JPS60238389A - Method for high-order desulfurization of gas - Google Patents
Method for high-order desulfurization of gasInfo
- Publication number
- JPS60238389A JPS60238389A JP59095276A JP9527684A JPS60238389A JP S60238389 A JPS60238389 A JP S60238389A JP 59095276 A JP59095276 A JP 59095276A JP 9527684 A JP9527684 A JP 9527684A JP S60238389 A JPS60238389 A JP S60238389A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- desulfurization
- sulfur compound
- hydrodesulfurization
- 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)
- Industrial Gases (AREA)
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は、イオウ化合物を含有するガスの高次脱硫方法
に関する。本発明方法は、水蒸気改質、メタン化、水添
処理等に供される各種ガスの脱硫に特に適している。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for high-level desulfurization of gases containing sulfur compounds. The method of the present invention is particularly suitable for desulfurizing various gases used in steam reforming, methanation, hydrogenation treatments, and the like.
従来技術
従来、例えば、炭化水素の水蒸気改質を行なう場合、第
２図に示す如く、先ず炭化水素をライン■から水添脱硫
装置−に送って水添脱硫を行なった後、ライン（ホ）を
経て吸着脱硫装置（財）においてＺｎＯ等による吸着脱
硫を行ない、かくして精製された炭化水素をライン四を
経て引続く工程における原料として使用している。しか
しながら、この様な脱硫方法においては、水添脱硫装置
−内の化合物が直接接触して、触媒を使用不能とする危
険性がある。又、吸着脱硫処理匈においては、壓Ｅ（Ｑ
平衡式から明らかな如く、温度の高い場合やＰ’Ｈ２０
・の大きな場合には、無視し得なｎ量のＨ，８のスリッ
プが認められる。更に又、第２図に示す形式の脱硫方法
によれば、全ての反応が正常に行なわれた場合において
も、ガス中のＨ，８濃度を０、Ｏ２ｐｐｍ以下とするこ
とは、実用上困難である。Prior Art Conventionally, for example, when carrying out steam reforming of hydrocarbons, as shown in Fig. 2, the hydrocarbons are first sent from line ① to a hydrodesulfurization unit and subjected to hydrodesulfurization, and then transferred to line ①. After that, the hydrocarbons are adsorbed and desulfurized using ZnO or the like in an adsorption desulfurization equipment (incorporated), and the thus purified hydrocarbons are used as a raw material in the subsequent process via line 4. However, in such a desulfurization method, there is a risk that the compounds in the hydrodesulfurization apparatus will come into direct contact with each other, rendering the catalyst unusable. In addition, in adsorption desulfurization treatment, 壓E(Q
As is clear from the equilibrium equation, when the temperature is high and P'H20
When ・is large, a negligible amount of H,8 slip is observed. Furthermore, according to the desulfurization method of the type shown in Figure 2, even if all reactions are performed normally, it is practically difficult to reduce the H,8 concentration in the gas to 0.02 ppm or less. be.
従って、より高活性の触媒を使用する様になって来たが
為にＨｇＳ の悪影響をより大きく受ける様になった技
術の現況から、より高次の脱硫を簡易に行ない得る新た
な方法の実用化が切望されている。Therefore, as more highly active catalysts are being used, the current state of the technology has become more susceptible to the negative effects of HgS, and a new method that can easily perform higher-order desulfurization has been put into practical use. It is desperately needed.
発 明 の 惜 成
本発明者は、上記の如き技術の現状に鑑みて種々研究を
重ねた結果、イオウ化合物含有ガスを脱硫するに際し、
水添脱硫及び吸着脱硫を行なった後、銅系脱硫剤による
吸着脱硫を行なう場合には、ガス中のイオウ化合物濃度
を０．１ ｐｐｍ〜１ ｐｐｂ程度まで低減させ得るこ
とを見出した。即ち、本発明は、イオウ化合物含有ガス
を水添脱硫処理及び徴とするガスの高次脱硫方法に関す
る。The inventor of the present invention has conducted various studies in view of the current state of the technology as described above, and has found that when desulfurizing gas containing sulfur compounds,
It has been found that when adsorption desulfurization using a copper-based desulfurization agent is performed after hydrodesulfurization and adsorption desulfurization, the concentration of sulfur compounds in the gas can be reduced to about 0.1 ppm to 1 ppb. That is, the present invention relates to a high-level desulfurization method for a gas that uses a sulfur compound-containing gas as a hydrodesulfurization treatment.
本発明において使用する銅系脱硫剤は、ガス中のイオウ
化合物濃度ｉ ｐｐｍ〜１ ｐｐｂ程度の場合並びにガ
ス中にチオフェン等の有機イオウ化合物が含まれている
場合に特に優れたイオウ化合物吸着効果を奏する。従っ
て、水添脱硫及び亜鉛系脱硫剤による吸着脱硫により、
ガス中のイオウ化合物濃度を上記の範囲まで低下させた
後、銅系脱硫剤による吸着処理を行なうことが好ましい
。The copper-based desulfurization agent used in the present invention has a particularly excellent sulfur compound adsorption effect when the sulfur compound concentration in the gas is about i ppm to 1 ppb and when the gas contains organic sulfur compounds such as thiophene. play. Therefore, by hydrodesulfurization and adsorption desulfurization using zinc-based desulfurization agents,
After reducing the concentration of sulfur compounds in the gas to the above range, it is preferable to perform an adsorption treatment using a copper-based desulfurization agent.
以下、図面に示す本発明の一実施態様に係るフローチャ
ートを参照しつつ、本発明の詳細な説明する。EMBODIMENT OF THE INVENTION Hereinafter, the present invention will be described in detail with reference to a flowchart according to an embodiment of the present invention shown in the drawings.
第１図において、イオウ化合物を含有するガスは、ライ
ン（１）を経て水添脱硫装置（３）に供給される。In FIG. 1, a gas containing sulfur compounds is supplied to a hydrodesulfurization apparatus (3) via a line (1).
水添脱硫に際しての条件は、公知の水添脱硫におけるそ
れと特に異なるところはなく、例えばＮ１ＭＯ８系、Ｏ
ｏＭｏＳ系等の触媒の存在下温度８５０〜４００℃程度
、圧力１０ ｋｆｌｏｍ”Ｇ程度、ｓｖｇｏｏｏ程度の
条件が採用される。The conditions for hydrodesulfurization are not particularly different from those in known hydrodesulfurization, such as N1MO8 system, O
In the presence of an oMoS-based catalyst or the like, conditions are adopted: a temperature of about 850 to 400° C., a pressure of about 10 kflom"G, and about svgooo.
水添脱硫を終えたガスは、ライン（５）を通って吸着脱
硫装置＜７）に送られる。吸着脱硫時の条件も、公知技
術のそれと特に異なるところはないが、後続の銅系吸−
剤によるイオウ化合物吸着効果を最大限に発揮させる為
に、ガス中のイオウ化合物濃度をｌ〜ｏ、 ｉ ｐｐｍ
程度とすることが望ましい。従つて亜鉛系脱硫剤の存在
下温度８５０〜４００℃程度、圧力１０ ｋｙ７ｏｔｌ
−ａ程度、５ｖｉｏｏｏ程度の条件を採用することが好
ましいが、その他の条件も当然採用可能である。The gas that has undergone hydrodesulfurization is sent to the adsorption desulfurization device <7) through line (5). The conditions during adsorption desulfurization are not particularly different from those of known technology, but the conditions for subsequent copper-based adsorption
In order to maximize the sulfur compound adsorption effect of the agent, the sulfur compound concentration in the gas should be adjusted to l~o, i ppm.
It is desirable to keep it at a certain level. Therefore, in the presence of a zinc-based desulfurization agent, the temperature is about 850 to 400°C and the pressure is 10 ky7otl.
It is preferable to adopt conditions of about -a and about 5viooo, but other conditions can of course be adopted.
イオウ化合物の濃度を１〜０．１ ｐｐｍ程度にまで低
減されたガスは、ライン（９）を舒で銅系脱硫剤を使用
する第二の吸着脱硫装置Ｑ時に供給される。銅系脱硫剤
としては、銅又は酸化鋼を５チ以上含有し、必要に応じ
て酸化亜鉛、アルミナ、シリカ等の少なくとも１種を併
せて含有するものが挙げられる。吸着時の条件は、温度
２００〜２５・０°Ｃ程度、圧力１〜１００ ｋｊｌｌ
ｏｎ” ・Ｇ程度、Ｐｈ２ｄθ〜２０ ｋｆｌｏｍ２−
Ｇ程度、５Ｖ１００Ｏ程度とす、ることか好ましい。使
用する銅系脱硫剤は、イオウ化合物濃度１〜０．０１
ｐｐｍの範囲において特に顕著なイオウ化合物吸着効果
を奏するので、ＨＩ！８のリークはない。更に、有機イ
オウ化合物をも吸着し得るので、水添脱硫装置ｔ （３
）内の触媒が劣化して有機イオウ化合物の水添が十分に
行なわれない場合にも、高次の脱硫が可能である。The gas whose sulfur compound concentration has been reduced to about 1 to 0.1 ppm is supplied to the second adsorption desulfurization device Q using a copper desulfurization agent via a line (9). Examples of the copper-based desulfurization agent include those containing 5 or more copper or oxidized steel and, if necessary, at least one of zinc oxide, alumina, silica, and the like. The conditions for adsorption are a temperature of about 200 to 25.0°C and a pressure of 1 to 100 kjll.
on” ・G degree, Ph2dθ~20 kflom2-
It is preferable to set the voltage to about G and about 5V to 100O. The copper desulfurization agent used has a sulfur compound concentration of 1 to 0.01.
It has a particularly remarkable sulfur compound adsorption effect in the ppm range, so HI! There is no leak of 8. Furthermore, since organic sulfur compounds can also be adsorbed, the hydrodesulfurization equipment t (3
Even if the catalyst in ) deteriorates and the organic sulfur compound is not sufficiently hydrogenated, high-level desulfurization is possible.
本発明で使用する銅系脱硫剤は、例えば、以下の様にし
て製造される。The copper-based desulfurization agent used in the present invention is produced, for example, as follows.
Ｏｕ及びＺｎ成分を含む溶液から共沈法により得られた
沈澱に助剤を加え、打錠、焼成等の一般の低温シフト触
媒の製法に類似の方法で調製すれば良い。It may be prepared by adding an auxiliary agent to a precipitate obtained by a coprecipitation method from a solution containing Ou and Zn components, and using a method similar to a general method for producing a low-temperature shift catalyst, such as tableting and calcination.
発明の効果 本発明によれば、以下の如き効果が達成される。Effect of the invention According to the present invention, the following effects are achieved.
（１） ガス中に含まれるイオウ化合物濃度を０． ｌ
ｐｐｍ以下、最大限ｉ ｐｐｂ程度まで容易に低減させ
ることができる。(1) The concentration of sulfur compounds contained in the gas is set to 0. l
It can be easily reduced to less than ppm, to about i ppb at the maximum.
（２）従って、後続の水蒸気改質、メタン化、水添分解
等における触媒の被毒を防止し、もって触媒寿命の大巾
な延長をはかることができる。(2) Therefore, poisoning of the catalyst in subsequent steam reforming, methanation, hydrogenolysis, etc. can be prevented, and the life of the catalyst can be greatly extended.
実 施 例
以下に実施例を示し、本発明の特徴とするところをより
明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
実施例１
イオウ化合物含有量１５０ ｐｐｍ （８として）のコ
ークス炉ガスを常法に従ってＮｉＭｏ系触媒の存在下温
度８８０℃、圧力１０ ｋｆ／ａｍ２−Ｇ、 ５Ｖ８０
００の条件下に水添分解した後、ＺｎＯ系脱硫剤に接触
させて、脱硫した。得られたガス中のイオウ化合物濃度
は、約５ ｍＦ−８／Ｎｍ８ （１０００時間平均）で
あった。Example 1 Coke oven gas having a sulfur compound content of 150 ppm (as 8) was treated in the presence of a NiMo catalyst according to a conventional method at a temperature of 880°C, a pressure of 10 kf/am2-G, and a 5V80
After hydrogenolysis under the conditions of 0.00, it was brought into contact with a ZnO-based desulfurization agent to desulfurize it. The sulfur compound concentration in the obtained gas was about 5 mF-8/Nm8 (1000 hour average).
かくして得られた一次精製ガス４００ｊ？／ｈｒをＯｕ
ｏ ８０ ％ −ＺｎＯ７０９１ｙからなる脱硫触媒５
０ｆＩを充填する吸着脱硫装置（触媒層長、ｔｏａｍ）
に供給し、温度１８０〜２５０°Ｃ１圧力８ｋｆ／ａｍ
”・Ｇの条件下に脱硫した。The thus obtained primary purified gas 400j? /hour
o 80% - Desulfurization catalyst 5 consisting of ZnO7091y
Adsorption desulfurization equipment filled with 0fI (catalyst layer length, toam)
temperature 180-250°C1 pressure 8kf/am
”・Desulfurization was carried out under the conditions of G.
最終的に得られた精製ガ′ス中のイオウ化合物濃度は、
常に０．０１ ｍｆ−８／Ｎｍ８未満であった。The concentration of sulfur compounds in the final purified gas is
It was always less than 0.01 mf-8/Nm8.
実施例２
ナフサ及びＨ２からなる混合物（Ｈ２／ナフサのモル比
０．８．イオウ化合物含有量１００ ｐｐｍ ）を常法
によｆｉ Ｎ１Ｍ０系触媒の存在下温度８８０°Ｃ１圧
力１０ ｋｆ／ａｍ−Ｇ％ＳＹ ８００の条件下に水添
分解した後、ＺｎＯ系脱硫剤に接触させて、脱硫した。Example 2 A mixture of naphtha and H2 (H2/naphtha molar ratio 0.8, sulfur compound content 100 ppm) was heated in the presence of a fi N1M0 catalyst at a temperature of 880° C. and a pressure of 10 kf/am-G. After hydrogenolysis under the condition of %SY 800, it was brought into contact with a ZnO-based desulfurization agent to be desulfurized.
得られた精製ガス中のイオウ化合物濃度は。What is the concentration of sulfur compounds in the purified gas obtained?
約５ ｍＦ−８／Ｎｍ” （１０００時間平均）であっ
た。It was about 5 mF-8/Nm'' (1000 hour average).
かくして得た精製ガス４００１／ｈｒを０ｕ０８０係−
Ｚｎ０７０チからなる脱硫触媒５０１を収容する吸着脱
硫装置（触媒層長１０ｃｍ）に供給し、温度約２００℃
、圧力８ ｋｆｌｏ−・Ｇの条件下に脱硫した。The thus obtained purified gas 4001/hr was transferred to 0u080
It is supplied to an adsorption desulfurization device (catalyst layer length 10 cm) containing a desulfurization catalyst 501 made of Zn070, and the temperature is about 200°C.
, and a pressure of 8 kflo-G.
最終的に得られた精製ガス中のイオウ化合物濃度は、常
に０．０１ｍｇ・８／Ｎｍ８未満であった。The sulfur compound concentration in the finally obtained purified gas was always less than 0.01 mg·8/Nm8.
第１図は、本発明実施態様の一例を示すフローチャート
である。第２図は、従来方法によるガス精製の一例を示
すフローチャートである。
（３）・・・水添脱硫装置、（７）・・・吸着脱硫装置
、αｐ・・・吸着脱硫装置、 翰・・・水添脱硫装置、
■・・・吸着脱硫装置。
（以上）
７゛−
第１図
ｉ５ どソFIG. 1 is a flowchart showing an example of an embodiment of the present invention. FIG. 2 is a flowchart showing an example of gas purification by a conventional method. (3)...Hydrodesulfurization equipment, (7)...Adsorption desulfurization equipment, αp...Adsorption desulfurization equipment, Kan...Hydrodesulfurization equipment,
■・・・Adsorption desulfurization equipment. (more than) 7゛- Figure 1 i5
Claims (1)
硫剤を使用する吸着脱硫処理に供した後、銅系脱硫剤を
使用する吸着脱硫処理に供することを特徴とするガスの
高次脱硫方法。■ A high-order desulfurization method for gas, which comprises subjecting a sulfur compound-containing gas to hydrodesulfurization treatment and adsorption desulfurization treatment using a zinc-based desulfurization agent, and then subjecting it to adsorption desulfurization treatment using a copper-based desulfurization agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59095276A JPS60238389A (en) | 1984-05-11 | 1984-05-11 | Method for high-order desulfurization of gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59095276A JPS60238389A (en) | 1984-05-11 | 1984-05-11 | Method for high-order desulfurization of gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60238389A true JPS60238389A (en) | 1985-11-27 |
| JPH0471435B2 JPH0471435B2 (en) | 1992-11-13 |
Family
ID=14133247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59095276A Granted JPS60238389A (en) | 1984-05-11 | 1984-05-11 | Method for high-order desulfurization of gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60238389A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02302303A (en) * | 1989-05-17 | 1990-12-14 | Osaka Gas Co Ltd | Power generation system of fuel cell |
| JPH02302301A (en) * | 1989-05-15 | 1990-12-14 | Osaka Gas Co Ltd | Improvement of hydrocarbon by water vapor |
| JPH02307803A (en) * | 1989-05-18 | 1990-12-21 | Osaka Gas Co Ltd | Production of gaseous fuel for phosphoric acid electrolyte fuel cell |
| US5302470A (en) * | 1989-05-16 | 1994-04-12 | Osaka Gas Co., Ltd. | Fuel cell power generation system |
| US5685890A (en) * | 1987-12-17 | 1997-11-11 | Osaka Gas Company Limited | Process for steam reforming of hydrocarbons |
| US7799210B2 (en) | 2004-05-14 | 2010-09-21 | Exxonmobil Research And Engineering Company | Process for removing sulfur from naphtha |
| JP2012158489A (en) * | 2011-01-31 | 2012-08-23 | Panasonic Corp | Hydrogen generating device and operation method of fuel cell system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415759B (en) * | 2013-08-30 | 2016-05-25 | 中国石油化工股份有限公司 | The sulfur method of desulphurization catalyst and preparation method thereof and sulfurous fuels oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227404A (en) * | 1975-07-09 | 1977-03-01 | New Jersey Zinc Co | Zinc oxide mold goods |
| JPS52114590A (en) * | 1976-03-24 | 1977-09-26 | Babcock Hitachi Kk | Treatment of h2s containing gas and adsorbent therefor |
| US4163708A (en) * | 1975-06-27 | 1979-08-07 | Chevron Research Company | Process for the removal of thiols from hydrocarbon oils |
| JPS57147592A (en) * | 1981-03-10 | 1982-09-11 | Mitsubishi Heavy Ind Ltd | Cleaning of coal gasified gas |
| US4446005A (en) * | 1982-09-17 | 1984-05-01 | Exxon Research And Engineering Co. | Guard bed for the removal of sulfur and nickel from feeds previously contacted with nickel containing sulfur adsorption catalysts |
-
1984
- 1984-05-11 JP JP59095276A patent/JPS60238389A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4163708A (en) * | 1975-06-27 | 1979-08-07 | Chevron Research Company | Process for the removal of thiols from hydrocarbon oils |
| JPS5227404A (en) * | 1975-07-09 | 1977-03-01 | New Jersey Zinc Co | Zinc oxide mold goods |
| JPS52114590A (en) * | 1976-03-24 | 1977-09-26 | Babcock Hitachi Kk | Treatment of h2s containing gas and adsorbent therefor |
| JPS57147592A (en) * | 1981-03-10 | 1982-09-11 | Mitsubishi Heavy Ind Ltd | Cleaning of coal gasified gas |
| US4446005A (en) * | 1982-09-17 | 1984-05-01 | Exxon Research And Engineering Co. | Guard bed for the removal of sulfur and nickel from feeds previously contacted with nickel containing sulfur adsorption catalysts |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5685890A (en) * | 1987-12-17 | 1997-11-11 | Osaka Gas Company Limited | Process for steam reforming of hydrocarbons |
| JPH02302301A (en) * | 1989-05-15 | 1990-12-14 | Osaka Gas Co Ltd | Improvement of hydrocarbon by water vapor |
| US5302470A (en) * | 1989-05-16 | 1994-04-12 | Osaka Gas Co., Ltd. | Fuel cell power generation system |
| JPH02302303A (en) * | 1989-05-17 | 1990-12-14 | Osaka Gas Co Ltd | Power generation system of fuel cell |
| JPH02307803A (en) * | 1989-05-18 | 1990-12-21 | Osaka Gas Co Ltd | Production of gaseous fuel for phosphoric acid electrolyte fuel cell |
| US7799210B2 (en) | 2004-05-14 | 2010-09-21 | Exxonmobil Research And Engineering Company | Process for removing sulfur from naphtha |
| JP2012158489A (en) * | 2011-01-31 | 2012-08-23 | Panasonic Corp | Hydrogen generating device and operation method of fuel cell system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471435B2 (en) | 1992-11-13 |
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