JP2003246992A - Method for treatment of aqueous liquid containing aromatic compound - Google Patents
Method for treatment of aqueous liquid containing aromatic compoundInfo
- Publication number
- JP2003246992A JP2003246992A JP2002051188A JP2002051188A JP2003246992A JP 2003246992 A JP2003246992 A JP 2003246992A JP 2002051188 A JP2002051188 A JP 2002051188A JP 2002051188 A JP2002051188 A JP 2002051188A JP 2003246992 A JP2003246992 A JP 2003246992A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous liquid
- catalyst
- treatment
- aromatic compound
- liquid
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 63
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000002309 gasification Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002737 fuel gas Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 aromatic carboxylic acids Chemical class 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、芳香族化合物を含
む水性液を処理する方法に関する。本発明において、
「芳香族化合物を含む水性液」とは、水に液状および／
または固形状の芳香族化合物が溶解し、懸濁し、分散し
或いは単に混合して存在している液状物を意味する。本
明細書においては、この様な「芳香族化合物を含む水性
液」を単に水性液ということがある。TECHNICAL FIELD The present invention relates to a method for treating an aqueous liquid containing an aromatic compound. In the present invention,
“Aqueous liquid containing an aromatic compound” means a liquid in water and / or
Alternatively, it means a liquid substance in which a solid aromatic compound is dissolved, suspended, dispersed or simply mixed. In the present specification, such an “aqueous liquid containing an aromatic compound” may be simply referred to as an aqueous liquid.
【０００２】[0002]
【従来技術とその問題点】従来、芳香族化合物を含む水
性液(例えば、化学工場廃水など)の処理は、湿式酸化処
理、オゾン処理、活性炭吸着などにより行われている。
しかしながら、この様な処理は、処理コストが高く、か
つ有用成分として利用出来る筈の芳香族化合物を最終的
に二酸化炭素にまで酸化分解してしまう。2. Description of the Related Art Conventionally, treatment of an aqueous liquid containing an aromatic compound (for example, wastewater of a chemical factory) has been carried out by wet oxidation treatment, ozone treatment, activated carbon adsorption and the like.
However, such a treatment has a high treatment cost and eventually oxidizes and decomposes aromatic compounds that should be usable as useful components into carbon dioxide.
【０００３】近年液状有機性廃棄物(本発明が対象とす
る水性液もその一種である)の発生量が増加し、同時に
廃棄物に対する規制が強化されつつある現状において、
上記の様な従来技術により各種の液状廃棄物を処理する
方法では、次第に対処し難くなっている。In recent years, the amount of liquid organic waste (including the aqueous liquid targeted by the present invention) is increasing, and at the same time, regulations on waste are being tightened.
The method of treating various liquid wastes by the conventional techniques as described above is gradually becoming difficult to deal with.
【０００４】また、現今の大きな技術的課題である「限
りある資源の有効利用」という視点からは、この様な液
状廃棄物を資源として再利用することも必要である。From the viewpoint of "effective use of limited resources", which is a big technical problem at present, it is also necessary to reuse such liquid waste as resources.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明は、芳
香族化合物を含む水性液を高いガス化効率で処理するこ
とにより、燃料ガス、電力、熱エネルギーなどの有用な
形態で回収し、再利用するための新たな技術を提供する
ことを主な目的とする。Therefore, according to the present invention, by treating an aqueous liquid containing an aromatic compound with high gasification efficiency, it is recovered in a useful form such as fuel gas, electric power, thermal energy and the like, and re-used. Its main purpose is to provide new technologies for use.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記の様な
技術の現状に鑑みて、芳香族化合物を含む水性液を処理
する技術について研究を進めた結果、水性液を液状の形
態で特定の条件下に湿式加熱処理する場合には、上記の
課題をほぼ達成し得ることを見出した。In view of the above-mentioned state of the art, the present inventor has conducted research on a technique for treating an aqueous liquid containing an aromatic compound, and as a result, the aqueous liquid has a liquid form. It has been found that the above problems can be almost achieved when the wet heat treatment is performed under specific conditions.
【０００７】すなわち、本発明は、水性液の処理方法を
提供する；
１．芳香族化合物を含む水性液の処理方法において、水
性液を下記特性を有するNi担持多孔質炭素触媒の存在下
に加熱/加圧処理に供することを特徴とする方法：
(a)触媒の寸法は、0.3-2mmの範囲にある。
(b)触媒中のNi担持量は、35-50重量％の範囲にある。
(c)BET比表面積は、150-200m2/gの範囲にある。
(d)炭素担体の細孔径は、1-10nmの範囲にある。
(e)水性液中の有機成分を選択的に細孔内に取り込む機
能を有する。
２．水性液の加熱/加圧処理を250℃以上の温度で上記項
1に記載の方法。
３．水性液の加熱/加圧処理を1MPa以上の圧力で行う上
記項１に記載の方法。
４．水性液の加熱/加圧処理を超臨界条件下に行う上記
項１に記載の方法。That is, the present invention provides a method for treating an aqueous liquid; A method for treating an aqueous liquid containing an aromatic compound, which comprises subjecting the aqueous liquid to a heating / pressurizing treatment in the presence of a Ni-supporting porous carbon catalyst having the following characteristics: (a) the size of the catalyst , In the range of 0.3-2 mm. (b) The amount of Ni supported in the catalyst is in the range of 35 to 50% by weight. (c) The BET specific surface area is in the range of 150-200 m 2 / g. (d) The pore size of the carbon support is in the range of 1-10 nm. (e) It has a function of selectively incorporating the organic component in the aqueous liquid into the pores. 2. Heat / pressure treatment of aqueous liquid at a temperature of 250 ° C or higher
The method described in 1. 3. The method according to item 1 above, wherein the heating / pressurizing treatment of the aqueous liquid is performed at a pressure of 1 MPa or more. 4. The method according to item 1 above, wherein the heating / pressurizing treatment of the aqueous liquid is performed under supercritical conditions.
【０００８】[0008]
【発明の実施の形態】本発明が処理対象とする水性液
は、水に液状および固形状の芳香族化合物の少なくとも
１種が溶解乃至分散した状態の液状物を全て包含する。BEST MODE FOR CARRYING OUT THE INVENTION The aqueous liquid to be treated in the present invention includes all liquid substances in which at least one liquid or solid aromatic compound is dissolved or dispersed in water.
【０００９】この様な水性液に含まれる芳香族化合物と
しては、特に限定されず、代表的には、ベンゼン、トル
エン、キシレン、芳香族カルボン酸、フェノール類、お
よびそれらの誘導体などの液状化合物およびリグニンな
どの固形状物質などが例示される。The aromatic compound contained in such an aqueous liquid is not particularly limited, and typically, liquid compounds such as benzene, toluene, xylene, aromatic carboxylic acids, phenols and their derivatives, and Examples include solid substances such as lignin.
【００１０】本発明が処理対象とする水性液は、処理す
べき芳香族化合物を含む限り、特に限定されない。具体
的には、液状芳香族化合物を含む産業廃水、固形状芳香
族化合物廃棄物を粉砕し、粉砕物を水に分散させた分散
液などである。或いは、固形状芳香族化合物廃棄物を粉
砕した後、液状芳香族化合物を含む産業廃水に分散させ
液状物を処理しても良い。また、この様な水性液は、芳
香族化合物量を超えない量の炭素-水素系物質(バイオマ
スなど)を含んでいても良い。以下においては、芳香族
化合物と炭素-水素系物質を被処理成分と総称すること
がある。The aqueous liquid to be treated in the present invention is not particularly limited as long as it contains an aromatic compound to be treated. Specifically, it is an industrial wastewater containing a liquid aromatic compound, a dispersion liquid obtained by pulverizing solid aromatic compound waste, and dispersing the pulverized product in water. Alternatively, the solid aromatic compound waste may be crushed and then dispersed in industrial wastewater containing the liquid aromatic compound to treat the liquid. Further, such an aqueous liquid may contain a carbon-hydrogen-based substance (biomass or the like) in an amount not exceeding the amount of the aromatic compound. Hereinafter, the aromatic compound and the carbon-hydrogen-based substance may be collectively referred to as the components to be treated.
【００１１】本発明において使用するNi担持多孔質炭素
触媒は、例えば、Miura K. et al., " Low-temperatur
e conversion of NO to N2 by use of a novel Ni load
edporous carbon," Chemical Engineering Science, 56
(2001)1623-1629 に記載された手法により、調製するこ
とが出来る。すなわち、硫酸ニッケル(II)水溶液にメタ
アクリル酸タイプのイオン交換樹脂とアンモニア水とを
加え、攪拌して、Niでイオン交換する。次いで、Niを吸
着したイオン交換樹脂を窒素雰囲気下、約500℃で焼成
して、樹脂を分解させることにより、多孔質炭素担体上
にNiを担持した触媒が得られる。触媒の形状は、Niの存
在により、焼成後にも当初のイオン交換樹脂の形状をほ
ぼそのまま維持している。例えば、イオン交換樹脂が球
状である場合には、触媒も球状となる。なお、上記文献
は、得られたNi担持多孔質炭素触媒が芳香族化合物分解
用の触媒として有用であることは、一切開示していな
い。また、本発明で使用する触媒は、所定の要件を備え
る限り、その製造方法は、上記文献に記載された方法に
限定されるものではない。The Ni-supported porous carbon catalyst used in the present invention is, for example, Miura K. et al., "Low-temperatur.
e conversion of NO to N 2 by use of a novel Ni load
edporous carbon, "Chemical Engineering Science, 56
(2001) 1623-1629, it can be prepared. That is, a methacrylic acid type ion exchange resin and ammonia water are added to a nickel (II) sulfate aqueous solution, stirred, and Ni is ion-exchanged. Next, the Ni-adsorbed ion exchange resin is fired at about 500 ° C. in a nitrogen atmosphere to decompose the resin, whereby a catalyst supporting Ni on the porous carbon support is obtained. Due to the presence of Ni, the shape of the catalyst maintains the original shape of the ion exchange resin almost as it is even after firing. For example, when the ion exchange resin has a spherical shape, the catalyst also has a spherical shape. The above document does not disclose that the obtained Ni-supported porous carbon catalyst is useful as a catalyst for decomposing aromatic compounds. In addition, the catalyst used in the present invention is not limited to the method described in the above-mentioned document as long as it has predetermined requirements.
【００１２】本発明で使用する触媒は、下記の様なパラ
メーターにより特徴づけることができる。
(a)触媒の寸法は、0.3-2mm程度(より好ましくは0.5〜1m
m程度)の範囲にある。
(b)触媒中のNi担持量は、35-50重量％程度(より好まし
くは45〜50重量％)の範囲にある。
(c)BET比表面積は、150-200m2/g程度と非常に大きい。
(d)炭素担体の細孔径は、1-10nm程度の範囲にあるの
で、大きな分子もとりこめる。
(e)疎水性の炭素が担体を構成しているので、水性液中
の有機成分を選択的に細孔内に取り込んで、有機成分を
極めて高い効率で分解する機能を発揮する。The catalyst used in the present invention can be characterized by the following parameters. (a) The size of the catalyst is about 0.3-2 mm (more preferably 0.5-1 m
m range). The amount of Ni supported in the catalyst (b) is in the range of about 35 to 50% by weight (more preferably 45 to 50% by weight). (c) The BET specific surface area is very large, about 150-200 m 2 / g. (d) Since the pore diameter of the carbon support is in the range of about 1-10 nm, large molecules can be incorporated. (e) Since the hydrophobic carbon constitutes the carrier, it exerts a function of selectively taking the organic component in the aqueous liquid into the pores and decomposing the organic component with extremely high efficiency.
【００１３】さらに、本発明で使用する触媒は、以下の
様な性質を具備している。
(f)強度が極めて大きい。
(g)Niが、触媒全体に均一に分散している。
(h)耐酸性および耐アルカリ性に優れている。
(i)耐熱性および耐圧性に優れている。例えば、約500℃
における焼成操作において、イオン交換樹脂単独では、
溶融し、流動変形するのに対し、Niを担持させた状態で
は、実質的に変形を生じない。
(j)従って、過酷な条件下において、高効率で被処理物
の処理を行うことができる。
(k)触媒製造に際し、焼成終了段階で、Niが金属状態で
存在しているので、従来のNi系触媒と異なって、水素還
元の必要がない。Further, the catalyst used in the present invention has the following properties. (f) Extremely high strength. (g) Ni is uniformly dispersed throughout the catalyst. (h) Excellent in acid resistance and alkali resistance. (i) It has excellent heat resistance and pressure resistance. For example, about 500 ℃
In the firing operation in, the ion exchange resin alone,
While it melts and undergoes flow deformation, substantially no deformation occurs when Ni is supported. (j) Therefore, it is possible to process the object to be processed with high efficiency under severe conditions. (k) Since Ni is present in a metallic state at the end of firing in the catalyst production, unlike the conventional Ni-based catalyst, hydrogen reduction is not necessary.
【００１４】本発明による水性液の処理方法は、触媒を
充填した耐熱反応容器内に水性液を導入して、接触反応
を進行させることにより、実施することができる。The method for treating an aqueous liquid according to the present invention can be carried out by introducing the aqueous liquid into a heat-resistant reaction vessel filled with a catalyst and allowing the catalytic reaction to proceed.
【００１５】反応様式としては、連続方式或いはバッチ
方式のいずれを採用しても良い。また、接触反応は、固
定床或いは流動床のいずれを用いて行っても、良い。As the reaction mode, either a continuous system or a batch system may be adopted. Further, the contact reaction may be carried out using either a fixed bed or a fluidized bed.
【００１６】反応条件は、芳香族化合物を分解し得る温
度および圧力条件を選択する。原理的には、温度と条件
との組み合わせにおいて、水性液の少なくとも一部が液
相として存在しうる湿式系、水性液がガス化して存在す
るガス化系、および超臨界系のいずれにおいても、実施
可能である。より具体的には、反応時の温度は、250℃
程度以上とすることが好ましく、より好ましくは、300
〜400℃程度である。圧力は、1MPa程度以上とすること
が好ましく、より好ましくは15〜20MPa程度である。As the reaction conditions, temperature and pressure conditions capable of decomposing the aromatic compound are selected. In principle, in the combination of temperature and conditions, in at least a wet system in which at least a part of the aqueous liquid can exist as a liquid phase, a gasification system in which the aqueous liquid is gasified, and a supercritical system, It is feasible. More specifically, the temperature during the reaction is 250 ° C.
It is preferable that the degree is at least about 300, more preferably 300.
It is about 400 ℃. The pressure is preferably about 1 MPa or higher, more preferably about 15 to 20 MPa.
【００１７】水性液処理時の温度が高い程、被処理成分
の分解が促進されて、反応時間が短縮されるが、反面に
おいて設備費が増大するので、反応温度は、被処理成分
の濃度、運転費、建設費などを総合的に考慮して、定め
れば良い。The higher the temperature during the aqueous liquid treatment, the faster the decomposition of the components to be treated and the shorter the reaction time, but on the other hand, the equipment cost increases, so the reaction temperature depends on the concentration of the components to be treated. It may be set in consideration of operating costs, construction costs, etc.
【００１８】本発明によれば、芳香族化合物は、メタ
ン、水素および二酸化炭素に分解される。また、炭素-
水素系物質が共存する場合には、これらもメタン、水素
および二酸化炭素にまで分解される。メタンおよび水素
は、必要に応じて、常法に従って、精製および回収さ
れ、燃料などとして利用される。また、高温の反応液か
ら常法に従って熱回収を行うこともできる。According to the invention, aromatic compounds are decomposed into methane, hydrogen and carbon dioxide. Also carbon-
When hydrogen-based substances coexist, these are also decomposed into methane, hydrogen and carbon dioxide. Methane and hydrogen are refined and recovered, if necessary, according to a conventional method, and used as fuel and the like. Further, heat can be recovered from the high temperature reaction solution by a conventional method.
【００１９】[0019]
【発明の効果】本発明方法によれば、水性液中の芳香族
化合物(および併存することがあるバイオマス)を高い効
率で有用なガスに変換させることができるので、水性液
の処理製造コストが著しく低減される。EFFECTS OF THE INVENTION According to the method of the present invention, the aromatic compound in the aqueous liquid (and the biomass that may coexist) can be converted into a useful gas with high efficiency. Significantly reduced.
【００２０】また、本発明方法によれば、芳香族化合物
を含む液状の廃棄物を資源として再利用することによ
り、CO2削減を含む地球環境の保全に大きく貢献するこ
とができる。Further, according to the method of the present invention, by recycling the liquid waste containing the aromatic compound as a resource, it is possible to greatly contribute to the preservation of the global environment including the reduction of CO 2 .
【００２１】さらに、本発明方法によれば、ダイオキシ
ンなどの有害物質は発生しないので、大気、土壌などの
環境汚染を実質的に解消乃至著しく軽減することができ
る。Furthermore, according to the method of the present invention, no harmful substances such as dioxins are generated, and therefore environmental pollution such as air and soil can be substantially eliminated or significantly reduced.
【００２２】さらにまた、本発明方法によれば、従来の
焼却処分を主とする処理方法に比して、電力、熱エネル
ギーなどをより効率良くかつ大量に回収することができ
る。Furthermore, according to the method of the present invention, it is possible to recover electric power, thermal energy, etc. more efficiently and in a large amount, as compared with the conventional treatment method mainly involving incineration.
【００２３】[0023]
【実施例】以下に実施例および参考例を示し、本発明の
特徴とするところをより一層明確にする。
実施例１
1.0Nの硫酸ニッケル(II)水溶液100mLにメタアクリル酸
タイプのイオン交換樹脂(“WK11”、三菱化学(株)製)10
gとアンモニア水30mLとを加え、24時間攪拌して、Niで
イオン交換した。次いで、Niを吸着したイオン交換樹脂
を窒素雰囲気下、約500℃で20分間焼成して、樹脂を分
解させることにより、多孔質炭素担体にNiを担持した触
媒を調製した。触媒は、直径350μm、Ni含有量45wt％、
表面積170m2/gであった。次いで、上記で調製したNi担
持多孔質炭素触媒0.5gを充填した固定床方式の反応容器
(内容積6CC)に高圧ポンプを用いて、18MPaに加圧した水
を0.75mL/分で連続供給しつつ、10℃/分の昇温速度で35
0℃まで昇温した後、同温度で30分間定常化操作を行っ
た。次いで、フェノール含有水性液(濃度600ppm)を反応
容器内に導入し、滞留時間4.5分で上記の圧力および温
度条件下に処理を行った。結果は、図1に示す通りであ
る。フェノールが完全に分解されて、メタン、水素およ
び二酸化炭素に転換されていることが明らかである。
実施例２
フェノール含有水性液に代えて、ベンゼン含有水性液
(濃度600ppm)を反応容器内に導入する以外は、実施例1
と同様の条件下に処理を行った。結果は、図1に示す通
りである。ベンゼンが完全に分解されて、メタン、水素
および二酸化炭素に転換されていることが明らかであ
る。
実施例３
フェノール含有水性液に代えて、トルエン含有水性液
(濃度350ppm)を反応容器内に導入する以外は、実施例1
と同様の条件下に処理を行った。結果は、図1に示す通
りである。トルエンが完全に分解されて、メタン、水素
および二酸化炭素に転換されていることが明らかであ
る。
実施例４
フェノール含有水性液に代えて、フェノール/リグニン
含有水性液(いずれも濃度600ppm)を反応容器内に導入す
る以外は、実施例1と同様の条件下に処理を行った。EXAMPLES Examples and reference examples will be shown below to further clarify the features of the present invention. Example 1 100 mL of a 1.0 N nickel (II) sulfate aqueous solution was added with a methacrylic acid type ion exchange resin (“WK11”, manufactured by Mitsubishi Chemical Corporation) 10
g and 30 mL of aqueous ammonia were added, and the mixture was stirred for 24 hours and ion-exchanged with Ni. Next, the Ni-adsorbed ion-exchange resin was baked in a nitrogen atmosphere at about 500 ° C. for 20 minutes to decompose the resin, thereby preparing a catalyst having Ni supported on a porous carbon carrier. The catalyst has a diameter of 350 μm, a Ni content of 45 wt%,
The surface area was 170 m 2 / g. Then, a fixed-bed type reaction vessel filled with 0.5 g of the Ni-supported porous carbon catalyst prepared above
Using a high-pressure pump in (internal volume 6CC), while continuously supplying water pressurized to 18 MPa at 0.75 mL / min, at a temperature rising rate of 10 ° C / min, 35
After the temperature was raised to 0 ° C, a steady operation was performed at the same temperature for 30 minutes. Then, a phenol-containing aqueous liquid (concentration: 600 ppm) was introduced into the reaction vessel, and the treatment was performed under the above pressure and temperature conditions with a residence time of 4.5 minutes. The results are shown in Figure 1. It is clear that the phenol has been completely decomposed and converted to methane, hydrogen and carbon dioxide. Example 2 Instead of the phenol-containing aqueous liquid, a benzene-containing aqueous liquid
Example 1 except that (concentration 600 ppm) was introduced into the reaction vessel.
The treatment was carried out under the same conditions as above. The results are shown in Figure 1. It is clear that benzene has been completely decomposed and converted into methane, hydrogen and carbon dioxide. Example 3 Instead of phenol-containing aqueous liquid, toluene-containing aqueous liquid
Example 1 except that (concentration 350 ppm) was introduced into the reaction vessel.
The treatment was carried out under the same conditions as above. The results are shown in Figure 1. It is clear that the toluene has been completely decomposed and converted to methane, hydrogen and carbon dioxide. Example 4 A treatment was carried out under the same conditions as in Example 1 except that a phenol / lignin-containing aqueous liquid (each having a concentration of 600 ppm) was introduced into the reaction vessel instead of the phenol-containing aqueous liquid.
【００２４】この場合にも、フェノールとリグニンが完
全に分解されて、メタン、水素および二酸化炭素に転換
された。
実施例５
フェノール含有水性液に代えて、フェノール/ベンゼン/
リグニン/ショ糖含有水性液(いずれも濃度600ppm)を反
応容器内に導入する以外は、実施例1と同様の条件下に
処理を行った。In this case too, the phenol and lignin were completely decomposed and converted into methane, hydrogen and carbon dioxide. Example 5 Instead of phenol-containing aqueous liquid, phenol / benzene /
The treatment was carried out under the same conditions as in Example 1 except that the lignin / sucrose-containing aqueous liquid (concentration: 600 ppm) was introduced into the reaction vessel.
【００２５】この場合にも、全ての成分が完全に分解さ
れて、メタン、水素および二酸化炭素に転換された。
参考例１〜２
フェノール含有水性液に代えて、リグニン含有水性液
(濃度600ppm：参考例１)或いはショ糖含有水性液(濃度6
00ppm：参考例２)を反応容器内に導入する以外は、実施
例1と同様の条件下に処理を行った。結果は、図1に併せ
て示す通りである。リグニンおよびショ糖が完全に分解
されて、メタン、水素および二酸化炭素に転換されてい
ることが明らかである。In this case as well, all components were completely decomposed and converted into methane, hydrogen and carbon dioxide. Reference Examples 1-2 Instead of phenol-containing aqueous liquid, lignin-containing aqueous liquid
(Concentration 600ppm: Reference Example 1) or sucrose-containing aqueous liquid (concentration 6
00 ppm: Treatment was carried out under the same conditions as in Example 1 except that Reference Example 2) was introduced into the reaction vessel. The results are as shown in FIG. It is clear that lignin and sucrose are completely decomposed and converted into methane, hydrogen and carbon dioxide.
【図１】本発明実施例および参考例による水性液処理の
結果を示すグラフである。FIG. 1 is a graph showing the results of aqueous liquid treatment according to Examples of the present invention and Reference Examples.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三和 正宏 京都府京都市左京区吉田本町 京都大学大 学院工学研究科内 (72)発明者 中川 浩行 京都府京都市左京区吉田本町 京都大学大 学院工学研究科内 Ｆターム(参考） 4G069 AA03 AA08 BA08A BA08B BA23C BC68A BC68B CA05 CA11 DA06 EA02X EA02Y EB18X EB18Y EC03X EC03Y EC13X EC14X FA01 FA02 FB26 FB34 FC02 FC08 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masahiro Sanwa Kyoto University, Sakyo Ward, Kyoto City, Kyoto Prefecture Graduate School of Engineering (72) Inventor Hiroyuki Nakagawa Kyoto University, Sakyo Ward, Kyoto City, Kyoto Prefecture Graduate School of Engineering F-term (reference) 4G069 AA03 AA08 BA08A BA08B BA23C BC68A BC68B CA05 CA11 DA06 EA02X EA02Y EB18X EB18Y EC03X EC03Y EC13X EC14X FA01 FA02 FB26 FB34 FC02 FC08
Claims (4)
いて、水性液を下記特性を有するNi担持多孔質炭素触媒
の存在下に加熱/加圧処理に供することを特徴とする方
法： 1.触媒の寸法は、0.3-2mmの範囲にある、 2.触媒中のNi担持量は、35-50重量％の範囲にある、 3.BET比表面積は、150-200m2/gの範囲にある、 4.炭素担体の細孔径は、1-10nmの範囲にある、 5.水性液中の有機成分を選択的に細孔内に取り込む機能
を有する。1. A method for treating an aqueous liquid containing an aromatic compound, which comprises subjecting the aqueous liquid to heat / pressure treatment in the presence of a Ni-supporting porous carbon catalyst having the following characteristics: 1. The size of the catalyst is in the range of 0.3-2 mm, 2. The Ni loading in the catalyst is in the range of 35-50 wt%, 3. The BET specific surface area is in the range of 150-200 m 2 / g 4. The pore size of the carbon support is in the range of 1-10 nm. 5. It has a function of selectively incorporating the organic component in the aqueous liquid into the pores.
で行う請求項1に記載の方法。2. The method according to claim 1, wherein the heating / pressurizing treatment of the aqueous liquid is carried out at a temperature of 250 ° C. or higher.
で行う請求項１に記載の方法。3. The method according to claim 1, wherein the heating / pressurizing treatment of the aqueous liquid is performed at a pressure of 1 MPa or more.
行う請求項１に記載の方法。4. The method according to claim 1, wherein the heating / pressurizing treatment of the aqueous liquid is carried out under supercritical conditions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009082908A (en) * | 2007-09-12 | 2009-04-23 | Mitsubishi Chemicals Corp | Metal-supported carbon catalyst and method for decomposing and removing volatile organic compound |
| JP2015180506A (en) * | 2015-07-10 | 2015-10-15 | 大阪瓦斯株式会社 | Method and device of producing metal catalyst |
-
2002
- 2002-02-27 JP JP2002051188A patent/JP3629523B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009082908A (en) * | 2007-09-12 | 2009-04-23 | Mitsubishi Chemicals Corp | Metal-supported carbon catalyst and method for decomposing and removing volatile organic compound |
| JP2015180506A (en) * | 2015-07-10 | 2015-10-15 | 大阪瓦斯株式会社 | Method and device of producing metal catalyst |
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