WO2025192523A1 - 炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制剤の製造方法、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法 - Google Patents
炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制剤の製造方法、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法Info
- Publication number
- WO2025192523A1 WO2025192523A1 PCT/JP2025/008797 JP2025008797W WO2025192523A1 WO 2025192523 A1 WO2025192523 A1 WO 2025192523A1 JP 2025008797 W JP2025008797 W JP 2025008797W WO 2025192523 A1 WO2025192523 A1 WO 2025192523A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon resource
- heat generation
- carbon
- spontaneous heat
- resource
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Definitions
- the present disclosure relates to a spontaneous heat generation inhibitor for carbon resources, a method for producing a spontaneous heat generation inhibitor for carbon resources, a method for suppressing spontaneous heat generation for carbon resources, and a method for storing carbon resources.
- carbon resources are resources that contain carbon atoms.
- Carbon resources are used, for example, to obtain heat by burning carbon atoms or as reducing agents.
- Carbon resources include, for example, petroleum, coal, and biomass carbonaceous materials.
- Biomass carbonaceous materials are carbonaceous materials obtained by dry distilling biomass.
- Patent Documents 1 to 3 disclose technologies for suppressing spontaneous combustion of carbon resources.
- Patent Document 4 also discloses suppressing the spontaneous combustion of coal by coating the coal with components extracted from the coal using a non-hydrogen-donating solvent. The example discloses that coal is mixed with methylnaphthalene and subjected to extraction processing using an autoclave at a temperature of 360°C and a pressure of 2 MPa.
- Patent Document 4 is a technique in which extraction processing is performed in a limited environment, that is, in an autoclave, which is disadvantageous in terms of cost.
- pitches for example, by-products obtained during coal carbonization
- mixing pitches with a carbon resource can suppress spontaneous heating of the carbon resource. This is thought to be because pitches cover the particles of the carbon resource, preventing contact between the carbon resource and oxygen gas, and furthermore, donating hydrogen atoms from the pitches to the carbon resource can suppress radical reactions.
- the production of pitches is costly, and furthermore, there is a problem in that a large amount of CO2 gas is generated during the production of pitches.
- This disclosure has been made in consideration of the above problems, and its purpose is to provide a spontaneous heat generation inhibitor for carbon resources that can be produced at low cost and is effective in small amounts.
- the gist of this disclosure is as follows.
- a spontaneous heat generation inhibitor for a second carbon resource which is a component contained in a first carbon resource or a dry distillation product of the first carbon resource, and is soluble in hexane, or is insoluble in the hexane and soluble in toluene.
- the spontaneous heat generation inhibitor for a second carbon resource according to (1) characterized in that the first carbon resource includes at least one selected from petroleum, coal, and biomass carbonaceous materials.
- a method for producing a spontaneous heat generation inhibitor for a second carbon resource comprising a first step of extracting a first carbon resource or a dry distillation product of the first carbon resource with hexane.
- a method for suppressing spontaneous heat generation of a second carbon resource comprising the step of adding 1 mass % or more of the spontaneous heat generation inhibitor for a second carbon resource according to (1) or (2) to the first carbon resource.
- a method for storing a second carbon resource comprising storing a mixture obtained by the method for suppressing spontaneous heat generation of a second carbon resource according to (5).
- a spontaneous heat generation inhibitor for carbon resources that can be produced at low cost and is effective in small amounts. Furthermore, according to the present disclosure, it is possible to provide a method for producing a spontaneous heat generation inhibitor for carbon resources that can be produced at low cost and is effective in small amounts. Furthermore, according to the present disclosure, it is possible to provide a method for suppressing spontaneous heat generation in carbon resources and a method for storing carbon resources that use a spontaneous heat generation inhibitor for carbon resources that is low cost and is effective in small amounts.
- Example 1 is a graph according to Example 1 showing the relationship between the elapsed time from the start of a spontaneous heating evaluation test and the sample temperature.
- 10 is a graph according to Example 2 showing the relationship between the elapsed time from the start of the spontaneous heating evaluation test and the sample temperature.
- 10 is a graph showing the relationship between the elapsed time from the start of the spontaneous heating evaluation test and the sample temperature according to Example 3.
- the present inventors have discovered that petroleum-based binders (sometimes called binders depending on the application) used as binders for low-quality coals are effective in suppressing spontaneous heating of carbon resources.
- Spontaneous heating refers to heat generated in air at room temperature and atmospheric pressure.
- Petroleum-based binders are mixtures obtained by distilling and refining petroleum. The present inventors then fractionated the petroleum-based binders by solvent extraction, and added each fraction to the carbon resource. As a result, they found that some fractions have a greater effect on suppressing spontaneous heating than adding the petroleum-based binder itself, even at the same addition rate.
- Method for producing a spontaneous heat generation inhibitor for a second carbon resource A method for producing a spontaneous heat generation inhibitor for a carbon resource will be described.
- a carbon resource used as a raw material for the spontaneous heat generation inhibitor will be referred to as a first carbon resource
- a carbon resource whose spontaneous heat generation is to be suppressed will be referred to as a second carbon resource (or simply as a carbon resource).
- the first carbon resource and the second carbon resource may be different or the same.
- a raw material is prepared.
- the raw material is a first carbon resource or a dry distillation product of the first carbon resource.
- the first carbon resource is a resource containing carbon atoms, and heat is obtained by burning the carbon atoms.
- the first carbon resource is, for example, petroleum, coal, or biomass carbonaceous material.
- the pyrolysis product of the first carbon resource is, for example, a carbonaceous material obtained by pyrolyzing coal or biomass carbonaceous material, more specifically, coal tar.
- the pyrolysis product of the first carbon resource is, for example, an ASP (atomic phase petroleum) obtained from petroleum as a raw material.
- the first carbon resource or the dry distillation product of the first carbon resource is extracted with hexane (first step). Specifically, for example, the first carbon resource or the dry distillation product of the first carbon resource is thoroughly mixed with hexane and allowed to stand. The liquid portion is then recovered, and the hexane is removed from the liquid portion. This yields a spontaneous heat generation inhibitor (HS) for the second carbon resource. As shown in the examples, the spontaneous heat generation inhibitor (HS) for the second carbon resource has a sufficient spontaneous heat generation inhibitory effect.
- the first step is carried out in the following manner. 1. Place 2 g of the first carbon source in a centrifuge tube. 2. Add 50 cc of hexane to the centrifuge tube in 1 and apply ultrasonic vibration for 10 minutes. 3. The centrifuge tube from step 2 is placed in a centrifuge to separate the solid from the liquid. 4. The supernatant obtained in step 3 is collected and filtered using filter paper to obtain the extracted components (hexane-soluble components). 5. Repeat steps 2 to 4 twice on the extraction residue in the centrifuge tube after step 4 (for a total of three times). 6. The extract obtained in steps 1 to 5 above is evaporated to remove the solvent (hexane). 7.
- the extract (hexane-soluble components) and extraction residue (hexane-insoluble components) recovered in step 6, and the extraction residue (hexane-insoluble components) on the filter paper recovered in steps 1 to 5, are placed in a vacuum dryer and allowed to stand at 80°C for 12 hours to remove the solvent contained in the extraction residue, thereby obtaining the hexane-soluble components and hexane-insoluble components.
- the method for producing a spontaneous heat generation inhibitor for a second carbon resource may be completed when the spontaneous heat generation inhibitor for a second carbon resource (HS) is obtained, but the following second step may be further carried out. That is, the insoluble residue from the first step is extracted with toluene (second step). For example, the insoluble residue from the first step and toluene are thoroughly mixed and allowed to stand. Next, the liquid portion is recovered, and the toluene is removed from the liquid portion. This yields a spontaneous heat generation inhibitor (HI-TS) for a second carbon resource. As shown in the examples, the spontaneous heat generation inhibitor (HI-TS) for a second carbon resource has a sufficient spontaneous heat generation inhibitory effect.
- the second step is carried out in the following manner. 8. Repeat steps 1 to 7 multiple times to obtain 2 g or more of the hexane-insoluble component, and collect 2 g of the hexane-insoluble component and place it in a centrifuge tube. 9. Add 50 cc of toluene to the centrifuge tube in step 8 and apply ultrasonic vibration for 10 minutes. 10.9 The centrifuge tube is placed in a centrifuge to separate the solid from the liquid. 11. The supernatant obtained in step 10 is collected and filtered to obtain the extract (toluene-soluble component). 12. Repeat steps 9 to 11 twice for the extraction residue in the centrifuge tube after step 11 (for a total of three times). 13.
- the extract obtained in steps 12 above is evaporated to remove the solvent (toluene). 14.
- the extract (toluene-soluble component) and extraction residue (toluene-insoluble component) recovered in the operation of 13, and the extraction residue (toluene-insoluble component) on the filter paper recovered in the operations up to 12 are placed in a vacuum dryer and left to stand at 80°C for 12 hours to remove the solvent contained in the extraction residue, thereby obtaining a hexane-insoluble/toluene-soluble component and a toluene-insoluble component.
- the first step may include a step of mixing the first carbon resource with hexane (corresponding to steps 1 and 2 above), a step of solid-liquid separation of the mixture of the first carbon resource with hexane (corresponding to step 3 above), and a filtration step (corresponding to step 4 above), performed in this order.
- the first step may include adding hexane again to the residue after the filtration step (corresponding to step 2 above), and further performing the solid-liquid separation step and the filtration step.
- the first step may be a first hexane removal step (corresponding to step 6 above) in which hexane is removed after the filtration step.
- the first step may be a second hexane removal step (corresponding to step 7 above) in which hexane is removed from the hexane-soluble component as the extracted component and the hexane-insoluble component as the residue after the first hexane removal step.
- the second step may include a step of mixing the hexane-insoluble component with toluene (corresponding to steps 8 and 9 above), a step of solid-liquid separation of the mixture of the hexane-insoluble component and toluene (corresponding to step 10 above), and a step of filtration (corresponding to step 11 above) performed in this order.
- the second step may include adding toluene again to the residue after the filtration step (corresponding to step 9 above), and further performing the solid-liquid separation step and the filtration step.
- a first toluene removal step (corresponding to the above-mentioned 13) for removing toluene may be carried out after the filtration step.
- a second toluene removal step (corresponding to the above-mentioned 14) for removing toluene from the toluene-soluble component as the extracted component and the toluene-insoluble component as the residue may be carried out after the first toluene removal step.
- the first step was carried out after the first step, but the first step may also be carried out after the second step.
- the first carbon resource in 1 above should be read as the toluene-insoluble component
- the hexane-insoluble component in 8 above should be read as the first carbon resource.
- the hexane-soluble component and the toluene-soluble component do not depend on the order of the extraction operation with toluene and the extraction operation with hexane.
- the spontaneous heat generation inhibitor for the second carbon resource according to this embodiment is a component contained in the first carbon resource or the dry distillation product of the first carbon resource, and is soluble in hexane or insoluble in hexane and soluble in toluene.
- the spontaneous heat generation inhibitor for the second carbon resource according to this embodiment is produced by solvent fractionation of the first carbon resource or the dry distillation product of the first carbon resource, and can be produced at low cost.
- Soluble means that when a solvent is added to a compound, a solid or solid substance becomes liquid.
- soluble means that a liquid is mixed with another liquid compound to form a homogeneous liquid.
- solubility is the maximum amount of solute that can be dissolved in a solvent at a given temperature. If the extraction operations of the first and second steps described above are performed on a spontaneous heat generation inhibitor and a total of 1% by mass or more of components that are soluble in hexane and/or extracted components that are insoluble in hexane and soluble in toluene (excluding residues) are obtained, then this corresponds to the spontaneous heat generation inhibitor of this embodiment.
- the coal coating agent disclosed in Patent Document 4 is produced at high temperatures, resulting in high costs.
- the second method for producing a spontaneous heat generation inhibitor for carbon resources according to this embodiment can be carried out at room temperature and atmospheric pressure, which has the advantage of being low cost.
- Second method for suppressing spontaneous heat generation of carbon resources In the method for suppressing spontaneous heat generation of a second carbon resource according to this embodiment, the spontaneous heat generation inhibitor for the second carbon resource according to this embodiment is added in an amount of 1 mass % or more relative to the second carbon resource. Therefore, even a small amount of the spontaneous heat generation inhibitor for the second carbon resource is effective. As shown in the examples, a sufficient spontaneous heat generation suppression effect can be obtained by setting the mass ratio of the spontaneous heat generation inhibitor for the second carbon resource to 1 mass % or more. Furthermore, because the spontaneous heat generation inhibitor is uniformly added to the carbon resource and kneaded, it is more preferable to add the spontaneous heat generation inhibitor for the second carbon resource in an amount of 3 mass % or more relative to the second carbon resource.
- the upper limit of the mass ratio is not particularly limited, but is, for example, 30 mass % or less.
- the second spontaneous heat generation inhibitor may be added in an amount of less than 20 mass %, more preferably less than 10 mass %, relative to the second carbon resource.
- the second carbon resource storage method involves storing the mixture obtained by the second carbon resource spontaneous heat suppression method.
- the atmosphere during storage is not particularly limited, and the mixture may be stored in the air.
- the present disclosure also includes use of a spontaneous heat generation inhibitor for a second carbon resource, which is a component contained in a first carbon resource or a dry distillation product of the first carbon resource, and which is soluble in hexane or insoluble in hexane and soluble in toluene.
- the first carbon resource may include any one or more selected from petroleum, coal, and biomass carbonaceous materials.
- the spontaneous heat generation inhibitor for the second carbon resource may have the features of the above-described embodiment. Furthermore, the spontaneous heat generation inhibitor for the second carbon resource may be produced by the above-described production method.
- acacia-derived woody biomass charcoal was prepared as a second carbon resource whose spontaneous heat generation is to be suppressed.
- Acacia-derived woody biomass charcoal has high spontaneous heat generation properties.
- acacia-derived woody biomass charcoal will be abbreviated as acacia charcoal.
- a spontaneous heat generation inhibitor for a second carbon resource was prepared using the following process.
- a dry distillation product (ASP) obtained from petroleum was prepared.
- Commercially available ASP was used.
- 2 g of ASP was extracted with 50 cc of hexane using the procedure described in the above embodiment (first process). The extraction was performed at a temperature of 25°C and atmospheric pressure.
- the additive (HS) which is the residue obtained by evaporating the hexane, was obtained.
- additive 2 g of the insoluble residue from the first step was extracted with 50 cc of toluene. The extraction was carried out at a temperature of 25°C and atmospheric pressure. This yielded additive (HI-TS). The insoluble residue that was insoluble in toluene was designated additive (TI).
- a spontaneous heating evaluation test was conducted.
- the following samples were prepared: 1.00 g of acacia carbonaceous material alone; 0.95 g of acacia carbonaceous material with 5% by mass (50 mg) of ASP added; the same amount of acacia carbonaceous material with 5% by mass (50 mg) of additive (HS); the same amount of acacia carbonaceous material with 5% by mass (50 mg) of additive (HI-TS) added; and the same amount of acacia carbonaceous material with 5% by mass (50 mg) of additive (TI) added.
- the horizontal axis shows the elapsed time (min) from the start of the spontaneous heating evaluation test
- the vertical axis shows the sample temperature.
- Graph L1 shows the test results when the sample consisted of only acacia carbonaceous material
- graph L2 shows the test results when the sample consisted of acacia carbonaceous material with 5% by mass of ASP added
- graph L3 shows the test results when the sample consisted of acacia carbonaceous material with 5% by mass of additive (HS) added
- graph L4 shows the test results when the sample consisted of acacia carbonaceous material with 5% by mass of additive (HI-TS) added
- graph L5 shows the test results when the sample consisted of acacia carbonaceous material with 5% by mass of additive (TI) added.
- Example 2 In this example, a woody biomass carbonaceous material F other than acacia was prepared as a second carbon resource whose spontaneous heat generation was to be suppressed.
- Example 2 The same ASP as in Example 1 was prepared as a spontaneous heat generation inhibitor for the second carbon resource. Furthermore, an additive (HS) was obtained from the ASP using the same procedure as in Example 1 as a spontaneous heat generation inhibitor for the second carbon resource. Next, an additive (HI-TS) and an insoluble residue additive (TI) were obtained from the ASP using the same procedure as in Example 1 as spontaneous heat generation inhibitors for the second carbon resource.
- HS spontaneous heat generation inhibitor
- HI-TS insoluble residue additive
- TI insoluble residue additive
- Example 2 1 g of these samples was taken and loaded into the sample cell of the spontaneous heating evaluation device. The sample cell was then placed in the sample holder chamber, and the atmosphere inside the device was replaced with nitrogen. The sample temperature was then raised to 130°C under the nitrogen atmosphere. The sample temperature was measured using a thermocouple. The atmosphere inside the device was then switched from nitrogen to air, the test began, and the temperature behavior of the sample was measured. The results are shown in Figure 2.
- the horizontal axis represents the time (min) elapsed since the start of the spontaneous heating evaluation test
- the vertical axis represents the sample temperature.
- Graph L1 shows the test results when the sample consisted of only biomass carbonaceous material F
- graph L2 shows the test results when the sample consisted of biomass carbonaceous material F with 5% by mass of ASP added
- graph L3 shows the test results when the sample consisted of biomass carbonaceous material F with 5% by mass of an additive (HS) obtained from ASP added
- graph L4 shows the test results when the sample consisted of biomass carbonaceous material F with 5% by mass of an additive (HI-TS) obtained from ASP added
- graph L5 shows the test results when the sample consisted of biomass carbonaceous material F with 5% by mass of an additive (TI) obtained from ASP added.
- Example 3 In this example, a woody biomass carbonaceous material PC other than acacia was prepared as a second carbon resource whose spontaneous heat generation was to be suppressed.
- Example 2 1 g of these samples was taken and loaded into the sample cell of the spontaneous heating evaluation device. The sample cell was then placed in the sample holder chamber, and the atmosphere inside the device was replaced with nitrogen. The sample temperature was then raised to 130°C under the nitrogen atmosphere. The sample temperature was measured using a thermocouple. The atmosphere inside the device was then switched from nitrogen to air, the test began, and the temperature behavior of the sample was measured. The results are shown in Figure 3.
- the horizontal axis shows the elapsed time (min) from the start of the spontaneous heating evaluation test
- the vertical axis shows the sample temperature.
- Graph L1 shows the test results when the sample consisted of only biomass carbonaceous material PC
- graph L2 shows the test results when the sample consisted of biomass carbonaceous material PC with 5 mass% of an additive (HS) obtained from carbon resource S added
- graph L3 shows the test results when the sample consisted of biomass carbonaceous material PC with 5 mass% of an additive (HI-TS) obtained from carbon resource S added
- graph L4 shows the test results when the sample consisted of biomass carbonaceous material PC with 5 mass% of an additive (TI) obtained from carbon resource S added.
- a spontaneous heat generation inhibitor (HS) for the second carbon resource according to the above embodiment i.e., additive (HS) or spontaneous heat generation inhibitor (HI-TS) for the second carbon resource
- HS spontaneous heat generation inhibitor
- HI-TS spontaneous heat generation inhibitor
- Example 4 Next, the time required to reach 200°C was investigated when the type and amount of spontaneous heat generation inhibitor for the second carbon resource were changed.
- the second carbon resource to be suppressed from spontaneous heating was the above-mentioned 10 g of acacia carbonaceous material, to which ASP, additive (HS), additive (HI-TS), and additive (TI) were added in amounts of 1, 3, or 5 mass%.
- the spontaneous heating evaluation test described above was carried out on these samples.
- the time from the start of the test until the sample temperature reached 200°C was measured.
- the results are shown in Table 1.
- the values in the table indicate the time (min) required to reach 200°C.
- the time required to reach 200°C which was not achieved without adding 5% by mass of ASP, can be achieved with 1% by mass of additive (HS) or additive (HI-TS).
- the present disclosure it is possible to provide a spontaneous heat generation inhibitor for carbon resources that can be produced at low cost and is effective in small amounts. Furthermore, according to the present disclosure, it is possible to provide a method for producing a spontaneous heat generation inhibitor for carbon resources that can be produced at low cost and is effective in small amounts. Furthermore, according to the present disclosure, it is possible to provide a method for suppressing spontaneous heat generation in carbon resources and a method for storing carbon resources that use a spontaneous heat generation inhibitor for carbon resources that is low cost and is effective in small amounts. Therefore, the invention according to the present disclosure is extremely useful industrially.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本願は、2024年3月15日に、日本に出願された特願2024-040975号に基づき優先権を主張し、その内容をここに援用する。
また、ピッチ類(例えば石炭乾留時に得られる副生成物)は、炭素資源の自然発熱を抑制することができることが知られている。例えば、ピッチ類と炭素資源を混錬することで、炭素資源の自然発熱を抑制することができる。これは、ピッチ類が炭素資源の粒子を覆うことで炭素資源と酸素ガスとの接触を防止することができ、さらに、ピッチ類から炭素資源への水素原子供与によってラジカル反応が抑制できるからであると考えられている。しかし、ピッチ類の製造にはコストがかかり、さらに、ピッチ類の製造時に多量のCO2ガスを発生するという問題がある。
(1)
第一の炭素資源または前記第一の炭素資源の乾留生成物に含まれる成分であり、ヘキサンに可溶、または前記ヘキサンに不溶かつトルエンに可溶である、ことを特徴とする第二の炭素資源の自然発熱抑制剤。
(2)
前記第一の炭素資源には、石油、石炭、及びバイオマス炭材から選択されるいずれか1種以上が含まれる、ことを特徴とする(1)に記載の第二の炭素資源の自然発熱抑制剤。
(3)
第一の炭素資源または前記第一の炭素資源の乾留生成物をヘキサンで抽出する第1の工程を含む、ことを特徴とする第二の炭素資源の自然発熱抑制剤の製造方法。
(4)
前記第1の工程の不溶残留物をトルエンで抽出する第2の工程を含む、ことを特徴とする(3)に記載の第二の炭素資源の自然発熱抑制剤の製造方法。
(5)
(1)又は(2)に記載の第二の炭素資源の自然発熱抑制剤を前記第一の炭素資源に対して1質量%以上添加する工程を含む、ことを特徴とする第二の炭素資源の自然発熱抑制方法。
(6)
(5)に記載の第二の炭素資源の自然発熱抑制方法で得た混合物を貯蔵する、ことを特徴とする第二の炭素資源の貯蔵方法。
本発明者は、劣質炭の粘結剤として用いられている石油系粘結剤(なお、粘結剤は用途に応じてバインダーと称される場合もある)が炭素資源の自然発熱の抑制に効果があることを見出した。自然発熱とは、常温、大気圧下の空気中における発熱を意味する。石油系粘結剤は石油を蒸留し、さらに精製することで得られる混合物である。そこで、本発明者は、石油系粘結剤を溶媒抽出により分画した各分画成分を炭素資源へ添加した。この結果、添加率が同じでも石油系粘結剤自体を添加するよりも自然発熱抑制効果が大きい分画成分が存在することがわかった。
なお、石油系粘結剤は石油を蒸留し、さらに精製することで得られるものであるので、石油に類する炭材、すなわち炭素資源または炭素資源の乾留生成物を溶媒抽出により分画しても、同様の効果が期待できる。本実施形態は、以上の知見によりなされたものである。
炭素資源の自然発熱抑制剤の製造方法について説明する。本明細書では、自然発熱抑制剤の原料として用いられる炭素資源を第一の炭素資源、自然発熱を抑制すべき炭素資源を第二の炭素資源(あるいは、単に炭素資源)と称する。第一の炭素資源と第二の炭素資源は異なることもあり、同じこともある。
第一の炭素資源は、例えば、石油、石炭、バイオマス炭材である。第一の炭素資源の乾留生成物は、例えば、石炭やバイオマス炭材を乾留することで得られる炭材であり、より具体的にはコールタール等である。第一の炭素資源の乾留生成物は、例えば、石油を原料として得た乾留生成物(ASP)である。
1.第一の炭素資源2gを遠沈管に入れる。
2.1の遠沈管にヘキサン50ccを加え、10分間超音波振動を与える。
3.2の遠沈管を遠心分離機に供し、固液分離する。
4.3の操作で得た上澄みを回収し、ろ紙を用いてろ過することで抽出成分(ヘキサン可溶成分)を得る。
5.4の操作後の遠沈管内の抽出残渣に、2~4の操作を2回繰り返す(合計3回実施する)。
6.上記5までの操作で得た抽出物をエバポレーターに供し、溶媒(ヘキサン)を除去する。
7.6の操作で回収した抽出物(ヘキサン可溶成分)、および、抽出残渣(ヘキサン不溶成分)と5までの操作で回収したろ紙上の抽出残渣(ヘキサン不溶成分)を減圧乾燥機に入れ、80℃で12時間静置することで抽出残渣に含まれる溶媒を除去し、ヘキサン可溶成分およびヘキサン不溶成分を得る。
すなわち、第1の工程の不溶残留物をトルエンで抽出する(第2の工程)。例えば、第1の工程の不溶残留物とトルエンとを十分に混合して静置する。ついで、液体部分を回収し、液体部分からトルエンを除去する。これにより、第二の炭素資源の自然発熱抑制剤(HI-TS)を得る。実施例で示されるように、第二の炭素資源の自然発熱抑制剤(HI-TS)は十分な自然発熱抑制効果を有する。
8.ヘキサン不溶成分が2g以上得られるように1~7の操作を複数回実施し、ヘキサン不溶成分を2g回収し、遠沈管に入れる。
9.8の遠沈管にトルエン50ccを加え、10分間超音波振動を与える。
10.9の遠沈管を遠心分離機に供し、固液分離する。
11.10の操作で得た上澄みを回収し、ろ過することで抽出成分(トルエン可溶成分)を得る。
12.11の操作後の遠沈管内に抽出残渣に、9~11の操作を2回繰り返す(合計3回実施する )。
13.上記12までの操作で得た抽出物をエバポレーターに供し、溶媒(トルエン)を除去する。
14.13の操作で回収した抽出物(トルエン可溶成分)、および、抽出残渣(トルエン不溶成分)と12までの操作で回収したろ紙上の抽出残渣(トルエン不溶成分)を減圧乾燥機に入れ、80℃で12時間静置することで抽出残渣に含まれる溶媒を除去することで、ヘキサン不溶-トルエン可溶成分およびトルエン不溶成分を得る。
また、第1の工程としては、ろ過工程の後に、ヘキサンを除去する第1ヘキサン除去工程(上記の6に対応)を実施してもよい。さらに、第1の工程としては、第1ヘキサン除去工程の後に、抽出成分であるヘキサン可溶成分と残渣であるヘキサン不溶成分からヘキサンを除去する第2ヘキサン除去工程を実施してもよい(上記の7に対応)。
また、第2の工程としては、ろ過工程の後に、トルエンを除去する第1トルエン除去工程(上記の13に対応)を実施してもよい。さらに、第2の工程としては、第1トルエン除去工程の後に、抽出成分であるトルエン可溶成分と残渣であるトルエン不溶成分からトルエンを除去する第2トルエン除去工程を実施してもよい(上記の14に対応)。
したがって、本実施形態に係る第二の炭素資源の自然発熱抑制剤は、第一の炭素資源または第一の炭素資源の乾留生成物に含まれる成分であり、ヘキサンに可溶、またはヘキサンに不溶かつトルエンに可溶である。本実施形態に係る第二の炭素資源の自然発熱抑制剤は、第一の炭素資源または第一の炭素資源の乾留生成物の溶媒分画で製造されるので、低コストで製造できる。
本実施形態に係る第二の炭素資源の自然発熱抑制方法は、本実施形態に係る第二の炭素資源の自然発熱抑制剤を第二の炭素資源に対して1質量%以上添加する。したがって、少量の第二の炭素資源の自然発熱抑制剤で効果を発揮する。実施例で示されるように、第二の炭素資源の自然発熱抑制剤の質量比を1質量%以上とすることで、十分な自然発熱抑制効果が得られる。また、炭素資源に対して均質に自然発熱抑制剤を添加し混錬するという理由から、第二の炭素資源の自然発熱抑制剤を第二の炭素資源に対して3質量%以上添加することがより好ましい。また、質量比の上限は特に制限されないが、例えば30質量%以下である。あるいは、自然発熱抑制剤の粘性が高いため質量比が高いとハンドリング性が悪くなるという理由から、第二の自然発熱抑制剤を第二の炭素資源に対して20質量%未満、より好ましくは10質量%未満添加してもよい。
本実施形態に係る第二の炭素資源の貯蔵方法は、第二の炭素資源の自然発熱抑制方法により得られた混合物を貯蔵するものである。貯蔵時の雰囲気は特に制限されず、大気中に貯蔵してもよい。
第一の炭素資源または第一の炭素資源の乾留生成物に含まれる成分であり、ヘキサンに可溶、または前記ヘキサンに不溶かつトルエンに可溶であることを特徴とする第二の炭素資源の自然発熱抑制剤の自然発熱抑制剤としての使用も本開示に含まれる。この第一の炭素資源には、石油、石炭、及びバイオマス炭材から選択されるいずれか1種以上が含まれてもよい。この第二の炭素資源の自然発熱抑制剤は、上述した実施形態の特徴を備えていてもよい。また、この第二の炭素資源の自然発熱抑制剤は、上述した製造方法によって製造されてもよい。
つぎに、本実施形態の実施例について説明する。本実施例では、自然発熱の抑制対象となる第二の炭素資源としてアカシア由来の木質バイオマス炭材を準備した。アカシア由来の木質バイオマス炭材は自然発熱性が高い。以下、アカシア由来の木質バイオマス炭材をアカシア炭材と略称する。
本実施例では、自然発熱の抑制対象となる第二の炭素資源としてアカシア以外の木質バイオマス炭材Fを準備した。
本実施例では、自然発熱の抑制対象となる第二の炭素資源としてアカシア以外の木質バイオマス炭材PCを準備した。
次に、第二の炭素資源の自然発熱抑制剤の種類と添加量を変えた時の200℃到達時間を調べた。
自然発熱の抑制対象となる第二の炭素資源は上述した10gのアカシア炭材とし、これに、ASP、添加剤(HS)、添加剤(HI-TS)及び添加剤(TI)を添加量が、1、3、5質量%のいずれかとなるように添加した。
表中の数値は200℃到達時間(min)を示す。表1に示すように、ASPを5質量%添加しなければ得られなかった200℃到達時間は、添加剤(HS)または添加剤(HI-TS)であれば1質量%で得られることが分かる。
Claims (6)
- 第一の炭素資源または前記第一の炭素資源の乾留生成物に含まれる成分であり、
ヘキサンに可溶、または前記ヘキサンに不溶かつトルエンに可溶である、
ことを特徴とする第二の炭素資源の自然発熱抑制剤。 - 前記第一の炭素資源には、石油、石炭、及びバイオマス炭材から選択されるいずれか1種以上が含まれる、
ことを特徴とする請求項1に記載の第二の炭素資源の自然発熱抑制剤。 - 第一の炭素資源または前記第一の炭素資源の乾留生成物をヘキサンで抽出する第1の工程を含む、
ことを特徴とする第二の炭素資源の自然発熱抑制剤の製造方法。 - 前記第1の工程の不溶残留物をトルエンで抽出する第2の工程を含む、
ことを特徴とする請求項3に記載の第二の炭素資源の自然発熱抑制剤の製造方法。 - 請求項1又は2に記載の第二の炭素資源の自然発熱抑制剤を前記第一の炭素資源に対して1質量%以上添加する工程を含む、
ことを特徴とする第二の炭素資源の自然発熱抑制方法。 - 請求項5に記載の第二の炭素資源の自然発熱抑制方法で得た混合物を貯蔵する、
ことを特徴とする第二の炭素資源の貯蔵方法。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2025545193A JP7810941B1 (ja) | 2024-03-15 | 2025-03-10 | 炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制剤の製造方法、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2024040975 | 2024-03-15 | ||
| JP2024-040975 | 2024-03-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2025192523A1 true WO2025192523A1 (ja) | 2025-09-18 |
Family
ID=97063729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2025/008797 Pending WO2025192523A1 (ja) | 2024-03-15 | 2025-03-10 | 炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制剤の製造方法、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法 |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7810941B1 (ja) |
| TW (1) | TW202603146A (ja) |
| WO (1) | WO2025192523A1 (ja) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558295A (en) * | 1978-10-23 | 1980-04-30 | Conoco Inc | Coal fuel treating composition |
| JPS56151791A (en) * | 1980-04-24 | 1981-11-24 | Kansai Coke & Chem Co Ltd | Agent for preventing coal from self-heating |
| JPS5974189A (ja) | 1982-10-20 | 1984-04-26 | Idemitsu Kosan Co Ltd | 低品位炭の安定化方法 |
| JP2001164254A (ja) | 1999-12-02 | 2001-06-19 | Lion Corp | 炭素質粉体の昇温・自然発火抑制剤 |
| JP2005520532A (ja) * | 2002-03-27 | 2005-07-14 | インデナ・ソチエタ・ペル・アチオニ | 高リコペン含量のトマトエキスの調製方法 |
| JP2007161926A (ja) | 2005-12-15 | 2007-06-28 | Kobe Steel Ltd | 改質石炭、および改質石炭の製造方法 |
| JP2008007711A (ja) * | 2006-06-30 | 2008-01-17 | Mitsubishi Corp | バイオ燃料用マスキング剤及びバイオ燃料 |
| JP2009545326A (ja) * | 2006-08-02 | 2009-12-24 | ソレイ リミテッド ライアビリティ カンパニー | 凝固タンパク質を含有する食品組成物及びその製造方法 |
| JP2011201947A (ja) | 2010-03-24 | 2011-10-13 | Mitsubishi Heavy Ind Ltd | 改質石炭製造装置 |
| JP2015063576A (ja) * | 2013-09-24 | 2015-04-09 | 株式会社神戸製鋼所 | 改質石炭の製造方法及び改質石炭 |
| KR20190068196A (ko) * | 2017-12-08 | 2019-06-18 | 이승훈 | 석탄 자연발화 억제제 |
| JP2020176184A (ja) * | 2019-04-16 | 2020-10-29 | 出光興産株式会社 | 石炭の自然発火抑制方法、貯炭設備及び搬送設備 |
| JP2024040975A (ja) | 2022-09-13 | 2024-03-26 | 富士フイルムビジネスイノベーション株式会社 | 画像処理装置及びプログラム |
| WO2024150818A1 (ja) * | 2023-01-12 | 2024-07-18 | 日本製鉄株式会社 | 固体炭素資源の自然発熱抑制方法およびこれを用いた固体炭素資源貯蔵方法 |
-
2025
- 2025-03-10 JP JP2025545193A patent/JP7810941B1/ja active Active
- 2025-03-10 WO PCT/JP2025/008797 patent/WO2025192523A1/ja active Pending
- 2025-03-12 TW TW114109095A patent/TW202603146A/zh unknown
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558295A (en) * | 1978-10-23 | 1980-04-30 | Conoco Inc | Coal fuel treating composition |
| JPS56151791A (en) * | 1980-04-24 | 1981-11-24 | Kansai Coke & Chem Co Ltd | Agent for preventing coal from self-heating |
| JPS5974189A (ja) | 1982-10-20 | 1984-04-26 | Idemitsu Kosan Co Ltd | 低品位炭の安定化方法 |
| JP2001164254A (ja) | 1999-12-02 | 2001-06-19 | Lion Corp | 炭素質粉体の昇温・自然発火抑制剤 |
| JP2005520532A (ja) * | 2002-03-27 | 2005-07-14 | インデナ・ソチエタ・ペル・アチオニ | 高リコペン含量のトマトエキスの調製方法 |
| JP2007161926A (ja) | 2005-12-15 | 2007-06-28 | Kobe Steel Ltd | 改質石炭、および改質石炭の製造方法 |
| JP2008007711A (ja) * | 2006-06-30 | 2008-01-17 | Mitsubishi Corp | バイオ燃料用マスキング剤及びバイオ燃料 |
| JP2009545326A (ja) * | 2006-08-02 | 2009-12-24 | ソレイ リミテッド ライアビリティ カンパニー | 凝固タンパク質を含有する食品組成物及びその製造方法 |
| JP2011201947A (ja) | 2010-03-24 | 2011-10-13 | Mitsubishi Heavy Ind Ltd | 改質石炭製造装置 |
| JP2015063576A (ja) * | 2013-09-24 | 2015-04-09 | 株式会社神戸製鋼所 | 改質石炭の製造方法及び改質石炭 |
| KR20190068196A (ko) * | 2017-12-08 | 2019-06-18 | 이승훈 | 석탄 자연발화 억제제 |
| JP2020176184A (ja) * | 2019-04-16 | 2020-10-29 | 出光興産株式会社 | 石炭の自然発火抑制方法、貯炭設備及び搬送設備 |
| JP2024040975A (ja) | 2022-09-13 | 2024-03-26 | 富士フイルムビジネスイノベーション株式会社 | 画像処理装置及びプログラム |
| WO2024150818A1 (ja) * | 2023-01-12 | 2024-07-18 | 日本製鉄株式会社 | 固体炭素資源の自然発熱抑制方法およびこれを用いた固体炭素資源貯蔵方法 |
Non-Patent Citations (1)
| Title |
|---|
| "Handbook of the Aromatic and Tar Industry", THE JAPAN AROMATIC INDUSTRY ASSOCIATION, INC |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7810941B1 (ja) | 2026-02-04 |
| TW202603146A (zh) | 2026-01-16 |
| JPWO2025192523A1 (ja) | 2025-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Leng et al. | The migration and transformation behavior of heavy metals during co-liquefaction of municipal sewage sludge and lignocellulosic biomass | |
| Florentino-Madiedo et al. | Evaluation of synergy during co-pyrolysis of torrefied sawdust, coal and paraffin. A kinetic and thermodynamic study | |
| Santos et al. | Application of orange peel waste in the production of solid biofuels and biosorbents | |
| Li et al. | Supercritical water treatment of heavy metal and arsenic metalloid-bioaccumulating-biomass | |
| AU2007307596B2 (en) | Method for production of ashless coal | |
| Leng et al. | Study on demetalization of sewage sludge by sequential extraction before liquefaction for the production of cleaner bio-oil and bio-char | |
| AU2010263737B2 (en) | Method for producing carbon materials | |
| TWI876831B (zh) | 固體碳資源之自然發熱抑制方法及利用其之固體碳資源貯藏方法 | |
| KR20140101778A (ko) | 무회탄의 제조 방법 | |
| JP7810941B1 (ja) | 炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制剤の製造方法、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法 | |
| Rampe et al. | Study of pore length and chemical composition of charcoal that results from the pyrolysis of coconut shell in Bolaang Mongondow, Sulawesi, Indonesia | |
| JP5221997B2 (ja) | 炭化水素油の分解方法 | |
| US20230265352A1 (en) | Continuous oil recovery process from spent oily solid material | |
| JP2010531903A (ja) | 吸収によるコークス炉ガスからの芳香族炭化水素の除去方法 | |
| RU2581526C1 (ru) | Способ обезжиривания отработанных фильтровальных порошков, полученных при рафинации растительных масел | |
| JP2009215402A (ja) | 無灰炭の製造方法 | |
| CN105505427B (zh) | 从含油物质提取油的方法 | |
| Quoc | Study on kinetics of pyrolysis reaction (degradation) of rice husk, corn cob and sugarcane bagasse as agricultural residues in Vietnam | |
| Chauhan et al. | Study of kinetic characteristics of pyrolysis of sewage sludge and waste biomass using thermogravimetry | |
| CN110903852B (zh) | 回收费托合成蜡的方法 | |
| JPS5927984A (ja) | 石炭液化方法 | |
| WO2025192528A1 (ja) | 炭素資源の自然発熱抑制剤、炭素資源の自然発熱抑制方法、及び炭素資源の貯蔵方法 | |
| TWI682993B (zh) | 燃料油精煉方法 | |
| WO2010128216A1 (fr) | Procede de demercurisation total en une etape de charges hydrocarbonees liquides utilisant un materiau hybride organique-inorganique | |
| BR102017001445A2 (pt) | uso de um bioadsorvente produzido a partir de sementes de mangaba para remoção de contaminantes de águas e efluentes líquidos |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref document number: 2025545193 Country of ref document: JP Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2025545193 Country of ref document: JP |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 25769492 Country of ref document: EP Kind code of ref document: A1 |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112026018890 Country of ref document: BR |