JPH1033989A - Activated carbon production method - Google Patents
Activated carbon production methodInfo
- Publication number
- JPH1033989A JPH1033989A JP8216062A JP21606296A JPH1033989A JP H1033989 A JPH1033989 A JP H1033989A JP 8216062 A JP8216062 A JP 8216062A JP 21606296 A JP21606296 A JP 21606296A JP H1033989 A JPH1033989 A JP H1033989A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- titanium
- titanium dioxide
- coal
- activation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 46
- 230000004913 activation Effects 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000003245 coal Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002802 bituminous coal Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010840 domestic wastewater Substances 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
(57)【要約】
【課題】 活性炭の光触媒能を向上させる。
【解決手段】 活性炭の製造に際して、賦活より前の段
階で、チタン及び／又はチタン化合物（二酸化チタンを
除く）を添加することを特徴とする活性炭の製造方法。
【効果】 活性炭の光触媒能が大幅に向上する。(57) [Summary] [PROBLEMS] To improve the photocatalytic ability of activated carbon. SOLUTION: In the production of activated carbon, a method for producing activated carbon characterized by adding titanium and / or a titanium compound (excluding titanium dioxide) at a stage prior to activation. [Effect] The photocatalytic ability of activated carbon is greatly improved.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、活性炭の製造方法
に関するものである。本発明により製造される活性炭
は、粒径の小さい二酸化チタンの活性炭粒への固定化と
いう点において極めて優れており、活性炭の細孔を埋め
ることなく、表面に二酸化チタンが存在するものであ
る。このため、本発明により製造される活性炭は、紫外
線や太陽光照射下における、水中或いは気相中有害物質
の除去能及び寿命が大幅に向上され、上水処理、下水処
理、廃液処理、廃気ガス処理、悪臭除去等に好適に使用
される。TECHNICAL FIELD The present invention relates to a method for producing activated carbon. The activated carbon produced by the present invention is extremely excellent in immobilizing titanium dioxide having a small particle size to activated carbon particles, and has titanium dioxide on the surface without filling pores of the activated carbon. For this reason, the activated carbon produced by the present invention has a significantly improved ability to remove harmful substances in water or gaseous phase and a long life under irradiation of ultraviolet rays or sunlight, and is capable of treating tap water, sewage treatment, waste liquid treatment and waste air. It is suitably used for gas treatment, odor removal, and the like.
【０００２】[0002]
【従来技術】活性炭は、高比表面積であるため、優れた
吸着能を有しており、水中或いは気相中の有害物質を吸
着除去するために用いられている。近年、生活排水や産
業排水による水質汚染や海洋汚染、大気汚染などが地球
的規模で広がっている。合成洗剤などを含む生活排水に
よる湖・河川の富栄養化、ハイテク産業やクリーニング
店で使われている有機溶剤による地下水や水源の汚染、
ゴルフ場で使用される農薬の流出による水質の汚染等
が、その代表例である。2. Description of the Related Art Activated carbon has a high specific surface area and therefore has an excellent adsorption capacity, and is used for adsorbing and removing harmful substances in water or in the gas phase. In recent years, water pollution, marine pollution, air pollution, and the like due to domestic wastewater and industrial wastewater have spread on a global scale. Eutrophication of lakes and rivers with domestic wastewater containing synthetic detergents, pollution of groundwater and water sources with organic solvents used in high-tech industries and laundry shops,
Water pollution due to the outflow of pesticides used at golf courses is a typical example.
【０００３】現在広く行われている排水処理法の殆どが
活性汚泥法であるが、微生物を用いるため、温度、ｐ
Ｈ、ガス雰囲気、毒性などの条件が厳しく、しかも上述
の農薬や有機溶剤（含 ハロゲン化合物）、界面活性剤
などを分解、除去しにくく、これらに対して無力である
という欠点をもっている。このような生物学的に難分解
性の有機物の処理法としては、塩素処理法、オゾン処理
法、焼却処理法、活性炭吸着法などがある。塩素処理法
は、過剰注入による残留塩素、あるいは、被処理水中に
含まれる有機物と反応して発癌性を持つトリハロメタン
に代表される有機ハロゲン化合物を生成するなどの問題
がある。また、最近、浄水場等において、高度浄水処理
法として、オゾン処理が脚光を浴びているが、設備費、
運転費共に高価であるという問題がある。焼却処理法
は、希薄溶液の場合には現実的でない。活性炭吸着法
は、非常に有効な方法ではあるが、有機ハロゲン化合物
の吸着除去能が若干劣り、水中の有害物質全てに対して
有効というわけではなかった。Most of the wastewater treatment methods widely used at present are activated sludge methods.
H, gas atmosphere, and toxic conditions are severe, and the above-mentioned agricultural chemicals, organic solvents (halogen-containing compounds), surfactants, and the like are difficult to decompose and remove, and are ineffective against them. Examples of a method for treating such a biologically hardly decomposable organic substance include a chlorination method, an ozone treatment method, an incineration treatment method, and an activated carbon adsorption method. The chlorination method has a problem such as residual chlorine due to excessive injection, or reaction with an organic substance contained in the water to be treated to generate an organic halogen compound represented by carcinogenic trihalomethane. Recently, ozone treatment has been in the spotlight as an advanced water purification method in water treatment plants, but equipment costs,
There is a problem that both operating costs are expensive. The incineration method is not practical for dilute solutions. The activated carbon adsorption method is a very effective method, but has a slightly inferior ability to adsorb and remove organic halogen compounds and is not effective for all harmful substances in water.
【０００４】大気汚染や悪臭物質等の気相中有害物質の
除去においても、活性炭の吸着除去は有効である。一般
に、気相中の汚染成分を対象とする吸着技術は、水蒸気
や炭酸ガスの共存下で低濃度ガスに対して有効なもので
なければならない。活性炭は、そのような条件下で多種
類の有機、無機化合物に対して使用される。気相用活性
炭は、特に大きい比表面積と小孔径の細孔構造を持ち、
低濃度ガスに対する吸着親和性が大きい。また、その表
面が疎水性であるために水蒸気に対する吸着親和性が小
さく、気相中に混在する有害ガスや臭気物質、特に有機
化合物を効率良く除去することができる。しかし、吸着
親和性が弱いガスもあり、活性炭の吸着除去能は、全て
の場合において万能というわけではなかった。In the removal of harmful substances in the gas phase, such as air pollution and malodorous substances, adsorption and removal of activated carbon is effective. In general, an adsorption technique for a contaminant in a gas phase must be effective for a low-concentration gas in the presence of water vapor or carbon dioxide gas. Activated carbon is used for many types of organic and inorganic compounds under such conditions. Activated carbon for gas phase has a particularly large specific surface area and a small pore size pore structure,
High adsorption affinity for low concentration gas. In addition, since its surface is hydrophobic, its adsorption affinity for water vapor is low, and harmful gases and odorous substances, particularly organic compounds, mixed in the gas phase can be efficiently removed. However, some gases have weak adsorption affinity, and the ability to remove activated carbon by adsorption was not universal in all cases.
【０００５】一方、二酸化チタンの結晶を光電極とする
半導体光電極を用いて、光エネルギーを直接的に水の分
解に利用できることが、１９６９年に発見されて以来
（本多−藤嶋効果）、二酸化チタンに代表される光触媒
は、光エネルギーを化学エネルギーへ変換する有力な手
段になり得るものとして、世界的に様々な分野で研究開
発が活発に進められている。光触媒反応は、（１）半導
体が光を吸収し、励起して電子−正孔対を生じる光励起
過程と、（２）生成した電子および正孔が、半導体粒子
内電位勾配や拡散により各々表面に移動する電荷分離と
移動の過程、（３）表面に移動した正孔および電子が触
媒に吸着した基質と電子移動を起こし、各々酸化還元反
応を行う表面反応過程に分かれる。On the other hand, since it was discovered in 1969 that light energy could be directly used for decomposition of water using a semiconductor photoelectrode using a titanium dioxide crystal as a photoelectrode (Honda-Fujishima effect), BACKGROUND ART Photocatalysts represented by titanium dioxide can be a powerful means for converting light energy into chemical energy, and research and development are being actively promoted in various fields worldwide. The photocatalytic reaction involves (1) a photo-excitation process in which a semiconductor absorbs light and excites it to generate an electron-hole pair, and (2) generated electrons and holes are generated on the surface by potential gradient and diffusion in semiconductor particles. The process of moving charge separation and movement, and (3) the surface reaction process in which holes and electrons transferred to the surface cause the transfer of electrons to the substrate adsorbed on the catalyst, and each undergoes an oxidation-reduction reaction.
【０００６】これらの知見に基づき、本発明者らは、光
触媒能を有する二酸化チタンを表面に適度に存在させた
活性炭として、先に、二酸化チタンが表面に存在し、明
度Ｌ値が５０以下であることを特徴とする活性炭（特願
平７−０３７７５８）、石炭を粉砕し、造粒し、解砕
し、炭化し、賦活して石炭系活性炭を製造する方法にお
いて、造粒前の石炭に、二酸化チタンを添加することを
特徴とする石炭系活性炭及びその製造方法（特願平７−
１８７９５４）、並びに原料炭を微粉砕し、粘結材と混
練し、造粒し、硬化炭化し、賦活して造粒活性炭を製造
する方法において、造粒前の原料炭に、二酸化チタンを
添加することを特徴とする造粒活性炭及びその製造方法
（特願平７−２２１９６５）を開発した。[0006] Based on these findings, the present inventors have proposed, as an activated carbon in which titanium dioxide having photocatalytic activity is appropriately present on the surface, titanium dioxide is first present on the surface and the lightness L value is 50 or less. Activated carbon (Japanese Patent Application No. Hei 7-037758) characterized by the fact that coal is pulverized, granulated, crushed, carbonized, and activated to produce coal-based activated carbon. Activated carbon and a method for producing the same based on the addition of titanium dioxide
187954) and, in a method of pulverizing raw coal, kneading with a binder, granulating, hardening and carbonizing, and activating to produce granulated activated carbon, adding titanium dioxide to raw coal before granulation. And a method for producing the same (Japanese Patent Application No. 7-221965).
【０００７】しかしながら、光触媒能に大きく影響する
二酸化チタンの粒径は、活性炭製造時の賦活より前の工
程で添加される二酸化チタンの粒径で決まるため、光触
媒能向上のために、さらなる小粒径化という課題が残さ
れていた。However, the particle size of titanium dioxide, which greatly affects the photocatalytic activity, is determined by the particle size of titanium dioxide added in a step prior to activation during the production of activated carbon. The problem of diameter reduction remained.
【０００８】[0008]
【発明が解決しようとする課題】そこで、本発明者は、
上記の課題を解決すべく鋭意検討した結果、活性炭を製
造する際に、特定の時点で二酸化チタン以外のチタン化
合物を添加することにより、賦活工程後には、光触媒能
の高い極めて粒径の小さなアナターゼ型やルチル型Ｔｉ
Ｏ2として存在する活性炭が得られることを見い出し
た。さらに、こうして得られた活性炭は、活性炭粒に二
酸化チタンがしっかりと固定化され、二酸化チタンの離
散が極めて少ない組織となっていることを見い出し本発
明に到達した。Therefore, the present inventor has proposed:
As a result of intensive studies to solve the above problems, when producing activated carbon, by adding a titanium compound other than titanium dioxide at a specific point in time, after the activation step, an anatase having an extremely small particle size having a high photocatalytic activity is high. Type and rutile type Ti
It has been found that activated carbon present as O 2 is obtained. Furthermore, the activated carbon thus obtained has been found to have a structure in which titanium dioxide is firmly immobilized on the activated carbon granules, and has a structure in which titanium dioxide is dispersed very little.
【０００９】[0009]
【課題を解決するための手段】即ち、本発明は、活性炭
の製造に際して、賦活より前の段階で、チタン及び／又
はチタン化合物（二酸化チタンを除く）を添加すること
を特徴とする活性炭の製造方法、に存する。That is, the present invention provides a method for producing activated carbon, which comprises adding titanium and / or a titanium compound (excluding titanium dioxide) at a stage prior to activation in the production of activated carbon. The way, lies in.
【００１０】[0010]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明の最大の特徴は、活性炭の製造に際して、賦活よ
り前の段階において、チタン及び／又はチタン化合物
（二酸化チタンを除く）を添加することにあり、これを
各種の活性炭の製造方法に応用できる。具体的には、例
えば石炭を粉砕し、造粒し、破砕し、炭化し、賦活して
破砕状石炭系活性炭を製造するに際して、造粒前の石炭
に、チタン及び／又はチタン化合物を添加する方法、原
料炭を微粉砕し、粘結剤と混練し、造粒し、硬化炭化
し、賦活して造粒活性炭を製造するに際して、造粒前の
原料炭にチタン化合物を添加する方法、等が採用でき
る。もちろん、粉末活性炭、繊維状活性炭の製造に際し
ても、本発明により賦活より前の段階でチタン及び／又
はチタン化合物を添加することができる。こうして賦活
より前の段階でチタン及び／又はチタン化合物を添加す
ることにより、二酸化チタンを活性炭粒中に強固に固定
化でき、しかも光触媒能を有する極めて小粒径の二酸化
チタンが活性炭粒の表面に存在するものとすることがで
きる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The greatest feature of the present invention is that, in the production of activated carbon, at the stage before activation, titanium and / or a titanium compound (excluding titanium dioxide) are added, which can be applied to various production methods of activated carbon. . Specifically, for example, when coal is pulverized, granulated, crushed, carbonized, and activated to produce crushed coal-based activated carbon, titanium and / or a titanium compound is added to the coal before granulation. Method, pulverizing raw coal, kneading it with a binder, granulating, hardening and carbonizing, and activating it to produce granulated activated carbon, adding a titanium compound to raw coal before granulation, etc. Can be adopted. Of course, in the production of powdered activated carbon and fibrous activated carbon, titanium and / or a titanium compound can be added at a stage before activation according to the present invention. By adding titanium and / or a titanium compound at a stage before the activation in this way, titanium dioxide can be firmly fixed in the activated carbon particles, and very small particle diameter titanium dioxide having photocatalytic ability can be applied to the surface of the activated carbon particles. Can be present.
【００１１】本発明により破砕状石炭系活性炭を製造す
る場合、用いられる石炭としては、特に限定されない
が、一般的には造粒性がその選定条件となる。例えば、
瀝青炭、褐炭、無煙炭、亜炭、草炭、泥炭等を用いるこ
とができ、必要に応じて造粒性向上のために、タール、
ピッチを混合してもよい。これら石炭のうち、粘結性の
ある瀝青炭が特に好ましい。In the case of producing a crushed coal-based activated carbon according to the present invention, the coal to be used is not particularly limited, but generally the granulation property is a selection condition. For example,
Bituminous coal, lignite, anthracite, lignite, peat, peat, etc. can be used, and if necessary, tar,
The pitch may be mixed. Of these coals, caking bituminous coal is particularly preferred.
【００１２】本発明により造粒活性炭を製造する場合、
用いることのできる原料炭としては特に限定されず、例
えば、ヤシ殻炭、コークス、木炭、石炭等が挙げられ
る。原料炭を微粉砕して、粒度として好ましくは１００
μｍ以下、好ましくは７５μｍ以下とするのがよい。こ
の微粉砕炭に、必要に応じコールタール、ピッチ、糖
密、樹液、デンプンなどの粘結剤とチタン化合物とを加
え、加熱混練し、ペレタイザー、コンパクターや射出プ
レス等の造粒機で造粒する。When producing granulated activated carbon according to the present invention,
The raw coal that can be used is not particularly limited, and examples thereof include coconut shell charcoal, coke, charcoal, and coal. The raw coal is pulverized to a particle size of preferably 100
μm or less, preferably 75 μm or less. If necessary, a binder such as coal tar, pitch, molasses, sap and starch and a titanium compound are added to this finely pulverized coal, and the mixture is kneaded by heating and granulated with a granulator such as a pelletizer, a compactor or an injection press. I do.
【００１３】本発明により繊維状活性炭を製造する場
合、用いられる繊維原料としては特に限定されず、例え
ば、セルロース系、アクリロニトリル系、フェノール
系、ピッチ系、塩化ビリニデン等が挙げられる。本発明
で使用されるチタン化合物としては、二酸化チタン以外
であれば特に限定されず、活性炭の製造工程において酸
化チタンとなりうるものであれば足りる。具体的には、
ＴｉＣｌ4、Ｔｉ（ＳＯ4)2、ＴｉＯＳＯ4、（ＮＨ4)2TｉＯ
（Ｃ2Ｏ4)2・２Ｈ2Ｏなどの水溶液、または、これらから
生成したチタン酸の沈澱物、チタンテトライソプロポキ
シド、チタンテトラブトキシド、チタン２エチル１ヘキ
サノラートなどＴｉの有機金属塩をアルコール等の有機
溶媒に溶解させた溶液が好適である。When producing a fibrous activated carbon according to the present invention, the fibrous raw material to be used is not particularly limited, and examples thereof include a cellulose type, an acrylonitrile type, a phenol type, a pitch type, and a vinylidene chloride. The titanium compound used in the present invention is not particularly limited as long as it is other than titanium dioxide, and any compound that can become titanium oxide in the production process of activated carbon is sufficient. In particular,
TiCl 4 , Ti (SO 4 ) 2 , TiOSO 4 , (NH 4 ) 2 TiO
Aqueous solution of (C 2 O 4) 2 · 2H 2 O , or precipitate titanate produced from these, titanium tetraisopropoxide, titanium tetrabutoxide, alcohol organometallic salts of Ti, such as titanium 2-ethyl 1 Hekisanorato A solution dissolved in an organic solvent such as described above is preferable.
【００１４】原料炭へのチタン及び／又はチタン化合物
（二酸化チタンを除く）の混合の時期については、賦活
工程より前であれば特に限定されないが、好ましくは炭
化工程前に行うのがよい。例えば、破砕状石炭系活性炭
を製造する場合、石炭の粉砕前にチタン及び／又はチタ
ン化合物を添加してもよいし、粉砕後に添加してもよい
が、いずれにしても、炭化工程前で添加することが好ま
しい。The timing of mixing titanium and / or a titanium compound (excluding titanium dioxide) into the raw coal is not particularly limited as long as it is before the activation step, but it is preferably performed before the carbonization step. For example, when producing crushed coal-based activated carbon, titanium and / or a titanium compound may be added before pulverizing the coal, or may be added after pulverization. Is preferred.
【００１５】最終的な活性炭と二酸化チタンの割合は、
賦活の程度により異なってくる。原料炭へのチタン及び
／又はチタン化合物の添加量は特に制限されないが、造
粒性や紡糸を損ねない程度が好ましく、通常、大まかに
４０重量％以下、特に好ましくは３０重量％以下が適当
である。更に好ましくは、活性炭表面が二酸化チタンで
覆い尽くされることなく、適度に表面を覆っている状態
の活性炭とするのがよく、これを具体的に数値で表すた
め、二酸化チタンが白く、活性炭が黒色であることを利
用して、表面の状態を表面の明度で規定し、明度（Ｌ
値）で５０以下、好ましくは４０以下の状態の活性炭が
好適に使用される。The final ratio of activated carbon and titanium dioxide is:
It depends on the degree of activation. The amount of titanium and / or titanium compound added to the raw coal is not particularly limited, but is preferably such that granulation properties and spinning are not impaired, and is generally approximately 40% by weight or less, and particularly preferably 30% by weight or less. is there. More preferably, the activated carbon surface is not completely covered with titanium dioxide, and it is preferable to use activated carbon in a state in which the surface is appropriately covered.In order to specifically express the numerical value, titanium dioxide is white and activated carbon is black. By utilizing the fact that the surface state is defined by the brightness of the surface, the brightness (L
(Value) is preferably 50 or less, preferably 40 or less.
【００１６】炭化工程は、５００〜９００℃程度で行
い、加熱乾留することで炭素質有機物を分解炭化する。
続いて賦活を行う。賦活の方法は、水蒸気賦活、薬品賦
活等の公知の方法を用いることができ、この賦活時の温
度は、水蒸気賦活であれば、９００〜１１００℃が好適
であり、薬品賦活であれば、５００〜８００℃が好適で
ある。コストの面からは、水蒸気賦活がより好ましい
が、二酸化チタンの粒成長を抑える点では、より低温で
の薬品賦活が好ましいと言える。炭化及び賦活工程にお
いて、二酸化チタン以外のチタン化合物が酸化され、二
酸化チタンになる。そしてかかる方法で得られた二酸化
チタンは図３に示すように、数十ｎｍという極めて小さ
い粒径とすることができ、少量でも大きな効果を得るこ
とができる。The carbonization step is performed at about 500 to 900 ° C., and carbonized organic matter is decomposed and carbonized by heating to dry distillation.
Subsequently, activation is performed. A known method such as water vapor activation or chemical activation can be used for the activation method. The temperature at the time of this activation is preferably 900 to 1100 ° C. if it is water vapor activation, and is 500 if it is chemical activation. ~ 800 ° C is preferred. From the viewpoint of cost, steam activation is more preferable, but from the viewpoint of suppressing grain growth of titanium dioxide, it can be said that chemical activation at lower temperature is preferable. In the carbonization and activation step, titanium compounds other than titanium dioxide are oxidized to titanium dioxide. As shown in FIG. 3, the titanium dioxide obtained by such a method can have an extremely small particle size of several tens nm, and a large effect can be obtained even with a small amount.
【００１７】また、本発明の方法において、コスト面を
重視する場合には、二酸化チタン以外のチタン化合物と
同時に、通常の二酸化チタン粒子も添加して、低コスト
化をはかってもよい。本発明により得られる活性炭は、
従来使用されている活性炭と同様に使用することがで
き、流動床、固定床等の使用法を問わない。従来の装置
がそのまま使用可能であり、装置を大型化する必要もな
い。さらに、本発明の活性炭を紫外線や太陽光照射下で
使用することにより、水中あるいは気相中の有害物質の
除去は、活性炭のみによる吸着除去に比べ、二酸化チタ
ンの光触媒反応による分解除去が加わるため、その除去
能は飛躍的に増加することになる。特に、活性炭では従
来、吸着除去が難しかった有機ハロゲン化合物、臭気物
質などが多く含まれる被処理水あるいは被処理ガスなど
にも好適に使用される。また、活性炭に藻が生えにくく
なることや、活性炭の再生までの時間がより長くなるこ
と等の長所があるため、装置の維持・管理が今まで以上
に容易になる。In the method of the present invention, when importance is placed on cost, ordinary titanium dioxide particles may be added simultaneously with a titanium compound other than titanium dioxide to reduce the cost. Activated carbon obtained by the present invention,
It can be used in the same manner as conventionally used activated carbon, and it does not matter how to use the fluidized bed, fixed bed and the like. The conventional device can be used as it is, and there is no need to increase the size of the device. Further, by using the activated carbon of the present invention under irradiation of ultraviolet rays or sunlight, removal of harmful substances in water or in the gas phase is compared with adsorption removal by activated carbon alone, because decomposition and removal by titanium dioxide photocatalytic reaction are added. , Its removal ability will increase dramatically. In particular, activated carbon is preferably used for water to be treated or gas to be treated which contains a large amount of organic halogen compounds and odorous substances which have been difficult to remove by adsorption. In addition, since there are advantages such as the difficulty of algae growing on the activated carbon and the longer time required for regeneration of the activated carbon, the maintenance and management of the apparatus becomes easier than ever.
【００１８】[0018]
【実施例】以下、本発明を実施例により更に具体的に説
明する。 （実施例１）（ＮＨ4)2ＴｉＯ（Ｃ2Ｏ4)2・２Ｈ2Ｏ ３
０ｇを水１.５ｌｇに溶解し、４４μｍ以下に粉砕した
瀝青炭１５０ｇと混合し、ロータリーエバポレータで水
分を除去し、造粒後、０．５〜２．０ｍｍ程度に破砕し
た。窒素５リットル／ｍｉｎの気流中７５０℃で３０分
間炭化を行い、水蒸気５０ｖｏｌ％を含む窒素ガスを１
リットル／ｍｉｎで導入した９００℃のキルン内で２ｈ
賦活を行った。カルロエルバ社製（「ソープトマチック
２１００」）の窒素吸着装置でＢＥＴ法により測定した
ところ、得られた試料の比表面積は１１７０ｍ2/ｇであ
った。得られた試料のＸ線回折測定を行ったところ、炭
素と二酸化チタン（アナターゼとルチル）のみであり、
副生成物は検出されなかった。二酸化チタンの固形分濃
度は、ＩＣＰ発光分光分析より求めたところ、１５ｗｔ
％であった。二酸化チタンの活性炭粒中での存在状態を
確認するため、ＳＥＭ観察（含むＥＤＸ）とＴＥＭ観察
（含むＥＤＸ）を行った。図１に、ＳＥＭ写真を示す。
白色の数十ｎｍの粒が二酸化チタンであることは、ＳＥ
Ｍ−ＥＤＸ（ＳＥＭ：（株）日立製作所製 「Ｓ−４５
００」、ＥＤＸ：Ｋｅｖｅｘ社製 「Ｄｅｌｔａ Ｓｙ
ｓｔｅｍ」）により、ＴｉのＸ線スペクトルから確認し
た。図２、３にＴＥＭ写真を示す（「日立Ｈ−９０００
ＵＨＲ」）。これより、二酸化チタンが数十ｎｍレベル
で活性炭中に存在し、しかも、強固に固定化されている
ことがわかる。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. (Example 1) (NH 4) 2 TiO (C 2 O 4) 2 · 2H 2 O 3
0 g was dissolved in 1.5 lg of water, mixed with 150 g of bituminous coal pulverized to 44 μm or less, water was removed by a rotary evaporator, and after granulation, the mixture was crushed to about 0.5 to 2.0 mm. Carbonization is performed at 750 ° C. for 30 minutes in a stream of nitrogen at 5 liters / min.
2 hours in a kiln at 900 ° C introduced at liter / min
Activation was performed. The specific surface area of the obtained sample was 1170 m 2 / g as measured by a BET method using a nitrogen adsorption apparatus manufactured by Carlo Elba (“Soapmatic 2100”). When an X-ray diffraction measurement of the obtained sample was performed, only carbon and titanium dioxide (anatase and rutile) were obtained.
No by-products were detected. The solid content concentration of titanium dioxide was 15 wt% as determined by ICP emission spectroscopy.
%Met. SEM observation (including EDX) and TEM observation (including EDX) were performed to confirm the existence state of titanium dioxide in the activated carbon particles. FIG. 1 shows an SEM photograph.
The fact that the white tens of nm particles are titanium dioxide means that
M-EDX (SEM: "S-45" manufactured by Hitachi, Ltd.)
00 ”, EDX:“ Delta Sy ”manufactured by Kevex
stem ") to confirm from the X-ray spectrum of Ti. 2 and 3 show TEM photographs (“Hitachi H-9000”).
UHR "). This indicates that titanium dioxide is present in the activated carbon at a level of several tens of nanometers and is firmly fixed.
【００１９】こうして得られた活性炭０．１ｇをクロロ
ホルム２１ｐｐｍの原水１３０ｍｌの入った三角フラス
コに入れ、スターラー撹拌しながら、１４０Ｗの紫外線
ランプ照射下で、クロロホルム除去テストを行った。２
時間後、ヘッドスペース法でクロロホルム濃度の測定を
行ったところ、４ｐｐｍに減少していた。0.1 g of the activated carbon thus obtained was placed in an Erlenmeyer flask containing 130 ml of raw water containing 21 ppm of chloroform, and subjected to a chloroform removal test under irradiation with a 140 W ultraviolet lamp while stirring with a stirrer. 2
After a lapse of time, the concentration of chloroform was measured by the headspace method and found to be reduced to 4 ppm.
【００２０】（比較例１）実施例１で、紫外線ランプを
照射しない以外は同様の操作により、クロロホルム除去
テストを行ったところ、２時間後のクロロホルム濃度は
９ｐｐｍであった。これより、光触媒能の効果により、
除去能が向上していることが良くわかる。Comparative Example 1 A chloroform removal test was carried out in the same manner as in Example 1 except that no ultraviolet lamp was irradiated. As a result, the chloroform concentration after 2 hours was 9 ppm. From this, due to the effect of photocatalytic ability,
It can be clearly seen that the removal ability has been improved.
【００２１】（比較例２）１ｍｍ程度に粉砕した瀝青炭
１５０ｇと、石原産業（株）製二酸化チタン（「アナタ
ーゼ ＭＣ−５０」）７.５ｇと混合し、更に振動式の
粉砕機にて、４５μm以下に粉砕し、造粒後、０.５〜
２.０ｍｍ程度に破砕した。実施例１と同様に、炭化、
賦活し、得られた試料の比表面積を測定したところ、１
１５０ｍ2/ｇであった。また、得られた試料のＸ線回折
測定を行ったところ、炭素と二酸化チタン（アナターゼ
とルチル）のみであり、副生成物は検出されなかった。
二酸化チタンの固形分濃度は、ＩＣＰ発光分光分析より
求めたところ、１５ｗｔ％であった。活性炭粒中での二
酸化チタンの粒径を確認するため、ＳＥＭ観察およびＴ
ＥＭ観察を行ったところ、数百ｎｍ程度の粒径であっ
た。こうして得られた活性炭について、実施例１と同様
の操作により、クロロホルム除去テストを行ったとこ
ろ、２時間後のクロロホルム濃度は６ｐｐｍであった。(Comparative Example 2) 150 g of bituminous coal pulverized to about 1 mm and 7.5 g of titanium dioxide ("Anatase MC-50") manufactured by Ishihara Sangyo Co., Ltd. were further mixed with a vibrating pulverizer to 45 μm. After crushing and granulating,
Crushed to about 2.0 mm. As in Example 1, carbonization,
The sample was activated and the specific surface area of the obtained sample was measured.
It was 150 m 2 / g. Further, when the obtained sample was subjected to X-ray diffraction measurement, it was only carbon and titanium dioxide (anatase and rutile), and no by-product was detected.
The solid concentration of titanium dioxide was 15 wt% as determined by ICP emission spectroscopy. To confirm the particle size of titanium dioxide in the activated carbon particles, SEM observation and T
As a result of EM observation, the particle diameter was about several hundred nm. The activated carbon thus obtained was subjected to a chloroform removal test in the same manner as in Example 1. As a result, the chloroform concentration after 2 hours was 6 ppm.
【００２２】[0022]
【発明の効果】本発明の活性炭は、水中あるいは気相中
有害物質の除去能を大幅に向上することができ、多大な
工業的利益を提供するものである。Industrial Applicability The activated carbon of the present invention can greatly improve the ability to remove harmful substances in water or in the gas phase, and provides a great industrial advantage.
【図１】実施例１で得られた活性炭の表面に存在する二
酸化チタン粒子の形状を示す、走査型電子顕微鏡写真
（ＳＥＭ写真）による粒子構造を示す図FIG. 1 is a diagram showing a particle structure by a scanning electron micrograph (SEM photograph) showing the shape of titanium dioxide particles present on the surface of activated carbon obtained in Example 1.
【図２】実施例１で得られた活性炭の表面に存在する二
酸化チタン粒子の形状を示す、透過型電子顕微鏡写真
（ＴＥＭ写真）による粒子構造を示す図FIG. 2 is a diagram showing a particle structure by a transmission electron micrograph (TEM photograph) showing the shape of titanium dioxide particles present on the surface of the activated carbon obtained in Example 1.
【図３】実施例１で得られた活性炭の表面に存在する二
酸化チタン粒子の形状を示す、透過型電子顕微鏡写真
（ＴＥＭ写真）による粒子構造を示す図FIG. 3 is a view showing a particle structure by a transmission electron microscope photograph (TEM photograph) showing a shape of titanium dioxide particles present on a surface of the activated carbon obtained in Example 1.
Claims (6)
で、チタン及び／又はチタン化合物（二酸化チタンを除
く）を添加することを特徴とする活性炭の製造方法。1. A method for producing activated carbon, comprising adding titanium and / or a titanium compound (excluding titanium dioxide) at a stage prior to activation in producing activated carbon.
賦活して破砕状石炭系活性炭を製造するに際して、造粒
前の石炭に、チタン及び／又はチタン化合物（二酸化チ
タンを除く）を添加することを特徴とする請求項１記載
の活性炭の製造方法。2. Coal is crushed, granulated, crushed, carbonized,
The method for producing activated carbon according to claim 1, wherein, when activated to produce crushed coal-based activated carbon, titanium and / or a titanium compound (excluding titanium dioxide) is added to the coal before granulation.
し、硬化炭化し、賦活して造粒活性炭を製造するに際し
て、造粒前の原料炭に、チタン及び／又はチタン化合物
（二酸化チタンを除く）を添加することを特徴とする請
求項１記載の活性炭の製造方法。3. When the raw coal is pulverized, kneaded with a binder, granulated, hardened and carbonized, and activated to produce granulated activated carbon, titanium and / or titanium is added to the raw coal before granulation. The method for producing activated carbon according to claim 1, wherein a titanium compound (excluding titanium dioxide) is added.
製造方法。4. The method according to claim 1, wherein the activated carbon is powdered activated carbon.
の製造方法。5. The method according to claim 1, wherein the activated carbon is fibrous activated carbon.
タンを除く）を、溶液の形で添加する請求項１〜５のい
ずれかに記載の活性炭の製造方法。6. The method for producing activated carbon according to claim 1, wherein titanium and / or a titanium compound (excluding titanium dioxide) is added in the form of a solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216062A JPH1033989A (en) | 1996-07-29 | 1996-07-29 | Activated carbon production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216062A JPH1033989A (en) | 1996-07-29 | 1996-07-29 | Activated carbon production method |
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| Publication Number | Publication Date |
|---|---|
| JPH1033989A true JPH1033989A (en) | 1998-02-10 |
Family
ID=16682687
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001321677A (en) * | 2000-05-18 | 2001-11-20 | Kohjin Co Ltd | Titanium oxide / carbon composite particles and method for producing the same |
| JP2005254123A (en) * | 2004-03-11 | 2005-09-22 | Ohbayashi Corp | Porous material provided with photocatalyst and method for producing the same |
| CN102432326A (en) * | 2011-08-25 | 2012-05-02 | 上海交通大学 | Porous carbon-titanium dioxide composite material and its preparation method |
| CN107876102A (en) * | 2017-10-12 | 2018-04-06 | 常州工学院 | A kind of photocatalyst material |
| CN114790015A (en) * | 2021-05-07 | 2022-07-26 | 浙江施维康生物医学材料有限公司 | Slow-release sustained-effect water purifying agent and preparation method thereof |
-
1996
- 1996-07-29 JP JP8216062A patent/JPH1033989A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001321677A (en) * | 2000-05-18 | 2001-11-20 | Kohjin Co Ltd | Titanium oxide / carbon composite particles and method for producing the same |
| JP2005254123A (en) * | 2004-03-11 | 2005-09-22 | Ohbayashi Corp | Porous material provided with photocatalyst and method for producing the same |
| CN102432326A (en) * | 2011-08-25 | 2012-05-02 | 上海交通大学 | Porous carbon-titanium dioxide composite material and its preparation method |
| CN107876102A (en) * | 2017-10-12 | 2018-04-06 | 常州工学院 | A kind of photocatalyst material |
| CN114790015A (en) * | 2021-05-07 | 2022-07-26 | 浙江施维康生物医学材料有限公司 | Slow-release sustained-effect water purifying agent and preparation method thereof |
| CN114790015B (en) * | 2021-05-07 | 2023-10-20 | 浙江施维康生物医学材料有限公司 | Sustained-release and sustained-effect water purifying agent and preparation method thereof |
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