WO2025192528A1 - 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 - 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方法、及び炭素資源の貯蔵方法Info
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- WO2025192528A1 WO2025192528A1 PCT/JP2025/008812 JP2025008812W WO2025192528A1 WO 2025192528 A1 WO2025192528 A1 WO 2025192528A1 JP 2025008812 W JP2025008812 W JP 2025008812W WO 2025192528 A1 WO2025192528 A1 WO 2025192528A1
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- carbon
- heat generation
- spontaneous heat
- resource
- spontaneous
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- 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
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- 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
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
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- 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
-
- 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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
Definitions
- the present disclosure relates to 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 heat generation of carbon resources.
- the present inventors considered that the techniques disclosed in Patent Documents 1 to 3 cannot sufficiently suppress spontaneous heat generation of carbon resources.
- the present disclosure has been made in consideration of the above problems, and an object of the present disclosure is to provide a spontaneous heat generation inhibitor for carbon resources that can more reliably suppress spontaneous heat generation of carbon resources.
- the gist of this disclosure is as follows.
- a spontaneous heat generation inhibitor for carbon resources characterized by containing naphthenic ring carbon atoms in a ratio of 1 mmol/g or more.
- the spontaneous heat generation inhibitor for carbon resources according to (1) characterized in that it contains naphthenic ring carbon atoms in a ratio of 5 mmol/g or more.
- the spontaneous heat generation inhibitor for carbon resources according to (1) or (3) characterized in that the naphthenic ring having the naphthenic ring carbon atom has an unsaturated carbon bond.
- the spontaneous heat generation inhibitor for carbon resources according to (1) or (2) characterized in that it has a condensed ring structure in its molecular structure, and a naphthenic ring carbon atom is contained in the condensed ring structure.
- the spontaneous heat generation inhibitor for carbon resources according to any one of (1) to (5) which is composed of a mixture having a molecular weight of 200 to 1000.
- the spontaneous heat generation inhibitor for a carbon resource according to any one of (1) to (7) which is a component contained in a carbon resource or a dry distillation product of the carbon resource.
- a method for suppressing spontaneous heat generation of a carbon resource comprising the step of adding 1 mass % or more of the spontaneous heat generation inhibitor for a carbon resource according to any one of (1) to (8) to the carbon resource.
- (10) (9) A method for storing a carbon resource, comprising storing a mixture obtained by the method for suppressing spontaneous heat generation of a carbon resource according to (9).
- a spontaneous heat generation inhibitor for carbon resources that can more reliably suppress spontaneous heat generation in carbon resources. 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 can more reliably suppress spontaneous heat generation in carbon resources.
- 1 is a graph showing the relationship between the elapsed time from the start of a spontaneous heating evaluation test and the sample temperature.
- the naphthenic ring means a ring having a 4- to 6-membered ring structure of carbon atoms, and a carbon atom bonded to two hydrogen atoms (naphthenic ring carbon atom) is included in the ring structure.
- the cyclic structure constituting the naphthenic ring may be a single cyclic structure or a plurality of condensed cyclic structures.
- the naphthenic rings of (a), (c), and (d) have an unsaturated bond in the cyclic structure.
- the naphthenic ring of (b) has a cyclic structure formed by a saturated bond.
- the naphthenic ring of (d) is formed by the condensation of two cyclic structures.
- the above example shows only a portion of the molecular structure, and the compound constituting the spontaneous heat generation inhibitor according to this embodiment does not necessarily have such a compound. That is, the naphthenic ring as described above may be included as part of the structure of the compound described below.
- any of the carbon atoms constituting the naphthenic ring may be bonded to a carbon atom or another functional group to form the compound.
- Naphthenic ring carbon atoms easily release hydrogen atoms.
- naphthenic ring carbon atoms have hydrogen-donating properties.
- the inventors believed that the hydrogen atoms released from naphthenic ring carbon atoms capture free radicals that could induce spontaneous heating of carbon resources, thereby suppressing spontaneous heating of carbon resources.
- no quantitative study had been conducted to date on the necessary proportion of naphthenic ring carbon atoms to suppress spontaneous heating of carbon resources.
- Examples of substances that contain naphthenic ring carbon atoms and are relatively inexpensive and easily available include petroleum pitch. However, since it is the naphthenic ring carbon atoms that suppress the spontaneous heat generation of carbon resources, any substance that contains a large number of naphthenic ring carbon atoms should function as a spontaneous heat generation suppressant for carbon resources, regardless of its origin. This embodiment was made based on the above findings.
- the spontaneous heating inhibitor for carbon resources according to this embodiment is a substance having a molecular structure containing naphthenic rings, and contains naphthenic ring carbon atoms at a ratio of 1 mmol/g or more.
- naphthenic ring carbon atoms have hydrogen-donating properties. Therefore, hydrogen atoms released from the naphthenic ring carbon atoms capture free radicals that could induce spontaneous heating of the carbon resource, thereby suppressing spontaneous heating of the carbon resource.
- the spontaneous heating inhibitor contains at least 1 mmol/g of naphthenic ring carbon atoms.
- the spontaneous heating inhibitor according to this embodiment may preferably contain naphthenic ring carbon atoms at a ratio of 5 mmol/g or more.
- the upper limit of the content of naphthenic ring carbon atoms is not particularly limited, but may be 30 mmol/g or less, 25 mmol/g or less, or 15 mmol/g or less.
- the content of naphthenic ring carbon atoms can be calculated based on the molecular structure of the spontaneous heat generation inhibitor and the number of naphthenic ring carbon atoms contained in one molecule. Specifically, the molecular weight is determined from the molecular structure, and the content of naphthenic ring carbon atoms can be calculated based on the molecular weight and the number of naphthenic ring carbon atoms contained in one molecule.
- the average molecular structure can be determined using the following procedure.
- the average molecular structure does not necessarily match the actual molecular structure of the candidate substance for the spontaneous heat generation inhibitor, but it does reflect the molecular structure characteristics of the candidate substance for the spontaneous heat generation inhibitor (type and number of functional groups, etc.).
- the content (mass %) of each element is determined, and the average molecular structure is determined.
- the content of each element is determined by performing elemental analysis of the spontaneous heat generation inhibitor using a method in accordance with JIS M 8813:2006.
- the average molecular structure is determined by 1 H NMR and 13 C NMR measurements.
- the results of 1 H NMR measurement reveal the proportions of four types of H, namely Ha, H ⁇ , H ⁇ , and H ⁇ .
- the proportion of H refers to the proportion of Ha, H ⁇ , H ⁇ , or H ⁇ relative to the total amount of H contained in the spontaneous heating inhibitor.
- the four types of H can be distinguished from one another because they exhibit chemical shift values in the ranges of Ha: 9.0-6.0 ppm, H ⁇ : 5.0-2.0 ppm, H ⁇ : 2.0-1.05 ppm, and H ⁇ : 1.05-0.5 ppm in the 1 H NMR spectrum.
- results of 13 C NMR measurement reveal the number of aromatic carbon atoms and the number of oxygen-containing groups such as aldehyde groups, ketone groups, and carboxyl groups.
- an average molecular structure is constructed.
- the specific method for constructing the average molecular structure follows the method described in Yuki Hata, et al., ISIJ International, Vol. 62 (2022), No. 5, pp. 948-95.
- the specific conditions for the NMR measurement are as follows: A deuterated solvent such as deuterated chloroform is used. 1 H NMR spectra are measured by the single pulse method. 13 C NMR spectra are measured by the single pulse method, and NOE (nuclear Overhauser effect) is not used.
- the molecular weight is further determined by mass spectrometry or GPC (Gel Permeation Chromatography). Then, based on the obtained molecular weight and the number of naphthenic ring carbon atoms contained in the average molecular structure, the content of naphthenic ring carbon atoms is calculated.
- the spontaneous heat generation inhibitor according to this embodiment is a compound or a mixture. More preferably, the spontaneous heat generation inhibitor is a mixture.
- the mixture is composed of two or more different compounds.
- the average molecular structure of such a mixture can be determined using the method described above, and the content of naphthenic ring carbon atoms contained in the average molecular structure can be calculated.
- the spontaneous heat generation inhibitor is a mixture and the molecular structure of each compound contained in the mixture is required, the content of naphthenic ring carbon atoms in the mixture can be calculated by adding up the naphthenic ring carbon atoms contained in each compound. Also, if the spontaneous heat generation inhibitor is a single compound, the content of naphthenic ring carbon atoms in the molecular structure of that compound can be calculated.
- spontaneous heat generation inhibitors When spontaneous heat generation inhibitors are made from natural resources, they are often composed of a mixture of multiple compounds due to the raw materials and processing steps. When a spontaneous heat generation inhibitor is a mixture of multiple compounds, the mixture may contain tens of thousands of compounds, making it difficult to identify the compounds, but it is known that the molecular weight of the mixture ranges from 200 to 10,000.
- the spontaneous heat generation inhibitor of this embodiment is made of a mixture with a molecular weight of 200 to 1000, thereby achieving a greater inhibitory effect.
- the spontaneous heat generation inhibitor consists of a mixture with a molecular weight of 200 to 1000
- the molecular weight peak measured using an FD-MS device is in the range of 200 to 1000.
- the molecular weight peak is measured as follows.
- the molecular weight was measured using FD-MS, and the molecular weight peak was measured.
- 1 mg of sample was dissolved in tetrahydrofuran and applied to an emitter (a tungsten wire with a diameter of approximately 10 ⁇ m and carbon whiskers attached to the surface).
- the current applied to the emitter was adjusted under high vacuum, and the sample molecules were directly ionized in combination with a high electric field, and a mass spectrum was obtained using a mass spectrometer.
- the detector voltage was set to 2200 V, the measurement mass range was 50 to 1600 m/z, and drift correction was performed using the mass number of C20H16 (252.09396).
- the spontaneous heat generation inhibitor according to this embodiment may have a fused ring structure within its molecular structure, and this fused ring structure may have a naphthenic ring carbon atom.
- the naphthenic ring carbon atom contained in the fused ring structure may have high hydrogen donating properties.
- fused ring structures contained in the compounds that constitute the spontaneous heat generation inhibitor according to this embodiment are shown below. Note that the structures exemplified below only show part of the molecular structure, and the compounds that constitute the spontaneous heat generation inhibitor do not necessarily have the structure shown below. In other words, the compound according to this embodiment contains a fused ring structure like the one shown below as part of its structure.
- any of the carbon atoms constituting the above fused ring structure may be bonded to a carbon atom or another functional group to form a compound.
- the compound constituting the spontaneous heat generation inhibitor according to this embodiment may be an alicyclic compound having a cyclic aliphatic structure.
- the spontaneous heat generation inhibitor according to this embodiment may have a structure in which the naphthenic rings (a) to (d) described above are condensed.
- the carbon resource according to this embodiment may be solid at room temperature. This is because compounds having naphthenic rings often have sublimation properties and therefore react efficiently with carbon resources even in a solid state. Furthermore, the spontaneous heat generation inhibitor according to this embodiment, although solid, has viscosity, and therefore has high adhesion to solid carbon resources, resulting in high reaction efficiency.
- the spontaneous heat generation inhibitor according to this embodiment preferably has an unsaturated carbon bond in the naphthenic ring having a naphthenic ring carbon atom. Having an unsaturated carbon bond in the naphthenic ring has the effect of increasing hydrogen donating properties.
- the unsaturated carbon bond of the naphthenic ring having a naphthenic ring carbon atom has aromaticity.
- the unsaturated carbon bond is an aromatic carbon bond. This has the effect of improving hydrogen donating performance and stabilizing radicals generated during oxidation.
- the spontaneous heat generation inhibitor for carbon resources is a component contained in the carbon resource or a carbon resource dry distillation product. Therefore, the spontaneous heat generation inhibitor for carbon resources according to this embodiment can be extracted from the carbon resource or a carbon resource dry distillation product by solvent fractionation.
- the explanation will be given on the premise that there are two carbon resources: a carbon resource as a raw material for the carbon resource spontaneous heat generation inhibitor, and a carbon resource whose spontaneous heat generation is to be suppressed; however, these two carbon resources may be the same carbon resource or may be different.
- the raw material is prepared.
- the raw material is a carbon resource or a carbon resource distillation product.
- a carbon resource is a resource that contains carbon atoms, and heat is obtained by burning the carbon atoms.
- Examples of carbon resources are petroleum, coal, and woody biomass carbonaceous material.
- Woody biomass carbonaceous material is biomass made from wood.
- a carbon resource distillation product is, for example, petroleum pitch, or carbonaceous material obtained by distilling coal or woody biomass carbonaceous material, more specifically, coal tar, etc.
- the carbon resource or the carbon resource dry distillation product is extracted with hexane (first step). Specifically, for example, the carbon resource or the carbon resource dry distillation product 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 for the first carbon resource. As shown in the examples, the spontaneous heat generation inhibitor for the first 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. The supernatant obtained in step 4.3 is collected and filtered to obtain the extract (hexane-soluble component). 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 left 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 carbon resource may be completed when the spontaneous heat generation inhibitor for a first carbon resource is obtained, but the following second step may also be 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 is thoroughly mixed with toluene and allowed to stand. The liquid portion is then recovered and the toluene is removed from the liquid portion. This yields a spontaneous heat generation inhibitor for a second carbon resource. As shown in the examples, the spontaneous heat generation inhibitor for a second carbon resource has sufficient spontaneous heat generation suppression 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 tubes are 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.
- step 11 the extraction residue in the centrifuge tube is subjected to steps 2 to 4, which are repeated twice (for a total of three times) with the solvent changed from 50 cc of hexane to 50 cc of toluene. 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 spontaneous heat generation inhibitor for the second carbon resource often contains more naphthenic ring carbon atoms than the spontaneous heat generation inhibitor for the first carbon resource. Therefore, the spontaneous heat generation inhibitor for the second carbon resource can more reliably suppress the spontaneous heat generation of the carbon resource than the spontaneous heat generation inhibitor for the first carbon resource. Because this production method is a simple method involving solvent fractionation of the carbon resource or the carbon resource dry distillation product, the spontaneous heat generation inhibitor for the carbon resource can be produced at low cost and does not generate CO2 gas during production.
- the spontaneous heat generation inhibitor according to this embodiment only needs to contain naphthenic ring carbon atoms in a proportion of 1 mmol/g or more, so a substance having such a molecular structure may be directly produced by organic synthesis. Substances obtained in this way also constitute spontaneous heat generation inhibitors according to this embodiment.
- the spontaneous heat generation inhibitor for a carbon resource according to this embodiment is added in an amount of 1 mass % or more relative to the carbon resource.
- a sufficient spontaneous heat generation suppression effect can be obtained by adding the agent for suppressing spontaneous heat generation of a carbon resource according to this embodiment in an amount of 1 mass % or more relative to the carbon resource.
- the spontaneous heat generation inhibitor is preferably added in an amount of 3% by mass or more, and even more preferably 5% by mass or more, relative to the carbon resource.
- the upper limit of the mass ratio is not particularly limited, but may be, for example, 30% by mass.
- Carbon resource storage methods In the method for storing a carbon resource according to this embodiment, the mixture obtained by the method for suppressing spontaneous heat generation of a carbon resource is stored.
- 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 of a carbon resource characterized by containing naphthenic ring carbon atoms in a proportion of 1 mmol/g or more as a spontaneous heat generation inhibitor.
- the present disclosure also includes use of a spontaneous heat generation inhibitor of a carbon resource characterized by containing naphthenic ring carbon atoms in a ratio of 5 mmol/g or more as a spontaneous heat generation inhibitor.
- This carbon resource spontaneous heat inhibitor may have the features of the above-described embodiments.
- Example 1 Next, an example of this embodiment will be described.
- acacia-derived woody biomass charcoal was prepared as a carbon resource whose spontaneous heat generation is to be suppressed.
- Acacia-derived woody biomass charcoal has a high spontaneous heat generation property.
- a spontaneous heat generation inhibitor for carbon resources was prepared using the following process.
- petroleum-based pitch (ASP) was prepared.
- commercially available petroleum-based pitch was used.
- 2 g of petroleum-based pitch was extracted with 50 cc of hexane (first process) using the procedure described in the above embodiment. The extraction was performed at a temperature of 25°C and atmospheric pressure.
- an additive which is the residue obtained by evaporating the hexane, was obtained.
- HS corresponds to the first spontaneous heat generation inhibitor for carbon resources in the above embodiment.
- HI-TS additive
- TI additive
- the average molecular structures of HS, HI-TS, and TI were determined by the method described above. That is, elemental analysis of HS, HI-TS, and TI was performed according to a method in accordance with JIS M 8813 or JIS M 8819, and the mass percentage of each element was determined. Next, 1 H NMR measurement and 13 C NMR measurement were performed (the solvent was deuterated chloroform). Based on these results, the average molecular structure was constructed. The specific construction of the average molecular structure was performed according to Yuki Hata, et al., ISIJ International, Vol. 62 (2022), No. 5, pp. 948-95.
- the molecular weight was determined from the average molecular structure thus determined, and the content of naphthenic ring carbon atoms was calculated based on the molecular weight and the number of naphthenic ring carbon atoms contained in the average molecular structure.
- HS and HI-TS contain naphthenic ring carbon atoms at a ratio of 1 mmol/g or more, and therefore correspond to the spontaneous heat generation inhibitor for carbon resources according to the above-mentioned embodiment.
- the horizontal axis represents the elapsed time (min) from the start of the spontaneous heating evaluation test
- the vertical axis represents the sample temperature.
- Graph L1 shows the test results when the sample is made of only carbon resources
- graph L2 shows the test results when the sample is made of carbon resources to which 5% by mass of HS has been added
- graph L3 shows the test results when the sample is made of carbon resources to which 5% by mass of HI-TS has been added
- graph L4 shows the test results when the sample is made of carbon resources to which 5% by mass of TI has been added.
- Example 2 In this example, an experiment similar to that in Example 1 was carried out to examine the time required to reach 200°C when the amount of spontaneous heat generation inhibitor added was changed.
- the carbon resource to be suppressed from spontaneous heating was the above-mentioned 10 g of acacia-derived wood biomass charcoal, to which additive (HS), additive (HI-TS), and additive (TI) were added in amounts of 1, 3, or 5 mass%.
- Table 2 shows that adding 1% by mass or more of the spontaneous heat generation inhibitor for carbon resources according to this embodiment to carbon resources produces significant effects.
- the present disclosure it is possible to provide a spontaneous heat generation inhibitor for carbon resources that can more reliably suppress spontaneous heat generation in carbon resources. 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 can more reliably suppress spontaneous heat generation in carbon resources. Therefore, the invention according to the present disclosure is extremely useful industrially.
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Abstract
Description
本願は、2024年3月15日に、日本に出願された特願2024-040976号に基づき優先権を主張し、その内容をここに援用する。
本開示は、上記問題に鑑みてなされたものであり、本開示の目的は、炭素資源の自然発熱をより確実に抑制することが可能な、炭素資源の自然発熱抑制剤を提供することにある。
(1)
ナフテン環炭素原子を1mmol/g以上の割合で含む、ことを特徴とする炭素資源の自然発熱抑制剤。
(2)
ナフテン環炭素原子を5mmol/g以上の割合で含む、ことを特徴とする(1)に記載の炭素資源の自然発熱抑制剤。
(3)
前記ナフテン環炭素原子を有するナフテン環に不飽和炭素結合を有する、ことを特徴とする(1)または(3)に記載の炭素資源の自然発熱抑制剤。
(4)
前記不飽和炭素結合が芳香族炭素結合である、ことを特徴とする(3)に記載の炭素資源の自然発熱抑制剤。
(5)
分子構造内に縮合環構造を有し、ナフテン環炭素原子が前記縮合環構造に含まれている、ことを特徴とする(1)または(2)に記載の炭素資源の自然発熱抑制剤。
(6)
分子量200~1000の混合物からなる、ことを特徴とする(1)から(5)のいずれか1項に記載の炭素資源の自然発熱抑制剤。
(7)
常温で固体である、ことを特徴とする(1)から(6)のいずれか1項に記載の炭素資源の自然発熱抑制剤。
(8)
炭素資源または前記炭素資源の乾留生成物に含まれる成分である、ことを特徴とする(1)~(7)のいずれか1項に記載の炭素資源の自然発熱抑制剤。
(9)
(1)~(8)のいずれか1項に記載の炭素資源の自然発熱抑制剤を前記炭素資源に対して1質量%以上添加する工程を含む、ことを特徴とする炭素資源の自然発熱抑制方法。
(10)
(9)に記載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、ことを特徴とする炭素資源の貯蔵方法。
炭素資源の自然発熱には、炭素資源に含まれる物質に生成したフリーラジカルが関与しているとの指摘がある。また、ナフテン環炭素は水素供与性があり、例えば、石炭液化反応において、石炭の熱分解ラジカルに水素を供与して、石炭由来の低分子を安定化させる化学的性質が重要であるとされている。自然発熱とは、酸素雰囲気下における発熱を意味し、常圧下の空気中における発熱も意味する。
ナフテン環を構成する環状構造は、単一の環状構造であってもよく、複数の環状構造が縮合したものであってもよい。
なお、上記の例では分子構造の一部のみを示しており、本実施形態に係る自然発熱抑制剤を構成する化合物が上記のような化合物を有するとは限らない。すなわち、後述する化合物の構造の一部として、上記のようなナフテン環が含まれていてもよい。例えば、上記のナフテン環を構成する炭素原子のいずれかが、炭素原子、あるいは他の官能基と結合して化合物を構成していてもよい。
本実施形態に係る炭素資源の自然発熱抑制剤(以下では、単に「自然発熱抑制剤」とも称する)は、ナフテン環を含む分子構造を有する物質であって、ナフテン環炭素原子を1mmol/g以上の割合で含む。上述したように、ナフテン環炭素原子は、水素供与性能がある。このため、ナフテン環炭素原子から放出された水素原子が炭素資源の自然発熱を誘起しうるフリーラジカルを捕捉し、炭素資源の自然発熱が抑制される。ただし、後述する実施例に示されるように、このような効果は、自然発熱抑制剤にナフテン環炭素原子が少なくとも1mmol/g含まれる場合に得られる。
また、ナフテン環炭素原子の含有量の上限値は特に制限されないが、30mmol/g以下、25mmol/g以下、あるいは15mmol/g以下であってもよい。
各元素の含有量は、JIS M 8813:2006に準拠した方法で、自然発熱抑制剤の元素分析を行うことで求める。
1H NMR測定の結果からは、Ha、Hα、Hβ及びHγの4種のHの存在割合がわかる。Hの存在割合とは、自然発熱抑制剤に含まれる全てのHに対する、Ha、Hα、Hβ又はHγのそれぞれの割合である。
4種のHは、1H NMRスペクトルにおいて、Ha:9.0-6.0ppm、Hα:5.0-2.0ppm、Hβ:2.0-1.05ppm、Hγ:1.05-0.5ppmという範囲の化学シフト値を示すため、これらのHを判別できる。
溶媒は、重クロロホルム等の重溶媒を使用する。1H NMRスペクトルはSingle Pulse法で測定する。13C NMRスペクトルでは、Single Pulse法で測定し、NOE(核オーバーハウザー効果)は使用しない。
FD-MS法を用いて、分子量を測定し、分子量のピークを測定した。具体的には、試料1mgをテトラヒドロフランに溶解させ、エミッター(約10μmΦのタングステンワイヤー表面に炭素ウィスカーが付着)に塗布し、高真空下でエミッターに印加する電流を調整しながら、高電界と合わせて直接試料分子をソフトにイオン化し、質量分析計で質量スペクトルを取得する。検出器の電圧は2200Vとし、測定質量範囲は50~1600m/z、ドリフト補正はC20H16の質量数(252.09396)で行う。
つぎに、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。本発明者は、炭素資源の自然発熱抑制剤は、炭素資源または炭素資源の乾留生成物に含まれる成分であることを見出した。したがって、溶媒分画により炭素資源または炭素資源の乾留生成物から本実施形態に係る炭素資源の自然発熱抑制剤を抽出することができる。
ここで、炭素資源の自然発熱抑制剤の原料としての炭素資源と、自然発熱を抑制すべき炭素資源の2つの炭素資源の存在を前提に説明するが、これら2つの炭素資源は、同じ炭素資源であってもよく、相異なるものであってもよい。
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することで、ヘキサン可溶成分およびヘキサン不溶成分を得る。
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の抽出残渣に、溶媒ヘキサン50ccからトルエン50ccに変更して2~4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。
本実施形態に係る炭素資源の自然発熱抑制方法では、本実施形態に係る炭素資源の自然発熱抑制剤を炭素資源に対して1質量%以上添加する。実施例で示されるように、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。
均質に混錬するという理由から、自然発熱抑制剤を炭素資源に対して3質量%以上添加することがより好ましい。5質量%以上添加することが更に好ましい。また、質量比の上限は特に制限されないが、例えば30質量%であってもよい。
本実施形態に係る炭素資源の貯蔵方法では、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。
ナフテン環炭素原子を1mmol/g以上の割合で含むことを特徴とする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。
ナフテン環炭素原子を5mmol/g以上の割合で含むことを特徴とする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。
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。
グラフL1は試料が炭素資源のみとなる場合の試験結果を示し、グラフL2は試料が炭素資源にHSを5質量%添加したものとなる場合の試験結果を示し、グラフL3は試料が炭素資源にHI-TSを5質量%添加したものとなる場合の試験結果を示し、グラフL4は試料が炭素資源にTIを5質量%添加したものとなる場合の試験結果を示す。
本実施例では、実施例1と同様の実験を行い、自然発熱抑制剤の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炭素資源は上述した10gのアカシア由来の木質バイオマス炭材とし、これに、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。
Claims (10)
- ナフテン環炭素原子を1mmol/g以上の割合で含む、
ことを特徴とする炭素資源の自然発熱抑制剤。 - ナフテン環炭素原子を5mmol/g以上の割合で含む、
ことを特徴とする請求項1に記載の炭素資源の自然発熱抑制剤。 - 前記ナフテン環炭素原子を有するナフテン環に不飽和炭素結合を有する、
ことを特徴とする請求項1または2に記載の炭素資源の自然発熱抑制剤。 - 前記不飽和炭素結合が芳香族炭素結合である、
ことを特徴とする請求項3に記載の炭素資源の自然発熱抑制剤。 - 分子構造内に縮合環構造を有し、ナフテン環炭素原子が前記縮合環構造に含まれている、
ことを特徴とする請求項1から4のいずれか1項に記載の炭素資源の自然発熱抑制剤。 - 分子量200~1000の混合物からなる、
ことを特徴とする請求項1から5のいずれか1項に記載の炭素資源の自然発熱抑制剤。 - 常温で固体である、
ことを特徴とする請求項1から6のいずれか1項に記載の炭素資源の自然発熱抑制剤。 - 炭素資源または前記炭素資源の乾留生成物に含まれる成分である、
ことを特徴とする請求項1から7のいずれか1項に記載の炭素資源の自然発熱抑制剤。 - 請求項1から8のいずれか1項に記載の炭素資源の自然発熱抑制剤を、前記炭素資源に対して1質量%以上添加する工程を含む、
ことを特徴とする炭素資源の自然発熱抑制方法。 - 請求項9に記載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、
ことを特徴とする炭素資源の貯蔵方法。
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