JPH06256779A - Method for desulfurizing town bas - Google Patents
Method for desulfurizing town basInfo
- Publication number
- JPH06256779A JPH06256779A JP5325935A JP32593593A JPH06256779A JP H06256779 A JPH06256779 A JP H06256779A JP 5325935 A JP5325935 A JP 5325935A JP 32593593 A JP32593593 A JP 32593593A JP H06256779 A JPH06256779 A JP H06256779A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrogen
- desulfurization
- desulfurizing agent
- copper
- 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
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は都市ガスの脱硫方法に関
し、より詳細には、水素ガスを含まない都市ガス中の硫
黄含有量を長時間安定して高度に低下させ得る脱硫方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a desulfurization method for city gas, and more particularly to a desulfurization method capable of stably reducing the sulfur content in city gas containing no hydrogen gas for a long time to a high degree.
【０００２】[0002]
【従来の技術】都市ガス中には、多くの場合、硫黄濃度
として約５ｐｐｍ以上の硫黄化合物が付臭剤として含ま
れている。付臭剤としては、その目的から、ジメチルサ
ルファイド等、物理化学的に安定で、容易に吸着されな
い硫黄化合物が採用されている。これらの硫黄化合物
は、触媒等を用いて都市ガスを改質・燃焼する場合に
は、それらの触媒に悪影響を与える原因となるので、脱
硫剤を用いた脱硫工程に付され、硫黄分を除去したのち
使用される。このような安定な硫黄化合物を除去する方
法としては、化学プロセスで石油留分等の脱硫に使われ
ている水添脱硫法、活性炭等による吸着脱硫等が考えら
れる。しかし、前者においては、到達可能な脱硫レベル
は０．１ｐｐｍ程度であるので、触媒の被毒を完全に防
止することができない。また、後者においては、活性炭
は都市ガス中に数千ｐｐｍのオーダーで含まれる炭素数
３〜６以上の炭化水素も同時に吸着してしまうため、本
来、硫黄化合物が吸着すべきサイトのほとんどが利用で
きず、十分な硫黄吸着量を確保しようとすると、必要活
性炭量が膨大になるという問題がある。2. Description of the Related Art City gas often contains a sulfur compound having a sulfur concentration of about 5 ppm or more as an odorant. As the odorant, for that purpose, a sulfur compound such as dimethyl sulfide that is physically and chemically stable and is not easily adsorbed is used. When sulfur gas is reformed and burned using a catalyst, etc., these sulfur compounds may cause adverse effects on these catalysts, so they are subjected to a desulfurization process using a desulfurizing agent to remove sulfur content. It will be used later. As a method for removing such a stable sulfur compound, a hydrodesulfurization method used for desulfurization of petroleum fractions in a chemical process, an adsorptive desulfurization with activated carbon, etc. can be considered. However, in the former case, since the attainable desulfurization level is about 0.1 ppm, poisoning of the catalyst cannot be completely prevented. In the latter case, activated carbon also adsorbs hydrocarbons containing 3 to 6 or more carbon atoms contained in the city gas in the order of several thousand ppm at the same time, so most of the sites where sulfur compounds should be adsorbed should be used. However, there is a problem that the required amount of activated carbon becomes enormous when trying to secure a sufficient sulfur adsorption amount.
【０００３】[0003]
【発明が解決しようとする課題】そこで、特開平２−３
０２４９６号公報に開示されているように、銅系脱硫剤
を用いて都市ガスを脱硫する方法がある。この方法では
都市ガス中の硫黄含有量を０．１ｐｐｂ以下に脱硫する
ことが可能であり、かつ活性炭と比較して十分なライフ
を持っているが、実際のプロセスに組み込み長時間安定
して使用するには、更に長時間のライフを持つことが要
求されている。本発明は、上記従来技術の問題点を解消
するために創案されたもので、本発明者等が種々研究を
重ねた結果、水素ガスを含有しない都市ガスを、共沈法
により調製された銅−亜鉛系脱硫剤を用いて脱硫する際
に、ジメチルサルファイドなど吸着脱硫では除去しにく
い硫黄化合物の脱硫に、微量の水素が重要な役割をして
おり、都市ガスに少量の水素を添加して脱硫することに
より、都市ガス中の硫黄化合物を長時間安定して、著し
く低減できることを見出して完成したもので、本発明は
都市ガスを高度に且つ長時間安定して脱硫できる脱硫方
法を提供することを目的とする。[Patent Document 1] Japanese Patent Laid-Open No. 2-3
As disclosed in Japanese Patent No. 02496, there is a method of desulfurizing city gas using a copper-based desulfurizing agent. With this method, the sulfur content in city gas can be desulfurized to less than 0.1 ppb and has a sufficient life compared to activated carbon, but it can be incorporated into the actual process and used stably for a long time. To do so, it is required to have a longer life. The present invention was devised in order to solve the above-mentioned problems of the prior art. As a result of various researches conducted by the present inventors, city gas containing no hydrogen gas was prepared by coprecipitation method. -When desulfurizing with a zinc-based desulfurizing agent, a small amount of hydrogen plays an important role in desulfurizing sulfur compounds such as dimethyl sulfide that are difficult to remove by adsorption desulfurization. The present invention has been completed by finding that sulfur compounds in city gas can be stably reduced for a long time and can be significantly reduced by desulfurization, and the present invention provides a desulfurization method capable of desulfurizing city gas highly stably for a long time. The purpose is to
【０００４】[0004]
【課題を解決するための手段】上記の課題を解決すべく
なされた、本発明の都市ガスの脱硫方法は、水素ガスを
含有しない都市ガスに水素を添加し、共沈法により調製
された銅−亜鉛系脱硫剤を用いて脱硫することからな
る。特に、都市ガスに、約０．０１％（容量％、以下同
様）以上の水素を添加することによって行われるが、水
素添加量をむやみに多くしても脱硫効果に変わりはな
く、その場合にはむしろ経済的に不利になる。従って、
０．０１〜１０％程度の水素、好ましくは０．１〜７％
程度の水素、より好ましくは１〜５％程度の水素を添加
しながら、都市ガスを脱硫する方法が好適である。本発
明の方法によれば、脱硫後の都市ガス中の硫黄含有量を
確実に５ｐｐｂ（硫黄分として、以下同様）以下、通常
の条件では１ｐｐｂ以下、好ましい条件では０．１ｐｐ
ｂ以下に低減することができる。The city gas desulfurization method of the present invention, which has been made to solve the above problems, is a copper prepared by a coprecipitation method by adding hydrogen to city gas containing no hydrogen gas. -Desulfurization using a zinc-based desulfurizing agent. Particularly, it is carried out by adding about 0.01% (volume%, the same below) of hydrogen to city gas, but even if the amount of hydrogen added is excessively increased, the desulfurization effect does not change. Would rather be economically disadvantaged. Therefore,
0.01-10% hydrogen, preferably 0.1-7%
A method of desulfurizing the city gas while adding approximately hydrogen, more preferably approximately 1 to 5% hydrogen is suitable. According to the method of the present invention, the sulfur content in the city gas after desulfurization is reliably 5 ppb or less (as sulfur content, the same applies hereinafter), 1 ppb or less under normal conditions, and 0.1 pp under preferred conditions.
It can be reduced to b or less.
【０００５】本発明において、水素ガスを含有しない都
市ガスには、例えば、１３Ａなどのガス事業法で定めら
れた分類名称で呼ばれるガスや、パイプライン又はボン
ベで供給されるＬＰＧなどが包含され、より具体的に
は、Ｃ1〜Ｃ5の炭化水素を主成分とするガス、例えば、
天然ガス、液化天然ガス、液化石油ガス、石油精製オフ
ガス、及びこれらの混合ガスが包含される。本発明の脱
硫方法は、脱硫剤として、共沈法により調製された銅−
亜鉛系脱硫剤を用い、都市ガスに水素を添加しながら当
該脱硫剤に接触させることにより行われる。銅−亜鉛系
脱硫剤としては、少なくとも銅及び酸化亜鉛を含有し、
共沈法により調製された脱硫剤であれば特に限定される
ものではないが、好ましくは下記に示すような方法によ
り調製されたＣｕ−Ｚｎ系脱硫剤、Ｃｕ−Ｚｎ−Ａｌ系
脱硫剤などが好適に使用される。In the present invention, city gas that does not contain hydrogen gas includes, for example, a gas referred to by a classification name defined by the Gas Business Act such as 13A, LPG supplied by a pipeline or a cylinder, More specifically, a gas containing a C 1 to C 5 hydrocarbon as a main component, for example,
Natural gas, liquefied natural gas, liquefied petroleum gas, petroleum refinery off-gas, and a mixed gas thereof are included. The desulfurization method of the present invention is a desulfurizing agent containing copper prepared by a coprecipitation method.
It is carried out by using a zinc-based desulfurizing agent and bringing it into contact with the desulfurizing agent while adding hydrogen to the city gas. The copper-zinc-based desulfurizing agent contains at least copper and zinc oxide,
It is not particularly limited as long as it is a desulfurizing agent prepared by a coprecipitation method, but preferably a Cu-Zn-based desulfurizing agent, a Cu-Zn-Al-based desulfurizing agent, etc. prepared by a method as shown below. It is preferably used.
【０００６】（１）Ｃｕ−Ｚｎ系脱硫剤 銅化合物（例えば、硝酸銅、酢酸銅等）及び亜鉛化合物
（例えば、硝酸亜鉛、酢酸亜鉛等）を含む水溶液とアル
カリ物質（例えば、炭酸ナトリウム、炭酸カリウム等）
の水溶液を混合して沈殿を生じさせる（共沈法）。生成
した沈殿は十分に水で洗浄した後、濾過し、乾燥する。
次にこれを約２７０〜４００℃で焼成し、一旦水でスラ
リーとした後、濾過・乾燥し、酸化銅−酸化亜鉛の焼結
体を得る。酸化銅及び酸化亜鉛の配合比は、原子比で通
常、銅：亜鉛＝１：約０．３〜１０、好ましくは１：約
０．５〜３、より好ましくは１：約１〜２．３程度とす
ることが好ましい。亜鉛量が少なすぎる場合には、銅の
シンタリングを効果的に防止することができず、一方亜
鉛量が多すぎる場合には、銅系脱硫剤としての十分な脱
硫性能を発揮しない。次いで、かくして得られた混合酸
化物を水素還元する。水素還元は、好ましくは、水素含
有量６％以下、より好ましくは０．５〜４容量％程度と
なるように、反応に関与しないガス（例えば、窒素ガ
ス、アルゴンガス、メタンガス等）により希釈された水
素ガスの存在下に、１５０〜３５０℃程度で上記混合物
を還元処理することにより行われる。このようにして得
られるＣｕ−Ｚｎ系脱硫剤は、他の担体成分としてある
種の金属化合物、例えば、酸化クロムなどを含有してい
てもよい。また、上記の工程において、沈殿物を焼成す
る際又は焼結体を水素還元する際に、必要に応じて助剤
を加えた後、タブレットや押出成形物などの形状に成形
するのが好ましい。(1) Cu-Zn Desulfurizing Agent An aqueous solution containing a copper compound (eg, copper nitrate, copper acetate, etc.) and a zinc compound (eg, zinc nitrate, zinc acetate, etc.) and an alkaline substance (eg, sodium carbonate, carbonic acid). Potassium etc.)
The aqueous solution of is mixed to cause precipitation (coprecipitation method). The precipitate formed is thoroughly washed with water, filtered, and dried.
Next, this is baked at about 270 to 400 ° C., once made into a slurry with water, then filtered and dried to obtain a copper oxide-zinc oxide sintered body. The compounding ratio of copper oxide and zinc oxide is usually atomic ratio of copper: zinc = 1: about 0.3-10, preferably 1: about 0.5-3, more preferably 1: about 1-2.3. It is preferable to set the degree. If the amount of zinc is too small, copper sintering cannot be effectively prevented, while if the amount of zinc is too large, sufficient desulfurization performance as a copper-based desulfurizing agent is not exhibited. Next, the mixed oxide thus obtained is reduced with hydrogen. The hydrogen reduction is preferably performed by diluting with a gas not involved in the reaction (eg, nitrogen gas, argon gas, methane gas, etc.) so that the hydrogen content is 6% or less, more preferably about 0.5 to 4% by volume. In the presence of hydrogen gas, the mixture is reduced at about 150 to 350 ° C. The Cu-Zn-based desulfurizing agent thus obtained may contain a certain metal compound such as chromium oxide as another carrier component. In addition, in the above-mentioned step, it is preferable to add a auxiliary agent, if necessary, when firing the precipitate or reducing the sintered body with hydrogen, and then shaping into a shape such as a tablet or an extruded product.
【０００７】（２）Ｃｕ−Ｚｎ−Ａｌ系脱硫剤 銅化合物（例えば、硝酸銅、酢酸銅等）及び亜鉛化合物
（例えば、硝酸亜鉛、酢酸亜鉛等）及びアルミニウム化
合物（例えば、水酸化アルミニウム、硝酸アルミニウ
ム、アルミン酸ナトリウム等）を含む水溶液とアルカリ
物質（例えば、炭酸ナトリウム、炭酸カリウム等）の水
溶液を混合して、沈殿を生じさせる（共沈法）。この
時、アルミニウム化合物はアルカリ物質の溶液に加えて
おいて、この溶液と銅化合物及び亜鉛化合物を含む水溶
液を混合して沈殿を生成してもよい。次いで、生成した
沈殿は十分に水で洗浄した後、濾過し、乾燥する。次に
これを約２７０〜４００℃で焼成し、一旦水でスラリー
とした後、濾過、乾燥し、酸化銅−酸化亜鉛−酸化アル
ミニウムの焼結体を得る。酸化銅、酸化亜鉛及び酸化ア
ルミニウムの配合比は、原子比で通常、銅：亜鉛：アル
ミニウム＝１：約０．３〜１０：約０．０５〜２、より
好ましくは１：約０．６〜３：約０．３〜１程度とする
ことが好ましい。亜鉛量が少なすぎる場合には、銅のシ
ンタリングを効果的に防止することができず、一方亜鉛
量が多すぎる場合には、銅系脱硫剤としての十分な脱硫
性能を発揮しない。また、アルミニウム量が少なすぎる
場合には、Ｃｕ−ＺｎＯ構造を安定化することができ
ず、一方アルミニウム量が多すぎる場合には、脱硫性能
が低下する。次いで、かくして得られた混合酸化物を水
素還元する。水素還元は、好ましくは、水素含有量６％
以下、より好ましくは０．５〜４容量％程度となるよう
に、反応に関与しないガス（例えば、窒素ガス、アルゴ
ンガス、メタンガス等）により希釈された水素ガスの存
在下に、１５０〜３５０℃程度で上記混合物を還元処理
することにより行われる。このようにして得られるＣｕ
−Ｚｎ−Ａｌ系脱硫剤は、他の担体成分としてある種の
金属化合物、例えば、酸化クロムなどを含有していても
よい。また、上記の工程において、沈殿物を焼成する際
又は焼結体を水素還元する際に、必要に応じて助剤を加
えた後、タブレットや押出成形物などの形状に成形する
のが好ましい。(2) Cu-Zn-Al-based desulfurizing agent Copper compounds (eg copper nitrate, copper acetate etc.) and zinc compounds (eg zinc nitrate, zinc acetate etc.) and aluminum compounds (eg aluminum hydroxide, nitric acid) An aqueous solution containing aluminum, sodium aluminate, etc.) and an aqueous solution of an alkaline substance (eg, sodium carbonate, potassium carbonate, etc.) are mixed to cause precipitation (coprecipitation method). At this time, the aluminum compound may be added to the solution of the alkaline substance, and this solution may be mixed with an aqueous solution containing the copper compound and the zinc compound to generate a precipitate. Then, the formed precipitate is thoroughly washed with water, filtered, and dried. Next, this is baked at about 270 to 400 ° C., once made into a slurry with water, then filtered and dried to obtain a copper oxide-zinc oxide-aluminum oxide sintered body. The compounding ratio of copper oxide, zinc oxide and aluminum oxide is usually atomic ratio of copper: zinc: aluminum = 1: about 0.3-10: about 0.05-2, more preferably 1: about 0.6-. 3: It is preferably about 0.3 to 1. If the amount of zinc is too small, copper sintering cannot be effectively prevented, while if the amount of zinc is too large, sufficient desulfurization performance as a copper-based desulfurizing agent is not exhibited. Further, when the amount of aluminum is too small, the Cu-ZnO structure cannot be stabilized, while when the amount of aluminum is too large, desulfurization performance is deteriorated. Next, the mixed oxide thus obtained is reduced with hydrogen. Hydrogen reduction preferably has a hydrogen content of 6%
Below, in the presence of hydrogen gas diluted with a gas that does not participate in the reaction (for example, nitrogen gas, argon gas, methane gas, etc.) at 150 to 350 ° C., more preferably about 0.5 to 4% by volume. It is carried out by subjecting the mixture to a reduction treatment to a degree. Cu obtained in this way
The —Zn—Al-based desulfurizing agent may contain a certain metal compound as another carrier component, for example, chromium oxide. In addition, in the above-mentioned step, it is preferable to add a auxiliary agent, if necessary, when firing the precipitate or reducing the sintered body with hydrogen, and then shaping into a shape such as a tablet or an extruded product.
【０００８】上記（１）及び（２）における混合酸化物
の水素還元に関し、銅は融点が低いため、熱により粒径
が増大し、表面積が減少しやすく、また、過度の熱によ
り細孔構造が微妙に変化して、その結果、脱硫剤として
の特性が大きく変化する。更に、酸化銅の水素還元は発
熱反応である。従って、混合酸化物の水素還元に際して
は、混合酸化物の水素還元を温和な条件下に進行させる
のが好ましく、前記のように水素含有量６％以下、より
好ましくは０．５〜４容量％程度となるように、反応に
関与しないガスにより希釈された水素ガスの存在下に、
１５０〜３５０℃程度の温度に維持しつつ還元処理する
方法が好適である。反応に関与しないガスとしては、窒
素ガス等の不活性ガスが好適に使用される。Regarding the hydrogen reduction of the mixed oxide in the above (1) and (2), since copper has a low melting point, the particle size increases due to heat, the surface area tends to decrease, and the pore structure due to excessive heat. Changes subtly, and as a result, the characteristics as a desulfurizing agent change greatly. Further, the hydrogen reduction of copper oxide is an exothermic reaction. Therefore, in the hydrogen reduction of the mixed oxide, it is preferable to proceed the hydrogen reduction of the mixed oxide under mild conditions, and as described above, the hydrogen content is 6% or less, more preferably 0.5 to 4% by volume. To the extent of the presence of hydrogen gas diluted with a gas that does not participate in the reaction,
A method of performing the reduction treatment while maintaining the temperature at about 150 to 350 ° C is suitable. An inert gas such as nitrogen gas is preferably used as the gas that does not participate in the reaction.
【０００９】上記の方法で得られる銅−亜鉛系脱硫剤
は、微粒子の凝集体からなる緻密な構造をしており、非
常に小さい銅微粒子が、酸化亜鉛粒子表面に均一に分散
しているとともに、酸化亜鉛との化学的な相互作用によ
り高活性状態になっている。また、Ｃｕ−Ｚｎ−Ａｌ系
脱硫剤においては、酸化アルミニウムは全体に分布し、
熱による銅粒子、酸化亜鉛粒子のシンタリングを防いで
高活性な状態を保持している。従って、これらの脱硫剤
を使用する場合には、都市ガス中の硫黄含有量を確実に
５ｐｐｂ以下、通常の条件では１ｐｐｂ以下、更に適当
な条件では容易に０．１ｐｐｂ以下とすることができ
る。特にＣｕ−Ｚｎ−Ａｌ系脱硫剤にあっては、酸化ア
ルミニウムの作用により、耐熱性に優れ、高温での強度
低下及び硫黄吸着力の低下を著しく減少させることがで
きるという利点が得られるため、使用温度域の制約が緩
和される。The copper-zinc-based desulfurizing agent obtained by the above method has a dense structure composed of agglomerates of fine particles, and very small copper fine particles are uniformly dispersed on the surface of zinc oxide particles. , It is in a highly active state due to its chemical interaction with zinc oxide. Further, in the Cu-Zn-Al-based desulfurizing agent, aluminum oxide is distributed throughout,
It prevents the copper particles and zinc oxide particles from sintering due to heat and maintains a highly active state. Therefore, when these desulfurizing agents are used, the sulfur content in the city gas can be reliably reduced to 5 ppb or less, 1 ppb or less under normal conditions, and easily 0.1 ppb or less under appropriate conditions. In particular, in the Cu-Zn-Al-based desulfurizing agent, due to the action of aluminum oxide, it is possible to obtain the advantages that it is excellent in heat resistance and can significantly reduce strength deterioration at high temperature and sulfur adsorption strength. The restrictions on the operating temperature range are alleviated.
【００１０】本発明の脱硫方法は、上記のようにして調
製された銅−亜鉛系脱硫剤を１５０〜３００℃の温度範
囲で使用する。Ｃｕ−Ｚｎ−Ａｌ系脱硫剤にあっては、
１５０〜４００℃程度の温度範囲で使用してもよい。好
ましくは、都市ガスを脱硫する前に、加熱器を用いるか
又は脱硫ガスと熱交換することにより都市ガスを予熱
し、１５０〜４００℃程度で脱硫すればよい。脱硫温度
は硫黄化合物の分解反応速度を速くするという点では、
より高い温度で脱硫することが望ましいが、一方、あま
り温度が高いと脱硫剤の銅成分がシンタリングを起こし
脱硫剤の表面積が減少する。従って、実際には２００〜
３５０℃、より好ましくは２５０〜３００℃で使用する
ことが好ましい。In the desulfurization method of the present invention, the copper-zinc desulfurizing agent prepared as described above is used in the temperature range of 150 to 300 ° C. For the Cu-Zn-Al-based desulfurizing agent,
You may use it in the temperature range of about 150-400 degreeC. Preferably, before desulfurizing the city gas, the city gas may be preheated by using a heater or by exchanging heat with the desulfurizing gas, and desulfurized at about 150 to 400 ° C. Desulfurization temperature increases the decomposition reaction rate of sulfur compounds,
It is desirable to desulfurize at a higher temperature, while too high a temperature causes the copper component of the desulfurizing agent to sinter and reduce the surface area of the desulfurizing agent. Therefore, in practice
It is preferably used at 350 ° C, more preferably 250 to 300 ° C.
【００１１】本発明の脱硫方法は、通常、銅−亜鉛系脱
硫剤が充填された脱硫管に都市ガスと水素を通じること
により行われる。添加する水素量は厳密には都市ガス中
に含まれている硫黄の種類、量などに応じて調整される
が、実際含まれている硫黄量はｐｐｍオーダーの量であ
るため、少なくとも０．０１％以上の水素を添加するこ
とによって行われる。しかし、水素添加量をむやみに多
くしても脱硫効果に変わりはなく、その場合にはむしろ
経済的に不利になる。従って、０．０１〜１０％程度の
水素、好ましくは０．１〜７％程度の水素、より好まし
くは１〜５％程度の水素を添加しながら、都市ガスを脱
硫する方法が好ましい。また、水蒸気改質プロセスの前
処理の脱硫として使用する場合には、水蒸気改質反応に
よってできた水素を一部リサイクルすることによって使
用することができる。充填すべき脱硫剤の量は、都市ガ
ス中の硫黄含有量、使用条件等により適宜設定される
が、通常、ＧＨＳＶが２００〜４０００（ｌ／ｈ）程
度、好ましくは３００〜２０００（ｌ／ｈ）程度となる
ように定めればよい。The desulfurization method of the present invention is usually carried out by passing city gas and hydrogen through a desulfurization pipe filled with a copper-zinc-based desulfurizing agent. Strictly speaking, the amount of hydrogen added is adjusted according to the type and amount of sulfur contained in the city gas, but the actual amount of sulfur contained is at least 0.01 because the amount of sulfur is in the ppm order. This is done by adding more than% hydrogen. However, even if the amount of hydrogen added is excessively increased, the desulfurization effect does not change, and in that case, it is rather economically disadvantageous. Therefore, a method of desulfurizing the city gas while adding about 0.01 to 10% of hydrogen, preferably about 0.1 to 7% of hydrogen, and more preferably about 1 to 5% of hydrogen is preferable. When used as desulfurization in the pretreatment of the steam reforming process, it can be used by partially recycling the hydrogen produced by the steam reforming reaction. The amount of the desulfurization agent to be filled is appropriately set depending on the sulfur content in the city gas, the use conditions, etc., but normally GHSV is about 200 to 4000 (l / h), preferably 300 to 2000 (l / h). ) It should be determined so that it becomes a degree.
【００１２】また、銅−亜鉛系脱硫剤の寿命を延ばすに
は、銅−亜鉛系脱硫剤の前に酸化亜鉛系吸着脱硫剤を充
填し、酸化亜鉛で吸着され得る硫黄化合物を予め除去す
ることが望ましい。この方法によれば、都市ガス中に含
まれている硫化水素等が酸化亜鉛で除去されるので、銅
−亜鉛系脱硫剤の負荷が軽減され、結果として寿命が延
長される。また、メルカプタン系の硫黄化合物が都市ガ
スに含まれている場合にも、酸化亜鉛で吸着されるの
で、銅−亜鉛系脱硫剤の負荷が軽減され、結果として寿
命が延長される。Further, in order to extend the life of the copper-zinc desulfurizing agent, a zinc oxide adsorbing desulfurizing agent is filled before the copper-zinc desulfurizing agent to remove sulfur compounds which can be adsorbed by zinc oxide in advance. Is desirable. According to this method, hydrogen sulfide and the like contained in the city gas are removed by zinc oxide, so that the load of the copper-zinc-based desulfurizing agent is reduced and, as a result, the life is extended. Further, even when a mercaptan-based sulfur compound is contained in the city gas, it is adsorbed by zinc oxide, so that the load of the copper-zinc-based desulfurizing agent is reduced, and as a result, the life is extended.
【００１３】[0013]
【発明の効果】本発明によれば、脱硫性能が極めて優れ
た銅−亜鉛系脱硫剤が使用されているとともに共存する
水素の効果により、少量の脱硫剤で、高度に脱硫された
都市ガスを長時間安定して容易に得ることができるとい
う効果を奏する。従って、硫黄被毒に弱い触媒を使用し
て都市ガスを改質する場合等において、触媒の硫黄被毒
を実用上完全に防止することができるなど、硫黄による
悪影響を極めて高度なレベルまで排除することが可能で
ある。EFFECTS OF THE INVENTION According to the present invention, a highly desulfurizing city gas is produced with a small amount of desulfurizing agent due to the effect of coexisting hydrogen with the use of a copper-zinc type desulfurizing agent having extremely excellent desulfurizing performance. The effect is that it can be obtained stably for a long time and easily. Therefore, when reforming city gas using a catalyst weak against sulfur poisoning, it is possible to completely prevent sulfur poisoning of the catalyst practically, and to eliminate the adverse effects of sulfur to an extremely high level. It is possible.
【００１４】[0014]
【実施例】以下、実施例及び比較例に基づいて本発明を
より詳細に説明するが、本発明はこれら実施例に限定さ
れるものではない。 実施例１ 硝酸銅と硝酸亜鉛をモル比１：１の割合で含有する混合
水溶液と、炭酸ナトリウムの水溶液を、８０℃程度に保
持した精製水に撹拌下一定の速度で同時滴下した。生成
した沈殿を熟成、洗浄、濾過、乾燥後、直径１／８イン
チ×長さ１／８インチに打錠成形し、更に約２８０℃で
焼成した。次いで該焼成体約１５０ｃｃを充填した脱硫
管（脱硫層長さ３０ｃｍ）に水素１容量％を含む窒素ガ
スを流通させ、温度２００℃で還元した後、該脱硫管に
下記表１に示される組成からなる都市ガス（以下、１３
Ａガスという）１５０（ｌ／ｈ）と水素１．５（ｌ／
ｈ）を通じ（ＧＨＳＶ＝１０００ｈ-1）、温度２００
℃、圧力０．０２ｋｇ／ｃｍ2・Ｇの条件下に脱硫し
た。脱硫ガス中の硫黄含有量をコールドトラップ法で経
時的に測定したところ、２０００時間の運転にわたり、
０．１ｐｐｂ以下であった。The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples. Example 1 A mixed aqueous solution containing copper nitrate and zinc nitrate in a molar ratio of 1: 1 and an aqueous solution of sodium carbonate were simultaneously added dropwise to purified water kept at about 80 ° C. with stirring at a constant rate. The resulting precipitate was aged, washed, filtered and dried, and then tablet-molded to have a diameter of 1/8 inch and a length of 1/8 inch, and was further calcined at about 280 ° C. Then, a nitrogen gas containing 1% by volume of hydrogen was passed through a desulfurization pipe (desulfurization layer length: 30 cm) filled with about 150 cc of the calcined body, and reduced at a temperature of 200 ° C., and then the desulfurization pipe had a composition shown in Table 1 below. City gas consisting of (hereinafter, 13
A (gas A) 150 (l / h) and hydrogen 1.5 (l / h)
h) (GHSV = 1000h −1 ), temperature 200
Desulfurization was carried out under the conditions of ° C and pressure of 0.02 kg / cm 2 · G. When the sulfur content in the desulfurization gas was measured with the cold trap method over time, over the operation for 2000 hours,
It was 0.1 ppb or less.
【００１５】[0015]
【表１】 [Table 1]
【００１６】比較例１ 実施例１と同じ脱硫剤で、１３Ａガス１５０（ｌ／ｈ）
を、水素を添加しないで通じ、温度２００℃、圧力０．
０２ｋｇ／ｃｍ2・Ｇの条件下に脱硫した。その結果、
約１２００時間で脱硫ガス中の硫黄濃度が０．１ｐｐｍ
に達した。Comparative Example 1 Using the same desulfurizing agent as Example 1, 13A gas 150 (l / h)
Through without adding hydrogen, at a temperature of 200 ° C. and a pressure of 0.
It was desulfurized under the condition of 02 kg / cm 2 · G. as a result,
About 1200 hours, the sulfur concentration in the desulfurization gas was 0.1 ppm
Reached
【００１７】実施例２ 水酸化ナトリウム水溶液に約１２０℃で水酸化アルミニ
ウムを溶解し、アルミン酸塩ができるまで撹拌する。こ
のアルミン酸ナトリウム溶液を炭酸ナトリウム溶液に加
え、この溶液を約６０℃に保つ。この溶液に硝酸銅及び
硝酸亜鉛をモル比１：１の割合で含有する混合水溶液を
撹拌しながら徐々に滴下し沈殿を生ずる。沈殿は十分に
水で洗浄した後、濾過し、乾燥する。次にこれを約２８
０℃で焼成し、一旦水でスラリーとした後、濾過、乾燥
し、直径１／８インチ×長さ１／８インチの大きさに成
形し、モル比で１：１：０．３の酸化銅−酸化亜鉛−酸
化アルミニウムの焼結体を得た。次いで該焼成体約１５
０ｃｃを充填した脱硫管（脱硫層長さ３０ｃｍ）に水素
１容量％を含む窒素ガスを流通させ、温度２００℃で還
元した後、該脱硫管に１３Ａガス１５０（ｌ／ｈ）と水
素１．５（ｌ／ｈ）を通じ（ＧＨＳＶ＝１０００
ｈ-1）、温度２００℃、圧力０．０２ｋｇ／ｃｍ2・Ｇ
の条件下に脱硫した。脱硫ガス中の硫黄含有量をコール
ドトラップ法で経時的に測定したところ、２４００時間
の運転に亘り、０．１ｐｐｂ以下であった。Example 2 Aluminum hydroxide was dissolved in a sodium hydroxide aqueous solution at about 120 ° C. and stirred until an aluminate was formed. The sodium aluminate solution is added to the sodium carbonate solution and the solution is kept at about 60 ° C. A mixed aqueous solution containing copper nitrate and zinc nitrate in a molar ratio of 1: 1 was gradually added dropwise to this solution with stirring to cause precipitation. The precipitate is washed thoroughly with water, filtered and dried. Next about 28
Firing at 0 ° C., once making a slurry with water, filtering and drying, shaping into a size of 1/8 inch in diameter × 1/8 inch in length, and oxidizing at a molar ratio of 1: 1: 0.3 A sintered body of copper-zinc oxide-aluminum oxide was obtained. Then about 15
Nitrogen gas containing 1% by volume of hydrogen was passed through a desulfurization tube (desulfurization layer length: 30 cm) filled with 0 cc and reduced at a temperature of 200 ° C., and then 150 A (13 / g) of 13A gas and hydrogen 1. Through 5 (l / h) (GHSV = 1000
h -1 ), temperature 200 ° C, pressure 0.02 kg / cm 2 · G
It was desulfurized under the conditions of. When the sulfur content in the desulfurization gas was measured with the cold trap method over time, it was 0.1 ppb or less over 2400 hours of operation.
【００１８】実施例３ 硝酸銅、硝酸亜鉛及び水酸化アルミニウムをモル比１：
１：０．３の割合で含有する混合水溶液を、約６０℃に
保った炭酸ナトリウム水溶液に撹拌しながら滴下し沈殿
を生成する。沈殿は十分に水で洗浄した後、濾過し、乾
燥する。次にこれを約２８０℃で焼成し、一旦水でスラ
リーとした後、濾過、乾燥し、直径１／８インチ×長さ
１／８インチの大きさに成形した。次いで該焼成体約１
５０ｃｃを充填した脱硫管（脱硫層長さ３０ｃｍ）に水
素１容量％を含む窒素ガスを流通させ、温度２００℃で
還元した後、該脱硫管に１３Ａガス１５０（ｌ／ｈ）と
水素１．５（ｌ／ｈ）を通じ（ＧＨＳＶ＝１０００
ｈ-1）、温度２００℃、圧力０．０２ｋｇ／ｃｍ2・Ｇ
の条件下に脱硫した。脱硫ガス中の硫黄含有量をコール
ドトラップ法で経時的に測定したところ、２４００時間
の運転に亘り、０．１ｐｐｂ以下であった。Example 3 Copper nitrate, zinc nitrate and aluminum hydroxide were used in a molar ratio of 1:
A mixed aqueous solution containing at a ratio of 1: 0.3 is added dropwise to an aqueous sodium carbonate solution kept at about 60 ° C. with stirring to generate a precipitate. The precipitate is washed thoroughly with water, filtered and dried. Next, this was baked at about 280 ° C., once made into a slurry with water, filtered, dried, and molded into a size of 1/8 inch in diameter × 1/8 inch in length. Then about 1 of the fired body
Nitrogen gas containing 1% by volume of hydrogen was circulated through a desulfurization pipe filled with 50 cc (desulfurization layer length 30 cm) and reduced at a temperature of 200 ° C., and then 150 A (13 / g) of 13A gas and hydrogen 1. Through 5 (l / h) (GHSV = 1000
h -1 ), temperature 200 ° C, pressure 0.02 kg / cm 2 · G
It was desulfurized under the conditions of. When the sulfur content in the desulfurization gas was measured with the cold trap method over time, it was 0.1 ppb or less over 2400 hours of operation.
【００１９】実施例４ 水素添加量を０．１％［０．１５（ｌ／ｈ）］とする以
外は、実施例３と同様にして、１３Ａガスの脱硫を行っ
た。その結果、脱硫ガス中の硫黄含有量は、２４００時
間の運転にわたり、０．１ｐｐｂ以下に抑制されてい
た。Example 4 13A gas was desulfurized in the same manner as in Example 3 except that the amount of hydrogen added was 0.1% [0.15 (l / h)]. As a result, the sulfur content in the desulfurization gas was suppressed to 0.1 ppb or less over the operation for 2400 hours.
【００２０】実施例５ 炭酸ナトリウム水溶液に水酸化アルミニウムを加え、こ
の溶液を６０℃に保ち、これに硝酸銅及び硝酸亜鉛をモ
ル比で１：１の割合で含有する混合水溶液を撹拌しなが
ら徐々に滴下し沈殿を生成させる。その後の処理は実施
例３と同様にして行い、モル比で１：１：０．３の酸化
銅−酸化亜鉛−酸化アルミニウムの焼結体を得た。次い
で該焼成体約１５０ｃｃを充填した脱硫管（脱硫層長さ
３０ｃｍ）に水素１容量％を含む窒素ガスを流通させ、
温度２００℃で還元した後、該脱硫管に１３Ａガス１５
０（ｌ／ｈ）と水素１．５（ｌ／ｈ）を通じ（ＧＨＳＶ
＝１０００ｈ-1）、温度２００℃、圧力０．０２ｋｇ／
ｃｍ2・Ｇの条件下に脱硫した。脱硫ガス中の硫黄含有
量をコールドトラップ法で経時的に測定したところ、２
４００時間の運転に亘り、０．１ｐｐｂ以下であった。Example 5 Aluminum hydroxide was added to an aqueous solution of sodium carbonate, the solution was kept at 60 ° C., and a mixed aqueous solution containing copper nitrate and zinc nitrate in a molar ratio of 1: 1 was gradually stirred. To form a precipitate. The subsequent treatment was performed in the same manner as in Example 3 to obtain a copper oxide-zinc oxide-aluminum oxide sintered body with a molar ratio of 1: 1: 0.3. Then, a nitrogen gas containing 1% by volume of hydrogen was passed through a desulfurization pipe (desulfurization layer length: 30 cm) filled with about 150 cc of the fired body,
After reduction at a temperature of 200 ° C., 13 A gas 15
Through 0 (l / h) and hydrogen 1.5 (l / h) (GHSV
= 1000h −1 ), temperature 200 ° C., pressure 0.02 kg /
It was desulfurized under the condition of cm 2 · G. When the sulfur content in the desulfurization gas was measured with the cold trap method over time, 2
It was 0.1 ppb or less over 400 hours of operation.
【００２１】実施例６ 実施例５と同じ脱硫剤を用い、脱硫温度を温度２５０℃
とする以外は実施例３と同様の条件で、１３Ａガスを脱
硫した。その結果、脱硫ガス中の硫黄含有量は、４００
０時間の運転にわたり、０．１ｐｐｂ以下に抑制されて
いた。Example 6 The same desulfurizing agent as in Example 5 was used, and the desulfurization temperature was 250 ° C.
13A gas was desulfurized under the same conditions as in Example 3 except that As a result, the sulfur content in the desulfurization gas was 400
It was suppressed to 0.1 ppb or less over the operation for 0 hours.
【００２２】実施例７ 実施例２と同様にして、ＬＰＧ（硫黄含有量５ｐｐｍ）
を１５０（ｌ／ｈ）の流量で、約１％の水素［１．５
（ｌ／ｈ）］を添加して脱硫を行った。その結果、脱硫
ガス中の硫黄含有量は、２０００時間の運転にわたり、
０．１ｐｐｂ以下に抑制されていた。Example 7 LPG (sulfur content: 5 ppm) was carried out in the same manner as in Example 2.
At a flow rate of 150 (l / h) and about 1% hydrogen [1.5
(L / h)] was added for desulfurization. As a result, the sulfur content in the desulfurization gas was over 2000 hours of operation.
It was suppressed to 0.1 ppb or less.
【００２３】実施例８ 都市ガスを原燃料とする汎用のリン酸型燃料電池発電シ
ステムの脱硫装置にＣｕ−Ｚｎ−Ａｌ系脱硫剤を充填
し、原燃料の脱硫試験を行った。脱硫装置としては、実
施例３と同様の製法で得られたＣｕ−Ｚｎ−Ａｌ系脱硫
剤３８リットルを充填した脱硫装置（脱硫層長さ約７６
ｃｍ）を用いた。原燃料として、上記表１に示される成
分からなる都市ガス１３Ａガスを用い、このガス（１２
Ｎｍ3／ｈ、ＧＨＳＶ＝３２０ｈ-1）を２００℃に予熱
した後、０．１Ｎｍ3の水素とともに上記脱硫装置に導
入して脱硫した。脱硫されたガスをＳ／Ｃ（炭化水素中
の炭素１モル当りの水蒸気のモル数）＝２．０、反応温
度４５０℃（入口）及び６６５℃（出口）、反応圧力
０．１kg/cm2で水蒸気改質反応に付した。水蒸気改質さ
れた燃料ガスは、市販の低温一酸化炭素変性触媒が充填
された熱交換反応器型一酸化炭素変成器において、変成
器出口温度１９０℃、反応圧力０．２kg/cm2の条件下に
変成した後、燃料電池本体の燃料極に導き、酸化極に導
入された空気中の酸素と反応させて、電気エネルギーを
取り出した。脱硫装置出口におけるガス中の硫黄含有量
を経時的に測定したが、６２００時間経過後も硫黄含有
量は０．１ｐｐｂ以下であり、水蒸気改質触媒は６２０
０時間経過後においても触媒活性の劣化反応開始直後と
同様な活性を維持しており、燃料電池は正常に作動し
た。Example 8 A desulfurization apparatus of a general-purpose phosphoric acid fuel cell power generation system using city gas as a raw fuel was filled with a Cu—Zn—Al-based desulfurizing agent, and a desulfurization test of the raw fuel was conducted. As the desulfurization device, a desulfurization device (desulfurization layer length of about 76) filled with 38 liters of a Cu—Zn—Al-based desulfurizing agent obtained by the same manufacturing method as in Example 3 was used.
cm) was used. As raw fuel, city gas 13A gas composed of the components shown in Table 1 above was used.
Nm 3 / h, GHSV = 320 h −1 ) was preheated to 200 ° C., and then introduced into the desulfurization device together with 0.1 Nm 3 of hydrogen for desulfurization. S / C (moles of water vapor per mole of carbon in hydrocarbon) = 2.0, reaction temperature 450 ° C. (inlet) and 665 ° C. (outlet), desulfurized gas, reaction pressure 0.1 kg / cm 2 The steam reforming reaction was carried out. The steam-reformed fuel gas was used in a heat exchange reactor type carbon monoxide shift converter filled with a commercially available low-temperature carbon monoxide modification catalyst under conditions of a shift outlet temperature of 190 ° C. and a reaction pressure of 0.2 kg / cm 2 . After the conversion to the lower side, it was led to the fuel electrode of the fuel cell body and reacted with oxygen in the air introduced into the oxidizing electrode to take out electrical energy. The sulfur content in the gas at the outlet of the desulfurizer was measured with time. The sulfur content was 0.1 ppb or less even after 6200 hours, and the steam reforming catalyst was 620.
Even after the lapse of 0 hours, the same activity as immediately after the start of the deterioration reaction of the catalyst activity was maintained, and the fuel cell operated normally.
【００２４】比較例２ 銅−亜鉛系脱硫剤に代えて、銅を担持した活性炭（表面
積約７００ｍ2／ｇ）１５０ｃｃを実施例１と同様の脱
硫管に充填し、１３Ａガス１５０（ｌ／ｈ）を通じ、温
度２５℃、圧力０．０２ｋｇ／ｃｍ2・Ｇの条件下に脱
硫した。その結果、脱硫ガス中の硫黄含有量は、約１０
０時間で、０．１ｐｐｍに達した。また、水素を添加し
ても脱硫効果は全く変わらなかった。Comparative Example 2 Instead of the copper-zinc-based desulfurizing agent, 150 cc of activated carbon carrying copper (surface area of about 700 m 2 / g) was filled in the same desulfurization tube as in Example 1, and 13A gas was supplied at 150 (l / h). ), And desulfurized under the conditions of a temperature of 25 ° C. and a pressure of 0.02 kg / cm 2 · G. As a result, the sulfur content in the desulfurization gas was about 10
At 0 hours, it reached 0.1 ppm. Further, even if hydrogen was added, the desulfurization effect did not change at all.
【００２５】実施例９ １３Ａガスを１３９．５（ｌ／ｈ）とし、水素添加量を
１０．５（ｌ／ｈ）とする以外は実施例３と同様にして
脱硫を行った。その結果、脱硫ガス中の硫黄含有量は、
２４００時間の運転にわたり、０．１ｐｐｂ以下に抑制
されていた。Example 9 Desulfurization was performed in the same manner as in Example 3 except that 13A gas was 139.5 (l / h) and the hydrogenation amount was 10.5 (l / h). As a result, the sulfur content in the desulfurization gas is
It was suppressed to 0.1 ppb or less over 2400 hours of operation.
【００２６】実施例１０ １３Ａガス１３５（ｌ／ｈ）とし、水素添加量を１５
（ｌ／ｈ）とする以外は実施例３と同様にして脱硫を行
った。その結果、脱硫ガス中の硫黄含有量は、２４００
時間の運転にわたり、０．１ｐｐｂ以下に抑制されてい
た。Example 10 13A gas was 135 (l / h), and the hydrogenation amount was 15
Desulfurization was performed in the same manner as in Example 3 except that (l / h) was used. As a result, the sulfur content in the desulfurization gas was 2400.
It was suppressed to 0.1 ppb or less over the operation for an hour.
【００２７】比較例３ 混練り法によって調製された銅−亜鉛系脱硫剤（高さ１
／８インチ×直径１／８インチのペレット、銅含有量＝
４１重量％、銅：亜鉛（原子比）＝１：０．７６）を実
施例１と同様の脱硫管に充填し、水素１容量％を含む窒
素ガスを流通させ、温度２００℃で還元した後、１３Ａ
ガス１５０（ｌ／ｈ）と水素１．５（ｌ／ｈ）を添加し
て、温度２００℃、圧力０．０２ｋｇ／ｃｍ2・Ｇの条
件下に脱硫した。その結果、運転開始から約２０８時間
後には脱硫ガス中の硫黄は、０．０５ｐｐｍに達してい
た。このように、混練り法によって調製された脱硫剤の
脱硫効果は、共沈法により調製された脱硫剤より劣って
いた。Comparative Example 3 A copper-zinc-based desulfurizing agent (height 1
/ 8 inch x 1/8 inch diameter pellet, copper content =
41% by weight, copper: zinc (atomic ratio) = 1: 0.76) was filled in a desulfurization tube similar to that in Example 1, nitrogen gas containing 1% by volume of hydrogen was passed through, and reduction was performed at a temperature of 200 ° C. , 13A
A gas of 150 (l / h) and hydrogen of 1.5 (l / h) were added, and desulfurization was performed under the conditions of a temperature of 200 ° C. and a pressure of 0.02 kg / cm 2 · G. As a result, about 208 hours after the start of operation, the sulfur content in the desulfurized gas reached 0.05 ppm. As described above, the desulfurization effect of the desulfurization agent prepared by the kneading method was inferior to that of the desulfurization agent prepared by the coprecipitation method.
【００２８】比較例４ 市販の硝酸亜鉛（日産ガードラー社製Ｇ−７２Ｄ）を粉
砕して約３ｍｍの大きさに篩い分けし、これに硝酸銅水
溶液を含浸させ加熱濃縮する。これを乾燥しさらに約２
８０℃で焼成し、酸化亜鉛−酸化銅混合物（モル比９
５：５）を得た。次いで、該焼成体約１５０ｃｃを実施
例１と同様の脱硫管に充填し、水素１容量％を含む窒素
ガスを流通させ、温度２００℃で還元した後、１３Ａガ
ス１５０（ｌ／ｈ）と水素１．５（ｌ／ｈ）を添加し
て、温度２００℃、圧力０．０２ｋｇ／ｃｍ2・Ｇの条
件下に脱硫した。その結果、運転開始直後から脱硫ガス
中に硫黄が検出され、さらに約１時間後には０．１ｐｐ
ｍに達していた。Comparative Example 4 Commercially available zinc nitrate (G-72D manufactured by Nissan Gardler) was crushed and sieved to a size of about 3 mm, which was impregnated with an aqueous solution of copper nitrate and concentrated by heating. This is dried and about 2 more
Baking at 80 ° C., zinc oxide-copper oxide mixture (molar ratio 9
5: 5) was obtained. Next, about 150 cc of the calcined material was filled in a desulfurization tube similar to that of Example 1, nitrogen gas containing 1% by volume of hydrogen was passed through, and reduction was performed at a temperature of 200 ° C., and then 13A gas 150 (l / h) and hydrogen were added. 1.5 (l / h) was added, and desulfurization was performed under the conditions of a temperature of 200 ° C. and a pressure of 0.02 kg / cm 2 · G. As a result, sulfur was detected in the desulfurization gas immediately after the start of operation, and 0.1 pp after about 1 hour.
had reached m.
【００２９】比較例５ 硝酸銅、硝酸亜鉛及び硝酸アルミニウムをモル比１：
１：０．３の割合で含有する混合水溶液と、炭酸ナトリ
ウムの水溶液を、８０℃程度に保持した精製水に撹拌下
一定の速度で同時に滴下した。この時、溶液のｐＨは７
〜７．５に維持しつつ沈殿生成を行う。生成した沈殿を
熟成、洗浄、濾過、乾燥後、直径１／８インチ×長さ１
／８インチに打錠成型し、更に約２８０℃で焼成した。
次いで該焼成体１５０ｃｃを脱硫管（脱硫層長さ３０ｃ
ｍ）に充填し、水素還元を事前に行わず、該脱硫管に１
３Ａガス１５０（ｌ／ｈ）と水素０．１５（ｌ／ｈ）を
通じ（ＧＨＳＶ＝１０００ｈ-1）、温度２００℃、圧力
０．０２ｋｇ／ｃｍ2・Ｇの条件下に脱硫した。その結
果、運転開始直後から脱硫ガス中に硫黄が検出され、約
３時間後には０．０５ｐｐｍに達していた。Comparative Example 5 Copper nitrate, zinc nitrate and aluminum nitrate were used in a molar ratio of 1:
The mixed aqueous solution contained in the ratio of 1: 0.3 and the aqueous solution of sodium carbonate were simultaneously added dropwise to the purified water kept at about 80 ° C. under stirring at a constant rate. At this time, the pH of the solution is 7
Precipitate is generated while maintaining at ~ 7.5. The formed precipitate is aged, washed, filtered and dried, then 1/8 inch in diameter x 1 in length
It was tablet-molded to / 8 inch and further baked at about 280 ° C.
Next, the fired body 150 cc was replaced with a desulfurization pipe (desulfurization layer length 30 c
m) and without hydrogen reduction in advance, the desulfurization pipe was filled with 1
Desulfurization was performed under the conditions of a temperature of 200 ° C. and a pressure of 0.02 kg / cm 2 · G by passing 3 A gas of 150 (l / h) and hydrogen of 0.15 (l / h) (GHSV = 1000 h −1 ). As a result, sulfur was detected in the desulfurization gas immediately after the start of operation, and reached 0.05 ppm after about 3 hours.
【００３０】比較例６ 比較例５と同じ製法で得た酸化銅−酸化亜鉛−酸化アル
ミニウム焼成物１５０ｃｃを脱硫管（脱硫層長さ３０ｃ
ｍ）に充填し、水素還元を事前に行わず、該脱硫管に１
３Ａガス１３５（ｌ／ｈ）と水素１５（ｌ／ｈ）を通じ
（ＧＨＳＶ＝１０００ｈ-1）、温度２００℃、圧力０．
０２ｋｇ／ｃｍ2・Ｇの条件下に脱硫した。その結果、
１３Ａガスと水素を導入した時に脱硫層の温度が５００
℃を越え、さらに、２００時間後には、０．０３ｐｐｍ
の硫黄が検出された。Comparative Example 6 150 cc of a copper oxide-zinc oxide-aluminum oxide fired product obtained by the same manufacturing method as in Comparative Example 5 was desulfurized pipe (desulfurized layer length 30 c).
m) and without hydrogen reduction in advance, the desulfurization pipe was filled with 1
3A gas 135 (l / h) and hydrogen 15 (l / h) (GHSV = 1000 h −1 ), temperature 200 ° C., pressure 0.
It was desulfurized under the condition of 02 kg / cm 2 · G. as a result,
The temperature of the desulfurization layer is 500 when 13A gas and hydrogen are introduced.
After exceeding 200 ℃, 0.03ppm after 200 hours
Sulfur was detected.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高見 晋 大阪市中央区平野町四丁目１番２号 大阪 瓦斯株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shin Takami 4-1-2 Hirano-cho, Chuo-ku, Osaka City Osaka Gas Co., Ltd.
Claims (4)
素を添加し、共沈法により調製された銅−亜鉛系脱硫剤
を用いて脱硫することを特徴とする都市ガスの脱硫方
法。1. A method for desulfurizing a city gas, which comprises adding hydrogen to a city gas containing no hydrogen gas, and desulfurizing it using a copper-zinc-based desulfurizing agent prepared by a coprecipitation method.
（容量％）添加する請求項１記載の都市ガスの脱硫方
法。2. City gas containing 0.01 to 10% hydrogen
The method for desulfurizing city gas according to claim 1, wherein the method comprises adding (volume%).
亜鉛混合物又は酸化銅−酸化亜鉛−酸化アルミニウム混
合物を水素還元して得られた脱硫剤である請求項１又は
２記載の都市ガスの脱硫方法。3. The city gas according to claim 1 or 2, wherein the copper-zinc-based desulfurizing agent is a desulfurizing agent obtained by hydrogen reduction of a copper oxide-zinc oxide mixture or a copper oxide-zinc oxide-aluminum oxide mixture. Desulfurization method.
以下に脱硫する請求項１から３のいずれかに記載の都市
ガスの脱硫方法。4. The sulfur content in city gas is 5 ppb.
The method for desulfurizing city gas according to claim 1, wherein the desulfurization is performed below.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32593593A JP3242514B2 (en) | 1992-11-27 | 1993-11-29 | City gas desulfurization method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-341235 | 1992-11-27 | ||
| JP34123592 | 1992-11-27 | ||
| JP32593593A JP3242514B2 (en) | 1992-11-27 | 1993-11-29 | City gas desulfurization method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000355811A Division JP2001200278A (en) | 1992-11-27 | 2000-11-22 | Process for desulfurizing town gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256779A true JPH06256779A (en) | 1994-09-13 |
| JP3242514B2 JP3242514B2 (en) | 2001-12-25 |
Family
ID=26572006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32593593A Expired - Lifetime JP3242514B2 (en) | 1992-11-27 | 1993-11-29 | City gas desulfurization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3242514B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000048733A1 (en) * | 1997-08-21 | 2000-08-24 | Osaka Gas Company Limited | Desulfurizing agent and method for desulfurization of hydrocarbon |
| JP2001205004A (en) * | 2000-01-28 | 2001-07-31 | Japan Energy Corp | Method for removing sulfur compound |
| US6875410B2 (en) * | 2000-02-01 | 2005-04-05 | Tokyo Gas Co., Ltd. | Adsorbent for removing sulfur compounds from fuel gases and removal method |
| EP3050944A1 (en) | 2015-02-02 | 2016-08-03 | Panasonic Intellectual Property Management Co., Ltd. | Desulfurization process and a desulfurizer |
| JP2016153368A (en) * | 2015-02-13 | 2016-08-25 | 新日鐵住金株式会社 | Method for producing hydrogen by reforming hydrocarbon, apparatus for producing hydrogen, operation method for fuel battery, and operation device for fuel battery |
| US10889597B2 (en) | 2018-03-30 | 2021-01-12 | Panasonic Intellectual Property Management Co., Ltd. | Desulfurizer, hydrogen generation device, and fuel cell system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018139108A1 (en) | 2017-01-26 | 2018-08-02 | パナソニック株式会社 | Desulfurization apparatus and desulfurization method |
-
1993
- 1993-11-29 JP JP32593593A patent/JP3242514B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000048733A1 (en) * | 1997-08-21 | 2000-08-24 | Osaka Gas Company Limited | Desulfurizing agent and method for desulfurization of hydrocarbon |
| JP2001205004A (en) * | 2000-01-28 | 2001-07-31 | Japan Energy Corp | Method for removing sulfur compound |
| US6875410B2 (en) * | 2000-02-01 | 2005-04-05 | Tokyo Gas Co., Ltd. | Adsorbent for removing sulfur compounds from fuel gases and removal method |
| EP3050944A1 (en) | 2015-02-02 | 2016-08-03 | Panasonic Intellectual Property Management Co., Ltd. | Desulfurization process and a desulfurizer |
| JP2016153368A (en) * | 2015-02-13 | 2016-08-25 | 新日鐵住金株式会社 | Method for producing hydrogen by reforming hydrocarbon, apparatus for producing hydrogen, operation method for fuel battery, and operation device for fuel battery |
| US10889597B2 (en) | 2018-03-30 | 2021-01-12 | Panasonic Intellectual Property Management Co., Ltd. | Desulfurizer, hydrogen generation device, and fuel cell system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3242514B2 (en) | 2001-12-25 |
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