WO2014125672A1 - Carbon-based material and method for producing same - Google Patents
Carbon-based material and method for producing same Download PDFInfo
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- WO2014125672A1 WO2014125672A1 PCT/JP2013/076909 JP2013076909W WO2014125672A1 WO 2014125672 A1 WO2014125672 A1 WO 2014125672A1 JP 2013076909 W JP2013076909 W JP 2013076909W WO 2014125672 A1 WO2014125672 A1 WO 2014125672A1
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- carbonaceous material
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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
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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 carbonaceous material containing amorphous carbon and a method for producing the same. Moreover, this invention relates to the solid acid and adsorbent which consist of the said carbonaceous material. Furthermore, this invention relates to the hydrolysis method using the solid acid which consists of said carbonaceous material as a catalyst.
- Amorphous carbon is used in various fields because it has excellent thermal and chemical stability and can be produced at low cost.
- Amorphous carbon generally refers to carbon that does not have a clear crystal structure, such as diamond or graphite.
- Amorphous carbon can be obtained by a method of carbonizing an organic substance under relatively mild conditions.
- Patent Documents 1 and 2 disclose that amorphous carbon into which sulfo groups are introduced can be obtained by heat-treating polycyclic aromatic hydrocarbons such as naphthalene, anthracene, perylene, coronene in concentrated sulfuric acid or fuming sulfuric acid. Is described.
- Patent Document 3 describes that amorphous carbon can be obtained by using cellulose as an organic substance and carbonizing the cellulose at 450 ° C. for 5 hours. It is described that amorphous carbon into which a sulfo group is introduced can be obtained by heat-treating the amorphous carbon in concentrated sulfuric acid or fuming sulfuric acid. It is described that this amorphous carbon having a sulfo group introduced is thermally and chemically stable and acts as a solid acid.
- a carbonaceous material having an acidic functional group such as a sulfo group
- the use value increases as the acid point increases.
- acid point an acidic functional group
- the adsorbing point increases as the acid point increases, resulting in an excellent adsorbent. Therefore, development of a carbonaceous material having a higher acid point has been desired.
- JP 2004-238111 A International Publication No. 2005/029508 JP 2009-268960 A
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a carbonaceous material containing amorphous carbon and having many acid points and a method for producing the same.
- the above problem is a carbonaceous material containing amorphous carbon; the amorphous carbon contains a graphene sheet, the carbonaceous material has a sulfo group, and the ratio of sulfur atoms to carbon atoms (S / C) is
- the peak temperature is in the range of 175 to 200 ° C.
- the acid score determined from the amount of ammonia desorbed at 100 to 400 ° C. is 30 ⁇ mol. It is solved by providing a carbonaceous material characterized by being / g or more.
- the ratio of hydrogen atoms to carbon atoms is preferably less than 1. It is also preferred that the total pore volume determined by the BJH method is 0.02 to 1 cm 3 / g and the average pore diameter is 2 to 30 nm.
- metal oxide particles are dispersed in an amorphous carbon matrix. It is also preferable that the coercive force is 500 Oe or less and the saturation magnetization is 0.1 emu / g or more.
- the above problem can also be solved by providing a solid acid made of the above carbonaceous material. Moreover, the said subject is solved also by providing the adsorbent which consists of the said carbonaceous material.
- the above-mentioned problem is a method for producing a carbonaceous material; a first step of mixing a water-soluble metal salt and a water-soluble polysaccharide in the presence of water, and carbonizing the mixture obtained in the first step.
- This can also be solved by providing a method for producing a carbonaceous material comprising a second step and a third step of sulfonating the carbide obtained in the second step.
- the mixture obtained in the first step is preferably heated at a temperature of 80 ° C. or higher in an inert gas atmosphere.
- the above-mentioned problem can also be solved by providing a cellulose hydrolysis method characterized by hydrolyzing cellulose using the solid acid as a catalyst.
- FIG. 3 is a diagram showing the result of 13 C-NMR measurement of the carbonaceous material of Example 1 after sulfonation treatment.
- FIG. 6 is a graph showing the measurement results of the carbonaceous materials of Examples 1 to 5 after sulfonation treatment by the ammonia temperature programmed desorption method. It is the figure which showed the result of the Raman spectroscopic measurement of the carbide
- FIG. 6 is a diagram showing magnetization curves of carbonaceous materials of Examples 1 to 5 after sulfonation treatment. It is the figure which showed the magnetization curve of the carbide
- the carbonaceous material of the present invention contains amorphous carbon.
- amorphous carbon generally refers to a substance made of carbon that does not have a clear crystal structure, such as diamond or graphite. It can be confirmed by measurement by X-ray diffraction that the carbonaceous material of the present invention contains amorphous carbon. Amorphous carbon does not detect a sharp peak in X-ray diffraction, or even if a peak is detected, the shape of the peak is broad. For example, in the case of the carbonaceous material obtained in the Examples of the present application, a broad peak is observed in the powder X-ray diffraction pattern near the half width (2 ⁇ ) of 10 to 30 °, and the carbonaceous material contains amorphous carbon. It can be seen that it does not contain carbon with a clear crystal structure.
- amorphous carbon includes a graphene sheet.
- the graphene sheet has a structure in which aromatic rings are condensed and connected on a two-dimensional plane.
- a peak called a D band caused by a carbon atom having a dangling bond is detected in the vicinity of 1350 cm ⁇ 1 in the Raman spectrum.
- the average size of the graphene sheet can be calculated based on the ratio (D / G) of the D band peak intensity to the G band peak intensity by Raman spectrum.
- the ratio (D / G) was about 0.8, and the average size of the graphene sheet contained therein was about 1 nm.
- a small ratio (D / G) indicates that the graphene sheet is large in size, and the resulting amorphous carbon has a homogeneous and stable structure.
- the ratio (D / G) is large, the resulting amorphous carbon is chemically active.
- the ratio (D / G) is preferably from 0.1 to 2.25, and more preferably from 0.5 to 2.0.
- the carbonaceous material of the present invention has a sulfo group, and the ratio of sulfur atom to carbon atom (S / C) is 0.005 to 0.15.
- the ratio of sulfur atoms to carbon atoms is less than 0.005
- the amount of sulfo groups (acidic functional groups) introduced into the carbonaceous material decreases, and a carbonaceous material having many acid sites cannot be obtained.
- the ratio of the sulfur atom to the carbon atom exceeds 0.15, the graphene sheet does not grow, and a carbonaceous material containing amorphous carbon cannot be obtained.
- the carbonaceous material of the present invention may have other acidic functional groups such as a carboxyl group and a hydroxyl group.
- the carbonaceous material of the present invention has a peak temperature in the range of 175 to 200 ° C. in the ammonia temperature-programmed desorption method, and has an acid point of 30 ⁇ mol / g or more determined from the amount of ammonia desorbed at 100 to 400 ° C. It is characterized by being. Conventionally, it is known that a solid acid in which a sulfo group is introduced into amorphous carbon can be obtained by carbonizing and sulfonating cellulose. The carbonaceous material of the present invention is characterized by having more acid sites than conventional solid acids.
- the acid point is less than 30 ⁇ mol / g, when the carbonaceous material of the present invention is used as a solid acid or an adsorbent, there is a possibility that excellent performance cannot be obtained.
- the acid point is preferably 50 ⁇ mol / g or more, and more preferably 100 ⁇ mol / g or more.
- the upper limit of the acid score is not particularly limited, but the acid score is usually 1000 ⁇ mol / g or less.
- the ammonia temperature-programmed desorption method (hereinafter sometimes abbreviated as NH 3 -TPD method) is a method in which ammonia is adsorbed to a solid sample and then the temperature is continuously increased by controlling the temperature at a constant rate. The amount of ammonia desorbed and the desorption temperature are measured.
- NH 3 -TPD method ammonia adsorbed at a weak acid site is desorbed at a low temperature, and ammonia adsorbed at a strong acid site is desorbed at a high temperature. Therefore, the acid strength of the solid sample can be measured from the peak temperature, and the acid point number of the solid sample can be measured from the total amount of desorbed ammonia.
- the carbonaceous material of the present invention preferably has a ratio of hydrogen atoms to carbon atoms (H / C) of less than 1.
- the ratio (H / C) is more preferably 0.8 or less.
- the ratio (H / C) is preferably 0.1 or more.
- the ratio (H / C) is more preferably 0.2 or more.
- the total pore volume determined by the BJH method is preferably 0.02 to 1 cm 3 / g.
- the total pore volume is less than 0.02 cm 3 / g, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material.
- the total pore volume exceeds 1 cm 3 / g, the mechanical strength of the carbonaceous material may be reduced.
- the average pore diameter determined by the BJH method is preferably 2 to 30 nm.
- the average pore diameter is less than 2 nm, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material.
- the average pore diameter exceeds 30 nm, the mechanical strength of the carbonaceous material may decrease.
- the carbonaceous material of the present invention has a BET specific surface area of 10 to 300 m 2 / g. If the BET specific surface area is less than 10 m 2 / g, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material, while if the BET specific surface area exceeds 300 m 2 / g, carbon The mechanical strength of the quality material may be reduced.
- metal oxide particles are preferably dispersed in an amorphous carbon matrix.
- Metal oxide is not particularly limited, iron, cobalt, nickel, chromium, manganese, magnesium, vanadium, yttrium, titanium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, aluminum, tin, sodium, lithium, Beryllium, potassium, calcium, scandium, rubidium, strontium, gallium, copper, molybdenum, zinc, cesium, platinum, gold, iridium, thorium, thallium, bismuth, lead, mercury, cerium, lanthanum, tungsten, niobium, neodymium, barium, Examples thereof include oxides such as gadolinium, samarium, and dysprodium.
- the oxide is iron oxide
- the type of iron oxide is not particularly limited, and examples thereof include magnetite (Fe 3 O 4 ), hematite ( ⁇ -Fe 2 O 3 ), maghemite ( ⁇ -Fe 2 O 3 ), and the like.
- the amorphous carbon matrix may contain a sulfate, and examples thereof include iron (III) sulfate (Fe 2 (SO 4 ) 3 ).
- the oxide particles are preferably fine.
- the average particle size of the oxide particles is preferably 2 to 100 nm, and more preferably 5 to 50 nm.
- the average particle diameter of the oxide particles is obtained by taking a transmission electron micrograph (TEM image) of the carbonaceous material and measuring the diameter of the particles in the obtained photograph. If the particles are not circular, the equivalent circle diameter is the diameter.
- the total ratio of metal atoms to carbon atoms is 0.001 to 0.5. It is preferable that If the ratio of metal atoms to carbon atoms (Metal / C) is less than 0.001, the acid score may be lowered.
- the metal atom is iron, cobalt, nickel, chromium, manganese, barium, gadolinium, samarium, dysprodium or the like, the carbonaceous material is insufficiently magnetized, and it may be difficult to control the movement by an external magnetic field.
- the total ratio of metal atoms to carbon atoms is preferably 0.005 or more, and more preferably 0.01 or more.
- the total ratio of metal atoms to carbon atoms exceeds 0.5, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material.
- the ratio of the total number of metal atoms to carbon atoms is preferably 0.25 or less, and more preferably 0.1 or less.
- the coercive force is small, that is, soft magnetism.
- the coercive force is preferably 500 Oe or less, more preferably 200 Oe or less, and further preferably 100 Oe or less.
- the coercive force exceeds 500 Oe, residual magnetization increases, and carbonaceous materials may be magnetically aggregated. Therefore, it is preferable that hysteresis is hardly seen in the magnetization curve of the carbonaceous material of the present invention.
- the saturation magnetization of the carbonaceous material is preferably 0.1 emu / g or more.
- the saturation magnetization is more preferably 2 emu / g or more.
- the upper limit of saturation magnetization is not particularly limited as long as it does not impair the effects of the present invention, but is usually 100 emu / g or less.
- the production method of the carbonaceous material of the present invention is not particularly limited, but the preferred production method includes a first step of mixing a water-soluble metal salt and a water-soluble polysaccharide in the presence of water.
- the second step of carbonizing the mixture obtained in the first step and the third step of sulfonating the carbide obtained in the second step are provided.
- the metal salt used in the first step is not particularly limited as long as it is a water-soluble metal salt.
- the cation component of the metal salt is not particularly limited, and iron, cobalt, nickel, chromium, manganese, magnesium, vanadium, yttrium, titanium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, aluminum, tin, sodium, Lithium, beryllium, potassium, calcium, scandium, rubidium, strontium, gallium, copper, molybdenum, zinc, cesium, platinum, gold, iridium, thorium, thallium, bismuth, lead, mercury, cerium, lanthanum, tungsten, niobium, neodymium, Examples include ions such as barium, gadolinium, samarium, dysprodium.
- the cation component of the metal salt is an ion such as iron, cobalt, nickel, chromium, manganese, barium, gadolinium, samarium, dysprodium, etc.
- an oxide that can control the movement of the carbonaceous material by an external magnetic field Particles can be formed.
- the anion component of the metal salt is not particularly limited, and examples thereof include nitrate ion, chloride ion, sulfate ion, phosphate ion, carbonate ion, borate ion, and carboxylic acid.
- nitrate ions are preferable because the decomposition temperature is low and the anion component does not remain after decomposition.
- one type of metal salt can be used alone, or two types of metal salts can be used in combination.
- the polysaccharide used in the first step is not particularly limited as long as it is a water-soluble polysaccharide.
- the polysaccharide include cellulose derivatives and salts thereof, starch, dextrin and the like. Among these, a cellulose derivative and a salt thereof are preferable, and a salt of a cellulose derivative is more preferable.
- Preferred examples of the cellulose derivative include carboxymethyl cellulose, and examples of the salt include alkali metal salts.
- the metal oxide particles can be dispersed in the amorphous carbon matrix by a subsequent carbonization treatment. Therefore, when obtaining a carbonaceous material in which metal oxide particles are dispersed in an amorphous carbon matrix, it is preferable to use a water-soluble polysaccharide.
- the mixing operation in the first step is not particularly limited.
- the polysaccharide powder may be added to and mixed with the metal salt aqueous solution, or the metal salt powder may be added to and mixed with the polysaccharide aqueous solution.
- Metal salt powder and polysaccharide powder may be added to water and mixed. Further, an aqueous solution of a metal salt and an aqueous solution of a polysaccharide may be mixed.
- the kind of water used at this time is not limited, and not only sufficiently purified water such as ion exchange water and distilled water but also tap water can be used.
- the mixture obtained in the first step is carbonized to obtain a carbide.
- the carbonization treatment is preferably performed by heating in an inert gas atmosphere such as argon gas or nitrogen gas. It is also preferable to carbonize the mixture obtained in the first step after drying in advance to remove moisture.
- the drying method is not particularly limited, and heat drying, reduced pressure drying, or the like can be employed.
- the drying temperature at the time of heat-drying will not be specifically limited if it is the temperature which can remove the water
- the drying temperature is more preferably 60 ° C. or higher.
- the drying temperature is usually 100 ° C. or less from the viewpoint of energy consumption and cost.
- the drying temperature at this time is a set temperature in the drying apparatus used for drying the mixture.
- the drying time is set in relation to the drying temperature, but may be set as appropriate so that water in the mixture can be sufficiently removed.
- the heating temperature in the second step is not particularly limited as long as the carbonization of the mixture proceeds, but is preferably 80 ° C. or higher. When the heating temperature is less than 80 ° C., the carbonization of the polysaccharide may be insufficient. Further, when a carbonaceous material in which metal oxide particles are dispersed in an amorphous carbon matrix is to be produced, if the heating temperature is less than 80 ° C., the metal salt may not be oxidized.
- the heating temperature at this time is a set temperature in the heating device used for carbonization of the mixture.
- the mixture obtained in the first step depends on the dry state and the type of metal salt used, but when heated to 80 ° C. or higher, self-combustion starts and the temperature of the mixture itself reaches 400 ° C.
- the heating temperature is more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher. On the other hand, it is also preferable that the heating temperature is 1000 ° C. or lower. When the heating temperature exceeds 1000 ° C., the graphene sheet in the carbonaceous material grows too much as a result of the progress of carbonization, which may make it difficult to introduce sulfo groups in the subsequent third step. From the viewpoint of energy consumption and cost, the heating temperature is more preferably 800 ° C. or less, and more preferably 600 ° C. or less.
- the heating time is set in relation to the heating temperature, but may be set as appropriate so that the carbonization of the polysaccharide proceeds sufficiently.
- the heating device is not particularly limited, and any heating device of an electric heating type, a hot air type, or a direct fire type can be used.
- a dust collector may be connected to the heating device in order to separate the gas generated by carbonization of the mixture from the solid particles contained in the gas.
- the dust collector is not particularly limited, and examples thereof include a cyclone dust collector and a filter dust collector. From the viewpoint of uniformity of carbonization treatment and continuous productivity of carbides, it is preferable to industrially use a rotary kiln to carbonize the mixture. Further, the generated gas is preferably exhausted after being previously washed with water or the like.
- the particle size of the carbide obtained in the second step is usually about several ⁇ m to several hundred ⁇ m, but it can be made finer by pulverization.
- a water-soluble metal salt or a water-soluble polysaccharide as a raw material may remain in the carbide obtained in the second step. Therefore, a step of washing carbide may be further added between the second step and the third step. By washing the carbide, metal salts and the like are removed, and a carbide having a larger specific surface area can be obtained.
- the method for washing the carbide is not particularly limited, such as a method of bringing water and carbide into contact with each other and extracting a metal salt contained in the carbide, a method of mixing water and carbide and then filtering using a filter medium, etc. Is mentioned.
- a Soxhlet extractor or the like can be used for extraction, and a Kiriyama funnel, a Buchner funnel, or the like can be used for filtration.
- cleaning is not specifically limited, Distilled water, ion-exchange water, etc. can be used. Further, an aqueous solution containing a small amount of acid such as hydrochloric acid or acetic acid may be used in order to efficiently remove metal salts and the like.
- the carbide obtained in the second step is sulfonated to obtain the carbonaceous material of the present invention.
- the sulfonation treatment method in the third step is not particularly limited as long as it is a method capable of introducing a sulfo group into the carbide, and examples thereof include a method using fuming sulfuric acid or concentrated sulfuric acid. At this time, it is preferable to treat with a mixed solution of fuming sulfuric acid and concentrated sulfuric acid, and heating is also preferable.
- the particle size of the carbonaceous material thus obtained is usually about several ⁇ m to several hundred ⁇ m, but it can be made finer by pulverization. Moreover, the carbonaceous material of a desired particle size can also be obtained by sieving using a sieve etc.
- a preferred embodiment of the present invention is a solid acid made of the above carbonaceous material. Since the carbonaceous material of the present invention has many strong acid sites on the surface, it becomes an excellent solid acid. In the carbonaceous material of the present invention, when metal oxide particles that react with magnetic force are dispersed in an amorphous carbon matrix, the movement of the carbonaceous material can be controlled by an external magnetic field. Therefore, it can also be used as a solid acid whose movement can be controlled by an external magnetic field.
- a preferred embodiment of the present invention is a cellulose hydrolysis method characterized by hydrolyzing cellulose using the solid acid as a catalyst.
- cellulose was hydrolyzed (saccharified), cellulose was hydrolyzed to produce disaccharide cellobiose and monosaccharide glucose.
- organic acids such as levoglucosan and formic acid, which are glucose degradation products, were produced.
- a stirrer is not put in a container containing cellulose and a carbonaceous material. It was also confirmed that the carbonaceous material can be stirred by an external magnetic field.
- a preferred embodiment of the present invention is an adsorbent made of the above carbonaceous material. Since the carbonaceous material of the present invention is porous and has many acid sites on its surface, it becomes an excellent adsorbent.
- the substance to be adsorbed on the carbonaceous material is not particularly limited, and examples thereof include alkali metal ions such as cesium ions, alkaline earth metal ions such as strontium ions, basic molecules such as methylene blue, and iodine. Since the carbonaceous material of the present invention has many strong acid sites (acidic functional groups) on the surface, an alkaline substance is suitable as the substance to be adsorbed.
- Example 1 Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 ⁇ 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in water 100 ml.
- 1.0 g of powdered sodium carboxymethylcellulose manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335, hereinafter sometimes abbreviated as CMC ⁇ Na
- CMC ⁇ Na powdered sodium carboxymethylcellulose
- Examples 2-5 The amount of iron (III) nitrate nonahydrate dissolved in 100 ml of water was 0.125 g (Example 2), 0.250 g (Example 3), 1.00 g (Example 4), 1.50 g (Example). After changing to 5) to obtain a carbide, a carbide was obtained in the same manner as in Example 1 except that the carbide was washed with distilled water for 6 hours or more using a Soxhlet extractor and then dried. And after sulfonating like Example 1, it washed and dried and obtained carbonaceous material.
- Example 6 Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 ⁇ 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in water 100 ml. Its cobalt (II) nitrate hexahydrate solution (Co (NO 3) 2 ⁇ 6H 2 O) was added and mixed 1.5 g. To the resulting aqueous solution, 1.0 g of powdery CMC ⁇ Na (manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335) was added and stirred to obtain a gel-like precipitate. And it dried at 65 degreeC for about 5 days using the constant temperature drying furnace until the water
- powdery CMC ⁇ Na manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335
- the dried precipitate was pulverized in an agate mortar.
- the pulverized precipitate was transferred to a three-necked flask and heated in a nitrogen atmosphere at 250 ° C. for 1 hour in the three-necked flask to obtain a carbide.
- Example 7 Carbide was obtained in the same manner as in Example 6 except that the amount of cobalt nitrate (II) hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 1.955 g of the obtained carbide was put into a mixed solution of 75 ml of fuming sulfuric acid (SO 3 concentration 20%) and 76 ml of concentrated sulfuric acid (concentration 96%), and 10 ° C. at 80 ° C. in a three-necked flask in a nitrogen atmosphere. The mixture was stirred for hours and subjected to sulfonation treatment. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 1.955 g of a carbonaceous material.
- SO 3 concentration 20% fuming sulfuric acid
- concentration 96% concentrated sulfuric acid
- Example 8 Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 ⁇ 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in water 100 ml. Its nickel (II) nitrate hexahydrate solution (Ni (NO 3) 2 ⁇ 6H 2 O) was added and mixed 1.5 g. To the resulting aqueous solution, 1.0 g of powdery CMC ⁇ Na (manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335) was added and stirred to obtain a gel-like precipitate. And it dried at 65 degreeC for about 5 days using the constant temperature drying furnace until the water
- powdery CMC ⁇ Na manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335
- the dried precipitate was pulverized in an agate mortar.
- the pulverized precipitate was transferred to a three-necked flask and heated in a nitrogen atmosphere at 250 ° C. for 1 hour in the three-necked flask to obtain a carbide.
- Example 9 Carbide was obtained in the same manner as in Example 8 except that the amount of nickel (II) nitrate hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 3.4168 g of the obtained carbide was put into a mixed solution of fuming sulfuric acid (SO 3 concentration 20%) 100 ml and concentrated sulfuric acid (concentration 96%) 100 ml, and in a three-neck flask at 80 ° C. in a nitrogen atmosphere. The mixture was stirred for hours and subjected to sulfonation treatment. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 3.4168 g of a carbonaceous material.
- SO 3 concentration 20% fuming sulfuric acid
- concentration 96% concentrated sulfuric acid
- Example 1 [Differential scanning thermal analysis] In Example 1, 3.554 mg of the carbide before the sulfonation treatment and 3.586 mg of the carbonaceous material after the sulfonation treatment were each measured in an air atmosphere using a differential heat / thermogravimetry apparatus (TG / DTA). Differential scanning calorimetry was performed under the temperature rising condition of ° C / min. The results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 1, in the carbide before the sulfonation treatment, an exothermic peak considered to be caused by oxidative decomposition was confirmed at around 330 ° C. and 420 ° C. Further, as shown in FIG.
- FIG. 3 is an electron micrograph (SEM image) of the carbide before the sulfonation treatment
- FIG. 4 is an electron micrograph (SEM image) of the carbonaceous material after the sulfonation treatment. From the photograph obtained, many holes of several nm to several tens of nm were confirmed in any sample.
- S-3000N manufactured by Hitachi High-Technologies Corporation was used.
- FIG. 9 is an electron micrograph (TEM image) of the carbonaceous material of Example 2 after sulfonation
- FIG. 9 is an electron micrograph (TEM image) of the carbonaceous material of Example 2 after sulfonation
- Example 10 is an electron micrograph (TEM image) of the carbonaceous material of Example 5 after sulfonation. ). From the obtained photographs, it was found that particles of about 5 to 50 nm were present in any sample. Here, when the particles were not circular, the equivalent circle diameter was taken as the diameter. As the transmission electron microscope apparatus, “EM002BF” manufactured by Topcon Techno House Co., Ltd. was used.
- FIG. 11 is a pore distribution curve analyzed by the BJH method for the carbide of Example 1 before the sulfonation treatment.
- FIG. 12 is a pore distribution curve analyzed by the BJH method for the carbonaceous material of Example 1 after sulfonation treatment.
- FIG. 13 is a pore distribution curve analyzed by the BJH method for the carbide of Example 6 before the sulfonation treatment.
- FIG. 14 is a pore distribution curve obtained by analyzing the carbide before sulfonation with the HK method.
- FIG. 15 is a pore distribution curve obtained by analyzing the carbonaceous material after the sulfonation treatment by the HK method.
- the specific surface area / pore distribution measuring apparatus used was “NOVE 4200e” manufactured by Quantachrome Instruments.
- the peak at half width (2 ⁇ ) around 45-50 ° is derived from sodium carbonate (Na 2 CO 3 ), and the carbide before the sulfonation treatment is sodium carbonate (Na 2 CO 3 ). It was found to contain.
- the broad peak with a half width (2 ⁇ ) of about 10 to 30 ° is derived from iron (III) sulfate and amorphous carbon, and the carbonaceous material after sulfonation treatment is sulfuric acid. It was found to further contain iron (III).
- FIG. 18 shows the measurement results of carbide before sulfonation.
- FIG. 19 shows the measurement results of the carbonaceous material after the sulfonation treatment. From the obtained results, the elements detected by the wide scan measurement were C 1s (carbon), N 1s (nitrogen), O 1s (oxygen), Fe 2p (iron), and Na 1s (sodium). Further, S 2p (sulfur) was also confirmed in the carbonaceous material after the sulfonation treatment.
- the measurement by narrow scan was also performed about the carbide
- a peak derived from maghemite ( ⁇ -Fe 2 O 3 ) a peak derived from an organic compound, a peak derived from SO 3 and SO 4, and a peak derived from Na 2 CO 3 Were confirmed.
- peaks derived from C—C (H), C—O, C ⁇ O, and —CO 3 were confirmed from the C 1s spectrum.
- maghemite ⁇ -Fe 2 O 3
- iron (III) sulfate Fe 2 (SO 4 ) 3
- the carbonaceous material after the sulfonation treatment was also confirmed to have peaks derived from SO 4 and SO 3 H groups of iron (III) sulfate in the S 2p spectrum.
- FIGS. As the X-ray photoelectron spectrometer, “Quantera SXM” manufactured by ULVAC-PHI Co., Ltd. was used.
- the carbide before the sulfonation treatment was analyzed on the assumption that all of the peaks were due to magnetic fission. As a result, the spectrum of the carbide before the sulfonation treatment could be interpreted as almost a single magnetic component ( ⁇ -Fe 2 O 3 ).
- the carbonaceous material after the sulfonation treatment is considered to contain iron (III) sulfate (Fe 2 (SO 4 ) 3 ) in addition to ⁇ -Fe 2 O 3 .
- the Neel point of Fe 2 (SO 4 ) 3 is 30K, it is considered to be consistent with the result of this measurement because it is paramagnetic at 78K.
- the carbonaceous material after sulfonation treatment the SO 3 to 1041cm -1
- the peak due to bending of OH to 1595 ⁇ 1603cm -1 was also confirmed.
- the Fourier transform infrared spectrometer “Nicolet 6700 FT-IR” manufactured by Thermo Fisher Scientific Co., Ltd. was used.
- the carbonaceous material after the sulfonation treatment has aromatic carbon, a sulfo group (SO 3 H group), a carboxyl group (COOH group), and a hydroxyl group (OH group). Further, since no signal appeared at 0 to 100 ppm, it was found that sp 3 carbon was hardly contained.
- the nuclear magnetic resonance apparatus “JNM-ECX400” manufactured by JEOL Ltd. was used.
- Preprocessing (1) A cell was filled with 0.05 g of a carbonaceous material. (2) While supplying helium to the cell at a flow rate of 50 mL / min, the temperature was increased to 400 ° C. at a temperature increase rate of 10 ° C./min. (3) When the temperature in the cell reached 400 ° C., helium was left for 1 hour while supplying the helium at a flow rate of 50 mL / min while maintaining the temperature.
- Ammonia adsorption treatment (1) The temperature in the cell was lowered to 100 ° C. Then, while maintaining the temperature, helium containing 0.5% by volume of ammonia was supplied into the cell at a flow rate of 100 mL / min for 30 minutes. (2) While maintaining the temperature in the cell at 100 ° C., helium was supplied at a flow rate of 50 mL / min for 30 minutes to remove ammonia in the cell.
- FIG. 27 The measurement results are shown in FIG. In FIG. 27, the horizontal axis indicates the temperature during the ammonia desorption treatment, and the vertical axis indicates the ammonia desorption amount converted per carbonaceous material weight. Table 3 shows the sum of the peak temperature value and the amount of ammonia desorbed during the ammonia desorption treatment.
- the strength and the number of acid points of carbon solid acids described in Examples of JP-A-2009-268960 were also measured. Specifically, the microcrystalline cellulose was heat-treated (carbonized) under a nitrogen gas flow, and then naturally cooled to obtain carbonized microcrystalline cellulose. Subsequently, the obtained carbonized microcrystalline cellulose was put into a mixed solution of sulfuric acid and fuming sulfuric acid, and was subjected to heat treatment (sulfonation treatment) under a nitrogen gas flow. Next, after sufficiently washing with water vapor, drying was performed to obtain a carbon solid acid of a control example. In accordance with the NH 3 -TPD method described above, the strength and the number of acid points of the carbon solid acid of the control example were measured. The measurement results are indicated by broken lines in FIG. Table 3 shows the sum of the peak temperature value and the amount of ammonia desorbed during the ammonia desorption treatment.
- ammonia adsorbed at weak acid sites is desorbed at a low temperature
- ammonia adsorbed at strong acid sites is desorbed at a high temperature. That is, in Table 3, the peak temperature value indicates the strength of the acid point.
- the total ammonia desorption amount indicates the adsorption point of ammonia existing on the sample surface, that is, the number of acid points.
- the strength of the acid point of the carbonaceous material after the sulfonation treatment of this example was almost the same as the carbon solid acid of the control example.
- the total amount of desorbed ammonia was higher for the carbonaceous material of this example than for the carbon solid acid of the control example. From this result, it was found that the carbonaceous material of this example had more acid sites than the carbon solid acid of the control example.
- the number of acid points varies depending on the amount of iron nitrate dissolved in water when the carbonaceous material is synthesized. In this example, when 1.00 g of iron nitrate was dissolved in 100 ml of water to obtain a carbonaceous material (Example 4), the acid point was the highest.
- the ratio of the D band to the peak intensity of the G band was about 0.8, and based on this, it was found that the average size of the graphene sheets contained in the carbide and the carbonaceous material was both about 1 nm.
- the Raman spectroscopic measurement apparatus “T-64000” manufactured by Jobin Yvon was used.
- the saturation magnetization of the carbide before the sulfonation treatment was about 12 emu / g, and the saturation magnetization of the carbonaceous material after the sulfonation treatment was about 6 emu / g.
- the magnetic properties of the carbonaceous materials of Examples 2 to 5 after the sulfonation treatment were also examined. The numerical values obtained by the measurement are shown in Table 4, and the magnetic curves are shown together in FIG. As shown in Table 4 and FIG. 30, the carbon material of Example 4 had the highest saturation magnetization value.
- the magnetic properties were measured by packing 63.84 mg of the carbide of Example 6 before sulfonation into an acrylic holder.
- the coercive force of the carbide of Example 6 before the sulfonation treatment was about 330.60 Oe
- the saturation magnetization was about 34.84 emu / g. 82.57 mg of the carbide of Example 8 before sulfonation was packed in an acrylic holder, and the magnetic properties were measured.
- the carbonaceous material of Example 8 before the sulfonation treatment had a coercive force of about 119.30 Oe and a saturation magnetization of about 26.15 emu / g.
- Table 4 shows the numerical values obtained by the measurement.
- FIG. 33 is a summary of FIGS. 29, 31, and 32.
- As the vibrating sample magnetometer “VSM-15” manufactured by Toei Industry Co., Ltd. was used.
- the sealed vial is immersed in a silicone oil bath (manufactured by As One Co., Ltd., model number: EO-200) placed on a strong magnetic stirrer (manufactured by Tokyo Glass Instrument Co., Ltd. model number: F-205D), The cellulose was hydrolyzed at a stirring speed of 400 rpm for 3 hours. Thereafter, the amount of glucose contained in the reaction solution in the sealed vial was measured by high performance liquid chromatography (manufactured by JASCO Corporation, model number: LC-2000 plus). The results are shown in FIG. As shown in FIG.
- microcrystalline cellulose is hydrolyzed and glucose (Glucose) is produced by using a carbonaceous material after sulfonation as a catalyst.
- glucose Glucose
- the amount of glucose produced was 0.211 mg.
- cellobiose, xylose, levoglucosan and formic acid were also confirmed. From this result, it was found that the carbonaceous material of Example 1 after the sulfonation treatment functions as a solid acid.
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Abstract
This carbon-based material contains amorphous carbon, and is characterized by the amorphous carbon containing graphene sheets, the carbon-based material having a sulfo- group, the ratio (S/C) of sulfur atoms to carbon atoms being 0.0005-0.15, and in an ammonia temperature-programmed desorption method, having a peak temperature in the range of 175-200°C and an acid center number determined from the amount of ammonia desorbed at 100-400°C of at least 30 μmol/g. As a result, it is possible to provide: a carbon-based material having numerous acid centers and containing amorphous carbon; and a method for producing same.
Description
本発明は無定形炭素を含む炭素質材料及びその製造方法に関する。また、本発明は上記炭素質材料からなる固体酸及び吸着剤に関する。さらに、本発明は上記炭素質材料からなる固体酸を触媒として用いる加水分解方法に関する。
The present invention relates to a carbonaceous material containing amorphous carbon and a method for producing the same. Moreover, this invention relates to the solid acid and adsorbent which consist of the said carbonaceous material. Furthermore, this invention relates to the hydrolysis method using the solid acid which consists of said carbonaceous material as a catalyst.
無定形炭素は、熱的、化学的安定性に優れ、低コストで製造できることから様々な分野で利用されている。無定形炭素とは、一般的に、ダイヤモンドやグラファイト(黒鉛)のような明確な結晶構造を持たないものをいう。無定形炭素は、比較的穏和な条件で有機物を炭化処理する方法などによって得ることができる。
Amorphous carbon is used in various fields because it has excellent thermal and chemical stability and can be produced at low cost. Amorphous carbon generally refers to carbon that does not have a clear crystal structure, such as diamond or graphite. Amorphous carbon can be obtained by a method of carbonizing an organic substance under relatively mild conditions.
ところで、近年、無定形炭素などの炭素質材料に化学的な処理を施すことにより当該炭素質材料に新たな機能を付加する手法が知られている。
By the way, in recent years, a method for adding a new function to a carbonaceous material by chemically treating the carbonaceous material such as amorphous carbon is known.
特許文献1及び2には、ナフタレン、アントラセン、ペリレン、コロネンなどの多環式芳香族炭化水素を濃硫酸あるいは発煙硫酸中で加熱処理することによりスルホ基が導入された無定形炭素が得られることが記載されている。
Patent Documents 1 and 2 disclose that amorphous carbon into which sulfo groups are introduced can be obtained by heat-treating polycyclic aromatic hydrocarbons such as naphthalene, anthracene, perylene, coronene in concentrated sulfuric acid or fuming sulfuric acid. Is described.
特許文献3には、有機物としてセルロースを用い、当該セルロースを450℃で5時間炭化処理することによって無定形炭素が得られることが記載されている。そして当該無定形炭素を濃硫酸または発煙硫酸中で加熱処理することにより、スルホ基が導入された無定形炭素が得られることが記載されている。スルホ基が導入されたこの無定形炭素は、熱的及び化学的に安定であり固体酸として作用することが記載されている。
Patent Document 3 describes that amorphous carbon can be obtained by using cellulose as an organic substance and carbonizing the cellulose at 450 ° C. for 5 hours. It is described that amorphous carbon into which a sulfo group is introduced can be obtained by heat-treating the amorphous carbon in concentrated sulfuric acid or fuming sulfuric acid. It is described that this amorphous carbon having a sulfo group introduced is thermally and chemically stable and acts as a solid acid.
スルホ基などの酸性官能基(酸点)を有する炭素質材料においては、酸点が多ければ利用価値が高まる。例えば、スルホ基が導入された炭素質材料を酸触媒として利用する場合、酸点が多くなれば触媒反応における活性点が増え、酸触媒としての利用価値が高まる。また、スルホ基が導入された炭素質材料を吸着剤として利用する場合、酸点が多くなれば吸着点が増えることになり、優れた吸着剤となる。そのため酸点のより多い炭素質材料の開発が望まれていた。
In a carbonaceous material having an acidic functional group (acid point) such as a sulfo group, the use value increases as the acid point increases. For example, when a carbonaceous material into which a sulfo group has been introduced is used as an acid catalyst, if the acid point increases, the active point in the catalytic reaction increases and the utility value as an acid catalyst increases. Further, when a carbonaceous material having a sulfo group introduced therein is used as an adsorbent, the adsorbing point increases as the acid point increases, resulting in an excellent adsorbent. Therefore, development of a carbonaceous material having a higher acid point has been desired.
本発明は上記課題を解決するためになされたものであり、無定形炭素を含み、かつ酸点の多い炭素質材料及びその製造方法を提供することを目的とするものである。
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a carbonaceous material containing amorphous carbon and having many acid points and a method for producing the same.
上記課題は、無定形炭素を含む炭素質材料であって;前記無定形炭素がグラフェンシートを含み、前記炭素質材料はスルホ基を有し、炭素原子に対する硫黄原子の比(S/C)が0.005~0.15であり、かつアンモニア昇温脱離法において、175~200℃の範囲にピーク温度を有するとともに、100~400℃で脱離するアンモニアの量から求められる酸点数が30μmol/g以上であることを特徴とする炭素質材料を提供することによって解決される。
The above problem is a carbonaceous material containing amorphous carbon; the amorphous carbon contains a graphene sheet, the carbonaceous material has a sulfo group, and the ratio of sulfur atoms to carbon atoms (S / C) is In the ammonia temperature-programmed desorption method, the peak temperature is in the range of 175 to 200 ° C., and the acid score determined from the amount of ammonia desorbed at 100 to 400 ° C. is 30 μmol. It is solved by providing a carbonaceous material characterized by being / g or more.
このとき、炭素原子に対する水素原子の比(H/C)が1未満であることが好ましい。BJH法により求められる全細孔容積が0.02~1cm3/gであり、平均細孔直径が2~30nmであることも好ましい。
At this time, the ratio of hydrogen atoms to carbon atoms (H / C) is preferably less than 1. It is also preferred that the total pore volume determined by the BJH method is 0.02 to 1 cm 3 / g and the average pore diameter is 2 to 30 nm.
また、無定形炭素のマトリックス中に金属の酸化物の粒子が分散してなることも好ましい。保磁力が500Oe以下であり、飽和磁化が0.1emu/g以上であることも好ましい。
It is also preferable that metal oxide particles are dispersed in an amorphous carbon matrix. It is also preferable that the coercive force is 500 Oe or less and the saturation magnetization is 0.1 emu / g or more.
上記課題は、上記炭素質材料からなる固体酸を提供することによっても解決される。また、上記課題は、上記炭素質材料からなる吸着剤を提供することによっても解決される。
The above problem can also be solved by providing a solid acid made of the above carbonaceous material. Moreover, the said subject is solved also by providing the adsorbent which consists of the said carbonaceous material.
上記課題は、炭素質材料の製造方法であって;水溶性の金属塩と水溶性の多糖とを水の存在下で混合する第1工程と、前記第1工程で得られた混合物を炭化させる第2工程と、前記第2工程で得られた炭化物をスルホン化処理する第3工程とを備えることを特徴とする炭素質材料の製造方法を提供することによっても解決される。
The above-mentioned problem is a method for producing a carbonaceous material; a first step of mixing a water-soluble metal salt and a water-soluble polysaccharide in the presence of water, and carbonizing the mixture obtained in the first step. This can also be solved by providing a method for producing a carbonaceous material comprising a second step and a third step of sulfonating the carbide obtained in the second step.
このとき、前記第2工程において、前記第1工程で得られた混合物を不活性ガス雰囲気下で80℃以上の温度で加熱することが好ましい。
At this time, in the second step, the mixture obtained in the first step is preferably heated at a temperature of 80 ° C. or higher in an inert gas atmosphere.
上記課題は、上記固体酸を触媒として用いセルロースを加水分解することを特徴とするセルロースの加水分解方法を提供することによっても解決される。
The above-mentioned problem can also be solved by providing a cellulose hydrolysis method characterized by hydrolyzing cellulose using the solid acid as a catalyst.
本発明により、無定形炭素を含み、かつ酸点の多い炭素質材料及びその製造方法を提供することができる。
According to the present invention, it is possible to provide a carbonaceous material containing amorphous carbon and having many acid points, and a method for producing the same.
本発明の炭素質材料は、無定形炭素を含む。ここで、無定形炭素とは、一般的に、ダイヤモンドやグラファイト(黒鉛)のような明確な結晶構造を持たない炭素からなる物質をいう。本発明の炭素質材料が無定形炭素を含むことは、X線回折法による測定で確認することができる。無定形炭素はX線回折において、シャープなピークが検出されないか、あるいはピークが検出されても、そのピークの形はブロードである。例えば、本願実施例で得られた炭素質材料の場合、粉末X線回折パターンにおいて半値幅(2θ)10~30°付近にブロードなピークが観測され、上記炭素質材料が無定形炭素を含み、明確な結晶構造を持った炭素を含まないことがわかる。
The carbonaceous material of the present invention contains amorphous carbon. Here, amorphous carbon generally refers to a substance made of carbon that does not have a clear crystal structure, such as diamond or graphite. It can be confirmed by measurement by X-ray diffraction that the carbonaceous material of the present invention contains amorphous carbon. Amorphous carbon does not detect a sharp peak in X-ray diffraction, or even if a peak is detected, the shape of the peak is broad. For example, in the case of the carbonaceous material obtained in the Examples of the present application, a broad peak is observed in the powder X-ray diffraction pattern near the half width (2θ) of 10 to 30 °, and the carbonaceous material contains amorphous carbon. It can be seen that it does not contain carbon with a clear crystal structure.
本発明の炭素質材料においては、無定形炭素がグラフェンシートを含む。ここで、グラフェンシートとは、芳香族環が2次元の平面上に縮合して連なった構造を有するものである。炭素質材料がグラフェンシートを含む場合、ラマンスペクトルにおいて、ダングリングボンドを持つ炭素原子に起因するDバンドとよばれるピークが1350cm-1付近に検出される。
In the carbonaceous material of the present invention, amorphous carbon includes a graphene sheet. Here, the graphene sheet has a structure in which aromatic rings are condensed and connected on a two-dimensional plane. When the carbonaceous material includes a graphene sheet, a peak called a D band caused by a carbon atom having a dangling bond is detected in the vicinity of 1350 cm −1 in the Raman spectrum.
グラフェンシートの平均的なサイズは、ラマンスペクトルによるGバンドのピーク強度に対するDバンドのピーク強度の比(D/G)を根拠に算出することができる。例えば、本願実施例で得られた炭素質材料では、比(D/G)が約0.8であり、そこに含まれるグラフェンシートの平均的なサイズが約1nmであった。一般的に、比(D/G)が小さいと、グラフェンシートのサイズが大きいこと示し、得られる無定形炭素は均質な安定した構造となる。一方、比(D/G)が大きいと、得られる無定形炭素は化学的に活性である。比(D/G)は、0.1~2.25であることが好適であり、0.5~2.0であることがより好適である。
The average size of the graphene sheet can be calculated based on the ratio (D / G) of the D band peak intensity to the G band peak intensity by Raman spectrum. For example, in the carbonaceous material obtained in the example of the present application, the ratio (D / G) was about 0.8, and the average size of the graphene sheet contained therein was about 1 nm. In general, a small ratio (D / G) indicates that the graphene sheet is large in size, and the resulting amorphous carbon has a homogeneous and stable structure. On the other hand, when the ratio (D / G) is large, the resulting amorphous carbon is chemically active. The ratio (D / G) is preferably from 0.1 to 2.25, and more preferably from 0.5 to 2.0.
本発明の炭素質材料はスルホ基を有し、炭素原子に対する硫黄原子の比(S/C)が0.005~0.15である。炭素原子に対する硫黄原子の比が0.005未満の場合、炭素質材料に導入されるスルホ基(酸性官能基)の量が少なくなり、多くの酸点を有する炭素質材料が得られない。一方、炭素原子に対する硫黄原子の比が0.15を超えるとグラフェンシートが成長せず、無定形炭素を含む炭素質材料が得られない。また、本発明の炭素質材料はスルホ基のほか、カルボキシル基や水酸基などの他の酸性官能基を有していてもよい。
The carbonaceous material of the present invention has a sulfo group, and the ratio of sulfur atom to carbon atom (S / C) is 0.005 to 0.15. When the ratio of sulfur atoms to carbon atoms is less than 0.005, the amount of sulfo groups (acidic functional groups) introduced into the carbonaceous material decreases, and a carbonaceous material having many acid sites cannot be obtained. On the other hand, if the ratio of the sulfur atom to the carbon atom exceeds 0.15, the graphene sheet does not grow, and a carbonaceous material containing amorphous carbon cannot be obtained. In addition to the sulfo group, the carbonaceous material of the present invention may have other acidic functional groups such as a carboxyl group and a hydroxyl group.
本発明の炭素質材料は、アンモニア昇温脱離法において、175~200℃の範囲にピーク温度を有するとともに、100~400℃で脱離するアンモニアの量から求められる酸点数が30μmol/g以上であることを特徴とする。従来、セルロースを炭化処理及びスルホン化処理することで、無定形炭素にスルホ基が導入された固体酸が得られることが知られている。本発明の炭素質材料は従来の固体酸よりも多くの酸点を有することに特徴がある。酸点数が30μmol/g未満の場合、本発明の炭素質材料を固体酸や吸着剤として用いた場合、優れた性能を得られないおそれがある。酸点数は50μmol/g以上あることが好適であり、100μmol/g以上であることがより好適である。一方、酸点数の上限は特に限定されないが、酸点数は通常1000μmol/g以下である。
The carbonaceous material of the present invention has a peak temperature in the range of 175 to 200 ° C. in the ammonia temperature-programmed desorption method, and has an acid point of 30 μmol / g or more determined from the amount of ammonia desorbed at 100 to 400 ° C. It is characterized by being. Conventionally, it is known that a solid acid in which a sulfo group is introduced into amorphous carbon can be obtained by carbonizing and sulfonating cellulose. The carbonaceous material of the present invention is characterized by having more acid sites than conventional solid acids. When the acid point is less than 30 μmol / g, when the carbonaceous material of the present invention is used as a solid acid or an adsorbent, there is a possibility that excellent performance cannot be obtained. The acid point is preferably 50 μmol / g or more, and more preferably 100 μmol / g or more. On the other hand, the upper limit of the acid score is not particularly limited, but the acid score is usually 1000 μmol / g or less.
ここで、アンモニア昇温脱離法(以下、NH3-TPD法と略すことがある)とは、固体試料にアンモニアを吸着させた後、一定の昇温速度に制御して連続的に昇温させてアンモニアを脱離させる方法であり、このとき脱離したアンモニアの量及び脱離温度を測定する。NH3-TPD法において、弱い酸点に吸着しているアンモニアは低い温度で脱離し、強い酸点に吸着しているアンモニアは高い温度で脱離する。したがって、ピーク温度から固体試料の酸強度を測定することができ、脱離したアンモニアの量の総和から固体試料の酸点数を測定することができる。
Here, the ammonia temperature-programmed desorption method (hereinafter sometimes abbreviated as NH 3 -TPD method) is a method in which ammonia is adsorbed to a solid sample and then the temperature is continuously increased by controlling the temperature at a constant rate. The amount of ammonia desorbed and the desorption temperature are measured. In the NH 3 -TPD method, ammonia adsorbed at a weak acid site is desorbed at a low temperature, and ammonia adsorbed at a strong acid site is desorbed at a high temperature. Therefore, the acid strength of the solid sample can be measured from the peak temperature, and the acid point number of the solid sample can be measured from the total amount of desorbed ammonia.
本発明の炭素質材料は、炭素原子に対する水素原子の比(H/C)が1未満であることが好適である。比(H/C)が1以上である場合、炭化が不十分となり、無定形炭素が得られないおそれがある。比(H/C)は0.8以下であることがより好適である。一方、比(H/C)は0.1以上であることが好適である。比(H/C)が0.1未満である場合、炭素質材料中のグラフェンシートが成長しすぎて化学的に安定化し、当該炭素質材料にスルホ基などの酸性官能基を導入することが難しくなるおそれがある。比(H/C)は0.2以上であることがより好適である。
The carbonaceous material of the present invention preferably has a ratio of hydrogen atoms to carbon atoms (H / C) of less than 1. When the ratio (H / C) is 1 or more, carbonization becomes insufficient, and amorphous carbon may not be obtained. The ratio (H / C) is more preferably 0.8 or less. On the other hand, the ratio (H / C) is preferably 0.1 or more. When the ratio (H / C) is less than 0.1, the graphene sheet in the carbonaceous material grows too much and is chemically stabilized, and acidic functional groups such as sulfo groups can be introduced into the carbonaceous material. May be difficult. The ratio (H / C) is more preferably 0.2 or more.
本発明の炭素質材料において、BJH法により求められる全細孔容積が0.02~1cm3/gであることが好適である。全細孔容積が0.02cm3/g未満である場合、炭素質材料にスルホ基などの酸性官能基を導入することが難しくなるおそれがある。一方、全細孔容積が1cm3/gを超えると、炭素質材料の機械的強度が低下するおそれがある。
In the carbonaceous material of the present invention, the total pore volume determined by the BJH method is preferably 0.02 to 1 cm 3 / g. When the total pore volume is less than 0.02 cm 3 / g, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material. On the other hand, if the total pore volume exceeds 1 cm 3 / g, the mechanical strength of the carbonaceous material may be reduced.
本発明の炭素質材料において、BJH法により求められる平均細孔直径が2~30nmであることが好適である。平均細孔直径が2nm未満である場合、炭素質材料にスルホ基などの酸性官能基を導入することが難しくなるおそれがある。一方、平均細孔直径が30nmを超えると、炭素質材料の機械的強度が低下するおそれがある。
In the carbonaceous material of the present invention, the average pore diameter determined by the BJH method is preferably 2 to 30 nm. When the average pore diameter is less than 2 nm, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material. On the other hand, if the average pore diameter exceeds 30 nm, the mechanical strength of the carbonaceous material may decrease.
本発明の炭素質材料のBET比表面積が10~300m2/gであることも好適である。BET比表面積が10m2/g未満である場合、炭素質材料にスルホ基などの酸性官能基を導入することが難しくなるおそれがある、一方、BET比表面積が300m2/gを超えると、炭素質材料の機械的強度が低下するおそれがある。
It is also preferred that the carbonaceous material of the present invention has a BET specific surface area of 10 to 300 m 2 / g. If the BET specific surface area is less than 10 m 2 / g, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material, while if the BET specific surface area exceeds 300 m 2 / g, carbon The mechanical strength of the quality material may be reduced.
本発明において、酸点の多い炭素質材料を得るためには、水溶性の金属塩と水溶性の多糖との混合物を炭化処理した後、スルホン化処理することが好適である。このとき得られる炭素質材料において、無定形炭素のマトリックス中に金属の酸化物の粒子が分散してなることが好ましい。金属の酸化物は特に限定されず、鉄、コバルト、ニッケル、クロム、マンガン、マグネシウム、バナジウム、イットリウム、チタン、ジルコニウム、ルテニウム、ロジウム、パラジウム、銀、カドニウム、インジウム、アルミニウム、スズ、ナトリウム、リチウム、ベリリウム、カリウム、カルシウム、スカンジウム、ルビジウム、ストロンチウム、ガリウム、銅、モリブデン、亜鉛、セシウム、白金、金、イリジウム、トリウム、タリウム、ビスマス、鉛、水銀、セリウム、ランタン、タングステン、ニオブ、ネオジム、バリウム、ガドリニウム、サマリウム、ジスプロジウム等の酸化物を挙げることができる。中でも、鉄、コバルト、ニッケル、クロム、マンガン、バリウム、ガドリニウム、サマリウム、ジスプロジウムなどの酸化物のように磁力に反応する粒子が無定形炭素のマトリックス中に分散している場合、外部磁場によって炭素質材料の動きを制御することができる。酸化物が酸化鉄である場合、酸化鉄の種類は特に限定されないが、マグネタイト(Fe3O4)、ヘマタイト(α-Fe2O3)、マグヘマイト(γ-Fe2O3)などが例示される。また、無定形炭素のマトリックス中に硫酸塩が含まれていてもよく、例えば、硫酸鉄(III)(Fe2(SO4)3)などが例示される。
In the present invention, in order to obtain a carbonaceous material having many acid points, it is preferable to carbonize a mixture of a water-soluble metal salt and a water-soluble polysaccharide and then to perform a sulfonation treatment. In the carbonaceous material obtained at this time, metal oxide particles are preferably dispersed in an amorphous carbon matrix. Metal oxide is not particularly limited, iron, cobalt, nickel, chromium, manganese, magnesium, vanadium, yttrium, titanium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, aluminum, tin, sodium, lithium, Beryllium, potassium, calcium, scandium, rubidium, strontium, gallium, copper, molybdenum, zinc, cesium, platinum, gold, iridium, thorium, thallium, bismuth, lead, mercury, cerium, lanthanum, tungsten, niobium, neodymium, barium, Examples thereof include oxides such as gadolinium, samarium, and dysprodium. In particular, when particles that react with magnetic force, such as oxides of iron, cobalt, nickel, chromium, manganese, barium, gadolinium, samarium, dysprodium, are dispersed in an amorphous carbon matrix, carbon is generated by an external magnetic field. The movement of the quality material can be controlled. When the oxide is iron oxide, the type of iron oxide is not particularly limited, and examples thereof include magnetite (Fe 3 O 4 ), hematite (α-Fe 2 O 3 ), maghemite (γ-Fe 2 O 3 ), and the like. The The amorphous carbon matrix may contain a sulfate, and examples thereof include iron (III) sulfate (Fe 2 (SO 4 ) 3 ).
酸化物の粒子は微細であることが好ましい。酸化物の粒子の平均粒径は2~100nmであることが好ましく、5~50nmであることがより好ましい。ここで、酸化物の粒子の平均粒径は、炭素質材料の透過型電子顕微鏡写真(TEM像)の撮影を行い、得られた写真中の粒子の直径を計測することによって得られる。粒子が円形でない場合には、円相当径を直径とする。
The oxide particles are preferably fine. The average particle size of the oxide particles is preferably 2 to 100 nm, and more preferably 5 to 50 nm. Here, the average particle diameter of the oxide particles is obtained by taking a transmission electron micrograph (TEM image) of the carbonaceous material and measuring the diameter of the particles in the obtained photograph. If the particles are not circular, the equivalent circle diameter is the diameter.
本発明の炭素質材料において、無定形炭素のマトリックス中に金属の酸化物の粒子が分散している場合、炭素原子に対する金属原子の合計の比(Metal/C)が0.001~0.5であることが好ましい。炭素原子に対する金属原子の比(Metal/C)が0.001未満であると、酸点数が低下するおそれがある。また、金属原子が鉄、コバルト、ニッケル、クロム、マンガン、バリウム、ガドリニウム、サマリウム、ジスプロジウムなどの場合、炭素質材料の磁性が不十分となり、外部磁場によって動きを制御し難くなるおそれがある。炭素原子に対する金属原子の合計の比(Metal/C)は0.005以上であることが好適であり、0.01以上であることがより好適である。一方、炭素原子に対する金属原子の合計の比(Metal/C)が0.5を超えると、炭素質材料にスルホ基などの酸性官能基を導入することが難しくなるおそれがある。炭素原子に対する金属原子の合計の比(Metal/C)は0.25以下であることが好適であり、0.1以下であることがより好適である。
In the carbonaceous material of the present invention, when metal oxide particles are dispersed in an amorphous carbon matrix, the total ratio of metal atoms to carbon atoms (Metal / C) is 0.001 to 0.5. It is preferable that If the ratio of metal atoms to carbon atoms (Metal / C) is less than 0.001, the acid score may be lowered. In addition, when the metal atom is iron, cobalt, nickel, chromium, manganese, barium, gadolinium, samarium, dysprodium or the like, the carbonaceous material is insufficiently magnetized, and it may be difficult to control the movement by an external magnetic field. The total ratio of metal atoms to carbon atoms (Metal / C) is preferably 0.005 or more, and more preferably 0.01 or more. On the other hand, if the total ratio of metal atoms to carbon atoms (Metal / C) exceeds 0.5, it may be difficult to introduce acidic functional groups such as sulfo groups into the carbonaceous material. The ratio of the total number of metal atoms to carbon atoms (Metal / C) is preferably 0.25 or less, and more preferably 0.1 or less.
炭素質材料に含まれる金属の酸化物の粒子が、磁力に反応する金属の酸化物の場合には、保磁力が小さいこと、すなわち軟磁性であることが好ましい。具体的には、保磁力が500Oe以下であることが好適であり、200Oe以下であることがより好適であり、100Oe以下であることがさらに好適である。保磁力が500Oeを超えると残留磁化が大きくなり、炭素質材料同士が磁気的に凝集するおそれがある。したがって、本発明の炭素質材料の磁化曲線は、ヒステリシスがほとんど見られないことが好ましい。
When the metal oxide particles contained in the carbonaceous material are metal oxides that react with magnetic force, it is preferable that the coercive force is small, that is, soft magnetism. Specifically, the coercive force is preferably 500 Oe or less, more preferably 200 Oe or less, and further preferably 100 Oe or less. When the coercive force exceeds 500 Oe, residual magnetization increases, and carbonaceous materials may be magnetically aggregated. Therefore, it is preferable that hysteresis is hardly seen in the magnetization curve of the carbonaceous material of the present invention.
炭素質材料の飽和磁化は0.1emu/g以上であることが好適である。飽和磁化が0.1emu/g未満である場合、外部磁場に対する炭素質材料の応答性が低下するため好ましくない。飽和磁化は2emu/g以上であることがより好適である。一方、飽和磁化の上限値は本発明の効果を阻害しない範囲であれば特に限定はされないが、通常100emu/g以下である。
The saturation magnetization of the carbonaceous material is preferably 0.1 emu / g or more. When the saturation magnetization is less than 0.1 emu / g, the responsiveness of the carbonaceous material to an external magnetic field is not preferable. The saturation magnetization is more preferably 2 emu / g or more. On the other hand, the upper limit of saturation magnetization is not particularly limited as long as it does not impair the effects of the present invention, but is usually 100 emu / g or less.
本発明の炭素質材料の製造方法は、特に限定されるものではないが、その好適な製造方法は、水溶性の金属塩と水溶性の多糖とを水の存在下で混合する第1工程と、前記第1工程で得られた混合物を炭化させる第2工程と、前記第2工程で得られた炭化物をスルホン化処理する第3工程とを備えるものである。
The production method of the carbonaceous material of the present invention is not particularly limited, but the preferred production method includes a first step of mixing a water-soluble metal salt and a water-soluble polysaccharide in the presence of water. The second step of carbonizing the mixture obtained in the first step and the third step of sulfonating the carbide obtained in the second step are provided.
第1工程で用いられる金属塩は、水溶性の金属塩であれば特に限定されない。上記金属塩のカチオン成分は特に限定されず、鉄、コバルト、ニッケル、クロム、マンガン、マグネシウム、バナジウム、イットリウム、チタン、ジルコニウム、ルテニウム、ロジウム、パラジウム、銀、カドニウム、インジウム、アルミニウム、スズ、ナトリウム、リチウム、ベリリウム、カリウム、カルシウム、スカンジウム、ルビジウム、ストロンチウム、ガリウム、銅、モリブデン、亜鉛、セシウム、白金、金、イリジウム、トリウム、タリウム、ビスマス、鉛、水銀、セリウム、ランタン、タングステン、ニオブ、ネオジム、バリウム、ガドリニウム、サマリウム、ジスプロジウム等のイオンを挙げることができる。中でも、上記金属塩のカチオン成分が、鉄、コバルト、ニッケル、クロム、マンガン、バリウム、ガドリニウム、サマリウム、ジスプロジウム等のイオンの場合、外部磁場によって炭素質材料の動きを制御することのできる酸化物粒子を形成することができる。上記金属塩のアニオン成分は特に限定されず、硝酸イオン、塩化物イオン、硫酸イオン、燐酸イオン、炭酸イオン、ホウ酸イオン、カルボン酸等を挙げることができる。中でも上記金属塩のアニオン成分としては、分解温度が低くて分解後に当該アニオン成分が残存しない点から硝酸イオンが好ましい。上記第1工程において、金属塩は1種類を単独で用いることもできるほか、2種類の金属塩を組み合わせて用いることもできる。
The metal salt used in the first step is not particularly limited as long as it is a water-soluble metal salt. The cation component of the metal salt is not particularly limited, and iron, cobalt, nickel, chromium, manganese, magnesium, vanadium, yttrium, titanium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, aluminum, tin, sodium, Lithium, beryllium, potassium, calcium, scandium, rubidium, strontium, gallium, copper, molybdenum, zinc, cesium, platinum, gold, iridium, thorium, thallium, bismuth, lead, mercury, cerium, lanthanum, tungsten, niobium, neodymium, Examples include ions such as barium, gadolinium, samarium, dysprodium. Above all, when the cation component of the metal salt is an ion such as iron, cobalt, nickel, chromium, manganese, barium, gadolinium, samarium, dysprodium, etc., an oxide that can control the movement of the carbonaceous material by an external magnetic field Particles can be formed. The anion component of the metal salt is not particularly limited, and examples thereof include nitrate ion, chloride ion, sulfate ion, phosphate ion, carbonate ion, borate ion, and carboxylic acid. Among these, as the anion component of the metal salt, nitrate ions are preferable because the decomposition temperature is low and the anion component does not remain after decomposition. In the first step, one type of metal salt can be used alone, or two types of metal salts can be used in combination.
第1工程で用いられる多糖は、水溶性の多糖であれば特に限定されない。上記多糖としては、セルロース誘導体及びその塩、デンプン、デキストリンなどが挙げられる。これらの中でも、セルロース誘導体及びその塩が好適であり、セルロース誘導体の塩がより好適である。セルロース誘導体としてはカルボキシメチルセルロース、塩としてはアルカリ金属塩などが好適なものとして例示される。第1工程において水溶性の多糖を用いると、炭素質材料を合成する際に水に溶解させることが可能になる。多糖が溶解した水溶液に金属塩を溶解させることによって、後の炭化処理で無定形炭素のマトリックス中に金属の酸化物の粒子を分散させることができる。したがって、無定形炭素のマトリックス中に金属の酸化物の粒子が分散した炭素質材料を得る場合、水溶性の多糖を用いることが好ましい。
The polysaccharide used in the first step is not particularly limited as long as it is a water-soluble polysaccharide. Examples of the polysaccharide include cellulose derivatives and salts thereof, starch, dextrin and the like. Among these, a cellulose derivative and a salt thereof are preferable, and a salt of a cellulose derivative is more preferable. Preferred examples of the cellulose derivative include carboxymethyl cellulose, and examples of the salt include alkali metal salts. When a water-soluble polysaccharide is used in the first step, it can be dissolved in water when a carbonaceous material is synthesized. By dissolving the metal salt in the aqueous solution in which the polysaccharide is dissolved, the metal oxide particles can be dispersed in the amorphous carbon matrix by a subsequent carbonization treatment. Therefore, when obtaining a carbonaceous material in which metal oxide particles are dispersed in an amorphous carbon matrix, it is preferable to use a water-soluble polysaccharide.
第1工程における混合操作は特に限定されない。金属塩の水溶液に多糖の粉体を加えて混合してもよいし、多糖の水溶液に金属塩の粉体を加えて混合してもよい。金属塩の粉体と多糖の粉体とを水に加えて混合してもよい。また、金属塩の水溶液と多糖の水溶液とを混合してもよい。このとき用いられる水の種類は限定されず、イオン交換水、蒸留水など十分精製した水だけでなく水道水も使用可能である。
The mixing operation in the first step is not particularly limited. The polysaccharide powder may be added to and mixed with the metal salt aqueous solution, or the metal salt powder may be added to and mixed with the polysaccharide aqueous solution. Metal salt powder and polysaccharide powder may be added to water and mixed. Further, an aqueous solution of a metal salt and an aqueous solution of a polysaccharide may be mixed. The kind of water used at this time is not limited, and not only sufficiently purified water such as ion exchange water and distilled water but also tap water can be used.
次に、第2工程において、上記第1工程で得られた混合物を炭化させて炭化物を得る。炭化処理は、アルゴンガス、窒素ガス等の不活性ガス雰囲気下で加熱することにより行うことが好適である。また、第1工程で得られた混合物を予め乾燥させて水分を取り除いた後に、炭化処理することも好適である。乾燥方法は特に限定されず、加熱乾燥や減圧乾燥などを採用することができる。加熱乾燥する際の乾燥温度は、混合物中の水分を取り除くことのできる温度であれば特に限定されないが、40℃以上であることが好適である。乾燥温度が40℃未満である場合、混合物中の水分を十分に取り除くことができないおそれがある。乾燥温度は60℃以上がより好適である。また、エネルギー消費の面やコストの面から、乾燥温度は通常100℃以下である。このときの乾燥温度とは、混合物の乾燥に用いられる乾燥装置内の設定温度のことである。乾燥時間は乾燥温度との関係で設定されるが、混合物中の水分を十分に取り除くことができるように適宜設定すればよい。
Next, in the second step, the mixture obtained in the first step is carbonized to obtain a carbide. The carbonization treatment is preferably performed by heating in an inert gas atmosphere such as argon gas or nitrogen gas. It is also preferable to carbonize the mixture obtained in the first step after drying in advance to remove moisture. The drying method is not particularly limited, and heat drying, reduced pressure drying, or the like can be employed. Although the drying temperature at the time of heat-drying will not be specifically limited if it is the temperature which can remove the water | moisture content in a mixture, It is suitable that it is 40 degreeC or more. When the drying temperature is less than 40 ° C., there is a possibility that water in the mixture cannot be sufficiently removed. The drying temperature is more preferably 60 ° C. or higher. Further, the drying temperature is usually 100 ° C. or less from the viewpoint of energy consumption and cost. The drying temperature at this time is a set temperature in the drying apparatus used for drying the mixture. The drying time is set in relation to the drying temperature, but may be set as appropriate so that water in the mixture can be sufficiently removed.
第2工程における加熱温度は、上記混合物の炭化が進行する温度であれば特に限定されないが、80℃以上であることが好適である。加熱温度が80℃未満である場合、多糖の炭化が不十分となるおそれがある。また、無定形炭素のマトリックス中に金属の酸化物の粒子が分散してなる炭素質材料を製造しようとする場合、加熱温度が80℃未満であると金属塩が酸化されないおそれがある。このときの加熱温度とは、混合物の炭化に用いられる加熱装置内の設定温度のことである。第1工程で得られた混合物は、乾燥状態や用いた金属塩の種類にもよるが、80℃以上に加熱すると自己燃焼が始まり当該混合物自体の温度が400℃以上に達して炭化を進行させることができる。加熱温度は100℃以上がより好適であり、150℃以上がさらに好適である。一方、加熱温度が1000℃以下であることも好適である。加熱温度が1000℃を超える場合、炭化が進行した結果、炭素質材料中のグラフェンシートが成長しすぎて、後の第3工程においてスルホ基の導入が困難になるおそれがある。エネルギー消費の面やコストの面から、加熱温度は800℃以下がより好適であり、600℃以下がさらに好適である。加熱時間は加熱温度との関係で設定されるが、多糖の炭化が十分に進行するように適宜設定すればよい。
The heating temperature in the second step is not particularly limited as long as the carbonization of the mixture proceeds, but is preferably 80 ° C. or higher. When the heating temperature is less than 80 ° C., the carbonization of the polysaccharide may be insufficient. Further, when a carbonaceous material in which metal oxide particles are dispersed in an amorphous carbon matrix is to be produced, if the heating temperature is less than 80 ° C., the metal salt may not be oxidized. The heating temperature at this time is a set temperature in the heating device used for carbonization of the mixture. The mixture obtained in the first step depends on the dry state and the type of metal salt used, but when heated to 80 ° C. or higher, self-combustion starts and the temperature of the mixture itself reaches 400 ° C. or higher to cause carbonization. be able to. The heating temperature is more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher. On the other hand, it is also preferable that the heating temperature is 1000 ° C. or lower. When the heating temperature exceeds 1000 ° C., the graphene sheet in the carbonaceous material grows too much as a result of the progress of carbonization, which may make it difficult to introduce sulfo groups in the subsequent third step. From the viewpoint of energy consumption and cost, the heating temperature is more preferably 800 ° C. or less, and more preferably 600 ° C. or less. The heating time is set in relation to the heating temperature, but may be set as appropriate so that the carbonization of the polysaccharide proceeds sufficiently.
また、加熱装置は特に限定されず、電熱式、熱風式、直火式のいずれの加熱装置も使用することができる。また、混合物の炭化により発生するガスと当該ガスに含まれる固体粒子とを分別するために、加熱装置に集塵装置が接続されていてもよい。集塵装置は特に限定されず、サイクロン式の集塵装置やフィルタ式の集塵装置などを挙げることができる。炭化処理の均一性や炭化物の連続生産性の観点から工業的にはロータリーキルンを使用して混合物を炭化することが好適に採用される。さらに、発生したガスは予め水などで洗浄してから排出することが好ましい。
Also, the heating device is not particularly limited, and any heating device of an electric heating type, a hot air type, or a direct fire type can be used. In addition, a dust collector may be connected to the heating device in order to separate the gas generated by carbonization of the mixture from the solid particles contained in the gas. The dust collector is not particularly limited, and examples thereof include a cyclone dust collector and a filter dust collector. From the viewpoint of uniformity of carbonization treatment and continuous productivity of carbides, it is preferable to industrially use a rotary kiln to carbonize the mixture. Further, the generated gas is preferably exhausted after being previously washed with water or the like.
上記第2工程で得られる炭化物の粒径は通常数μm~数百μm程度であるが、粉砕することにより、より細かい粒径とすることもできる。また、上記第2工程で得られる炭化物に、原料である水溶性の金属塩や水溶性の多糖などが残留していることがある。そのため、第2工程と第3工程との間に炭化物を洗浄する工程をさらに加えてもよい。炭化物を洗浄することで金属塩などが除去され比表面積のより大きな炭化物を得ることができる。
The particle size of the carbide obtained in the second step is usually about several μm to several hundred μm, but it can be made finer by pulverization. In addition, a water-soluble metal salt or a water-soluble polysaccharide as a raw material may remain in the carbide obtained in the second step. Therefore, a step of washing carbide may be further added between the second step and the third step. By washing the carbide, metal salts and the like are removed, and a carbide having a larger specific surface area can be obtained.
炭化物を洗浄する方法は特に限定されず、水と炭化物とを接触させ当該炭化物に含まれる金属塩などを抽出する方法や、水と炭化物とを混合してから濾材を用いて濾別する方法などが挙げられる。抽出にはソックスレー抽出器などを用いることができ、濾過には桐山ロート、ブフナロートなどを用いることができる。洗浄に使用する洗浄液は特に限定されないが、蒸留水やイオン交換水などを用いることができる。また、効率的に金属塩などを除去するために塩酸や酢酸などの酸が少量含まれた水溶液を用いてもよい。
The method for washing the carbide is not particularly limited, such as a method of bringing water and carbide into contact with each other and extracting a metal salt contained in the carbide, a method of mixing water and carbide and then filtering using a filter medium, etc. Is mentioned. A Soxhlet extractor or the like can be used for extraction, and a Kiriyama funnel, a Buchner funnel, or the like can be used for filtration. Although the washing | cleaning liquid used for washing | cleaning is not specifically limited, Distilled water, ion-exchange water, etc. can be used. Further, an aqueous solution containing a small amount of acid such as hydrochloric acid or acetic acid may be used in order to efficiently remove metal salts and the like.
次に、第3工程において、上記第2工程で得られた炭化物をスルホン化処理をして、本発明の炭素質材料を得る。第3工程におけるスルホン化処理の方法は、炭化物にスルホ基を導入することのできる方法であれば特に限定されないが、例えば、発煙硫酸や濃硫酸を用いる方法が挙げられる。このとき、発煙硫酸と濃硫酸との混合液で処理することが好適であり、加熱することも好適である。こうして得られた炭素質材料の粒径は通常数μm~数百μm程度であるが、粉砕することにより、より細かい粒径とすることもできる。また、篩いなどを用いて篩い分けをすることにより所望の粒径の炭素質材料を得ることもできる。
Next, in the third step, the carbide obtained in the second step is sulfonated to obtain the carbonaceous material of the present invention. The sulfonation treatment method in the third step is not particularly limited as long as it is a method capable of introducing a sulfo group into the carbide, and examples thereof include a method using fuming sulfuric acid or concentrated sulfuric acid. At this time, it is preferable to treat with a mixed solution of fuming sulfuric acid and concentrated sulfuric acid, and heating is also preferable. The particle size of the carbonaceous material thus obtained is usually about several μm to several hundred μm, but it can be made finer by pulverization. Moreover, the carbonaceous material of a desired particle size can also be obtained by sieving using a sieve etc.
本発明の好適な実施態様は上記炭素質材料からなる固体酸である。本発明の炭素質材料は、表面に多くの強い酸点を有するので優れた固体酸となる。また、本発明の炭素質材料において、無定形炭素のマトリックス中に磁力に反応する金属の酸化物の粒子が分散している場合、外部磁場によって当該炭素質材料の動きを制御することができる。したがって、外部磁場によって動きを制御することができる固体酸として用いることもできる。
A preferred embodiment of the present invention is a solid acid made of the above carbonaceous material. Since the carbonaceous material of the present invention has many strong acid sites on the surface, it becomes an excellent solid acid. In the carbonaceous material of the present invention, when metal oxide particles that react with magnetic force are dispersed in an amorphous carbon matrix, the movement of the carbonaceous material can be controlled by an external magnetic field. Therefore, it can also be used as a solid acid whose movement can be controlled by an external magnetic field.
本発明の好適な実施形態は上記固体酸を触媒として用いセルロースを加水分解することを特徴とするセルロースの加水分解方法である。本発明の炭素質材料を触媒として用いて、セルロースの加水分解(糖化)の実験を行うと、セルロースが加水分解されて、二糖であるセロビオースや単糖であるグルコースが生成することを確認した。さらに、グルコースの過分解物であるレボグルコサン、ギ酸等の有機酸が生成することも確認した。また、上記加水分解の実験において、無定形炭素のマトリックス中に磁力に反応する金属の酸化物の粒子が分散している場合、セルロースと炭素質材料とが入った容器に撹拌子を入れなくても外部磁場によって炭素質材料を撹拌させることができることも確認した。
A preferred embodiment of the present invention is a cellulose hydrolysis method characterized by hydrolyzing cellulose using the solid acid as a catalyst. Using the carbonaceous material of the present invention as a catalyst, it was confirmed that when cellulose was hydrolyzed (saccharified), cellulose was hydrolyzed to produce disaccharide cellobiose and monosaccharide glucose. . Furthermore, it was also confirmed that organic acids such as levoglucosan and formic acid, which are glucose degradation products, were produced. Further, in the above hydrolysis experiment, when metal oxide particles that react with magnetic force are dispersed in an amorphous carbon matrix, a stirrer is not put in a container containing cellulose and a carbonaceous material. It was also confirmed that the carbonaceous material can be stirred by an external magnetic field.
本発明の好適な実施態様は上記炭素質材料からなる吸着剤である。本発明の炭素質材料は、多孔質であり、表面に多くの酸点を有するので優れた吸着剤となる。炭素質材料に吸着させる物質は特に限定されないが、セシウムイオンなどのアルカリ金属イオン、ストロンチウムイオンなどのアルカリ土類金属イオン、メチレンブルーなどの塩基性分子、ヨウ素などを例示することができる。本発明の炭素質材料は表面に多くの強い酸点(酸性官能基)を有するので、吸着させる物質としてはアルカリ性の物質が好適である。
A preferred embodiment of the present invention is an adsorbent made of the above carbonaceous material. Since the carbonaceous material of the present invention is porous and has many acid sites on its surface, it becomes an excellent adsorbent. The substance to be adsorbed on the carbonaceous material is not particularly limited, and examples thereof include alkali metal ions such as cesium ions, alkaline earth metal ions such as strontium ions, basic molecules such as methylene blue, and iodine. Since the carbonaceous material of the present invention has many strong acid sites (acidic functional groups) on the surface, an alkaline substance is suitable as the substance to be adsorbed.
以下、実施例を用いて本発明を更に具体的に説明する。
Hereinafter, the present invention will be described more specifically using examples.
実施例1
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。得られた水溶液に粉状のカルボキシメチルセルロースナトリウム(和光純薬工業株式会社製、型番:039-01335、以下CMC・Naと略すことがある)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて60℃で約5日間乾燥した。その後、乾燥した沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、200℃で1時間加熱して炭化処理をして炭化物を得た。 Example 1
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved inwater 100 ml. 1.0 g of powdered sodium carboxymethylcellulose (manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335, hereinafter sometimes abbreviated as CMC · Na) was added to the obtained aqueous solution and stirred to obtain a gel-like precipitate. I got a thing. And it dried at 60 degreeC for about 5 days using the constant temperature drying furnace until the water | moisture content of the obtained gel-like deposit was lost. Thereafter, the dried precipitate was transferred to a three-necked flask, and carbonized by heating at 200 ° C. for 1 hour in a nitrogen atmosphere in the three-necked flask to obtain a carbide.
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。得られた水溶液に粉状のカルボキシメチルセルロースナトリウム(和光純薬工業株式会社製、型番:039-01335、以下CMC・Naと略すことがある)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて60℃で約5日間乾燥した。その後、乾燥した沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、200℃で1時間加熱して炭化処理をして炭化物を得た。 Example 1
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in
そして、得られた炭化物5gを、発煙硫酸(SO3濃度20%)75ml及び濃硫酸(濃度96%)75mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、5gの炭素質材料を得た。
Then, 5 g of the obtained carbide was put into a mixed solution of 75 ml of fuming sulfuric acid (SO 3 concentration 20%) and 75 ml of concentrated sulfuric acid (concentration 96%), and stirred in a three-necked flask at 80 ° C. for 10 hours in a nitrogen atmosphere. And then sulfonated. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 5 g of a carbonaceous material.
実施例2~5
100mlの水に溶かす硝酸鉄(III)九水和物の量を0.125g(実施例2)、0.250g(実施例3)、1.00g(実施例4)、1.50g(実施例5)にそれぞれ変更して炭化物を得た後、当該炭化物をソックスレー抽出器を用いて蒸留水で6時間以上洗浄してから乾燥させた以外は実施例1と同様にして炭化物を得た。そして、実施例1と同様にしてスルホン化処理した後、洗浄及び乾燥して炭素質材料を得た。 Examples 2-5
The amount of iron (III) nitrate nonahydrate dissolved in 100 ml of water was 0.125 g (Example 2), 0.250 g (Example 3), 1.00 g (Example 4), 1.50 g (Example). After changing to 5) to obtain a carbide, a carbide was obtained in the same manner as in Example 1 except that the carbide was washed with distilled water for 6 hours or more using a Soxhlet extractor and then dried. And after sulfonating like Example 1, it washed and dried and obtained carbonaceous material.
100mlの水に溶かす硝酸鉄(III)九水和物の量を0.125g(実施例2)、0.250g(実施例3)、1.00g(実施例4)、1.50g(実施例5)にそれぞれ変更して炭化物を得た後、当該炭化物をソックスレー抽出器を用いて蒸留水で6時間以上洗浄してから乾燥させた以外は実施例1と同様にして炭化物を得た。そして、実施例1と同様にしてスルホン化処理した後、洗浄及び乾燥して炭素質材料を得た。 Examples 2-5
The amount of iron (III) nitrate nonahydrate dissolved in 100 ml of water was 0.125 g (Example 2), 0.250 g (Example 3), 1.00 g (Example 4), 1.50 g (Example). After changing to 5) to obtain a carbide, a carbide was obtained in the same manner as in Example 1 except that the carbide was washed with distilled water for 6 hours or more using a Soxhlet extractor and then dried. And after sulfonating like Example 1, it washed and dried and obtained carbonaceous material.
実施例6
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。その水溶液に硝酸コバルト(II)六水和物(Co(NO3)2・6H2O)1.5gを加えて混合した。得られた水溶液に粉状のCMC・Na(和光純薬工業株式会社製、型番:039-01335)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて65℃で約5日間乾燥した。その後、乾燥した沈殿物をメノウ乳鉢で粉砕した。粉砕された沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、250℃で1時間加熱して炭化物を得た。 Example 6
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved inwater 100 ml. Its cobalt (II) nitrate hexahydrate solution (Co (NO 3) 2 · 6H 2 O) was added and mixed 1.5 g. To the resulting aqueous solution, 1.0 g of powdery CMC · Na (manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335) was added and stirred to obtain a gel-like precipitate. And it dried at 65 degreeC for about 5 days using the constant temperature drying furnace until the water | moisture content of the obtained gel-like deposit was lost. Thereafter, the dried precipitate was pulverized in an agate mortar. The pulverized precipitate was transferred to a three-necked flask and heated in a nitrogen atmosphere at 250 ° C. for 1 hour in the three-necked flask to obtain a carbide.
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。その水溶液に硝酸コバルト(II)六水和物(Co(NO3)2・6H2O)1.5gを加えて混合した。得られた水溶液に粉状のCMC・Na(和光純薬工業株式会社製、型番:039-01335)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて65℃で約5日間乾燥した。その後、乾燥した沈殿物をメノウ乳鉢で粉砕した。粉砕された沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、250℃で1時間加熱して炭化物を得た。 Example 6
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in
そして、得られた炭化物3.000gを、発煙硫酸(SO3濃度20%)75ml及び濃硫酸(濃度96%)75mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、3.000gの炭素質材料を得た。
Then, 3.000 g of the obtained carbide was put in a mixed solution of 75 ml of fuming sulfuric acid (SO 3 concentration 20%) and 75 ml of concentrated sulfuric acid (concentration 96%), and 10 ° C. at 80 ° C. under a nitrogen atmosphere in a three-necked flask. The mixture was stirred for hours and subjected to sulfonation treatment. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 3.000 g of a carbonaceous material.
実施例7
硝酸鉄の水溶液に溶かす硝酸コバルト(II)六水和物の量を0.5gに変更した以外は実施例6と同様にして炭化物を得た。そして、得られた炭化物1.955gを、発煙硫酸(SO3濃度20%)75ml及び濃硫酸(濃度96%)76mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、1.955gの炭素質材料を得た。 Example 7
Carbide was obtained in the same manner as in Example 6 except that the amount of cobalt nitrate (II) hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 1.955 g of the obtained carbide was put into a mixed solution of 75 ml of fuming sulfuric acid (SO 3concentration 20%) and 76 ml of concentrated sulfuric acid (concentration 96%), and 10 ° C. at 80 ° C. in a three-necked flask in a nitrogen atmosphere. The mixture was stirred for hours and subjected to sulfonation treatment. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 1.955 g of a carbonaceous material.
硝酸鉄の水溶液に溶かす硝酸コバルト(II)六水和物の量を0.5gに変更した以外は実施例6と同様にして炭化物を得た。そして、得られた炭化物1.955gを、発煙硫酸(SO3濃度20%)75ml及び濃硫酸(濃度96%)76mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、1.955gの炭素質材料を得た。 Example 7
Carbide was obtained in the same manner as in Example 6 except that the amount of cobalt nitrate (II) hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 1.955 g of the obtained carbide was put into a mixed solution of 75 ml of fuming sulfuric acid (SO 3
実施例8
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。その水溶液に硝酸ニッケル(II)六水和物(Ni(NO3)2・6H2O)1.5gを加えて混合した。得られた水溶液に粉状のCMC・Na(和光純薬工業株式会社製、型番:039-01335)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて65℃で約5日間乾燥した。その後、乾燥した沈殿物をメノウ乳鉢で粉砕した。粉砕された沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、250℃で1時間加熱して炭化物を得た。 Example 8
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved inwater 100 ml. Its nickel (II) nitrate hexahydrate solution (Ni (NO 3) 2 · 6H 2 O) was added and mixed 1.5 g. To the resulting aqueous solution, 1.0 g of powdery CMC · Na (manufactured by Wako Pure Chemical Industries, Ltd., model number: 039-01335) was added and stirred to obtain a gel-like precipitate. And it dried at 65 degreeC for about 5 days using the constant temperature drying furnace until the water | moisture content of the obtained gel-like deposit was lost. Thereafter, the dried precipitate was pulverized in an agate mortar. The pulverized precipitate was transferred to a three-necked flask and heated in a nitrogen atmosphere at 250 ° C. for 1 hour in the three-necked flask to obtain a carbide.
硝酸鉄(III)九水和物(Fe(NO3)3・9H2O)0.500gを100mlの水に溶かして硝酸鉄の水溶液を得た。その水溶液に硝酸ニッケル(II)六水和物(Ni(NO3)2・6H2O)1.5gを加えて混合した。得られた水溶液に粉状のCMC・Na(和光純薬工業株式会社製、型番:039-01335)1.0gを投入して撹拌し、ゲル状の沈殿物を得た。そして、得られたゲル状の沈殿物の水分が無くなるまで、恒温乾燥炉を用いて65℃で約5日間乾燥した。その後、乾燥した沈殿物をメノウ乳鉢で粉砕した。粉砕された沈殿物を三口フラスコに移し、当該三口フラスコ中において、窒素雰囲気下で、250℃で1時間加熱して炭化物を得た。 Example 8
Iron (III) nitrate nonahydrate the (Fe (NO 3) 3 · 9H 2 O) 0.500g to obtain an aqueous solution of iron nitrate dissolved in
実施例9
硝酸鉄の水溶液に溶かす硝酸ニッケル(II)六水和物の量を0.5gに変更した以外は実施例8と同様にして炭化物を得た。そして、得られた炭化物3.4168gを、発煙硫酸(SO3濃度20%)100ml及び濃硫酸(濃度96%)100mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、3.4168gの炭素質材料を得た。 Example 9
Carbide was obtained in the same manner as in Example 8 except that the amount of nickel (II) nitrate hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 3.4168 g of the obtained carbide was put into a mixed solution of fuming sulfuric acid (SO 3concentration 20%) 100 ml and concentrated sulfuric acid (concentration 96%) 100 ml, and in a three-neck flask at 80 ° C. in a nitrogen atmosphere. The mixture was stirred for hours and subjected to sulfonation treatment. Thereafter, the obtained carbide was washed with 3000 ml of distilled water and dried at 105 ° C. to obtain 3.4168 g of a carbonaceous material.
硝酸鉄の水溶液に溶かす硝酸ニッケル(II)六水和物の量を0.5gに変更した以外は実施例8と同様にして炭化物を得た。そして、得られた炭化物3.4168gを、発煙硫酸(SO3濃度20%)100ml及び濃硫酸(濃度96%)100mlの混合液に入れ、三口フラスコ中において、窒素雰囲気下で、80℃で10時間撹拌しスルホン化処理をした。その後、得られた炭化物を蒸留水3000mlで洗浄し、105℃で乾燥し、3.4168gの炭素質材料を得た。 Example 9
Carbide was obtained in the same manner as in Example 8 except that the amount of nickel (II) nitrate hexahydrate dissolved in the aqueous iron nitrate solution was changed to 0.5 g. Then, 3.4168 g of the obtained carbide was put into a mixed solution of fuming sulfuric acid (SO 3
[示差走査熱分析]
実施例1において、スルホン化処理前の炭化物3.554mg及びスルホン化処理後の炭素質材料3.586mgそれぞれについて、示差熱・熱重量測定装置(TG/DTA)を用いて、空気雰囲気下で10℃/minの昇温条件で示差走査熱分析を行った。結果を図1及び図2にそれぞれ示す。図1に示すように、スルホン化処理前の炭化物では、330℃及び420℃付近に酸化分解に起因すると考えられる発熱ピークが確認された。また、図2に示すように、スルホン化処理後の炭素質材料では、390℃及び400℃付近に酸化分解に起因すると考えられる発熱ピークが確認された。示差熱・熱重量測定装置は、株式会社リガク社製の「TG8120」を用いた。 [Differential scanning thermal analysis]
In Example 1, 3.554 mg of the carbide before the sulfonation treatment and 3.586 mg of the carbonaceous material after the sulfonation treatment were each measured in an air atmosphere using a differential heat / thermogravimetry apparatus (TG / DTA). Differential scanning calorimetry was performed under the temperature rising condition of ° C / min. The results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 1, in the carbide before the sulfonation treatment, an exothermic peak considered to be caused by oxidative decomposition was confirmed at around 330 ° C. and 420 ° C. Further, as shown in FIG. 2, in the carbonaceous material after the sulfonation treatment, an exothermic peak considered to be caused by oxidative decomposition was confirmed at around 390 ° C. and 400 ° C. As the differential heat / thermogravimetric measuring apparatus, “TG8120” manufactured by Rigaku Corporation was used.
実施例1において、スルホン化処理前の炭化物3.554mg及びスルホン化処理後の炭素質材料3.586mgそれぞれについて、示差熱・熱重量測定装置(TG/DTA)を用いて、空気雰囲気下で10℃/minの昇温条件で示差走査熱分析を行った。結果を図1及び図2にそれぞれ示す。図1に示すように、スルホン化処理前の炭化物では、330℃及び420℃付近に酸化分解に起因すると考えられる発熱ピークが確認された。また、図2に示すように、スルホン化処理後の炭素質材料では、390℃及び400℃付近に酸化分解に起因すると考えられる発熱ピークが確認された。示差熱・熱重量測定装置は、株式会社リガク社製の「TG8120」を用いた。 [Differential scanning thermal analysis]
In Example 1, 3.554 mg of the carbide before the sulfonation treatment and 3.586 mg of the carbonaceous material after the sulfonation treatment were each measured in an air atmosphere using a differential heat / thermogravimetry apparatus (TG / DTA). Differential scanning calorimetry was performed under the temperature rising condition of ° C / min. The results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 1, in the carbide before the sulfonation treatment, an exothermic peak considered to be caused by oxidative decomposition was confirmed at around 330 ° C. and 420 ° C. Further, as shown in FIG. 2, in the carbonaceous material after the sulfonation treatment, an exothermic peak considered to be caused by oxidative decomposition was confirmed at around 390 ° C. and 400 ° C. As the differential heat / thermogravimetric measuring apparatus, “TG8120” manufactured by Rigaku Corporation was used.
[SEM観察]
走査型電子顕微鏡装置(SEM)を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて電子顕微鏡写真(SEM像)の撮影を行った。図3はスルホン化処理前の炭化物の電子顕微鏡写真(SEM像)であり、図4はスルホン化処理後の炭素質材料の電子顕微鏡写真(SEM像)である。得られた写真から、いずれの試料も数nm~数十nmの孔が多数確認された。走査型電子顕微鏡装置は、株式会社日立ハイテクノロジーズ社製の「S-3000N」を用いた。 [SEM observation]
Using a scanning electron microscope apparatus (SEM), an electron micrograph (SEM image) was taken for each of the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment. FIG. 3 is an electron micrograph (SEM image) of the carbide before the sulfonation treatment, and FIG. 4 is an electron micrograph (SEM image) of the carbonaceous material after the sulfonation treatment. From the photograph obtained, many holes of several nm to several tens of nm were confirmed in any sample. As the scanning electron microscope apparatus, “S-3000N” manufactured by Hitachi High-Technologies Corporation was used.
走査型電子顕微鏡装置(SEM)を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて電子顕微鏡写真(SEM像)の撮影を行った。図3はスルホン化処理前の炭化物の電子顕微鏡写真(SEM像)であり、図4はスルホン化処理後の炭素質材料の電子顕微鏡写真(SEM像)である。得られた写真から、いずれの試料も数nm~数十nmの孔が多数確認された。走査型電子顕微鏡装置は、株式会社日立ハイテクノロジーズ社製の「S-3000N」を用いた。 [SEM observation]
Using a scanning electron microscope apparatus (SEM), an electron micrograph (SEM image) was taken for each of the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment. FIG. 3 is an electron micrograph (SEM image) of the carbide before the sulfonation treatment, and FIG. 4 is an electron micrograph (SEM image) of the carbonaceous material after the sulfonation treatment. From the photograph obtained, many holes of several nm to several tens of nm were confirmed in any sample. As the scanning electron microscope apparatus, “S-3000N” manufactured by Hitachi High-Technologies Corporation was used.
[TEM観察]
透過型電子顕微鏡装置(TEM)を用いて、スルホン化処理前の実施例1の炭化物、スルホン化処理後の実施例1の炭素質材料、スルホン化処理後の実施例2の炭素質材料及びスルホン化処理後の実施例5の炭素質材料それぞれについて電子顕微鏡写真(TEM像)の撮影を行った。図5及び6はスルホン化処理前の実施例1の炭化物の電子顕微鏡写真(TEM像)である。図7及び図8はスルホン化処理後の実施例1の炭素質材料の電子顕微鏡写真(TEM像)である。また、図9はスルホン化処理後の実施例2の炭素質材料の電子顕微鏡写真(TEM像)であり、図10はスルホン化処理後の実施例5の炭素質材料の電子顕微鏡写真(TEM像)である。得られた写真から、いずれの試料中にも5~50nm程度の粒子が存在することがわかった。ここで、粒子が円形でない場合には、円相当径を直径とした。透過型電子顕微鏡装置は、株式会社トプコンテクノハウス社製の「EM002BF」を用いた。 [TEM observation]
Using a transmission electron microscope (TEM), the carbide of Example 1 before sulfonation, the carbonaceous material of Example 1 after sulfonation, the carbonaceous material and sulfone of Example 2 after sulfonation An electron micrograph (TEM image) was taken for each carbonaceous material of Example 5 after the chemical treatment. 5 and 6 are electron micrographs (TEM images) of the carbide of Example 1 before the sulfonation treatment. 7 and 8 are electron micrographs (TEM images) of the carbonaceous material of Example 1 after the sulfonation treatment. FIG. 9 is an electron micrograph (TEM image) of the carbonaceous material of Example 2 after sulfonation, and FIG. 10 is an electron micrograph (TEM image) of the carbonaceous material of Example 5 after sulfonation. ). From the obtained photographs, it was found that particles of about 5 to 50 nm were present in any sample. Here, when the particles were not circular, the equivalent circle diameter was taken as the diameter. As the transmission electron microscope apparatus, “EM002BF” manufactured by Topcon Techno House Co., Ltd. was used.
透過型電子顕微鏡装置(TEM)を用いて、スルホン化処理前の実施例1の炭化物、スルホン化処理後の実施例1の炭素質材料、スルホン化処理後の実施例2の炭素質材料及びスルホン化処理後の実施例5の炭素質材料それぞれについて電子顕微鏡写真(TEM像)の撮影を行った。図5及び6はスルホン化処理前の実施例1の炭化物の電子顕微鏡写真(TEM像)である。図7及び図8はスルホン化処理後の実施例1の炭素質材料の電子顕微鏡写真(TEM像)である。また、図9はスルホン化処理後の実施例2の炭素質材料の電子顕微鏡写真(TEM像)であり、図10はスルホン化処理後の実施例5の炭素質材料の電子顕微鏡写真(TEM像)である。得られた写真から、いずれの試料中にも5~50nm程度の粒子が存在することがわかった。ここで、粒子が円形でない場合には、円相当径を直径とした。透過型電子顕微鏡装置は、株式会社トプコンテクノハウス社製の「EM002BF」を用いた。 [TEM observation]
Using a transmission electron microscope (TEM), the carbide of Example 1 before sulfonation, the carbonaceous material of Example 1 after sulfonation, the carbonaceous material and sulfone of Example 2 after sulfonation An electron micrograph (TEM image) was taken for each carbonaceous material of Example 5 after the chemical treatment. 5 and 6 are electron micrographs (TEM images) of the carbide of Example 1 before the sulfonation treatment. 7 and 8 are electron micrographs (TEM images) of the carbonaceous material of Example 1 after the sulfonation treatment. FIG. 9 is an electron micrograph (TEM image) of the carbonaceous material of Example 2 after sulfonation, and FIG. 10 is an electron micrograph (TEM image) of the carbonaceous material of Example 5 after sulfonation. ). From the obtained photographs, it was found that particles of about 5 to 50 nm were present in any sample. Here, when the particles were not circular, the equivalent circle diameter was taken as the diameter. As the transmission electron microscope apparatus, “EM002BF” manufactured by Topcon Techno House Co., Ltd. was used.
[比表面積、細孔容積、細孔直径の測定]
比表面積・細孔分布測定装置を用いて、窒素吸着法(BET法)により、スルホン化処理前の実施例1~5の炭化物、スルホン化処理後の実施例1~5の炭素質材料及びスルホン化処理前の実施例6の炭化物それぞれについて吸着等温線を測定した。また、各試料についてBJH(Barrett,Joyner,and Halenda)法による解析を行い、平均細孔直径及び全細孔容積をそれぞれ算出した。結果を表1にまとめて示す。表1において、スルホン化処理後の実施例1の炭素質材料としては、篩を用いて篩い分けをして得られた粒径が150μm以下の炭素質材料を用いた。 [Measurement of specific surface area, pore volume, pore diameter]
By using a specific surface area / pore distribution measuring device, the carbonized materials and sulfones of Examples 1 to 5 before sulfonation, Examples 1 to 5 after sulfonation by nitrogen adsorption method (BET method) An adsorption isotherm was measured for each of the carbides of Example 6 before the crystallization treatment. Each sample was analyzed by the BJH (Barrett, Joyner, and Halenda) method, and the average pore diameter and total pore volume were calculated. The results are summarized in Table 1. In Table 1, as the carbonaceous material of Example 1 after the sulfonation treatment, a carbonaceous material having a particle size of 150 μm or less obtained by sieving using a sieve was used.
比表面積・細孔分布測定装置を用いて、窒素吸着法(BET法)により、スルホン化処理前の実施例1~5の炭化物、スルホン化処理後の実施例1~5の炭素質材料及びスルホン化処理前の実施例6の炭化物それぞれについて吸着等温線を測定した。また、各試料についてBJH(Barrett,Joyner,and Halenda)法による解析を行い、平均細孔直径及び全細孔容積をそれぞれ算出した。結果を表1にまとめて示す。表1において、スルホン化処理後の実施例1の炭素質材料としては、篩を用いて篩い分けをして得られた粒径が150μm以下の炭素質材料を用いた。 [Measurement of specific surface area, pore volume, pore diameter]
By using a specific surface area / pore distribution measuring device, the carbonized materials and sulfones of Examples 1 to 5 before sulfonation, Examples 1 to 5 after sulfonation by nitrogen adsorption method (BET method) An adsorption isotherm was measured for each of the carbides of Example 6 before the crystallization treatment. Each sample was analyzed by the BJH (Barrett, Joyner, and Halenda) method, and the average pore diameter and total pore volume were calculated. The results are summarized in Table 1. In Table 1, as the carbonaceous material of Example 1 after the sulfonation treatment, a carbonaceous material having a particle size of 150 μm or less obtained by sieving using a sieve was used.
図11はスルホン化処理前の実施例1の炭化物についてBJH法により解析した細孔分布曲線である。図12はスルホン化処理後の実施例1の炭素質材料についてBJH法により解析した細孔分布曲線である。図13はスルホン化処理前の実施例6の炭化物についてBJH法により解析した細孔分布曲線である。
FIG. 11 is a pore distribution curve analyzed by the BJH method for the carbide of Example 1 before the sulfonation treatment. FIG. 12 is a pore distribution curve analyzed by the BJH method for the carbonaceous material of Example 1 after sulfonation treatment. FIG. 13 is a pore distribution curve analyzed by the BJH method for the carbide of Example 6 before the sulfonation treatment.
また、HK(Horvath-Kawazoe Method)法による解析から、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料の孔幅をそれぞれ算出したところ、いずれも孔幅が約0.8nmであった。図14はスルホン化処理前の炭化物についてHK法により解析した細孔分布曲線である。図15はスルホン化処理後の炭素質材料についてHK法により解析した細孔分布曲線である。比表面積・細孔分布測定装置は、Quantachrome Instruments社製の「NOVE 4200e」を用いた。
Further, from the analysis by the HK (Horvath-Kawazoe Method) method, the pore widths of the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment were calculated. Was about 0.8 nm. FIG. 14 is a pore distribution curve obtained by analyzing the carbide before sulfonation with the HK method. FIG. 15 is a pore distribution curve obtained by analyzing the carbonaceous material after the sulfonation treatment by the HK method. The specific surface area / pore distribution measuring apparatus used was “NOVE 4200e” manufactured by Quantachrome Instruments.
[粉末X線回折法による分析]
X線回折装置を用いて、Cu-Kα線による粉末X線回折法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて定性分析を行った。その結果を図16に示す。図16に示すように、半値幅(2θ)が10~30°付近にブロードなピークが確認され、いずれの試料もグラフェンシートが乱雑に集合した無定形炭素を含むことがわかった。図16に示すように半値幅(2θ)が45~50°付近のピークは炭酸ナトリウム(Na2CO3)由来であることがわかり、スルホン化処理前の炭化物は炭酸ナトリウム(Na2CO3)を含むことがわかった。また、図16に示すように半値幅(2θ)が10~30°付近のブロードなピークは硫酸鉄(III)及び無定形炭素由来であることがわかり、スルホン化処理後の炭素質材料は硫酸鉄(III)をさらに含むことがわかった。また、いずれの試料も半値幅(2θ)が30°、35°、43°、53°、57°、63°付近にピークが確認され、マグネタイト(Fe3O4)を含むこともわかった。また、いずれの試料も半値幅(2θ)が33°、35°、40°、63°付近にピークが確認され、マグヘマイト(γ-Fe2O3)を含むこともわかった。 [Analysis by powder X-ray diffraction method]
Using an X-ray diffractometer, qualitative analysis was performed on the carbide of Example 1 before sulfonation and the carbonaceous material of Example 1 after sulfonation by powder X-ray diffraction using Cu-Kα rays. . The result is shown in FIG. As shown in FIG. 16, a broad peak was confirmed at a half width (2θ) of around 10 to 30 °, and it was found that all the samples contained amorphous carbon in which graphene sheets were randomly assembled. As shown in FIG. 16, it can be seen that the peak at half width (2θ) around 45-50 ° is derived from sodium carbonate (Na 2 CO 3 ), and the carbide before the sulfonation treatment is sodium carbonate (Na 2 CO 3 ). It was found to contain. In addition, as shown in FIG. 16, it can be seen that the broad peak with a half width (2θ) of about 10 to 30 ° is derived from iron (III) sulfate and amorphous carbon, and the carbonaceous material after sulfonation treatment is sulfuric acid. It was found to further contain iron (III). In addition, in each sample, peaks were confirmed at half-value widths (2θ) of around 30 °, 35 °, 43 °, 53 °, 57 °, and 63 °, and it was also found that magnetite (Fe 3 O 4 ) was contained. In addition, in each sample, peaks were confirmed at half-value widths (2θ) of around 33 °, 35 °, 40 °, and 63 °, and it was also found that maghemite (γ-Fe 2 O 3 ) was contained.
X線回折装置を用いて、Cu-Kα線による粉末X線回折法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて定性分析を行った。その結果を図16に示す。図16に示すように、半値幅(2θ)が10~30°付近にブロードなピークが確認され、いずれの試料もグラフェンシートが乱雑に集合した無定形炭素を含むことがわかった。図16に示すように半値幅(2θ)が45~50°付近のピークは炭酸ナトリウム(Na2CO3)由来であることがわかり、スルホン化処理前の炭化物は炭酸ナトリウム(Na2CO3)を含むことがわかった。また、図16に示すように半値幅(2θ)が10~30°付近のブロードなピークは硫酸鉄(III)及び無定形炭素由来であることがわかり、スルホン化処理後の炭素質材料は硫酸鉄(III)をさらに含むことがわかった。また、いずれの試料も半値幅(2θ)が30°、35°、43°、53°、57°、63°付近にピークが確認され、マグネタイト(Fe3O4)を含むこともわかった。また、いずれの試料も半値幅(2θ)が33°、35°、40°、63°付近にピークが確認され、マグヘマイト(γ-Fe2O3)を含むこともわかった。 [Analysis by powder X-ray diffraction method]
Using an X-ray diffractometer, qualitative analysis was performed on the carbide of Example 1 before sulfonation and the carbonaceous material of Example 1 after sulfonation by powder X-ray diffraction using Cu-Kα rays. . The result is shown in FIG. As shown in FIG. 16, a broad peak was confirmed at a half width (2θ) of around 10 to 30 °, and it was found that all the samples contained amorphous carbon in which graphene sheets were randomly assembled. As shown in FIG. 16, it can be seen that the peak at half width (2θ) around 45-50 ° is derived from sodium carbonate (Na 2 CO 3 ), and the carbide before the sulfonation treatment is sodium carbonate (Na 2 CO 3 ). It was found to contain. In addition, as shown in FIG. 16, it can be seen that the broad peak with a half width (2θ) of about 10 to 30 ° is derived from iron (III) sulfate and amorphous carbon, and the carbonaceous material after sulfonation treatment is sulfuric acid. It was found to further contain iron (III). In addition, in each sample, peaks were confirmed at half-value widths (2θ) of around 30 °, 35 °, 43 °, 53 °, 57 °, and 63 °, and it was also found that magnetite (Fe 3 O 4 ) was contained. In addition, in each sample, peaks were confirmed at half-value widths (2θ) of around 33 °, 35 °, 40 °, and 63 °, and it was also found that maghemite (γ-Fe 2 O 3 ) was contained.
X線回折装置を用いて、Cu-Kα線による粉末X線回折法により、スルホン化処理前の実施例6の炭化物について定性分析を行った。その結果を図17に示す。図17に示すように、酸化コバルト(Co3O4、CoO)、マグヘマイト(γ-Fe2O3)、Fe3Co7のそれぞれに由来するピークが観測された。また、コバルトの単体に由来するピークも確認された。X線回折装置は、株式会社リガク社製の「RINT 2500HF」を用いた。
Using an X-ray diffractometer, qualitative analysis was performed on the carbide of Example 6 before sulfonation by powder X-ray diffraction using Cu—Kα rays. The result is shown in FIG. As shown in FIG. 17, peaks derived from cobalt oxide (Co 3 O 4 , CoO), maghemite (γ-Fe 2 O 3 ), and Fe 3 Co 7 were observed. Moreover, the peak derived from the simple substance of cobalt was also confirmed. As the X-ray diffractometer, “RINT 2500HF” manufactured by Rigaku Corporation was used.
X線光電子分光装置を用いて、X線光電子分光法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてワイドスキャン測定を行った。図18はスルホン化処理前の炭化物の測定結果である。図19はスルホン化処理後の炭素質材料の測定結果である。得られた結果より、ワイドスキャン測定により検出される元素が、C1s(炭素)、N1s(窒素)、O1s(酸素)、Fe2p(鉄)、及びNa1s(ナトリウム)であった。また、スルホン化処理後の炭素質材料は、さらに、S2p(硫黄)も確認された。
Using an X-ray photoelectron spectrometer, wide scan measurement was performed on the carbide of Example 1 before sulfonation and the carbonaceous material of Example 1 after sulfonation by X-ray photoelectron spectroscopy. FIG. 18 shows the measurement results of carbide before sulfonation. FIG. 19 shows the measurement results of the carbonaceous material after the sulfonation treatment. From the obtained results, the elements detected by the wide scan measurement were C 1s (carbon), N 1s (nitrogen), O 1s (oxygen), Fe 2p (iron), and Na 1s (sodium). Further, S 2p (sulfur) was also confirmed in the carbonaceous material after the sulfonation treatment.
また、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてナロースキャンによる測定も行った。その結果、O1sスペクトルより、マグヘマイト(γ-Fe2O3)に由来するピークと、有機化合物に由来するピークと、SO3、SO4に由来するピークと、Na2CO3に由来するピークがそれぞれ確認された。さらに、C1sスペクトルより、C-C(H)、C-O、C=O、-CO3に由来するピークがそれぞれ確認された。また、Fe2pスペクトルのメインピークの結合エネルギーの値から、マグヘマイト(γ-Fe2O3)の存在が確認できた。スルホン化処理後の炭素質材料は硫酸鉄(III)(Fe2(SO4)3)の存在が確認できた。さらにスルホン化処理後の炭素質材料は、S2pスペクトルにおいて、硫酸鉄(III)のSO4、SO3H基に由来するピークも確認された。結果を図20~23に示す。X線光電子分光装置は、アルバック・ファイ株式会社製の「Quantera SXM」を用いた。
Moreover, the measurement by narrow scan was also performed about the carbide | carbonized_material of Example 1 before a sulfonation process, and each carbonaceous material of Example 1 after a sulfonation process. As a result, from the O 1s spectrum, a peak derived from maghemite (γ-Fe 2 O 3 ), a peak derived from an organic compound, a peak derived from SO 3 and SO 4, and a peak derived from Na 2 CO 3 Were confirmed. Further, peaks derived from C—C (H), C—O, C═O, and —CO 3 were confirmed from the C 1s spectrum. The presence of maghemite (γ-Fe 2 O 3 ) was confirmed from the value of the binding energy of the main peak of the Fe 2p spectrum. The presence of iron (III) sulfate (Fe 2 (SO 4 ) 3 ) was confirmed in the carbonaceous material after the sulfonation treatment. Further, the carbonaceous material after the sulfonation treatment was also confirmed to have peaks derived from SO 4 and SO 3 H groups of iron (III) sulfate in the S 2p spectrum. The results are shown in FIGS. As the X-ray photoelectron spectrometer, “Quantera SXM” manufactured by ULVAC-PHI Co., Ltd. was used.
[メスバウアー分光法による分析]
メスバウアー分光装置を用いて、メスバウアー分光法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてメスバウアースペクトルを測定した。結果を図24に示す。図24に示すように、室温(293K)で測定を行った結果、いずれの試料もスペクトル中央付近に主要なピークとしてブロードな見かけ上のシングレットピークが観測された。スルホン化処理前の炭化物は、ブロードな磁気分裂ピークが観測された。スルホン化処理後の炭素質材料は、磁気分裂ピークは観測されなかったが、シングレットピークの裾がのびるかのように見える非常にブロードな吸収も観測された。いずれの試料も粉末X線回折法による測定結果から含有が予想される成分(γ-Fe2O3又はFe3O4)から大きく異なっており、常磁性成分が多くを占めていることがわかった。透過型電子顕微鏡写真から考察すると、超常磁性体(粒径10nm以下)がいずれの試料にも存在していることがわかった。また、磁気分裂ピークを観察するため、液体窒素温度(78K)で測定を行った。その結果、スルホン化処理前の炭化物においては、磁気分裂ピークが主要成分となった。スルホン化処理後の炭素質材料においては、常磁性成分は常磁性成分のままであるが、磁気分裂ピークがはっきりわかるようになった。 [Analysis by Mossbauer spectroscopy]
Using a Mossbauer spectrometer, a Mossbauer spectrum was measured for each of the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment by Mossbauer spectroscopy. The results are shown in FIG. As shown in FIG. 24, as a result of measurement at room temperature (293K), a broad apparent singlet peak was observed as a main peak near the center of the spectrum in all samples. A broad magnetic splitting peak was observed in the carbide before the sulfonation treatment. In the carbonaceous material after the sulfonation treatment, no magnetic splitting peak was observed, but a very broad absorption that seemed to extend the singlet peak was also observed. Each sample is greatly different from the component (γ-Fe 2 O 3 or Fe 3 O 4 ) expected to be contained from the measurement result by the powder X-ray diffraction method, and it is understood that the paramagnetic component occupies most. It was. Considering from transmission electron micrographs, it was found that superparamagnetic material (particle size of 10 nm or less) was present in any sample. Moreover, in order to observe a magnetic splitting peak, it measured at liquid nitrogen temperature (78K). As a result, the magnetic splitting peak became the main component in the carbide before the sulfonation treatment. In the carbonaceous material after the sulfonation treatment, the paramagnetic component remains the paramagnetic component, but the magnetic splitting peak can be clearly seen.
メスバウアー分光装置を用いて、メスバウアー分光法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてメスバウアースペクトルを測定した。結果を図24に示す。図24に示すように、室温(293K)で測定を行った結果、いずれの試料もスペクトル中央付近に主要なピークとしてブロードな見かけ上のシングレットピークが観測された。スルホン化処理前の炭化物は、ブロードな磁気分裂ピークが観測された。スルホン化処理後の炭素質材料は、磁気分裂ピークは観測されなかったが、シングレットピークの裾がのびるかのように見える非常にブロードな吸収も観測された。いずれの試料も粉末X線回折法による測定結果から含有が予想される成分(γ-Fe2O3又はFe3O4)から大きく異なっており、常磁性成分が多くを占めていることがわかった。透過型電子顕微鏡写真から考察すると、超常磁性体(粒径10nm以下)がいずれの試料にも存在していることがわかった。また、磁気分裂ピークを観察するため、液体窒素温度(78K)で測定を行った。その結果、スルホン化処理前の炭化物においては、磁気分裂ピークが主要成分となった。スルホン化処理後の炭素質材料においては、常磁性成分は常磁性成分のままであるが、磁気分裂ピークがはっきりわかるようになった。 [Analysis by Mossbauer spectroscopy]
Using a Mossbauer spectrometer, a Mossbauer spectrum was measured for each of the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment by Mossbauer spectroscopy. The results are shown in FIG. As shown in FIG. 24, as a result of measurement at room temperature (293K), a broad apparent singlet peak was observed as a main peak near the center of the spectrum in all samples. A broad magnetic splitting peak was observed in the carbide before the sulfonation treatment. In the carbonaceous material after the sulfonation treatment, no magnetic splitting peak was observed, but a very broad absorption that seemed to extend the singlet peak was also observed. Each sample is greatly different from the component (γ-Fe 2 O 3 or Fe 3 O 4 ) expected to be contained from the measurement result by the powder X-ray diffraction method, and it is understood that the paramagnetic component occupies most. It was. Considering from transmission electron micrographs, it was found that superparamagnetic material (particle size of 10 nm or less) was present in any sample. Moreover, in order to observe a magnetic splitting peak, it measured at liquid nitrogen temperature (78K). As a result, the magnetic splitting peak became the main component in the carbide before the sulfonation treatment. In the carbonaceous material after the sulfonation treatment, the paramagnetic component remains the paramagnetic component, but the magnetic splitting peak can be clearly seen.
スルホン化処理前の炭化物について、ピークの裾が全て磁気分裂によるものと仮定して解析を行った。その結果、スルホン化処理前の炭化物のスペクトルは、ほぼ単一の磁性成分(γ-Fe2O3)と解釈できた。スルホン化処理後の炭素質材料については、γ-Fe2O3に加え硫酸鉄(III)(Fe2(SO4)3)が存在すると考えられる。Fe2(SO4)3のメスバウワーのパラメーターは室温で、IS=0.39mm/s、QS=0.60mm/sであり、1.8Kでは550kOeの磁気分裂を示す。また、Fe2(SO4)3のネール点は30Kであるため78Kでは常磁性であるので本測定の結果と一致すると考えられる。
The carbide before the sulfonation treatment was analyzed on the assumption that all of the peaks were due to magnetic fission. As a result, the spectrum of the carbide before the sulfonation treatment could be interpreted as almost a single magnetic component (γ-Fe 2 O 3 ). The carbonaceous material after the sulfonation treatment is considered to contain iron (III) sulfate (Fe 2 (SO 4 ) 3 ) in addition to γ-Fe 2 O 3 . The parameters of Fe 2 (SO 4 ) 3 Mossbauer are IS = 0.39 mm / s, QS = 0.60 mm / s at room temperature, and show magnetic splitting of 550 kOe at 1.8 K. In addition, since the Neel point of Fe 2 (SO 4 ) 3 is 30K, it is considered to be consistent with the result of this measurement because it is paramagnetic at 78K.
[元素分析]
スルホン化処理前の実施例1~7の炭化物及びスルホン化処理後の実施例1~5の炭素質材料それぞれについて、燃焼法による元素分析を行った(分析A)。また、上記X線光電子分光装置を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料について、ナロースキャン測定による定量分析も行った(分析B)。結果を表2に示す。 [Elemental analysis]
Each of the carbides of Examples 1 to 7 before the sulfonation treatment and the carbonaceous materials of Examples 1 to 5 after the sulfonation treatment were subjected to elemental analysis by a combustion method (Analysis A). In addition, using the X-ray photoelectron spectrometer, quantitative analysis by narrow scan measurement was also performed on the carbide of Example 1 before sulfonation treatment and the carbonaceous material of Example 1 after sulfonation treatment (Analysis B). . The results are shown in Table 2.
スルホン化処理前の実施例1~7の炭化物及びスルホン化処理後の実施例1~5の炭素質材料それぞれについて、燃焼法による元素分析を行った(分析A)。また、上記X線光電子分光装置を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料について、ナロースキャン測定による定量分析も行った(分析B)。結果を表2に示す。 [Elemental analysis]
Each of the carbides of Examples 1 to 7 before the sulfonation treatment and the carbonaceous materials of Examples 1 to 5 after the sulfonation treatment were subjected to elemental analysis by a combustion method (Analysis A). In addition, using the X-ray photoelectron spectrometer, quantitative analysis by narrow scan measurement was also performed on the carbide of Example 1 before sulfonation treatment and the carbonaceous material of Example 1 after sulfonation treatment (Analysis B). . The results are shown in Table 2.
[赤外分光法による分析]
フーリエ変換赤外分光装置(FT-IR)を用いて、KBr法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて赤外分光測定を行った。結果を図25に示す。図25に示すように、1595~1603cm-1にOHのベンディングによるピークが確認された。また、スルホン化処理後の炭素質材料では、1041cm-1にSO3の、1377cm-1にO=S=Oのストレッチングによるピークがそれぞれ確認され、1595~1603cm-1にOHのベンディングによるピークも確認された。フーリエ変換赤外分光装置は、サーモフィッシャーサイエンティフィック株式会社製の「Nicolet 6700 FT-IR」を用いた。 [Analysis by infrared spectroscopy]
Using a Fourier transform infrared spectrometer (FT-IR), infrared spectroscopic measurement was performed on the carbide of Example 1 before sulfonation and the carbonaceous material of Example 1 after sulfonation by the KBr method. It was. The results are shown in FIG. As shown in FIG. 25, peaks due to OH bending were observed at 1595 to 1603 cm −1 . Further, the carbonaceous material after sulfonation treatment, the SO 3 to 1041cm -1, a peak due to stretching of the O = S = O is confirmed respectively 1377 cm -1, the peak due to bending of OH to 1595 ~ 1603cm -1 Was also confirmed. As the Fourier transform infrared spectrometer, “Nicolet 6700 FT-IR” manufactured by Thermo Fisher Scientific Co., Ltd. was used.
フーリエ変換赤外分光装置(FT-IR)を用いて、KBr法により、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについて赤外分光測定を行った。結果を図25に示す。図25に示すように、1595~1603cm-1にOHのベンディングによるピークが確認された。また、スルホン化処理後の炭素質材料では、1041cm-1にSO3の、1377cm-1にO=S=Oのストレッチングによるピークがそれぞれ確認され、1595~1603cm-1にOHのベンディングによるピークも確認された。フーリエ変換赤外分光装置は、サーモフィッシャーサイエンティフィック株式会社製の「Nicolet 6700 FT-IR」を用いた。 [Analysis by infrared spectroscopy]
Using a Fourier transform infrared spectrometer (FT-IR), infrared spectroscopic measurement was performed on the carbide of Example 1 before sulfonation and the carbonaceous material of Example 1 after sulfonation by the KBr method. It was. The results are shown in FIG. As shown in FIG. 25, peaks due to OH bending were observed at 1595 to 1603 cm −1 . Further, the carbonaceous material after sulfonation treatment, the SO 3 to 1041cm -1, a peak due to stretching of the O = S = O is confirmed respectively 1377 cm -1, the peak due to bending of OH to 1595 ~ 1603cm -1 Was also confirmed. As the Fourier transform infrared spectrometer, “Nicolet 6700 FT-IR” manufactured by Thermo Fisher Scientific Co., Ltd. was used.
[核磁気共鳴法による分析]
さらに、スルホン化処理後の実施例1の炭素質材料については、核磁気共鳴装置を用い、核磁気共鳴法により構造決定を行った。13C DD/MAS(Dipolar Decoupling/Magic Angle Spinning)NMRスペクトルを図26に示す。図26に示すように、化学シフト130ppm付近に芳香環の炭素、140ppm付近にスルホ基が結合した炭素、155ppm付近に水酸基の結合した炭素、185ppm付近にカルボキシル基が結合した炭素に由来するピークがそれぞれ観測された。その結果、スルホン化処理後の炭素質材料は、芳香族炭素、スルホ基(SO3H基)、カルボキシル基(COOH基)、及び水酸基(OH基)を有することがわかった。また、0~100ppmに信号が現れないことからsp3炭素はほとんど含まれていないこともわかった。核磁気共鳴装置は、日本電子株式会社製の「JNM-ECX400」を用いた。 [Analysis by nuclear magnetic resonance method]
Furthermore, the structure of the carbonaceous material of Example 1 after the sulfonation treatment was determined by a nuclear magnetic resonance method using a nuclear magnetic resonance apparatus. A 13 C DD / MAS (Dipolar Decoupling / Magic Angle Spinning) NMR spectrum is shown in FIG. As shown in FIG. 26, there is a peak derived from carbon having an aromatic ring near a chemical shift of 130 ppm, carbon having a sulfo group bonded to about 140 ppm, carbon having a hydroxyl group bonded to about 155 ppm, and carbon having a carboxyl group bonded to about 185 ppm. Each was observed. As a result, it was found that the carbonaceous material after the sulfonation treatment has aromatic carbon, a sulfo group (SO 3 H group), a carboxyl group (COOH group), and a hydroxyl group (OH group). Further, since no signal appeared at 0 to 100 ppm, it was found that sp 3 carbon was hardly contained. As the nuclear magnetic resonance apparatus, “JNM-ECX400” manufactured by JEOL Ltd. was used.
さらに、スルホン化処理後の実施例1の炭素質材料については、核磁気共鳴装置を用い、核磁気共鳴法により構造決定を行った。13C DD/MAS(Dipolar Decoupling/Magic Angle Spinning)NMRスペクトルを図26に示す。図26に示すように、化学シフト130ppm付近に芳香環の炭素、140ppm付近にスルホ基が結合した炭素、155ppm付近に水酸基の結合した炭素、185ppm付近にカルボキシル基が結合した炭素に由来するピークがそれぞれ観測された。その結果、スルホン化処理後の炭素質材料は、芳香族炭素、スルホ基(SO3H基)、カルボキシル基(COOH基)、及び水酸基(OH基)を有することがわかった。また、0~100ppmに信号が現れないことからsp3炭素はほとんど含まれていないこともわかった。核磁気共鳴装置は、日本電子株式会社製の「JNM-ECX400」を用いた。 [Analysis by nuclear magnetic resonance method]
Furthermore, the structure of the carbonaceous material of Example 1 after the sulfonation treatment was determined by a nuclear magnetic resonance method using a nuclear magnetic resonance apparatus. A 13 C DD / MAS (Dipolar Decoupling / Magic Angle Spinning) NMR spectrum is shown in FIG. As shown in FIG. 26, there is a peak derived from carbon having an aromatic ring near a chemical shift of 130 ppm, carbon having a sulfo group bonded to about 140 ppm, carbon having a hydroxyl group bonded to about 155 ppm, and carbon having a carboxyl group bonded to about 185 ppm. Each was observed. As a result, it was found that the carbonaceous material after the sulfonation treatment has aromatic carbon, a sulfo group (SO 3 H group), a carboxyl group (COOH group), and a hydroxyl group (OH group). Further, since no signal appeared at 0 to 100 ppm, it was found that sp 3 carbon was hardly contained. As the nuclear magnetic resonance apparatus, “JNM-ECX400” manufactured by JEOL Ltd. was used.
[酸点数の測定]
全自動昇温脱離スペクトル装置を用いて、アンモニア昇温脱離法によりスルホン化処理後の実施例1~5の炭素質材料の酸点の強度及び酸点数をそれぞれ測定した。具体的には、以下の(前処理)、(アンモニア吸着処理)及び(アンモニア脱離処理)の手順に従って炭素質材料の酸点の強度及び酸点数を測定した。全自動昇温脱離スペクトル装置は、日本ベル株式会社製の「TPD-1-ATw」を用いた。 [Measurement of acid points]
Using a fully automatic temperature programmed desorption spectrometer, the acid point strength and the number of acid points of the carbonaceous materials of Examples 1 to 5 after sulfonation were measured by the ammonia temperature programmed desorption method. Specifically, the strength and the number of acid points of the carbonaceous material were measured according to the following procedures (pretreatment), (ammonia adsorption treatment), and (ammonia desorption treatment). As a fully automatic temperature programmed desorption spectrometer, “TPD-1-ATw” manufactured by Nippon Bell Co., Ltd. was used.
全自動昇温脱離スペクトル装置を用いて、アンモニア昇温脱離法によりスルホン化処理後の実施例1~5の炭素質材料の酸点の強度及び酸点数をそれぞれ測定した。具体的には、以下の(前処理)、(アンモニア吸着処理)及び(アンモニア脱離処理)の手順に従って炭素質材料の酸点の強度及び酸点数を測定した。全自動昇温脱離スペクトル装置は、日本ベル株式会社製の「TPD-1-ATw」を用いた。 [Measurement of acid points]
Using a fully automatic temperature programmed desorption spectrometer, the acid point strength and the number of acid points of the carbonaceous materials of Examples 1 to 5 after sulfonation were measured by the ammonia temperature programmed desorption method. Specifically, the strength and the number of acid points of the carbonaceous material were measured according to the following procedures (pretreatment), (ammonia adsorption treatment), and (ammonia desorption treatment). As a fully automatic temperature programmed desorption spectrometer, “TPD-1-ATw” manufactured by Nippon Bell Co., Ltd. was used.
(前処理)
(1)炭素質材料0.05gをセルに充填した。
(2)上記セルにヘリウムを流量50mL/分で供給しながら、昇温速度10℃/分で400℃まで昇温した。
(3)セル内の温度が400℃に達したら、当該温度を保持したままヘリウムを流量50mL/分で供給しながら1時間放置した。 (Preprocessing)
(1) A cell was filled with 0.05 g of a carbonaceous material.
(2) While supplying helium to the cell at a flow rate of 50 mL / min, the temperature was increased to 400 ° C. at a temperature increase rate of 10 ° C./min.
(3) When the temperature in the cell reached 400 ° C., helium was left for 1 hour while supplying the helium at a flow rate of 50 mL / min while maintaining the temperature.
(1)炭素質材料0.05gをセルに充填した。
(2)上記セルにヘリウムを流量50mL/分で供給しながら、昇温速度10℃/分で400℃まで昇温した。
(3)セル内の温度が400℃に達したら、当該温度を保持したままヘリウムを流量50mL/分で供給しながら1時間放置した。 (Preprocessing)
(1) A cell was filled with 0.05 g of a carbonaceous material.
(2) While supplying helium to the cell at a flow rate of 50 mL / min, the temperature was increased to 400 ° C. at a temperature increase rate of 10 ° C./min.
(3) When the temperature in the cell reached 400 ° C., helium was left for 1 hour while supplying the helium at a flow rate of 50 mL / min while maintaining the temperature.
(アンモニア吸着処理)
(1)セル内の温度を100℃まで降温した。そして、当該温度を保持しつつセル内にアンモニアを0.5体積%含むヘリウムを流量100mL/分で30分間供給した。
(2)セル内の温度を100℃に保持したままヘリウムを流量50mL/分で30分間供給して、当該セル内のアンモニアを除去した。 (Ammonia adsorption treatment)
(1) The temperature in the cell was lowered to 100 ° C. Then, while maintaining the temperature, helium containing 0.5% by volume of ammonia was supplied into the cell at a flow rate of 100 mL / min for 30 minutes.
(2) While maintaining the temperature in the cell at 100 ° C., helium was supplied at a flow rate of 50 mL / min for 30 minutes to remove ammonia in the cell.
(1)セル内の温度を100℃まで降温した。そして、当該温度を保持しつつセル内にアンモニアを0.5体積%含むヘリウムを流量100mL/分で30分間供給した。
(2)セル内の温度を100℃に保持したままヘリウムを流量50mL/分で30分間供給して、当該セル内のアンモニアを除去した。 (Ammonia adsorption treatment)
(1) The temperature in the cell was lowered to 100 ° C. Then, while maintaining the temperature, helium containing 0.5% by volume of ammonia was supplied into the cell at a flow rate of 100 mL / min for 30 minutes.
(2) While maintaining the temperature in the cell at 100 ° C., helium was supplied at a flow rate of 50 mL / min for 30 minutes to remove ammonia in the cell.
(アンモニア脱離処理)
(1)セル内にヘリウムを流量50mL/分で供給しながら、昇温速度10℃/分で400℃まで昇温して、炭素質材料に吸着されたアンモニアを脱離させた。そしてこのとき脱離したアンモニアを、四重極質量分析計を用いてNH2 +(m/z=16)のピークを検出することにより定量した。 (Ammonia desorption treatment)
(1) While supplying helium into the cell at a flow rate of 50 mL / min, the temperature was increased to 400 ° C. at a rate of temperature increase of 10 ° C./min to desorb ammonia adsorbed on the carbonaceous material. The ammonia desorbed at this time was quantified by detecting the peak of NH 2 + (m / z = 16) using a quadrupole mass spectrometer.
(1)セル内にヘリウムを流量50mL/分で供給しながら、昇温速度10℃/分で400℃まで昇温して、炭素質材料に吸着されたアンモニアを脱離させた。そしてこのとき脱離したアンモニアを、四重極質量分析計を用いてNH2 +(m/z=16)のピークを検出することにより定量した。 (Ammonia desorption treatment)
(1) While supplying helium into the cell at a flow rate of 50 mL / min, the temperature was increased to 400 ° C. at a rate of temperature increase of 10 ° C./min to desorb ammonia adsorbed on the carbonaceous material. The ammonia desorbed at this time was quantified by detecting the peak of NH 2 + (m / z = 16) using a quadrupole mass spectrometer.
測定結果を図27に示す。図27において、横軸はアンモニア脱離処理時の温度、縦軸は炭素質材料重量当たりに換算したアンモニアの脱離量を示す。また、ピーク温度の値と、アンモニア脱離処理の間に脱離したアンモニアの量の総和を表3に示す。
The measurement results are shown in FIG. In FIG. 27, the horizontal axis indicates the temperature during the ammonia desorption treatment, and the vertical axis indicates the ammonia desorption amount converted per carbonaceous material weight. Table 3 shows the sum of the peak temperature value and the amount of ammonia desorbed during the ammonia desorption treatment.
対照例として特開2009-268960号公報の実施例に記載のカーボン固体酸の酸点の強度及び酸点数も測定した。具体的には、微結晶セルロースを窒素ガス流通下において加熱処理(炭化処理)した後、自然冷却して炭化微結晶セルロースを得た。次いで、得られた炭化微結晶セルロースを硫酸と発煙硫酸の混合液に投入し、窒素ガス流通下において加熱処理(スルホン化処理)した。次いで、水蒸気で十分に洗浄してから、乾燥して、対照例のカーボン固体酸を得た。上述したNH3-TPD法に従って、対照例のカーボン固体酸の酸点の強度及び酸点数を測定した。測定結果を図27において破線で示す。また、ピーク温度の値と、アンモニア脱離処理の間に脱離したアンモニアの量の総和を表3に示す。
As control examples, the strength and the number of acid points of carbon solid acids described in Examples of JP-A-2009-268960 were also measured. Specifically, the microcrystalline cellulose was heat-treated (carbonized) under a nitrogen gas flow, and then naturally cooled to obtain carbonized microcrystalline cellulose. Subsequently, the obtained carbonized microcrystalline cellulose was put into a mixed solution of sulfuric acid and fuming sulfuric acid, and was subjected to heat treatment (sulfonation treatment) under a nitrogen gas flow. Next, after sufficiently washing with water vapor, drying was performed to obtain a carbon solid acid of a control example. In accordance with the NH 3 -TPD method described above, the strength and the number of acid points of the carbon solid acid of the control example were measured. The measurement results are indicated by broken lines in FIG. Table 3 shows the sum of the peak temperature value and the amount of ammonia desorbed during the ammonia desorption treatment.
NH3-TPD法においては、弱い酸点に吸着しているアンモニアは低い温度で脱離し、強い酸点に吸着しているアンモニアは高い温度で脱離する。すなわち、表3において、ピーク温度の値は酸点の強度を示すものである。また、アンモニアの脱離量の総和は試料表面に存在するアンモニアの吸着点、すなわち酸点数を示すものである。
In the NH 3 -TPD method, ammonia adsorbed at weak acid sites is desorbed at a low temperature, and ammonia adsorbed at strong acid sites is desorbed at a high temperature. That is, in Table 3, the peak temperature value indicates the strength of the acid point. The total ammonia desorption amount indicates the adsorption point of ammonia existing on the sample surface, that is, the number of acid points.
図27及び表3に示すように、本実施例のスルホン化処理後の炭素質材料の酸点の強度は、対照例のカーボン固体酸とほぼ同じであった。一方、アンモニアの脱離量の総和は、対照例のカーボン固体酸と比べて本実施例の炭素質材料の方が多かった。この結果より本実施例の炭素質材料は、対照例のカーボン固体酸と比べて、より多くの酸点を有することがわかった。また、炭素質材料を合成する際に水に溶解させる硝酸鉄の量によって酸点数に違いが生じることもわかった。本実施例においては、1.00gの硝酸鉄を100mlの水に溶かして炭素質材料を得た場合(実施例4)に酸点が最も多かった。
As shown in FIG. 27 and Table 3, the strength of the acid point of the carbonaceous material after the sulfonation treatment of this example was almost the same as the carbon solid acid of the control example. On the other hand, the total amount of desorbed ammonia was higher for the carbonaceous material of this example than for the carbon solid acid of the control example. From this result, it was found that the carbonaceous material of this example had more acid sites than the carbon solid acid of the control example. It was also found that the number of acid points varies depending on the amount of iron nitrate dissolved in water when the carbonaceous material is synthesized. In this example, when 1.00 g of iron nitrate was dissolved in 100 ml of water to obtain a carbonaceous material (Example 4), the acid point was the highest.
[ラマン分光法による分析]
ラマン分光測定装置を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてラマン測定を行った。結果を図28に示す。図28に示すように、1580cm-1付近にGバンドと呼ばれるピークが、1350cm-1付近にDバンドと呼ばれるピークがそれぞれ確認された。Gバンドは炭素原子の六角格子内振動に起因するピークであり、Dバンドは無定形炭素等のダングリングボンドを持つ炭素原子に起因するピークである。そのため、Dバンド/Gバンドの強度比が大きければ大きいほど試料に含まれるグラフェンシートのサイズが大きくなる。Gバンドのピーク強度に対するDバンドの比が約0.8であり、これを根拠に、炭化物及び炭素質材料に含まれるグラフェンシートの平均的なサイズがいずれも約1nmであることがわかった。ラマン分光測定装置は、Jobin Yvon社製の「T-64000」を用いた。 [Analysis by Raman spectroscopy]
Using a Raman spectrometer, Raman measurement was performed on the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment. The results are shown in FIG. As shown in FIG. 28, a peak called G band around 1580 cm -1 is a peak called D band around 1350 cm -1 was confirmed, respectively. The G band is a peak caused by vibrations in the hexagonal lattice of carbon atoms, and the D band is a peak caused by carbon atoms having dangling bonds such as amorphous carbon. Therefore, the larger the intensity ratio of the D band / G band, the larger the size of the graphene sheet included in the sample. The ratio of the D band to the peak intensity of the G band was about 0.8, and based on this, it was found that the average size of the graphene sheets contained in the carbide and the carbonaceous material was both about 1 nm. As the Raman spectroscopic measurement apparatus, “T-64000” manufactured by Jobin Yvon was used.
ラマン分光測定装置を用いて、スルホン化処理前の実施例1の炭化物及びスルホン化処理後の実施例1の炭素質材料それぞれについてラマン測定を行った。結果を図28に示す。図28に示すように、1580cm-1付近にGバンドと呼ばれるピークが、1350cm-1付近にDバンドと呼ばれるピークがそれぞれ確認された。Gバンドは炭素原子の六角格子内振動に起因するピークであり、Dバンドは無定形炭素等のダングリングボンドを持つ炭素原子に起因するピークである。そのため、Dバンド/Gバンドの強度比が大きければ大きいほど試料に含まれるグラフェンシートのサイズが大きくなる。Gバンドのピーク強度に対するDバンドの比が約0.8であり、これを根拠に、炭化物及び炭素質材料に含まれるグラフェンシートの平均的なサイズがいずれも約1nmであることがわかった。ラマン分光測定装置は、Jobin Yvon社製の「T-64000」を用いた。 [Analysis by Raman spectroscopy]
Using a Raman spectrometer, Raman measurement was performed on the carbide of Example 1 before the sulfonation treatment and the carbonaceous material of Example 1 after the sulfonation treatment. The results are shown in FIG. As shown in FIG. 28, a peak called G band around 1580 cm -1 is a peak called D band around 1350 cm -1 was confirmed, respectively. The G band is a peak caused by vibrations in the hexagonal lattice of carbon atoms, and the D band is a peak caused by carbon atoms having dangling bonds such as amorphous carbon. Therefore, the larger the intensity ratio of the D band / G band, the larger the size of the graphene sheet included in the sample. The ratio of the D band to the peak intensity of the G band was about 0.8, and based on this, it was found that the average size of the graphene sheets contained in the carbide and the carbonaceous material was both about 1 nm. As the Raman spectroscopic measurement apparatus, “T-64000” manufactured by Jobin Yvon was used.
[磁気特性の測定]
試料振動式磁力計を用いて、スルホン化処理前の実施例1の炭化物11.00mg及びスルホン化処理後の実施例1の炭素質材料8.21mgをそれぞれアクリル製ホルダーに詰めて磁気特性を測定した。その結果、図29に示すように、スルホン化処理前の炭化物の保磁力は約100Oeであった。スルホン化処理後の炭素質材料の保磁力は約30Oeであった。そして、いずれの磁気曲線にもヒステリシスがほとんど見られず、軟磁性であることがわかった。スルホン化処理前の炭化物の飽和磁化は約12emu/gであり、スルホン化処理後の炭素質材料の飽和磁化は約6emu/gであった。また、スルホン化処理後の実施例2~5の炭素質材料の磁気特性も調べた。測定で得られた数値を表4に示し、磁気曲線を図30にまとめて示す。表4及び図30に示すように、実施例4の炭素材料の飽和磁化の値が最も高かった。 [Measurement of magnetic properties]
Using a vibrating sample magnetometer, 11.00 mg of the carbide of Example 1 before sulfonation and 8.21 mg of the carbonaceous material of Example 1 after sulfonation were packed in an acrylic holder, and the magnetic properties were measured. did. As a result, as shown in FIG. 29, the coercive force of the carbide before the sulfonation treatment was about 100 Oe. The coercive force of the carbonaceous material after the sulfonation treatment was about 30 Oe. And it was found that almost no hysteresis was observed in any of the magnetic curves, and it was soft magnetic. The saturation magnetization of the carbide before the sulfonation treatment was about 12 emu / g, and the saturation magnetization of the carbonaceous material after the sulfonation treatment was about 6 emu / g. In addition, the magnetic properties of the carbonaceous materials of Examples 2 to 5 after the sulfonation treatment were also examined. The numerical values obtained by the measurement are shown in Table 4, and the magnetic curves are shown together in FIG. As shown in Table 4 and FIG. 30, the carbon material of Example 4 had the highest saturation magnetization value.
試料振動式磁力計を用いて、スルホン化処理前の実施例1の炭化物11.00mg及びスルホン化処理後の実施例1の炭素質材料8.21mgをそれぞれアクリル製ホルダーに詰めて磁気特性を測定した。その結果、図29に示すように、スルホン化処理前の炭化物の保磁力は約100Oeであった。スルホン化処理後の炭素質材料の保磁力は約30Oeであった。そして、いずれの磁気曲線にもヒステリシスがほとんど見られず、軟磁性であることがわかった。スルホン化処理前の炭化物の飽和磁化は約12emu/gであり、スルホン化処理後の炭素質材料の飽和磁化は約6emu/gであった。また、スルホン化処理後の実施例2~5の炭素質材料の磁気特性も調べた。測定で得られた数値を表4に示し、磁気曲線を図30にまとめて示す。表4及び図30に示すように、実施例4の炭素材料の飽和磁化の値が最も高かった。 [Measurement of magnetic properties]
Using a vibrating sample magnetometer, 11.00 mg of the carbide of Example 1 before sulfonation and 8.21 mg of the carbonaceous material of Example 1 after sulfonation were packed in an acrylic holder, and the magnetic properties were measured. did. As a result, as shown in FIG. 29, the coercive force of the carbide before the sulfonation treatment was about 100 Oe. The coercive force of the carbonaceous material after the sulfonation treatment was about 30 Oe. And it was found that almost no hysteresis was observed in any of the magnetic curves, and it was soft magnetic. The saturation magnetization of the carbide before the sulfonation treatment was about 12 emu / g, and the saturation magnetization of the carbonaceous material after the sulfonation treatment was about 6 emu / g. In addition, the magnetic properties of the carbonaceous materials of Examples 2 to 5 after the sulfonation treatment were also examined. The numerical values obtained by the measurement are shown in Table 4, and the magnetic curves are shown together in FIG. As shown in Table 4 and FIG. 30, the carbon material of Example 4 had the highest saturation magnetization value.
スルホン化処理前の実施例6の炭化物63.84mgをアクリル製ホルダーに詰めて磁気特性を測定した。その結果、図31に示すように、スルホン化処理前の実施例6の炭化物の保磁力は約330.60Oeであり、飽和磁化は約34.84emu/gであった。スルホン化処理前の実施例8の炭化物82.57mgをアクリル製ホルダーに詰めて磁気特性を測定した。その結果、図32に示すように、スルホン化処理前の実施例8の炭素質材料の保磁力は約119.30Oeであり、飽和磁化は約26.15emu/gであった。測定で得られた数値を表4に示す。また、図33は、図29、31及び32をまとめた図である。振動試料型磁力計は、東英工業株式会社製の「VSM-15」を用いた。
The magnetic properties were measured by packing 63.84 mg of the carbide of Example 6 before sulfonation into an acrylic holder. As a result, as shown in FIG. 31, the coercive force of the carbide of Example 6 before the sulfonation treatment was about 330.60 Oe, and the saturation magnetization was about 34.84 emu / g. 82.57 mg of the carbide of Example 8 before sulfonation was packed in an acrylic holder, and the magnetic properties were measured. As a result, as shown in FIG. 32, the carbonaceous material of Example 8 before the sulfonation treatment had a coercive force of about 119.30 Oe and a saturation magnetization of about 26.15 emu / g. Table 4 shows the numerical values obtained by the measurement. FIG. 33 is a summary of FIGS. 29, 31, and 32. As the vibrating sample magnetometer, “VSM-15” manufactured by Toei Industry Co., Ltd. was used.
スルホン化処理後の実施例1の炭素質材料を酸触媒として用いたセルロースの加水分解(糖化)の実験を行った。当該炭素質材料30mgと、微結晶性セルロース(MERCK社製の商品名Avicel(Cellulose microcrystalline for column chromatography))30mgと、水0.3mlを密閉バイアル瓶(日電理化硝子株式会社製、型番:SVF-12、容量12ml)に入れ、当該密閉バイアル瓶に撹拌子を投入した。
Experiments on hydrolysis (saccharification) of cellulose using the carbonaceous material of Example 1 after sulfonation as an acid catalyst were conducted. 30 mg of the carbonaceous material, 30 mg of microcrystalline cellulose (trade name Avicel (Cellulose microcrystalline for column chromatography) manufactured by MERCK), and 0.3 ml of water are sealed vials (manufactured by Nippon Denka Glass Co., Ltd., model number: SVF- 12 and a volume of 12 ml), and a stirring bar was put into the sealed vial.
そして、上記密閉バイアル瓶を強磁力マグネティックスターラー(東京硝子器械株式会社製、型番:F-205D)上に設置したシリコンオイルバス(アズワン株式会社製、型番:EO-200)に浸し、120℃、3時間、撹拌速度400rpmでセルロースの加水分解を行った。その後、高速液体クロマトグラフィー(日本分光株式会社製、型番:LC-2000 plus)によって、密閉バイアル瓶の中の反応溶液に含まれるグルコースの量を測定した。結果を図34に示す。図34に示すように、スルホン化処理後の炭素質材料を触媒として用いるにより微結晶性セルロースが加水分解され、グルコース(Glucose)が生成することがわかった。このとき、グルコース生成量は0.211mgであった。また、セロビオース(Cellobiose)、キシロース(Xylose)、レボグルコサン(Levoglucosan)及びギ酸(Formic acid)も確認できた。この結果より、スルホン化処理後の実施例1の炭素質材料は固体酸として機能することがわかった。
Then, the sealed vial is immersed in a silicone oil bath (manufactured by As One Co., Ltd., model number: EO-200) placed on a strong magnetic stirrer (manufactured by Tokyo Glass Instrument Co., Ltd. model number: F-205D), The cellulose was hydrolyzed at a stirring speed of 400 rpm for 3 hours. Thereafter, the amount of glucose contained in the reaction solution in the sealed vial was measured by high performance liquid chromatography (manufactured by JASCO Corporation, model number: LC-2000 plus). The results are shown in FIG. As shown in FIG. 34, it was found that microcrystalline cellulose is hydrolyzed and glucose (Glucose) is produced by using a carbonaceous material after sulfonation as a catalyst. At this time, the amount of glucose produced was 0.211 mg. In addition, cellobiose, xylose, levoglucosan and formic acid were also confirmed. From this result, it was found that the carbonaceous material of Example 1 after the sulfonation treatment functions as a solid acid.
さらに、スルホン化処理後の実施例7の炭素質材料及びスルホン化処理後の実施例9の炭素質材料を酸触媒として用いたセルロースの加水分解(糖化)の実験を上記と同じ条件でそれぞれ行った。その結果、いずれの実験でも微結晶性セルロースが加水分解され、グルコース(Glucose)が生成することがわかった。したがって、スルホン化処理後の実施例7の炭素質材料及びスルホン化処理後の実施例9の炭素質材料ともに固体酸として機能することがわかった。
Further, the cellulose hydrolysis (saccharification) experiment using the carbonaceous material of Example 7 after the sulfonation treatment and the carbonaceous material of Example 9 after the sulfonation treatment as an acid catalyst was performed under the same conditions as described above. It was. As a result, it was found that microcrystalline cellulose was hydrolyzed and glucose (Glucose) was produced in any experiment. Therefore, it was found that both the carbonaceous material of Example 7 after the sulfonation treatment and the carbonaceous material of Example 9 after the sulfonation treatment function as a solid acid.
Claims (10)
- 無定形炭素を含む炭素質材料であって;
前記無定形炭素がグラフェンシートを含み、
前記炭素質材料はスルホ基を有し、
炭素原子に対する硫黄原子の比(S/C)が0.005~0.15であり、かつ
アンモニア昇温脱離法において、175~200℃の範囲にピーク温度を有するとともに、100~400℃で脱離するアンモニアの量から求められる酸点数が30μmol/g以上であることを特徴とする炭素質材料。 A carbonaceous material comprising amorphous carbon;
The amorphous carbon includes a graphene sheet;
The carbonaceous material has a sulfo group;
The ratio of sulfur atom to carbon atom (S / C) is 0.005 to 0.15, and the ammonia temperature programmed desorption method has a peak temperature in the range of 175 to 200 ° C., and at 100 to 400 ° C. A carbonaceous material characterized in that the number of acid points determined from the amount of desorbed ammonia is 30 μmol / g or more. - 炭素原子に対する水素原子の比(H/C)が1未満である請求項1記載の炭素質材料。 The carbonaceous material according to claim 1, wherein the ratio of hydrogen atoms to carbon atoms (H / C) is less than 1.
- BJH法により求められる全細孔容積が0.02~1cm3/gであり、平均細孔直径が2~30nmである請求項1又は2記載の炭素質材料。 3. The carbonaceous material according to claim 1, wherein the total pore volume determined by the BJH method is 0.02 to 1 cm 3 / g and the average pore diameter is 2 to 30 nm.
- 前記無定形炭素のマトリックス中に金属の酸化物の粒子が分散してなる請求項1~3のいずれか記載の炭素質材料。 4. The carbonaceous material according to claim 1, wherein metal oxide particles are dispersed in the amorphous carbon matrix.
- 保磁力が500Oe以下であり、飽和磁化が0.1emu/g以上である請求項4記載の炭素質材料。 The carbonaceous material according to claim 4, wherein the coercive force is 500 Oe or less and the saturation magnetization is 0.1 emu / g or more.
- 請求項1~5のいずれか記載の炭素質材料からなる固体酸。 A solid acid comprising the carbonaceous material according to any one of claims 1 to 5.
- 請求項1~5のいずれか記載の炭素質材料からなる吸着剤。 An adsorbent comprising the carbonaceous material according to any one of claims 1 to 5.
- 請求項1~5のいずれか記載の炭素質材料の製造方法であって;
水溶性の金属塩と水溶性の多糖とを水の存在下で混合する第1工程と、
前記第1工程で得られた混合物を炭化させる第2工程と、
前記第2工程で得られた炭化物をスルホン化処理する第3工程とを備えることを特徴とする炭素質材料の製造方法。 A method for producing a carbonaceous material according to any one of claims 1 to 5,
A first step of mixing a water-soluble metal salt and a water-soluble polysaccharide in the presence of water;
A second step of carbonizing the mixture obtained in the first step;
And a third step of sulfonating the carbide obtained in the second step. A method for producing a carbonaceous material, comprising: - 前記第2工程において、前記第1工程で得られた混合物を不活性ガス雰囲気下で80℃以上の温度で加熱する請求項8記載の炭素質材料の製造方法。 The method for producing a carbonaceous material according to claim 8, wherein in the second step, the mixture obtained in the first step is heated at a temperature of 80 ° C or higher in an inert gas atmosphere.
- 請求項6記載の固体酸を触媒として用いセルロースを加水分解することを特徴とするセルロースの加水分解方法。 A method for hydrolyzing cellulose, comprising hydrolyzing cellulose using the solid acid according to claim 6 as a catalyst.
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