
- the organic matter P including waste is supplied from the hopper 14 and supplied to the raw material supply pipe 15 connected so as to maintain the oxygen-free atmosphere (including the low oxygen atmosphere) of the kiln 2 on the start end side of the kiln 2. It is fed into the kiln 2 by a screw 16.
- the rotatable kiln 2 is carbonized from the drying unit 2a through the carbonization unit 2b by the action of the blades provided on the inner surface of the kiln 2 while rotating through a known drive system. Recycled charcoal Q carbonized in the section is discharged (collected) via the discharge pipe 17.
- a cooling device 18 such as a drain pipe is disposed around the discharge pipe 17, and by this cooling, organic carbide and inorganic carbide are generated and recovered as recycled coal according to the type of organic matter P or the like.
- the end portion of the kiln 2 and the discharge pipe 17 are connected so as to maintain an oxygen-free atmosphere (including a low oxygen atmosphere) of the kiln 2.
- the discharge pipe 17 is disposed below the end portion of the kiln 2 and is connected so as to collect carbides by falling due to its own weight, and is connected in the depth direction of FIG. 19 and the conveying screw 20 provided in the connecting pipe 19 dispose the carbides conveyed by the conveying screw 20 from the inside and outside (atmosphere) of the kiln 2.
- the conveying screw 21 also inside the discharge pipe 17. That is, by providing the conveying screw 20, the gas flow can be made unidirectional to the discharge port side and air intrusion is prevented.
- a reducing pipe 19 is provided at the start end side and the terminal end side of the kiln 2, and a dry distillation gas recovery part 8 that also serves as the deodorizing part 7 is connected to the reduction pipe 19, and this dry distillation gas recovery part Part of the dry distillation gas recovered in 8 is reused as a heat source for the combustion chamber 3, and the other part is exhausted from the exhaust pipe 3a.
- the dry distillation gas recovered from the inside of the kiln 2 is basically in a high temperature environment.
- the temperature of the dry distillation gas is increased by the heating of the auxiliary heating source 9 so as to maintain a temperature suitable for the kind of P (equal to or higher than the self-ignition temperature).
- a water distribution pipe 12 that also serves as a vapor smoke path 10 (or may be provided separately) is provided below the start end side of the kiln 2 via two pipe sections 5, and is generated inside the kiln 2. Of the water vapor, aerating water as water is collected.
- Aeration water is a liquid obtained by cooling the smoke generated in the initial stage of carbonization.
- organic matter P is mainly wood chips
- the regenerated charcoal is 25% of the weight of the wood. 20-30% aeration water can be collected with respect to the weight.
- the collected air mist is cooled (for example, for one month or more), it is separated into a wood tar, a wood vinegar solution, and a light oil, and a recycled fuel or the like can be collected.
- wood vinegar liquid (vinegar liquid) contains over 200 kinds of components such as alcohols and phenols, and products such as deodorants, human waste treatment agents, pharmaceuticals, animal feed additives, agriculture and forestry, etc. And can be reused in various fields.
- Wood tar is a pyrolysis liquid of hydrocarbon (lignin), and is a precipitate that is generated when air spilled water is cooled and left for about one month or more. It has strong sterilizing power and can be used as a deodorant. In addition, it can be divided into light oil, heavy oil, and pitch as fuel or as it is further separated into water and oil with a distillation device.
- hydrocarbon lignin
- dioxins and odors are removed from the odor gas introduced from the piping unit 5 to the deodorization unit (deodorization / detoxification combustion device) 7 under an environment of 850 to 1000 ° C.
- a tertiary combustion chamber 22 is disposed in connection with the deodorizing unit 7, and this tertiary combustion chamber 22 cleans the emulsion at 70 to 120 ° C. (low temperature harmless) ) May also be achieved.
- Emulsion purification is a mixture of microscopic water droplets that are uniformly distributed in high-temperature flammable gas or oil.
- the gas (oil droplets) that removes the water droplets is also refined to improve the mixing with the air, whereby the gas and oil can be completely burned.
- the gas and oil components become superfine during the emulsion combustion, the contact area with the air can be increased, and complete combustion can be achieved, greatly reducing the generation of unburned material and reducing dust. Can be significantly reduced.
- the particles become fine particles due to the micro-explosive action, so that low O2 combustion operation can be realized, and more complete combustion can be achieved, so that only the amount of dust in the exhaust gas can be achieved. NOx, SOx, etc. can be greatly reduced.
- waste materials / plastics for example, as shown in FIG. 3, waste materials / plastics, medical waste (3 cm or more), wood chips / sawdust (less than 3 cm), livestock feces (moisture content less than 60%) It can be applied to a wide range of waste materials such as food residue, livestock dung (water content 60% or more), sludge (after concentration / dehydration), etc. It is supplied to the kiln 2 after performing ultra-dehydration treatment.
- a high temperature environment of 850 ° C. could be realized, and combustion could be completed in a residence time of 2 seconds or more.
- the spiral blade and the stirring blade 1 are separated so that they can be independently driven by the drying unit 2a and the carbonizing unit 2b, or the carbonized unit 2b has a narrower pitch than the drying side 2a. It is also possible to clearly divide roles within one kiln 2. At this time, appropriate design changes, exchanges, and the like can be arbitrarily performed such as double spiraling of the spiral wings and changing the spiral shape (angle and maximum diameter).
- the processing capacity can be changed by changing the length and number of kilns 2, depending on the raw material used (such as organic matter P).
- the raw material used such as organic matter P
- the organic matter P has a size of about 3 cm or less, a moisture content of 10 to 60%, a bulk specific gravity of about 0.5, and a residence time until carbonization of 30 minutes or less. It is preferable to do this.
- a dry distillation gas outline calculation sheet (not shown) or the like, a combustion characteristic table of the dry distillation gas (self-ignition temperature list), or the like in advance.
- Raw material Coffee bean residue (water content 65%) was carbonized (50 minutes). Fuel calorific value was 7250 Kcal / kg per kg (fixed carbon rate 81.0%)
- the calorific value of coal is 7,190 Kcal / kg
- the calorific value of wood is 3,440 Kcal / kg.
- the organic matter P containing waste is put into one kiln 2 and the organic matter put into one kiln 2 is put into an oxygen-free atmosphere. It is possible to produce high energy regenerated coal using a wide range of raw materials by carbonizing by indirect heating and decomposition of organic matter etc. after storing heat in organic matter etc. while indirectly heating in reduced state and reducing moisture content. it can.
- Example 1 Hereinafter, a more specific configuration of the reduction carbonization processing system of the present invention will be described.
- the rice husk P containing waste is introduced from a hopper 7 by a supply screw 9 of a raw material supply pipe 8 connected to the inlet of the kiln 2 so as to maintain an oxygen-free atmosphere (including a low oxygen atmosphere) of the kiln 2. It is fed into the kiln 2.
- the rotatable kiln 2 rotates via a known drive system, and from the drying section A to the carbonization section B by the action of the spiral blade 25 and the stirring blade 26 provided on the inner surface of the kiln 2.
- the rice husk charcoal Q that has been carbonized and carbonized from the outlet of the kiln 2 is discharged (recovered) via the recovery unit 6 connected to the lower end of the discharge unit 24.
- a connection pipe 27 is provided at the inlet and the outlet of the kiln 2, and a dry distillation gas recovery unit 29 is connected to the connection pipe 27 via a reduction pipe 28, and is recovered by the dry distillation gas recovery unit 29.
- Part of the dry distillation gas is reused as a heat source for the combustion chamber 10 via the circulation pipe 14, and the other part is exhausted from the chimney 13.
- the dry distillation gas recovered from the inside of the kiln 2 is basically in a high temperature environment.
- the temperature of the dry distillation gas is increased by heating the auxiliary heating source 30 so as to maintain a temperature suitable for the type of P (above the self-ignition temperature).
- dioxins and odors are removed from the odor gas introduced to the dry distillation gas recovery unit 29 (deodorization / detoxification combustion device) under an environment of 850 to 1000 ° C.
- the rice husk P in the present invention is supplied into the kiln 2 without performing a so-called activation (activation) step.
- a high temperature environment of 500 ° C. could be realized, combustion could be completed in a residence time of 2 seconds or more, and continuous production in a short time could be realized.
- the carbonization temperature in the internal space was changed in units of 100 ° C. in the range of 300 to 600 ° C., and the pore structure after carbonization was enlarged and confirmed. As shown in FIGS. It was confirmed that generally good pore structures were obtained at °C, 500 °C, and 600 °C.
- 21 and 22 show the results of elemental analysis of rice husk charcoal obtained at each of these temperatures.
- a good adsorbent can be continuously produced.
- a rice husk charcoal adsorbent with high oil adsorption performance can be obtained by performing appropriately controlled carbonization without producing rice husk charcoal through multi-step processes such as activation. Can be obtained.
- the carbonization temperature shows a better adsorption capacity in the range of 450 to 550 ° C.
- Non-Patent Document 1 1 g of rice husk charcoal at each temperature is put into a non-woven fabric (polyethylene / polypropylene) tea pack, immersed in each oil for 5 minutes, and then the tea pack is pulled up and adsorbed by an oil drain stand. After dropping oil other than oil, the weight of the entire bag including the sample is measured with an electronic balance.
- a non-woven fabric polyethylene / polypropylene
- the amount of adsorption was calculated by taking the difference from the mass when only the bag was immersed in oil without putting the sample.
- the experimental value of one condition is an average value obtained by measuring three times.
- Example result> 19 and 20 show the amount of adsorption with respect to the carbonization temperature of rice husk charcoal of salad oil, A heavy oil, and kerosene.
- any graph FIG. 19B and FIG. 20B
- the amount of adsorption was maximized in rice husk charcoal carbonized at 500 ° C.
- the difference in the amount of adsorption depending on the type of oil is attributed to the viscosity of the oil.
- FIG. 21 to FIG. 22 are graphs showing the amount of each oil species adsorbed on rice husk charcoal carbonized at 500 ° C. in correlation with the viscosity coefficient.
- the adsorbed amount is 40% or more higher than the result by Akita Prefectural University.
- the rice husks were softened in high-temperature and high-pressure steam before carbonization and then crushed and opened along the fibers to increase the surface area of the rice husks, resulting in improved oil adsorption performance. ing. From this experimental result, it was found that the rice husk charcoal produced by this production method has an adsorption performance comparable to that without any pretreatment or the like.
- Example 2 In this example, the adsorption performance of ethylene gas, which is a neutral gas, was investigated for rice husk charcoal and paulownia charcoal.
- Gas adjustment method Based on nitrogen-based ethylene gas standard gas (100 ppm).
- Gas detector tube GASTEC, ethylene detector tube (172L)
- Sample carbide rice husk charcoal (carbonization temperature 300-700 ° C), paulownia charcoal (300-700 ° C)
- Remarks Comparison with commercially available ethylene adsorbent “ethylene control”, granular palladium activated carbon “deodorized charcoal / vegetable room” (manufactured by Este Co., Ltd.), and Chinese charcoal.
- the method of the present invention can produce high-quality carbides without going through an activation step, using rice husks, etc., which are currently treated as waste, as raw materials, with continuous and low energy consumption. Therefore, it can be supplied at a very low cost compared to conventional activated carbon or the like.
- the absolute performance increases to “ethylene control”, but by using cheap carbides in a somewhat early cycle, an overwhelming cost-effectiveness can be obtained.
- Example 3 In this example, the adsorption of ammonia gas, which is an alkaline gas, was experimented instead of the adsorption of ethylene gas.
- Example 4 In this example, the adsorption of acetic acid gas, which is an acidic gas, was experimented instead of the adsorption of ethylene gas. The experimental procedure was performed in the same manner as in Example 2.
- Example 5 In this example, an experiment was conducted to measure the relationship between the carbonization temperature and the pH of the carbide.
- the processing gas can be adsorbed more effectively.
- each carbide becomes lower as it is carbonized at a lower temperature. This is presumably because the organic matter in the material is not completely decomposed at low temperatures and remains as a dissociating group (COOH ⁇ ) on the carbide surface. Since one ammonia gas is basic, it is estimated that chemical adsorption occurs with a sample having a relatively low pH and a low carbonization temperature.
- Example 6 In this example, the relationship between carbonization temperature, specific surface area, and pore distribution was examined.
- the reduction sterilization carbonization machine shown in FIG. 1 is abbreviated as “SUMIX”.
- a sample was produced by a reduction sterilization carbonization machine (abbreviated as “SUMIX”) shown in FIG. 1 and a muffle furnace (abbreviated as “MUFFLE”) in a nitrogen gas atmosphere (flow rate: 1 L / min). .) Were used.
- SUMIX reduction sterilization carbonization machine
- MUFFLE muffle furnace
- Carbonization by a muffle furnace was maintained at a predetermined temperature for 30 minutes, and then naturally cooled in a nitrogen gas atmosphere to produce carbide.
- the measurement was performed using BELSORP-mini II, manufactured by Nippon Bell Co., Ltd., and the pretreatment was performed using BELSORP-vac II, manufactured by the same company.
- the specific surface area at 300 ° C for both SUMIX and MUFFLE furnaces is much smaller than that of activated carbon, etc., but the specific surface area increases as the carbonization temperature rises, and reaches a maximum at about 300 to 350 m 2 / g. Reach. This is about one third of the value of general activated carbon.
- this rice husk charcoal showed better performance than activated carbon.
- SUMIX has a specific surface area of 260 (BET method) to 330 (t method) m 2 / g at a carbonization temperature of 500 ° C, twice that of the sample carbonized at the same temperature in the MUFFLE furnace. It has a weak specific surface area.
- stirring is applied in the kiln during carbonization, so that heat conduction is excellent, and it is considered that high-performance carbide can be produced at a lower temperature. This is preferable both in terms of running cost and the yield of carbide to raw materials.
- the carbide produced by the method of the present invention has been found to have good adsorption power for three kinds of gases having different properties, and it can be sufficiently used as a freshness maintaining material, a deodorizing material, a deterioration preventing material and the like. It was done.
- the carbide (and hence the adsorbent) can be set to an arbitrary value by controlling the carbonization temperature, it can be produced as an adsorbent suitable for deodorizing alkali gas, for example.
- low-temperature carbide and medium / high-temperature carbide By mixing low-temperature carbide and medium / high-temperature carbide into an adsorbent, it can be made into an adsorbent having both chemical adsorption and physical adsorption, and it can be used as a deodorant that can handle complex odor gases. It is also possible to use it.
- the adsorbent In the case of an adsorbent that uses only alkaline carbide, the adsorbent adsorbs odorous gas while promoting the generation of ammonia gas.
- a carbide having a pH of (for example, higher pH) for example, alkaline ammonia gas can be chemisorbed and deodorized as a whole.
- an acid for example, dilute hydrochloric acid
- the oil or gas adsorbent of the present invention can be used by being stored in an oil-permeable or gas-permeable packaging, container, pack, capsule or the like.
- ⁇ Gases to be adsorbed include hydrogen sulfide (HS) and other gases besides ethylene, ammonia and acetic acid gas. It can also be used as a deodorizing material by adsorption of odor gas.
- HS hydrogen sulfide
- other gases besides ethylene, ammonia and acetic acid gas. It can also be used as a deodorizing material by adsorption of odor gas.
- gas adsorbents are placed at appropriate locations in the library, moisture in the hall is adsorbed, so sulfuric acid is produced by the reaction between aluminum sulfate and moisture used for printing, and the printed matter deteriorates due to the dehydration effect of sulfuric acid. It becomes possible to prevent.
- acetic acid gas is a cause of paper deterioration
- the gas adsorbent of the present application is effective in preventing the deterioration of the book. Note that an adsorbent may be sandwiched between thin sheets and used as a book cover sheet.
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Abstract
Description
特許文献5に係る技術は、図1に示す構造を有している。
1b 攪拌羽
2…キルン
2a 乾燥部
2b 炭化部
2d 蓄熱部
2c 内部空間
2in 入口
2out 出口
3…燃焼室
3a…排気管
4…加熱源
5…配管部
6…冷却部
7…脱臭部
8…乾留ガス回収部
9…補助加熱源
10…蒸気煙経路
11…油化部
12…配水管
13…ファン
14…ホッパ
15…原料供給配管
16…供給スクリュー
17…第2排出配管
18…冷却装置
19…接続管(下流側排ガス管)
19a 下流側排ガス管上管
19b 下流側排ガス管下管
20…搬送スクリュー
21…搬送スクリュー
22…蒸気抜きパイプ(上流側排ガス管)
22a 上流側排ガス管上管
22b 上流側排ガス管下管
23 煙突部
24 循環管
25 ガス抜きパイプ
30 接続部
60 回収部
図1は本発明の一実施形態に係る還元炭化処理システムの説明図、図2は本発明の一実施形態に係る還元炭化処理システムにおけるキルンの断面図である。
部にエリア設定された炭化部2bと、を備えている。
また、内部空間2cは、入口2inから出口2outに向かう搬送方向の上流側から下流側に向かって乾燥・熱分解(炭化)・蓄熱の各工程を行う区間2a,2b,2dが設定されている。この際、螺旋羽1aのピッチ間隔を、各区間2a,2b,2dで異ならせ、搬送方向下流側に向かう程にピッチ間隔を狭くすることによって内部空間2cにおける籾殻Pの滞在時間が搬送方向下流側に向かう程長くなっている。なお、螺旋羽1aのピッチ間隔は、乾燥・熱分解(炭化)・蓄熱の各工程順で各区間2a,2b,2dの単位で段階的に滞在時間が長くなるように設定されている。
図4では、かかる配管部を上流側(炭化素材投入口側)と下流側(炭化物取出し口側)に下流側排ガス管19と上流側排ガス管22として設けてある。
下流側排ガス管19は下流側排ガス管上管19aと下流側排ガス管下管19bとに分かれ、下流側排ガス管上管19aには水蒸気・臭気ガスが流れ、下流側排ガス管下管19bには主に乾留ガスが流れる。
図4に示す例では、下流側のみならず、上流側にも排ガス管が設けられている。上流側排ガス管22は上流側排ガス管上管22aと上流側排ガス管下管22bとに分かれ、上流側排ガス管上管22aには水蒸気・臭気ガスが流れ、上流側排ガス管下管22bには主に乾留ガスが流れる。下流側排ガス管上管19aと上流側排ガス管上管22aとは合流し、
水蒸気冷却タンクを通り燃焼炉で脱臭が行われる。また、下流側排ガス管下管19bと上流側排ガス管下管22bとは合流し、乾留ガス燃焼炉で燃焼後その廃熱を炭化のための熱源として再利用するようにしてある。
図4に示す例では、下流側のみならず、上流側にも排ガス管が設けられているため、水蒸気はいち早くキルン外部に排出されてしまう。したがって、キルン内における水蒸気圧を低くすることができ、その結果炭化素材の乾燥時間を著しく短縮することができる。さには、キルンの全長を短くすることができ、装置の小型化を達成させる。
2b 上流側排ガス管下管
本例では、キルン2は反時計方向に回転させている。
それに対して、含水量あるいは炭化素材の種類に応じた粘着力に応じてθを適宜の値に設定すれば、戻し量を任意の量に制御することが可能となる。乾燥しずらいものはθを大きくとればよい。
なお、θは、鋭角に限らず鈍角としてもよい。戻し量に対応したθを設定する。戻し量とθとの関係は予め実験などにより求めておけばよい。
なお、含水量が多い場合には、炭化素材をすくい上げてから頂点に達しても落下しないようにする場合もある。なお、好ましくは、30°<θ<90°である。
また、下流にいくほど含水量は減少するため上流側より下流側のθを小さくすればより短時間での炭化物の製造が可能となる。
また、螺旋羽1aのピッチ間距離は上流側を下流側より大きくしておくことが好ましい。これにより、キルン内への有機物の供給量を最大化することができる。
螺旋羽1aのキルン内面からの突出量は、上流から下流に向かうに従って減少するように設定することが好ましい。これにより、上流側においては有機物の搬送量を多くすることができる。下流側では、有機物の量は漸次減少するため螺旋羽1aの突出量は小さくても足りる。突出量を少なくすると中空面積が大きくなる。また、キルン内におけるガスの
(形態例2)
図7に他の形態例に係る装置を示す。
以下、本発明の還元炭化処理システムのより具体的な構成を説明する。廃棄物を含む有機物等Pは、ホッパ14から投入されて、キルン2の始端部側にキルン2の無酸素雰囲気(低酸素雰囲気を含む)を維持するように接続された原料供給配管15の供給スクリュー16によってキルン2内へと供給される。
以下、本発明の還元炭化処理システムのより具体的な構成を説明する。廃棄物を含む籾殻Pは、ホッパ7から投入されて、キルン2の入口にキルン2の無酸素雰囲気(低酸素雰囲気を含む)を維持するように接続された原料供給配管8の供給スクリュー9によってキルン2内へと供給される。
<実験試料>
油:灯油、サラダオイル、A重油
籾殻炭:300℃、400℃、500℃、600℃のそれぞれの温度で炭化させた籾殻炭
非特許文献1の実験結果に準じ、各温度の籾殻炭1gを不織布(ポリエチレン・ポリプロピレン)製のティーパックに入れ、各油中に5分間浸漬した後、ティーパックを引き上げて油切台で吸着油以外の油を落としてから、試料を含む袋全体の重量を電子天秤で測定する。
図19、20に、サラダ油、A重油、灯油の籾殻炭の炭化温度に対する吸着量を示す。いずれのグラフ(図19(B)及び図20(B))においても、500℃で炭化した籾殻炭において、吸着量が最大となった。この際、油の種類による吸着量の違いは油の粘性に起因するものである。図21~図22は、500℃で炭化した籾殻炭に対する、それぞれの油種の吸着量を粘性係数との相関で示したグラフである。
(吸着量 [g])=0.0712×(粘性係数 [mPa・s])+2.6311
であるから、本籾殻炭(500℃)のB重油吸着量は5.7g程度であると推定される。これは、同一条件の実験結果として、秋田県立大による結果より4割以上も吸着量が多いことになる。また、同大の実験では、炭化前に籾殻を高温高圧水蒸気中でやわらかくした後、つぶして繊維に沿って開く解繊処理を行って籾殻の表面積を増やし、その結果として油吸着性能を向上させている。本実験結果から、本製造方法によって作成した籾殻炭は、何ら前処理等を行わなくとも、それに匹敵する吸着性能を有することが判明した。
本例では、籾殻炭・桐炭について、中性ガスであるエチレンガスの吸着性能を調べた。
吸着性能は次の手順により実験を行った。
(1)20Lテドラーバックに後述の通り調整した対象ガスを封入し、室温(エアコン制御)で1時間以上静置
(2)1gの籾殻炭を5Lテドラーバックに入れて密閉した後、シリンジを用いて脱気
(3)20Lテドラーバックより、5Lテドラーバックへ対象ガスを導入
導入直後より一定時間毎にガス検知管を用いて、5Lテドラーバック内のガス濃度を測定
ガス調整方法:窒素ベースエチレンガス標準ガス(100ppm)による。
ガス検知管:GASTEC社製・エチレン検知管(172L)
サンプル炭化物:もみ殻炭(炭化処理温度300~700℃)、桐炭(300~700℃)
備考:市販のエチレン吸着材「エチレンコントロール」、粒状パラジウム活性炭「脱臭炭・野菜室用」(エステー株式会社製)、中国製くん炭との比較も行なった。
本例では、エチレンガスの吸着に代えて、アルカリ性ガスであるアンモニアガス吸着を実験した。
ガス調整方法:アンモニア水(10 w/v%)を20Lテドラーバックに注入
ガス検知管:GASTEC社製・アンモニア検知管(3La)
サンプル炭化物:もみ殻炭(300~700℃)、桐炭(300~700℃)
備考:実験毎のアンモニアガス濃度を一致させることが難しいため、ガス除去率で比較を行なった。
ガス除去率 [%] =(1-ガス濃度/ブランク濃度)×100
本例では、エチレンガスの吸着に代えて酸性ガスである酢酸ガス吸着を実験した。
実験手順などは実施例2と同様に行った。
ガス調整方法:酢酸試薬(10μL)を20Lテドラーバックに注入
ガス検知管:GASTEC社製・酢酸ガス検知管(81、81L)
サンプル炭化物:もみ殻炭(300~700℃)、桐炭(300~700℃)
備考:実験毎の酢酸ガス濃度を一致させることが難しいため、ガス除去率で比較を行なった。また、市販の活性炭(ノンスメル)との比較も行なった。
ガス除去率 [%] =(1-ガス濃度/ブランク濃度)×100
本例では、炭化処理温度と炭化物のpHとの関係を測定する実験を行った。
精製水200mLに炭化物1gを入れ、スターラーで数分間撹拌し、pH値が落着いた時点で測定した。
本例では、炭化温度と比表面積、細孔分布との関係について調べた。
Claims (21)
- 入口及び出口を有すると共に一連の内部空間で炭化される材料(以下「被炭化原料」という)の乾燥・熱分解・蓄熱をこの順で行う一つのキルンの前記内部空間に被炭化原料を供給し、該内部空間に供給された被炭化原料を、外部から酸素を導入させることのない還元雰囲気状態で間接加熱しつつ被炭化原料に蓄熱して含水率を低減したうえで、被炭化原料を間接加熱分解させることで炭化処理を行った炭からなる油乃至ガスの吸着材の製造方法。
- 前記炭化物は、籾殻炭又は桐炭であることを特徴とする請求項1記載の油乃至ガスの吸着材の製造方法。
- 前記炭化処理の温度は250~800℃である請求項1又は2記載の油乃至ガス吸着材の製造方法。
- ガスの吸着材が、籾殻炭からなる場合の前記炭化処理の温度は300~700℃であり、桐炭からなる場合の前記炭化処理温度は300~700℃である請求項1乃至3のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記ガスはエチレンガスである請求項1乃至4のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- ガスの吸着材が、籾殻炭からなる場合の前記炭化処理の温度は500℃以上であり、桐炭からなる場合の前記炭化処理温度は300℃以上である請求項5記載の油乃至ガスの吸着材の製造方法。
- 前記ガスはアンモニアガスである請求項1乃至4のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記炭化処理の温度は300~400℃である請求項7記載の油乃至ガスの吸着材の製造方法。
- 前記ガスは酢酸ガスである請求項1乃至4のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- ガスの吸着材が、籾殻炭からなる場合の前記炭化処理の温度は600℃以上であり、桐炭からなる場合の前記炭化処理温度は300℃以上である請求項9記載の油乃至ガスの吸着材の製造方法。
- 含水率が高い籾殻は、含水率の低い籾殻よりもキルン内における滞在時間が長くしながら炭化処理を行う請求項1乃至10のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記内部空間における籾殻の滞在時間が搬送方向下流側に向かう程長くすることを特徴とする請求項1乃至11のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 所定量以上の水分を含有する有機物は、進行と戻りを繰り返しながら搬送を行う請求項1乃至12のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- キルンの内周面には、キルンの長手方向に沿って螺旋状に延びる螺旋羽を有するとともに、内方に突出する攪拌羽を一以上有することを特徴とする請求項1乃至13のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記攪拌羽の長手方向の間隔は、上流側が下流側よりも大きいことを特徴とする請求項14記載の油乃至ガスの吸着材の製造方法。
- 前記滞在時間は、キルンの内周面に設けた攪拌羽の高さ、長手方向の間隔を、有機物の含水量、投入量に応じて変化させて行うことを特徴とする請求項11乃至15のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記キルン内の籾殻の分解により発生する乾留ガスを回収室において燃焼させ、燃焼により発生した熱によりキルン内の籾殻をキルン外部から加熱することを特徴とする請求項1乃至16のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 前記回収室における燃焼は、外部バーナーを用いることなく、回収室に空気を導入して行うことを特徴とする請求項1乃至17のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- キルン内部を180℃以下に設定することにより乾燥を行う請求項1乃至18のいずれか1項記載の油乃至ガスの吸着材の製造方法。
- 請求項1乃至19のいずれか1項記載の油乃至ガスの吸着材の製造方法により製造した油乃至ガスの吸着材。
- 炭化処理温度が異なる籾殻炭乃至桐炭を混合してなる請求項20記載油乃至ガスの吸着材。
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JP2013155254A (ja) * | 2012-01-27 | 2013-08-15 | Gaia Kankyo Gijutsu Kenkyusho:Kk | ゴム補強材、およびゴム組成物 |
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