JPS63267420A - Treatment method and device for gas mixture containing hydrogen sulfide - Google Patents
Treatment method and device for gas mixture containing hydrogen sulfideInfo
- Publication number
- JPS63267420A JPS63267420A JP62102052A JP10205287A JPS63267420A JP S63267420 A JPS63267420 A JP S63267420A JP 62102052 A JP62102052 A JP 62102052A JP 10205287 A JP10205287 A JP 10205287A JP S63267420 A JPS63267420 A JP S63267420A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- gas mixture
- gas
- hydrogen sulfide
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007789 gas Substances 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 17
- 238000000855 fermentation Methods 0.000 claims abstract description 4
- 230000004151 fermentation Effects 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 239000012716 precipitator Substances 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000012717 electrostatic precipitator Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 101100204239 Mus musculus Stk16 gene Proteins 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- 229910010389 TiMn Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硫化水素を含有する発酵生成ガス等の硫化水
素含有ガス混合物の処理方法及び装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method and apparatus for treating hydrogen sulfide-containing gas mixtures, such as fermentation product gases containing hydrogen sulfide.
硫化水素（ＨＩＯ）金含有するガス混合物からＨ，Ｓの
分離除去処理を行なう例として、都市ガス製造において
ナフサの脱硫で生成するＨ、８の処理（除去）について
説明する。Hydrogen sulfide (HIO) As an example of the separation and removal treatment of H and S from a gas mixture containing gold, the treatment (removal) of H and 8 generated by desulfurization of naphtha in city gas production will be described.
ナフサの脱硫は、ナフサの水蒸気改質プロセス例えばＩ
ＣＩ法で用いられるナフサのガス化触媒が原料中の硫黄
化合物により顕著に被毒され、その機能を有効に発揮し
えなくなるため（必要であり、通常１ ｐｐｍ以下の痕
跡量ま１で脱硫が行われる。Desulfurization of naphtha is carried out by the steam reforming process of naphtha, e.g.
Because the naphtha gasification catalyst used in the CI method is significantly poisoned by sulfur compounds in the raw material and cannot perform its function effectively (desulfurization is normally carried out to trace amounts of 1 ppm or less), It will be done.
該方法は、原料ナフサを予熱器及び加熱炉で加熱し、水
素と混合し、原料ナフサ中の硫黄化合物を水素と反応さ
せＨ，８に変換する。次いで、Ｈ，８＃ｉ酸化亜鉛を充
填した第１段目の吸収塔で吸着除去される。ここで、除
去できなかった硫黄化合物は水添触媒塔でＨｌＢに変換
され、次いで２段目の酸化亜鉛の吸収塔で除去される。In this method, raw material naphtha is heated in a preheater and a heating furnace, mixed with hydrogen, and sulfur compounds in the raw material naphtha are reacted with hydrogen to convert into H,8. Next, it is adsorbed and removed in the first stage absorption tower filled with H, 8#i zinc oxide. Here, the sulfur compounds that could not be removed are converted to HlB in the hydrogenation catalyst tower, and then removed in the second stage zinc oxide absorption tower.
酸化亜鉛によるＨＩＳ除去の反応式を次に示す。The reaction formula for removing HIS using zinc oxide is shown below.
ＺｎＯ＋ ＨｌＢ →ＺｎＳ ＋ ＨＩＯ（吸収除去）
酸化亜鉛とＨ雪Ｓの反応は、３５０〜４００℃のような
高温で良く反応するため、上記のＨ，８の除去は高温で
行われている。ZnO + HlB → ZnS + HIO (absorption removal)
Since the reaction between zinc oxide and H snow S occurs well at a high temperature such as 350 to 400°C, the above-mentioned removal of H and 8 is performed at a high temperature.
このため、次のような欠点がある。Therefore, there are the following drawbacks.
１、 反応剤として、酸化亜鉛が必要である。又、副生
物として硫化亜鉛（Ｚｎ８）が生じ、別途処理が必要で
ある。1. Zinc oxide is required as a reactant. Furthermore, zinc sulfide (Zn8) is produced as a by-product and requires separate treatment.
２ 高温が必要である。2. High temperature is required.
五 ＨｌＢはＺｎ８と水（ＨｓＯ）に変換され、資源の
有効利用（Ｈ，Ｓを水素と硫黄に分離すれば新しい資源
となる）の面から見直す必要がある。5. HlB is converted into Zn8 and water (HsO), which needs to be reconsidered from the perspective of effective resource utilization (separating H and S into hydrogen and sulfur will create a new resource).
また、特開昭５６−４５８０２号公報に絋、硫化水素中
にレーザ光を集光して硫化水素を水とイオウに防電破壊
して水素を製造方法が記載されているが、該方法におい
ては硫化水素のガス圧は２０ト一ル以上と高く、またレ
ーザ光出力も５０メガワット以上と非常に大きいもので
、その構成において本発明と異なり、また、特開昭５９
−１２９２８９号公報には、合成ガス中にｔまれる微量
の硫化水素ガスをレーザー元を用いて分解する方法が記
載されているが、該方法は常温で行なわれており、しか
も硫黄は銅パイプ表面に析出させるもので、特殊゛な硫
黄回収装置及び銅パイプ再生装置を必要とする〇〔発明
の構成〕
本発明は、 ＨＩＯを含有するガス混合物の処理方法に
関し、該ガス混合物に７０℃以上の温度でレーザｆｔ、
ｔ−照射してＨ，８０分解処理を行ない、生成した分解
生成物をガス混合物から捕集、分離又は回収することを
特徴とするＨ、８を含有するガス混合物の処理方法及び
装置である。Furthermore, Japanese Patent Application Laid-Open No. 56-45802 describes a method for producing hydrogen by concentrating a laser beam into hydrogen sulfide and breaking down the hydrogen sulfide into water and sulfur. The gas pressure of hydrogen sulfide is as high as 20 torr or more, and the laser light output is very large as 50 megawatts or more, and its structure is different from that of the present invention, and it is
Publication No. 129289 describes a method for decomposing trace amounts of hydrogen sulfide gas contained in synthesis gas using a laser source, but this method is carried out at room temperature, and the sulfur is removed through copper pipes. The present invention relates to a method for treating a gas mixture containing HIO, which requires a special sulfur recovery device and copper pipe regeneration device. laser ft at a temperature of
A method and apparatus for processing a gas mixture containing H, 8, characterized in that H, 80 decomposition treatment is performed by t-irradiation, and the generated decomposition products are collected, separated or recovered from the gas mixture.
本発明の一具体例として、バイオリアクターを用いた水
処理装置から発生するＨ、８ ’ｉ含む生成ガスの処理
に本発明方法を適用した概念図を＠１図に示す。As a specific example of the present invention, Figure @1 shows a conceptual diagram in which the method of the present invention is applied to the treatment of a generated gas containing H,8'i generated from a water treatment device using a bioreactor.
原水１は先ず前処理装置２に導入され、ｆ過処理等が行
なわれた後ポンプ（図示せず）でバイオリアクター３に
送られる０
バイオリアクタ−３は、嫌気性下で水中の有機物等が微
生物の作用により分解、処理される反応器であする。Raw water 1 is first introduced into a pre-treatment device 2, and after being subjected to overtreatment, etc., it is sent to a bioreactor 3 using a pump (not shown). It is a reactor that is decomposed and processed by the action of microorganisms.
バイオリアクター５で嫌気性処理された水は、後方の処
理装置４に送られ、膜分離や好気性生物処理が行なわれ
る。このようにして処理水５が得られ、これは放流され
るか又は他の用途に供される〇
一方、バイオリアクター３内の嫌気性処理においては、
有機物の分解、処理によって二酸化炭素（ＣＯｓ ）、
メタン（ＣＨａ ）−水（Ｈ２Ｏ）、 Ｈ，８及び微量
の亜酸化窒素（ＮｚＯ）等が生成する０これらの生成ガ
ス混合物はファン（図示せず）によリ「生成ガスの処理
、回収部」Ａに導かれ、Ｈ，８０分解処理及びＨ，Ｓの
分解処理により生成した硫黄又は硫黄含有物質及び水素
の回収、又ならびに共存するＣＨ４等の有価物質の回収
が行なわれている。The water that has been anaerobically treated in the bioreactor 5 is sent to the rear treatment device 4, where it is subjected to membrane separation and aerobic biological treatment. In this way, treated water 5 is obtained, which can be discharged or used for other purposes.On the other hand, in the anaerobic treatment inside the bioreactor 3,
Carbon dioxide (COs),
Methane (CHa) - water (H2O), H, 8, and a trace amount of nitrous oxide (NzO) are produced. These produced gas mixtures are removed by a fan (not shown) to the "Produced gas processing and recovery section. ``A, recovery of sulfur or sulfur-containing substances and hydrogen produced by H, 80 decomposition treatment and H, S decomposition treatment, as well as recovery of coexisting valuable substances such as CH4, is being carried out.
「生成ガス処理、回収部ＪＡｔ−説明する。``Produced gas processing and recovery section JAt - Explain.
例えば１，８００ ｐｐｍのＨ，Ｓ ’ｉ金含有るバイ
オリアクター３からの生成ガス混合物〔他にＣ０３＝６
５％、ＣＨ４： ６０ ％ ｅ Ｎｅｏ ： ２５０
ｐｐｍ ｆ含有し残りは空気と水よりなる〕は、加熱器
６８を併設したレーザ光照射器６１に導入され、Ｈ，８
は水素と硫黄に分解処理される。For example, the product gas mixture from bioreactor 3 containing 1,800 ppm H,S'i gold [in addition C03=6
5%, CH4: 60% e Neo: 250
ppm F and the rest consists of air and water] is introduced into a laser beam irradiator 61 equipped with a heater 68, and H,8
is decomposed into hydrogen and sulfur.
硫黄は後方の捕集装置Ｉｔ７で捕集され、回収される。Sulfur is collected and recovered by the rear collection device It7.
水素は、生成ガス混合物中のＣＨ４とともに膜分離器８
により分離され次後、水素回収装置？によりガス混合物
（水素とＣＨ４の混合ガス）から分離され、回収されて
いるｏｌｏｌは回収された水素の貯蔵タンクである。１
０８は、水素回収装置９で分離された（水素を分離した
残りのガス） ＣＨ４の貯蔵タンク（ガスホルダー）で
ある。Hydrogen is transferred to membrane separator 8 along with CH4 in the product gas mixture.
After separation, hydrogen recovery equipment? The olol, which is separated from the gas mixture (mixed gas of hydrogen and CH4) and recovered by the olol, is a storage tank for the recovered hydrogen. 1
08 is a storage tank (gas holder) for CH4 separated by the hydrogen recovery device 9 (remaining gas after hydrogen separation).
レーザ光照射器６！は、本発明の特長であるレーザ光の
照射によりＨ，８の分解が行なわれる反応器である。Laser light irradiator 6! This is a reactor in which H, 8 is decomposed by irradiation with laser light, which is a feature of the present invention.
レーザ光照射器６１の一具体例を第２図に基いて説明す
る。レーザ光照射器６１は、レーザ光発振管１１及びレ
ーザ光の照射によりＨ，Ｓの分解が行なわれる加熱され
た反応器１２よｐ成る。A specific example of the laser beam irradiator 61 will be explained based on FIG. 2. The laser beam irradiator 61 includes a laser beam oscillation tube 11 and a heated reactor 12 in which H and S are decomposed by laser beam irradiation.
レーザ光発振管１１からのレーザ光の波長は、処理対象
物質に吸収されれば良く、１５０〜２５０ ｎｍ、好ま
しくは１７０〜２２５ｎｍであるＯ
レーザの種類及び媒質ガスは、上記の波長のレーザ光を
発するものであれば良く、適用分野、共存物質等により
適宜選択して使用できる。即ち、Ｈ，８のみを処理する
か、後述のごとく共存する有害物質も同時に処理するか
等により適宜選択できる。The wavelength of the laser beam from the laser beam oscillation tube 11 is 150 to 250 nm, preferably 170 to 225 nm, as long as it is absorbed by the substance to be treated. It may be used as long as it emits , and can be appropriately selected and used depending on the field of application, coexisting substances, etc. In other words, it can be selected as appropriate depending on whether only H, 8 is to be treated or whether coexisting harmful substances are to be treated at the same time as will be described later.
通常レーザの種類はエキシマレーザ、又媒質ガスはＦｚ
、 ＡｒＦ 、 ＡｒＣ２，ＫｒＦ 、 ＫｒＣｔが
用いられ、これらは１種又は２′ＰＩｉ以上選択して使
用することができる。Usually the type of laser is excimer laser, and the medium gas is Fz
, ArF, ArC2, KrF, and KrCt, and these can be used singly or in combinations of 2'PIi or more.
レーザ光の照射方法は、ガスに均一かつ効果的に照射さ
れれば何れの方法でも良く周知の方法が適用できる。Any method of irradiating the laser light may be used as long as the gas can be irradiated uniformly and effectively, and well-known methods can be used.
通常、第２図に示すごとく、ガスの流れに対して向流に
照射するのが好ましく又、反応器１２内部に攪拌羽根等
の攪拌機構を設けるか又は旋回流により、ガスを攪拌し
ガスに均一照射するのが好ましい。Usually, as shown in Fig. 2, it is preferable to irradiate the gas in a countercurrent direction to the flow of the gas.In addition, a stirring mechanism such as a stirring blade is provided inside the reactor 12, or a swirling flow is used to stir the gas. Uniform irradiation is preferred.
又、レーザ光の照射は、適宜集光して、あるいは集光し
ないで行なうことが出来る。Further, the laser light irradiation can be performed with or without focusing as appropriate.
第２図において１５１及び１３：はガスの流れを示し、
１３１は入口、１３２１′ｉ出口のガスの流れを示し、
１４はレーザ光の照射窓である。In Fig. 2, 151 and 13: indicate gas flows;
131 indicates the gas flow at the inlet, 1321′i the gas flow at the outlet,
14 is a laser beam irradiation window.
本方式は、 Ｈ，８分解に対して温度は７０℃以上の比
較的高い温度が必要である。このため、温度の選定は、
装置の大ささ、効果、経済性などにより適宜決めること
ができるが１００℃以上の温度が好ましい。This method requires a relatively high temperature of 70°C or higher for H,8 decomposition. Therefore, temperature selection is
The temperature can be determined as appropriate depending on the size of the device, effectiveness, economical efficiency, etc., but a temperature of 100° C. or higher is preferable.
第１図に示す例においては、バイオリアクター３から排
出される２０〜３０℃の温度のガスをレーザ光照射器６
１に導入する。レーザ光照射器６１は加熱器６２により
加熱されるようになっている。In the example shown in FIG.
1. The laser beam irradiator 61 is heated by a heater 62.
Ｈ，Ｓは高温でのレーザ光の照射により水素と硫黄とに
分解されるが、室温程度の温度ではＨ，８はＨ８まで分
解されるにとどまり後処理を必要とする。H and S are decomposed into hydrogen and sulfur by laser beam irradiation at high temperatures, but at temperatures around room temperature, H and 8 are only decomposed to H8, requiring post-treatment.
Ｈａｓを含有するガス混合物が、燃焼排ガスのような付
着、凝縮性物質を含む場合、レーザ光照射器６１の温度
は、排ガス中の酸ミスト等の反応器への付着、凝縮が無
視し得る温度以上、一般的には例えば１２０℃以上の酸
露点以上の温度で照射を行なうのが好ましい。When the gas mixture containing Has contains adhering and condensable substances such as combustion exhaust gas, the temperature of the laser beam irradiator 61 is set to a temperature at which adhesion and condensation of acid mist and the like in the exhaust gas to the reactor can be ignored. As mentioned above, it is generally preferable to perform the irradiation at a temperature equal to or higher than the acid dew point, for example, 120° C. or higher.
ＨＩＳの分解生成物である硫黄は、捕集装置７で捕集さ
れ・る。捕集装置７は、硫黄をガス中より分離、捕集す
る機能があれば何れでも良い。Sulfur, which is a decomposition product of HIS, is collected by a collection device 7. The collection device 7 may be any device as long as it has the function of separating and collecting sulfur from the gas.
通常、電気集塵方式、フォルター集塵方式、遠心集塵方
式、或いは慣性集塵方式の捕実装ｕ′ｔ、を適用分野、
共存ガス成分、規模、効果、経済性等により適宜選択し
、１１ｍ又は２種以上組合わせて行なう周知の手段で実
施することが出来る。Usually, the application field is an electrostatic precipitator, a filter precipitator, a centrifugal precipitator, or an inertial precipitator.
It can be suitably selected depending on the coexisting gas components, scale, effect, economy, etc., and can be carried out by well-known means such as 11m or a combination of two or more.
捕集された硫黄は、捕集装［７よシ適宜回収され、精製
処理され、資源として有効に利用される。The collected sulfur is appropriately collected using a collection device [7], purified, and effectively used as a resource.
Ｈ，８の分解生成物としての水素は、共存するＣＨ４と
ともに生成ガス混合物より膜分離器８により分離後、永
素回収装［９によ膜分離、回収される。Hydrogen as a decomposition product of H,8 is separated from the produced gas mixture along with coexisting CH4 by a membrane separator 8, and then membrane-separated and recovered by an hydrogen recovery device [9].
水素回収装置９蝶、水素がガス中よｐ分離あるいは捕集
する機能があれば何れでも良い０通常、膜分離方式、水
素吸蔵会合方式を適用分野、共存ガスの成分、規模、効
果、経済性等により適宜用いることＫよシ、水素をガス
中の他の成分より効果的に分離あるいは捕集することが
出来る。Hydrogen recovery equipment 9.Any device is fine as long as it has the function of separating or capturing hydrogen from the gas.0 Normally, membrane separation method, hydrogen storage association method is applied, components of coexisting gas, scale, effect, economical efficiency. When used appropriately, hydrogen can be separated or collected more effectively than other components in the gas.
水素回収装置９で分離あるい紘捕集された水素は、回収
され、資源として有効に利用される０１０１は回収され
た水素の貯蔵タンクである０回収された水素の有効利用
の例としては、ナフサの脱硫におけろ水添脱硫工程の脱
硫用リサイクルへの利用等がある。The hydrogen separated or collected in the hydrogen recovery device 9 is recovered and used effectively as a resource. 0101 is a storage tank for the recovered hydrogen. 0 Examples of effective use of recovered hydrogen are: In the desulfurization of naphtha, it can be used to recycle the hydrodesulfurization process for desulfurization.
水素回収装ｆ１９に用いられる膜分離方式は、ガス混合
物より水素を選択的に透過される水素分離膜を用いたも
ので、周知の膜技術を適宜用いることが出来る〇
水素分離膜の例としては、パラジウム（合金）膜、ポリ
スルホン糸膜、ポリイミド系膜、セルロースアセテート
系膜がある。The membrane separation method used in the hydrogen recovery device f19 uses a hydrogen separation membrane that selectively permeates hydrogen from the gas mixture, and well-known membrane technologies can be used as appropriate. Examples of hydrogen separation membranes are: , palladium (alloy) membrane, polysulfone thread membrane, polyimide membrane, and cellulose acetate membrane.
水素回収装置９に用いられる水嵩吸蔵合金方式は、ガス
混合物より水素を捕集する水素吸蔵合金を用いるもので
、周知の該技術を用いることが出来る〇
水素吸蔵合金（金属水素化物）の例としては、ＴｉＭｎ
５．ｓ−水素化物、Ｔ１１）４Ｚｒ６４Ｃｒ６４Ｍｒｌ
ｌ−水素化物ｓ ＴｉＦｅ −水素化物、 ＭｍＮｉ
４，６Ａ／４４−水素化物を又２００℃程度であればＭ
ｇ１Ｎｉ−水素化物を好適に用いることができる。The water bulk storage alloy system used in the hydrogen recovery device 9 uses a hydrogen storage alloy that captures hydrogen from a gas mixture, and this well-known technology can be used as an example of a hydrogen storage alloy (metal hydride). is TiMn
5. s-hydride, T11)4Zr64Cr64Mrl
l-hydride s TiFe -hydride, MmNi
4,6A/44-hydride and M at about 200℃
g1Ni-hydride can be suitably used.
膜分離器８は、生成ガス混合物から水素とＣＨ４ｔ−膜
分離により分離するもので、周知の膜技術で実施するこ
とが出来る。この水素、 ＣＨ。The membrane separator 8 separates hydrogen and CH4t from the product gas mixture by membrane separation, and can be implemented using known membrane technology. This hydrogen, CH.
分離膜としては、ポリイミドをペースとする有機膜を用
いることができる■
ガスホルダー１０３に回収されたＣＨ４は、Ｈ，８が除
去され高純度のものであるので、クリーンな資源として
、有効利用される。As the separation membrane, an organic membrane based on polyimide can be used. CH4 recovered in the gas holder 103 has H and 8 removed and is of high purity, so it can be used effectively as a clean resource. Ru.
第１図に示す例においては、水素をＣＨ４とともに分離
した後水素の分離、回収を行なっているが、先ず水素の
みを分離し、次いでＣＨ４ｔ−分離しても良い０又、逆
に、ｃＨ４ｔ−分離し、次いで水素の分離を行なっても
良い。In the example shown in FIG. 1, hydrogen is separated and recovered after being separated together with CH4. However, it is also possible to first separate only hydrogen and then separate CH4t-, or conversely, cH4t- Separation and then hydrogen separation may be performed.
混合ガス中にＣＨ４の様な回収すべき物質がない場合は
ＣＨ４回収の部分鉱不要であることは言うまでもない。Needless to say, if there is no substance to be recovered such as CH4 in the mixed gas, there is no need for partial ore for CH4 recovery.
又、 Ｉ（，８の処理は、膜分離等でＣＨ４を分離、回
収後に行なっても良い。Further, the treatment of I(, 8) may be performed after CH4 is separated and recovered by membrane separation or the like.
本発明は、上述のごとく混合ガス中のＨ，８の処理に関
するものであるが、混合ガス中に他の有害物質が含まれ
る場合、レーザ光の波長等の選択により、共存する有害
物質も同様に処理される６例えば、Ｈ２Ｓとともに微量
に共存するＮ、Ｏは、レーザ光（媒質ガスＡｒＦ ）で
同時に分解処理することが出来る。As mentioned above, the present invention relates to the treatment of H, 8 in a mixed gas, but if other harmful substances are included in the mixed gas, the coexisting harmful substances can also be treated by selecting the wavelength of the laser beam, etc. For example, N and O, which coexist in small amounts with H2S, can be simultaneously decomposed using laser light (medium gas ArF).
表１にＨ，８と共存する有害ガスでＨ，８と同時に処理
しうるものについて、レーザ光波長と媒質ガスの例を示
す。Table 1 shows examples of laser light wavelengths and medium gases for harmful gases that coexist with H and 8 and can be treated simultaneously with H and 8.
表 １
実施例
第２図に示したレーザ光照射器に下水処理の嫌気性発酵
により生成したガス（Ｈ２８含有量１．０００ ｐｐｍ
）を１ｔ／分で流し、レーザ光の照射を行ない反応器
出口のＨ２Ｓ及び水素濃度全測定した。レーザ光照射器
後方にフィルターを設置し、レーザ光の照射状態で１時
間上記カスを流した後フィルターの捕集物を回収し測定
した。Table 1 Example Gas produced by anaerobic fermentation for sewage treatment (H28 content 1.000 ppm) was applied to the laser light irradiator shown in Figure 2.
) was flowed at a rate of 1 t/min, laser light was irradiated, and the H2S and hydrogen concentrations at the reactor outlet were all measured. A filter was installed behind the laser beam irradiator, and the debris was allowed to flow for one hour under laser beam irradiation, and then the collected material on the filter was collected and measured.
なお処理条件は次のとおりである〇
レーザ：エキシマレーザ、ＡｒＦ２０Ｗ反応器大きさ：
１を
反応器の温度＝２００℃
Ｈ！Ｓ及び水素の測定：ガスクロマトグラフフィルター
上捕集物の測定＝ＸＸ線回
析分析次のとおりであった。The processing conditions are as follows: Laser: excimer laser, ArF20W reactor size:
1 to reactor temperature = 200℃ H! Measurement of S and hydrogen: Measurement of the material collected on the gas chromatography filter = XX-ray diffraction analysis The results were as follows.
Ｈ，８のｅｆ５Ｊ＝ ： １ ’Ｏｐｐｍ以下水素の濃
度： ９５０ ｐｐｍ
フィルター捕果物ニア５岬
フィルター捕集物のＸ線回析分析の結果捕集物はイオウ
を生成物とするものでめった。H, 8 ef5J=: 1'Oppm or less Hydrogen concentration: 950 ppm X-ray diffraction analysis of the filter-collected material near 5-Misaki filter showed that the collected material contained sulfur as a product.
１、Ｈ，８１に含有するガス混合物に７０℃以上の温度
でレーザ光を照射することＫより、■ カス混合物中の
Ｈ，Ｓ ｔ−分解処理することができる。By irradiating a gas mixture containing 1, H, and 81 with a laser beam at a temperature of 70° C. or higher, (1) H, St-decomposition treatment in the scum mixture can be carried out.
■ Ｈ，８の分解処理により水素や硫黄の様な再利用可
能な物質に変換出来る。■ By decomposing H,8, it can be converted into reusable substances such as hydrogen and sulfur.
２、 Ｈ！８をレーザ光で分解後、分解生成物の捕集
、又は分ｍを、
■ 電気集塵方式、フィルター集塵方式、遠心集塵方式
、慣性集塵方式のいずれかで行なうことにより、硫黄又
は硫黄含有物質を捕集、回収できる。2.H! After decomposing 8 with a laser beam, the decomposition products are collected or separated by one of the following methods: ■ Electrostatic precipitator, filter precipitator, centrifugal precipitator, or inertial precipitator. Capable of collecting and recovering sulfur-containing substances.
■ 膜分離方式、水素吸蔵合金方式のいずれかでガスの
分離・捕集全行なうことで、水素を分離、捕集でき、高
純度水素が回収できる。■ By performing all gas separation and collection using either the membrane separation method or the hydrogen storage alloy method, hydrogen can be separated and collected, and high-purity hydrogen can be recovered.
＆ ガス混合物にＨａｓ以外の有害物質が共存する場合
、該有害物質もＨ，Ｓと同時に処理できる。& When harmful substances other than Has coexist in the gas mixture, these harmful substances can also be treated at the same time as H and S.
４、 乾式処理法でめるので、排水処理等の二次的な処
理は不要で、実用的な方法である。4. Since it is a dry treatment method, there is no need for secondary treatment such as wastewater treatment, making it a practical method.
第１図は、バイオリアクターを用いた水処理装置から発
生するＨ、Ｓ″Ｉｋ含む生成ガスから不発明方法によ５
Ｈ，８を分解する装［を示す概念図、第２図は本発明で
用いるレーザ光照射器の１例を示す概念図である。Figure 1 shows how the produced gas containing H and S''Ik generated from a water treatment device using a bioreactor is extracted by an uninvented method.
FIG. 2 is a conceptual diagram showing an example of a laser beam irradiator used in the present invention.
Claims (1)
でレーザ光を照射して硫化水素を分解し分解によつて生
成した分解生成物をガス混合物から捕集、分離又は回収
することを特徴とするガス混合物中の硫化水素の除去方
法。 ２、硫化水素の分解生成物である硫黄及び／又は硫黄含
有物質を電気集塵方式、フィルター集塵方式、遠心集塵
方式、慣性集塵方式の内何れか１種類以上の方式により
捕集、分離又は回収する特許請求の範囲第１項記載の方
法。 ３、硫化水素の分解生成物である水素を膜分離方式及び
／又は水素収蔵合金方式により分離又は回収する特許請
求の範囲第１項記載の方法。 ４、レーザ光の波長が１５０〜２５０ｎｍである特許請
求の範囲第１項、第２項又は第３項記載の方法。 ５、レーザ光の種類がエキシマレーザである特許請求の
範囲第４項記載の方法。 ６、媒質ガスが、Ｆ＿２、ＡｒＦ、ＡｒＣｌ、ＫｒＦ、
ＫｒＣｌ、の内いずれか１種類または２種類以上の混合
物である特許請求の範囲第４項又は第５項記載の方法。 ７、被処理ガス混合物が発酵生成ガスである特許請求の
範囲第１項乃至第６項のいずれかの一に記載の方法。 ８、加熱部を備えたレーザ照射部及び分解生成物の捕集
、分離又は回収部を備えてなる硫化水素を含有するガス
混合物の処理装置。 ９、分解生成物の捕集、分離又は回収部が、硫黄及び／
又は硫黄含有物質及び／又は、水素の捕集、分離又は回
収を行なう機能を有するものである特許請求の範囲第８
項記載の装置。 １０、分解生成物の捕集、分離又は回収部が電気集塵方
式、フィルター集塵方式、遠心集塵方式、慣性集塵方式
又は膜分離方式、水素吸蔵合金方式の内いずれか１種類
又は２種類以上の方式である特許請求の範囲第９項記載
の処理装置。[Claims] 1. A gas mixture containing hydrogen sulfide is irradiated with laser light at a temperature of 70°C or higher to decompose hydrogen sulfide, and the decomposition products generated by the decomposition are collected and separated from the gas mixture. or recovery of hydrogen sulfide in a gas mixture. 2. Collecting sulfur and/or sulfur-containing substances, which are decomposition products of hydrogen sulfide, by one or more of the following: electrostatic precipitator, filter precipitator, centrifugal precipitator, or inertial precipitator; A method according to claim 1 for separating or recovering. 3. The method according to claim 1, wherein hydrogen, which is a decomposition product of hydrogen sulfide, is separated or recovered by a membrane separation method and/or a hydrogen storage alloy method. 4. The method according to claim 1, 2 or 3, wherein the wavelength of the laser beam is 150 to 250 nm. 5. The method according to claim 4, wherein the type of laser light is an excimer laser. 6. The medium gas is F_2, ArF, ArCl, KrF,
The method according to claim 4 or 5, wherein the method is any one type or a mixture of two or more types of KrCl. 7. The method according to any one of claims 1 to 6, wherein the gas mixture to be treated is a fermentation product gas. 8. An apparatus for treating a gas mixture containing hydrogen sulfide, comprising a laser irradiation section equipped with a heating section and a decomposition product collection, separation or recovery section. 9. If the decomposition product collection, separation or recovery section contains sulfur and/or
or Claim 8, which has the function of collecting, separating, or recovering sulfur-containing substances and/or hydrogen.
Apparatus described in section. 10. The decomposition product collection, separation or recovery section is one or two of the following: electrostatic precipitator, filter precipitator, centrifugal precipitator, inertial precipitator, membrane separation method, and hydrogen storage alloy method. 10. The processing device according to claim 9, which is a system of more than one type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102052A JPS63267420A (en) | 1987-04-27 | 1987-04-27 | Treatment method and device for gas mixture containing hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102052A JPS63267420A (en) | 1987-04-27 | 1987-04-27 | Treatment method and device for gas mixture containing hydrogen sulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63267420A true JPS63267420A (en) | 1988-11-04 |
Family
ID=14316995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62102052A Pending JPS63267420A (en) | 1987-04-27 | 1987-04-27 | Treatment method and device for gas mixture containing hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63267420A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277205A (en) * | 1991-11-21 | 1993-10-26 | Tokyo Electric Power Co Inc:The | Method and device for continuously decomposing and separating chlorofluorocarbons |
| JP2020518438A (en) * | 2017-04-18 | 2020-06-25 | ブレイクスルー・テクノロジーズ・エルエルシーＢｒｅａｋｔｈｒｏｕｇｈ Ｔｅｃｈｎｏｌｏｇｉｅｓ， ＬＬＣ | Sulfur production |
-
1987
- 1987-04-27 JP JP62102052A patent/JPS63267420A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05277205A (en) * | 1991-11-21 | 1993-10-26 | Tokyo Electric Power Co Inc:The | Method and device for continuously decomposing and separating chlorofluorocarbons |
| JP2020518438A (en) * | 2017-04-18 | 2020-06-25 | ブレイクスルー・テクノロジーズ・エルエルシーＢｒｅａｋｔｈｒｏｕｇｈ Ｔｅｃｈｎｏｌｏｇｉｅｓ， ＬＬＣ | Sulfur production |
| US11697103B2 (en) | 2017-04-18 | 2023-07-11 | Breakthrough Technologies, LLC | Sulfur production through the use of microwave and ultraviolet light energy |
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