JP4537699B2 - Activated carbon slurry transport method - Google Patents
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- JP4537699B2 JP4537699B2 JP2003429551A JP2003429551A JP4537699B2 JP 4537699 B2 JP4537699 B2 JP 4537699B2 JP 2003429551 A JP2003429551 A JP 2003429551A JP 2003429551 A JP2003429551 A JP 2003429551A JP 4537699 B2 JP4537699 B2 JP 4537699B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 239
- 239000002002 slurry Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 97
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 48
- 239000001569 carbon dioxide Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 229960004424 carbon dioxide Drugs 0.000 description 45
- 239000007789 gas Substances 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 22
- 239000002253 acid Substances 0.000 description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 235000010755 mineral Nutrition 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- -1 sawdust Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000001994 activation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Description
本発明は、水によるスラリー輸送をした際、排水のｐH値を中性付近に保つことのできる活性炭、若しくは水処理用に使用した場合、速やかに処理水のpH値を中性付近に安定させる活性炭及びその製法に関する。 The present invention quickly stabilizes the pH value of the treated water near neutral when used for activated carbon that can maintain the pH value of the wastewater near neutral when the slurry is transported by water, or for water treatment. The present invention relates to activated carbon and its manufacturing method.
活性炭を吸着塔などに充填する際、水によってスラリーとしてポンプで輸送すれば、クレーンなどの重機を使用せずにすみ、活性炭の微粉除去も同時に行えるという利点がある。ところが、活性炭は、原料に由来して、または賦活工程におけるアルカリ剤の使用などにより、一般にアルカリ性であるので、そのままでスラリー輸送すると、水が著しくアルカリ性となり、排水をそのまま廃棄できないという問題点があった。
活性炭のｐH値を低下させる方法として、活性炭を鉱酸で洗浄するという方法があるが、今度は残留する酸が吸着塔を腐食させる恐れがあり、特に溶剤回収用など、ガス処理に活性炭を使用する場合、充填後は酸が洗い流されることがないため、設備の腐食の原因となることがある。
また、活性炭を湿潤化することでpH値を低下させる方法も知られているが、同時に表面酸化物が増加し、吸着性能の低下を招くので好ましくない。
When the activated carbon is packed in an adsorption tower or the like, if it is pumped as a slurry with water, there is an advantage that it is not necessary to use heavy equipment such as a crane and fine particles of the activated carbon can be removed at the same time. However, activated carbon originates from raw materials or is generally alkaline due to the use of an alkaline agent in the activation process, etc., and therefore, if the slurry is transported as it is, the water becomes extremely alkaline, and the wastewater cannot be discarded as it is. It was.
As a method of reducing the pH value of activated carbon, there is a method of washing activated carbon with mineral acid, but this time, residual acid may corrode the adsorption tower, and activated carbon is used for gas treatment, especially for solvent recovery. In this case, the acid is not washed away after filling, which may cause corrosion of the equipment.
Further, a method of lowering the pH value by wetting the activated carbon is also known, but it is not preferable because the surface oxide is increased at the same time and the adsorption performance is lowered.
特許文献１には、酸性ガスを活性炭と接触させることで、水を使用せずに活性炭のpH値を調整する方法が提示されている。ところが、使用する酸性ガスは、活性炭中のアルカリ金属の当量に合わせる必要があり、過剰に活性炭に酸性ガスを吸着させると、吸着の初期に処理水が酸性になることが併せて示されている。従ってこの場合もやはり処理水のｐH調整、装置の腐蝕対策が必要になる。また、この特許文献に示されている酸性ガスとは、塩化水素，臭化水素，二酸化硫黄，一酸化二窒素，一酸化窒素，二酸化窒素の内の１種以上と、いずれも毒性や腐蝕性を有するものであるから、pH調整操作に危険を伴う上、このような方法で調製した活性炭が高温にさらされた場合、これら有毒ガスが周囲に放出される危険性も懸念される。
活性炭は、種々の気体を吸着する性質があり、気体の分圧が高いほどその吸着量は多い。活性炭に二酸化炭素を通じると、二酸化炭素が活性炭に吸着され、常温でその吸着量は４０ｍｌ／ｇ程度である。これは、１.８ｍｍｏｌ/gの二酸化炭素に相当する。二酸化炭素1モルは、2価の塩基として働くから、活性炭中に多く含まれるカリウムに換算すると活性炭１ｇあたり１４０ｍｇ（＝１４％）に相当し、活性炭を中和するに十分な量である。
溶剤回収用活性炭は、触媒作用による被吸着物の変質を避けるため、鉱酸で洗浄して極力アルカリ金属分を減少させた後、装置の腐蝕防止のため、熱処理等により鉱酸を揮散せしめることがある。この場合、活性炭に残存するアルカリ金属分はごく微量であるにもかかわらず、活性炭処理水のpH値はアルカリ性を呈する。
Activated carbon has the property of adsorbing various gases, and the amount of adsorption increases as the partial pressure of the gas increases. When carbon dioxide is passed through activated carbon, carbon dioxide is adsorbed on the activated carbon, and the adsorption amount is about 40 ml / g at room temperature. This corresponds to 1.8 mmol / g carbon dioxide. Since 1 mol of carbon dioxide functions as a divalent base, it corresponds to 140 mg (= 14%) per 1 g of activated carbon when converted to potassium that is contained in a large amount in activated carbon, which is sufficient to neutralize the activated carbon.
Activated carbon for solvent recovery must be washed with mineral acid to reduce alkali metal content as much as possible to avoid alteration of the adsorbate by catalysis, and then volatilize mineral acid by heat treatment etc. to prevent corrosion of the equipment. There is. In this case, although the alkali metal content remaining on the activated carbon is very small, the pH value of the activated carbon treated water is alkaline.
本発明は、活性炭をスラリー化しても、水をアルカリ性にすることなくほぼ中性を保つことができ、スラリーから活性炭を分離したのちの排水をそのまま廃棄することができる活性炭および水処理用に使用した場合、速やかに処理水のpH値を中性付近に安定させる活性炭を提供することにある。 Even if activated carbon is slurried, the present invention can maintain neutrality without making water alkaline, and can be used for activated carbon and water treatment, which can be used as waste water after separating activated carbon from the slurry. In this case, it is to provide activated carbon that quickly stabilizes the pH value of the treated water near neutral.
本発明者らは、活性炭に二酸化炭素を吸着させることで、活性炭と接触した水のpH値の上昇を防止できることを見出した。さらに二酸化炭素は、活性炭に過剰に吸着させた場合でも、処理水のpH値は低くなりすぎないので、あらかじめ活性炭のｐＨを測定することなく吸着させても全く問題のないことも判明した。本発明はこれらの知見を基に更に検討をかさねて完成したものである。 The present inventors have found that an increase in pH value of water in contact with activated carbon can be prevented by adsorbing carbon dioxide on activated carbon. Further, even when carbon dioxide is adsorbed excessively on activated carbon, the pH value of the treated water does not become too low, and it has been found that there is no problem even if it is adsorbed without measuring the pH of activated carbon in advance. The present invention has been completed with further studies based on these findings.
即ち本発明は、
（１）乾燥活性炭に、その１g当たり２０ｍｌ以上の二酸化炭素を吸着させたのち水を加えてスラリー状にして輸送する活性炭のスラリー輸送方法、
（２）乾燥活性炭に二酸化炭素を吸着させる際、気密性の容器内で乾燥活性炭に分圧５０％以上の二酸化炭素を接触させる請求項１記載の活性炭のスラリー輸送方法、
である。
That is, the present invention
(1) A slurry transport method for activated carbon in which 20 ml or more of carbon dioxide per 1 g is adsorbed to dry activated carbon , and then water is added to form a slurry.
(2) When carbon dioxide is adsorbed on dry activated carbon, the activated carbon slurry transport method according to claim 1, wherein carbon dioxide having a partial pressure of 50% or more is brought into contact with dry activated carbon in an airtight container.
It is.
本発明において使用される原料活性炭の種類は特に限定されず、木材、鋸屑、木炭、素灰、ヤシ殻やクルミ殻などの果実殻、桃、梅などの果実種子、リグニン廃液のようなパルプ製造副生物、精糖廃物(バカス)、廃糖蜜などの植物系原料、泥炭、草炭、亜炭、褐炭、瀝青炭、無煙炭、コークス、コールタール、石油ピッチ等の鉱物系原料、アクリル樹脂、塩化ビニリデン樹脂、フェノール樹脂などの合成樹脂系原料若しくはそれらの炭化物など一般的に用いられるものであればいずれでも良い。
原料活性炭は、まず、賦活工程に付される。賦活方法も特に限定されず、たとえば「活性炭−基礎と応用」、講談社（1992）、p.61〜p.69の方法で製造される、水蒸気、酸素、炭酸ガスなどの活性ガスでの賦活炭や、リン酸、塩化亜鉛、水酸化カリウムを用いた薬品賦活炭などハロゲンガスで賦活した以外の活性炭が用いられる。
The type of raw material activated carbon used in the present invention is not particularly limited, and wood, sawdust, charcoal, raw ash, fruit shells such as coconut shells and walnut shells, fruit seeds such as peaches and plums, and pulp production such as lignin waste liquid By-products, plant raw materials such as refined sugar waste (bacus), molasses, peat, grass charcoal, lignite, lignite, bituminous coal, anthracite, coke, coal tar, petroleum pitch, mineral raw materials, acrylic resin, vinylidene chloride resin, phenol Any generally used material such as a synthetic resin material such as a resin or a carbide thereof may be used.
The raw material activated carbon is first subjected to an activation process. The activation method is also not particularly limited. For example, activated carbon produced by the method of “activated carbon-basics and application”, Kodansha (1992), p.61-p.69, with activated gas such as steam, oxygen, carbon dioxide, etc. Alternatively, activated carbon other than activated with a halogen gas such as chemical activated carbon using phosphoric acid, zinc chloride, or potassium hydroxide is used.
賦活された活性炭のＢＥＴ比表面積は、800〜2000ｍ２／ｇが好ましく、さらに900〜1800ｍ２／ｇが好ましい。
賦活された活性炭の平均粒径は、0.1〜10.0ｍｍのものが好ましく、さらに
0.5〜8.0ｍｍのものが好ましく、1.0〜5.0ｍｍのものが最も好ましい。
活性炭は、賦活後、水、あるいは希塩酸、希硝酸、希りん酸、希硫酸などの希鉱酸水溶液で洗浄しても良い。また、表面官能基調整の目的で活性炭を熱処理しても良い。活性炭の洗浄は、通常活性炭を希鉱酸水溶液に投入し、攪拌翼、バブリング等の方法により活性炭と希鉱酸水溶液をよく接触させた後、水を切り、その後必要に応じて水のみによる洗浄によって過剰の鉱酸を除去する工程によってなされる。
BET specific surface area of the activated activated carbon is preferably 800~2000m 2 / g, further 900~1800m 2 / g are preferred.
The activated activated carbon preferably has an average particle size of 0.1 to 10.0 mm,
The thing of 0.5-8.0 mm is preferable, and the thing of 1.0-5.0 mm is the most preferable.
Activated carbon may be washed with water or an aqueous solution of dilute mineral acid such as dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid or dilute sulfuric acid after activation. Moreover, you may heat-process activated carbon for the purpose of surface functional group adjustment. Activated carbon is usually poured into a dilute mineral acid aqueous solution, and the activated carbon and the dilute mineral acid aqueous solution are brought into good contact with each other by a stirring blade, bubbling, etc., and then water is removed. By removing excess mineral acid.
活性炭を熱処理するには、活性炭を窒素ガス、アルゴンガスなど酸素を含まない雰囲気で300℃〜900℃の温度範囲で加熱する。温度が800℃以下の場合は、雰囲気ガスとして水蒸気を用いることもできる。この操作によって、活性炭の表面に存在するカルボキシル基、水酸基などの官能基を除去あるいは減少させることができ、さらには酸洗浄で用いた鉱酸を除去することができる。 In order to heat-treat the activated carbon, the activated carbon is heated in a temperature range of 300 ° C. to 900 ° C. in an atmosphere containing no oxygen such as nitrogen gas or argon gas. When the temperature is 800 ° C. or lower, water vapor can be used as the atmospheric gas. By this operation, functional groups such as carboxyl groups and hydroxyl groups present on the surface of the activated carbon can be removed or reduced, and further, the mineral acid used in the acid cleaning can be removed.
このようにして得られた賦活化活性炭に、二酸化炭素を吸着させる。
活性炭へ二酸化炭素を吸着させるには、活性炭を密閉容器に収容し、あらかじめ二酸化炭素を空気、窒素ガスなどに希釈して二酸化炭素分圧を５０％以上、好ましくは、７０％以上となるように調整した気体を容器中に導入し、常温で活性炭に吸着させる。ここで常温とは、5℃〜35℃の範囲である通常の環境温度のことをいう。活性炭と二酸化炭素の接触時間は長いほうが好ましいが、通常吸着は速やかに起こるので、活性炭を充てんした容器、タンク等の下端から二酸化炭素ガスを吹き込み、容器、タンク内を二酸化炭素雰囲気に置換えながら吸着させることで本発明の二酸化炭素吸着活性炭を製造することができる。このとき、特に活性炭充てん層のかくはん、混合は必ずしも必要でない。活性炭を二酸化炭素分圧５０％以上の気体を接触させる場合の気体の圧力は、通常常圧でよいが、１０気圧以下の加圧下に行ってもよい。
なお、二酸化炭素による賦活方法が知られているが、活性炭と二酸化炭素との接触は850℃〜1000℃の高温であり、この温度での活性炭の二酸化炭素吸着性能はほとんどなく、本発明の活性炭を得ることはできない。
大気中の二酸化炭素濃度（約330ｐｐｍ）と平衡にある炭酸水のpH値は、5.6であるから、過剰の二酸化炭素が瞬時に飽和するまで水に溶解しない限り、通常用いられる水は種々のイオンを含み緩衝能力があるので、本発明の活性炭処理水のpH値は、実際上排水基準である5.8を下回ることがない。したがって、二酸化炭素を使用して活性炭のpH値を調整する場合は、活性炭中に残存するアルカリ金属分を全く考慮することなく、二酸化炭素を吸着させることができる。
Carbon dioxide is adsorbed on the activated activated carbon thus obtained.
In order to adsorb carbon dioxide on activated carbon, the activated carbon is accommodated in a sealed container, and carbon dioxide is diluted in advance with air, nitrogen gas, etc., so that the partial pressure of carbon dioxide is 50% or more, preferably 70% or more. The adjusted gas is introduced into a container and adsorbed on activated carbon at room temperature. Here, normal temperature refers to a normal environmental temperature in the range of 5 ° C to 35 ° C. Longer contact time between activated carbon and carbon dioxide is preferable, but usually adsorption occurs quickly, so carbon dioxide gas is blown from the lower end of a container or tank filled with activated carbon, and adsorption is performed while replacing the inside of the container or tank with a carbon dioxide atmosphere. By making it, the carbon dioxide adsorption activated carbon of this invention can be manufactured. At this time, stirring and mixing of the activated carbon packed layer are not necessarily required. When the activated carbon is brought into contact with a gas having a carbon dioxide partial pressure of 50% or more, the pressure of the gas is usually normal pressure, but may be performed under a pressure of 10 atm or less.
In addition, although the activation method by carbon dioxide is known, the contact between activated carbon and carbon dioxide is a high temperature of 850 ° C. to 1000 ° C., and there is almost no carbon dioxide adsorption performance of activated carbon at this temperature, and the activated carbon of the present invention Can't get.
Since the pH value of carbonated water in equilibrium with atmospheric carbon dioxide concentration (about 330 ppm) is 5.6, normally used water has various ions unless excess carbon dioxide dissolves in water until it is instantly saturated. Therefore, the pH value of the activated carbon treated water of the present invention does not actually fall below 5.8, which is the drainage standard. Therefore, when adjusting the pH value of activated carbon using carbon dioxide, it is possible to adsorb carbon dioxide without considering the alkali metal remaining in the activated carbon.
二酸化炭素の吸着が完了したかどうかを知るためには、酸素濃度計で容器出口(ベント孔等容器上部からの気体出口)の酸素濃度を測定すればよい。吸着が完了すると、出口ガスは二酸化炭素のみとなり、酸素濃度が急激に減少する。
二酸化炭素吸着量は、1気圧、25℃において、通常１０ｍｌ／ｇ以上あれば十分であるが、好ましくは２０ｍｌ／ｇ以上、より好ましくは３０ｍｌ／ｇ以上である。３０ｍｌ／ｇ以上あれば、保管条件の如何を問わず６ヶ月以上の長期間二酸化炭素処理の効果が持続する。
二酸化炭素活性炭の保管方法については、例えば、ポリエチレン製、ポリプロピレン製、ポリカーボネート製等の樹脂製、鋼製、ステンレス製、アルミ製等の金属製などの密閉袋あるいは密閉容器に封入するのが好ましいが、通常の活性炭の包装に用いられる内側からポリエチレン、クラフト紙(2〜3層)でもよい。
In order to know whether the adsorption of carbon dioxide has been completed, the oxygen concentration at the container outlet (the gas outlet from the upper part of the container such as the vent hole) may be measured with an oximeter. When the adsorption is completed, the outlet gas becomes only carbon dioxide, and the oxygen concentration decreases rapidly.
The amount of carbon dioxide adsorbed is usually 10 ml / g or more at 1 atm and 25 ° C., but is preferably 20 ml / g or more, more preferably 30 ml / g or more. If it is 30 ml / g or more, the effect of carbon dioxide treatment for a long period of 6 months or more will be maintained regardless of storage conditions.
As for the storage method of carbon dioxide activated carbon, for example, it is preferable to enclose in a sealed bag or a sealed container made of resin such as polyethylene, polypropylene, polycarbonate, etc., steel, stainless steel, aluminum, etc. Polyethylene and kraft paper (2 to 3 layers) may be used from the inside used for packaging of normal activated carbon.
このようにして得られた活性炭をスラリー状としてパイプや溝を通して容易に輸送するには、通常活性炭を水流、かくはん翼等を用いてかくはんしながらその５〜２０倍量の水に懸濁させる。具体的には、容器内において活性炭と所定量の水を加え、水流で混合しながらポンプを用いて、活性炭を充填する吸着塔などの設備へフレキシブル管の配管を経由して輸送し、金網、多孔性コンクリート、目皿など、活性炭の粒径より小さく、活性炭の流出が起きない資材により活性炭と排水が分離される。 In order to easily transport the activated carbon thus obtained as a slurry through pipes or grooves, the activated carbon is usually suspended in 5 to 20 times the amount of water while stirring using a water stream or a stirring blade. Specifically, activated carbon and a predetermined amount of water are added to the container, and the mixture is mixed with a water stream and transported to a facility such as an adsorption tower filled with activated carbon via a flexible pipe using a pump. Activated carbon and drainage are separated by materials that are smaller than the particle size of activated carbon, such as porous concrete and eye plates, and do not cause activated carbon to flow out.
吸着塔などへ輸送された活性炭は、過熱水蒸気などを通じて水分が5%以下になるまで乾燥してその後の使用に供することができる。また、排水処理、浄水処理に供する場合は、そのまま水を通じて使用することができる。
活性炭をスラリー輸送した後の水は、ほぼ中性を呈する水であり、有害な物質を溶解していないので、そのまま廃棄することができる。
The activated carbon that has been transported to the adsorption tower or the like can be dried until it reaches 5% or less through superheated steam, etc., and can be used thereafter. Moreover, when using for waste water treatment and water purification, it can be used as it is through water.
The water after slurry transporting the activated carbon is almost neutral water and does not dissolve harmful substances, and can be discarded as it is.
活性炭を吸着塔などに充てんする際、水によってスラリーとしてポンプ等で輸送すれば、クレーンなどの重機を使用せずにすみ、活性炭の微粉除去も同時に行える利点がある。しかし通常の活性炭は、アルカリ性であるので、そのままでスラリー輸送すると、水が著しくアルカリ性となり、排水をそのまま廃棄できないという問題点がある。
一方活性炭を鉱酸によって洗浄することにより水のｐＨを低下させた場合は、活性炭に酸が残留し、その酸が吸着塔を腐食させる恐れがあり、特に溶剤回収用など、ガス処理に活性炭を使用する場合、充填後は酸が完全に洗い流されることがないため、設備の腐食の原因となることがある。
When the activated carbon is packed in an adsorption tower or the like, if it is transported with water as a slurry by a pump or the like, there is an advantage that it is possible to remove fine particles of the activated carbon without using heavy equipment such as a crane. However, since normal activated carbon is alkaline, there is a problem that if the slurry is transported as it is, the water becomes extremely alkaline and the wastewater cannot be discarded as it is.
On the other hand, when the pH of water is lowered by washing the activated carbon with mineral acid, the acid may remain on the activated carbon and the acid may corrode the adsorption tower. When used, the acid is not completely washed away after filling, which may cause corrosion of the equipment.
しかし本発明の活性炭はスラリー化しても水をアルカリ性にすることなくほぼ中性を保つことができるので、排水をそのまま廃棄しても問題点はない。又処理水のｐＨ値は、実際上排水基準である5.8を下回ることもないので、設備などを腐食するという問題も起こらない。
また、水処理用活性炭として使用する場合、本活性炭は吸着タンク、吸着池に充てんした後速やかに処理水のｐＨ値が中性付近となるので捨て水が不要であり有利である。
However, even if the activated carbon of the present invention is slurried, the neutrality can be maintained without making the water alkaline, so there is no problem even if the wastewater is discarded as it is. Moreover, since the pH value of treated water does not actually fall below 5.8, which is the drainage standard, there is no problem of corroding equipment.
Further, when used as activated carbon for water treatment, the activated carbon is advantageous in that it does not require waste water since the pH value of the treated water becomes near neutral immediately after filling the adsorption tank and adsorption pond.
以下に実施例および比較例を挙げて本発明を具体的に説明する。 The present invention will be specifically described below with reference to examples and comparative examples.
原料活性炭として市販の溶剤回収用ヤシ殻活性炭（円柱状炭）、ＢＥＴ比表面1200ｍ２／ｇ、粒径3.35〜2.36ｍｍのものを用いた。
二酸化炭素吸着量の測定方法
活性炭10gを内径20ｍｍの石英管に入れ、片方の端に内容量10Lのガス捕集用袋を取り付け、片方の端から窒素ガスを100ｍｌ／分の割合で流しながら、石英管を150℃に保った電気炉にいれ、100分間出口ガスを捕集し、ガス中の二酸化炭素濃度をＴＣＤガスクロマトグラフ装置で測定した。
活性炭20Lを内容量25Lのポリエチレン製ドラムに入れ、25℃の二酸化炭素を容器の下部から50L/分の割合で10分間吹き込み、活性炭No.1を得た。活性炭の二酸化炭素吸着量は35ｍｌ／ｇであった。吹き込み終了後ガラス瓶に入れ、蓋をして常温で保管した。
As the raw material activated carbon, a commercially available coconut shell activated carbon for solvent recovery (cylindrical charcoal) having a BET specific surface of 1200 m 2 / g and a particle size of 3.35 to 2.36 mm was used.
Measurement method of carbon dioxide adsorption amount 10g of activated carbon is put in a quartz tube with an inner diameter of 20mm, a gas collection bag with an internal volume of 10L is attached to one end, and nitrogen gas is allowed to flow from one end at a rate of 100ml / min. The quartz tube was placed in an electric furnace maintained at 150 ° C., the outlet gas was collected for 100 minutes, and the carbon dioxide concentration in the gas was measured with a TCD gas chromatograph.
Activated carbon No. 1 was obtained by placing 20 L of activated carbon into a 25 L polyethylene drum and blowing carbon dioxide at 25 ° C. from the bottom of the container at a rate of 50 L / min for 10 minutes. The amount of carbon dioxide adsorbed by the activated carbon was 35 ml / g. After the completion of blowing, it was put in a glass bottle, covered and stored at room temperature.
二酸化炭素：窒素ガス＝１：１(体積比)で混合した希釈二酸化炭素ガスを上記と同様活性炭と反応させ、活性炭No.2を得た。活性炭の二酸化炭素吸着量は20ml/gであった。 Diluted carbon dioxide gas mixed with carbon dioxide: nitrogen gas = 1: 1 (volume ratio) was reacted with activated carbon in the same manner as above to obtain activated carbon No. 2. The amount of carbon dioxide adsorbed by the activated carbon was 20 ml / g.
二酸化炭素：窒素ガス＝１：１(体積比)で混合した希釈二酸化炭素ガスを温度35℃で活性炭と反応させ、活性炭No.3を得た。活性炭の二酸化炭素吸着量は15ml/gであった。
〔比較例１〕
Diluted carbon dioxide gas mixed with carbon dioxide: nitrogen gas = 1: 1 (volume ratio) was reacted with activated carbon at a temperature of 35 ° C. to obtain activated carbon No. 3. The amount of carbon dioxide adsorbed by the activated carbon was 15 ml / g.
[Comparative Example 1]
実施例１で、原料炭として用いた活性炭20Lを内容量25Lのポリエチレン瓶に入れ、そのまま蓋をして、常温で保管した(活性炭No.４)。活性炭の二酸化炭素吸着量は１ｍｌ／ｇ以下であった。
二酸化炭素：窒素ガス＝１：２(体積比)で混合した希釈二酸化炭素ガスを温度25℃で活性炭と反応させ、活性炭No.5を得た。活性炭の二酸化炭素吸着量は8ml/gであった。
〔実験例１〕
In Example 1, 20 L of activated carbon used as raw coal was placed in a 25 L polyethylene bottle, covered as it was, and stored at room temperature (activated carbon No. 4). The carbon dioxide adsorption amount of the activated carbon was 1 ml / g or less.
Diluted carbon dioxide gas mixed with carbon dioxide: nitrogen gas = 1: 2 (volume ratio) was reacted with activated carbon at a temperature of 25 ° C. to obtain activated carbon No. 5. The carbon dioxide adsorption amount of the activated carbon was 8 ml / g.
[Experimental Example 1]
活性炭のスラリー輸送実験
攪拌槽に実施例１で得られた製造６時間後の活性炭（活性炭No. 1）、製造後３ヶ月室温で蓋をしたまま保管したもの（活性炭No. 1※）、及び比較例１の通常の活性炭をポリエチレン瓶に入れ、蓋をして常温で３ヶ月保管したもの(活性炭No.６)および活性炭No.2〜No. 5それぞれ１ｋｇに対して水道水10Ｌの割合で加えてスラリーとした。この活性炭スラリーをかくはんしながら、１L/分の割合でポンプを用いて内径15ｍｍのシリコンチューブを経由して10ｍ先に輸送し、目開き2.0ｍｍの金網を用いて活性炭と排水を分離した。排水を経時的に採取し、そのｐＨ値を測定した。結果を表１に示した。実験に用いた水道水のpH値は7.5であった。
Activated charcoal slurry transport experiment Activated charcoal 6 hours after production (activated carbon No. 1) obtained in Example 1 in a stirred tank, stored with a lid at room temperature for 3 months after production (activated carbon No. 1 *), and put normal activated carbon of Comparative example 1 in a polyethylene bottle, which was stored for 3 months at room temperature with a lid (charcoal No.6) and activated carbon No.2~No. 5 at a rate of tap water 10L to each 1kg In addition, a slurry was obtained. While stirring this activated carbon slurry, it was transported 10 m ahead via a silicon tube with an inner diameter of 15 mm using a pump at a rate of 1 L / min, and the activated carbon and waste water were separated using a metal mesh with a mesh opening of 2.0 mm. The drainage was collected over time and the pH value was measured. The results are shown in Table 1. The pH value of tap water used in the experiment was 7.5.
本発明の製造６時間後の活性炭活性炭No.1および3ヶ月間保管した活性炭(No. 1※)、二酸化炭素吸着量が15ml/g(No.2)及び20ml/g(No.3)の活性炭のいずれでも排水のpH値は１０時間経過時点で中性付近に保たれている。しかし比較例1（No.4）、比較例２(No.5)及び実験例１で作成したNo.6の活性炭では、１０時間後には排水のpH値は放流するためにはpH調整が必要となる8.6以上にまで上昇した。 Activated carbon activated carbon No. 1 6 hours after production of the present invention and activated carbon (No. 1 *) stored for 3 months, carbon dioxide adsorption of 15 ml / g (No. 2) and 20 ml / g (No. 3) In any of the activated carbons, the pH value of the wastewater is kept near neutral after 10 hours. However, with the activated carbon of No. 6 prepared in Comparative Example 1 (No. 4), Comparative Example 2 (No. 5) and Experimental Example 1, the pH value of the wastewater needs to be adjusted to discharge after 10 hours. It rose to 8.6 or more.
本発明の１g当たり１０ｍｌ以上の二酸化炭素を吸着させた活性炭は、後工程でのpH調整なしにスラリー輸送などで接触する水のpH値を5.6から8.6の範囲に納めることができるので、スラリー輸送で充填設備に充てんされる溶剤回収用、水処理用活性炭として有利に用いることができる。
また、水処理用に使用した場合、速やかに処理水のpH値を中性付近に安定させることができるので、工業用水の処理剤や家庭用浄水器の吸着剤としても有利に使用することができる。
The activated carbon adsorbed with 10 ml or more of carbon dioxide per gram of the present invention can keep the pH value of water in contact with slurry transport within the range of 5.6 to 8.6 without adjusting the pH in the subsequent process. Therefore, it can be advantageously used as an activated carbon for solvent recovery and water treatment filled in the filling equipment.
In addition, when used for water treatment, the pH value of treated water can be quickly stabilized in the vicinity of neutrality, so it can be advantageously used as a treatment agent for industrial water or an adsorbent for household water purifiers. it can.
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| JPS5272393A (en) * | 1975-12-15 | 1977-06-16 | Takeda Chem Ind Ltd | Production of neutralized aceive carbon granuls by the activation with steam |
| JPS57112673A (en) * | 1980-12-29 | 1982-07-13 | Kubota Ltd | Drying of wet material |
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| JPH09248456A (en) * | 1996-03-18 | 1997-09-22 | Isao Mochida | Molecular sieve activated carbon fiber having selective adsorbing capacity and its production |
| JP2000503295A (en) * | 1996-02-06 | 2000-03-21 | カルゴン カーボン コーポレーション | Activated carbon treated with carbon dioxide for pH stabilization of treated water and for control of aluminum in treated water |
| JP2005008205A (en) * | 2003-06-18 | 2005-01-13 | Osaka Gas Co Ltd | Aerosol container |
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|---|---|---|---|---|
| JPS5272393A (en) * | 1975-12-15 | 1977-06-16 | Takeda Chem Ind Ltd | Production of neutralized aceive carbon granuls by the activation with steam |
| JPS57112673A (en) * | 1980-12-29 | 1982-07-13 | Kubota Ltd | Drying of wet material |
| JPH09155186A (en) * | 1995-12-05 | 1997-06-17 | Agency Of Ind Science & Technol | Adsorbent |
| JP2000503295A (en) * | 1996-02-06 | 2000-03-21 | カルゴン カーボン コーポレーション | Activated carbon treated with carbon dioxide for pH stabilization of treated water and for control of aluminum in treated water |
| JPH09248456A (en) * | 1996-03-18 | 1997-09-22 | Isao Mochida | Molecular sieve activated carbon fiber having selective adsorbing capacity and its production |
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