JPS5966491A - Gas purification - Google Patents
Gas purificationInfo
- Publication number
- JPS5966491A JPS5966491A JP57176393A JP17639382A JPS5966491A JP S5966491 A JPS5966491 A JP S5966491A JP 57176393 A JP57176393 A JP 57176393A JP 17639382 A JP17639382 A JP 17639382A JP S5966491 A JPS5966491 A JP S5966491A
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- hydrogen sulfide
- catalyst
- gas
- reducing
- 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
- 238000000746 purification Methods 0.000 title claims description 3
- 239000007789 gas Substances 0.000 claims abstract description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- -1 fluoropylene Chemical compound 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Carbon And Carbon Compounds (AREA)
- Industrial Gases (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は一酸化炭素や水素など還元ガス中から硫化水素
を除去する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing hydrogen sulfide from reducing gases such as carbon monoxide and hydrogen.
原油価格の高騰と我が国に輸入される原油の重質化が将
来の我が国のエネルギーの見通しに大きくカゲリをきた
している。この対応として原油から留出油を採取した残
分、いわゆる蒸留残渣、あるいは石炭を原料としてガス
化を行い、そこから得られる一酸化炭素（ＣＯ）や水素
口（２）を利用して、そのまま直接燃料とする方法、（
コ０、ｌ（２から燃料合成する方法あるいけ、従来石油
製品力ら得られていた、エチレン、フロピレン、酢酸等
へ転換する石油代替エネルギー政策が打ち出され２てい
る。The soaring price of crude oil and the heavier crude oil imported into Japan are greatly jeopardizing Japan's future energy outlook. To deal with this, gasification is performed using the residue obtained by extracting distillate oil from crude oil, so-called distillation residue, or coal as a raw material, and the carbon monoxide (CO) and hydrogen gas obtained from it are used to produce gas as it is. Direct fuel method (
There is a method of synthesizing fuel from 0, 1 (2), and an oil alternative energy policy has been launched to convert to ethylene, fluoropylene, acetic acid, etc., which were conventionally obtained from petroleum products.
このガス化の反応時に重質油や石炭中の硫黄化合物は硫
化物、主として１４．Ｓに転化しｃｏやＴ−１゜の還元
性ガス中に混入するために種々なｔ１￥！！！！法が提
案され、成るものは稼動中である。During this gasification reaction, the sulfur compounds in heavy oil and coal are sulfides, mainly 14. Various t1\! are converted to S and mixed into co and T-1° reducing gas! ! ! ! A law has been proposed and is in operation.
その一つに湿式法があって、硫化水素を化学吸収させて
除去するプロセスがある。この方法は水溶液に吸収させ
るため冷却の必要がありエネルギーロスや吸収液再生、
排水処理などの課題がある。One of these is the wet method, which is a process in which hydrogen sulfide is chemically absorbed and removed. This method requires cooling to absorb into the aqueous solution, which causes energy loss and absorption liquid regeneration.
There are issues such as wastewater treatment.
他の乾式法では酸化鉄に反応させて硫化鉄として固定す
る方法があるが、固定された１冷黄は再生処理によって
放散させないと酸化鉄として再度利用ができない。Another dry method involves reacting with iron oxide and fixing it as iron sulfide, but the fixed 1-cold yellow cannot be reused as iron oxide unless it is dissipated through a regeneration process.
そこで本発明者らは従来法の欠点のない硫化水素の除去
法につき鋭意研究の結束、本発明を完成するに到った。Therefore, the present inventors conducted extensive research into a method for removing hydrogen sulfide that does not have the drawbacks of conventional methods, and finally completed the present invention.
すなわち本発明は一酸化炭素や水素など寮元ガス中の硫
化水素を除去するプロセスに於いて、該ガス流中に二酸
化硫黄を混入しなる後に、）ψ元触媒の存在下で硫黄に
転化することを特徴とするガス精製法に関するものであ
る。That is, in the process of removing hydrogen sulfide from a dormitory source gas such as carbon monoxide and hydrogen, the present invention mixes sulfur dioxide into the gas stream and then converts it to sulfur in the presence of a primary catalyst. The present invention relates to a gas purification method characterized by the following.
本発明において使用する還元触媒としてけ、Ｎ１、Ｃｎ
、 Ｍｏ、 Ｗ、 Ｆｅ、 Ｃｒよりなる群より選ばれ
た１種又は２種以との金属の酸化物を、アルミナ、シリ
カ・アルミナ、チタニアなどに担持量１〜５０重景−程
度担持されたものが使用される。As the reduction catalyst used in the present invention, N1, Cn
, Mo, W, Fe, Cr, and one or more metal oxides are supported on alumina, silica/alumina, titania, etc. in an amount of 1 to 50%. things are used.
また硫化水素の硫黄への転化反応Ｈ″、下記（１）式
％式％（１
にみられるようＶｃＳ０２消失の２ （ｊ〜＠の１（２
Ｓが消去することによって行われるが、実際には下記（
２）式
％式％）
の反応も同時に生ずるので、Ｓ０２の消失量に比較１．
Ｈ２Ｓの消去能は少ない。、
このため、Ｓ０２の添加量は還元ガス中のＦＴ２ Ｓ量
に対し、化学量１論的に当量乃至２倍当量の範囲が好ま
しい。In addition, the conversion reaction H'' of hydrogen sulfide to sulfur, as seen in the following formula (1) % formula % (1), the disappearance of VcS02 (2
This is done by erasing S, but actually the following (
2) Since the reaction of formula % formula %) also occurs at the same time, the amount of S02 disappeared is compared to 1.
The erasing ability of H2S is low. Therefore, the amount of S02 added is preferably in the range of stoichiometrically equivalent to twice the amount of FT2 S in the reducing gas.
父、転化反応条件は、常圧〜２【】→／ｃｎ？ Ｏの圧
力範囲、５ ｎ Ｏ〜２０１’Ｉ ＯノＧＶ（ｈ−’１
）範囲、２０（〕〜４００℃の温度範囲が好ましい。Father, the conversion reaction conditions are normal pressure to 2[]→/cn? O pressure range, 5 n O ~ 201'IO no GV (h-'1
) range, and a temperature range of 20(] to 400°C is preferred.
本発明の方法はガスの冷却もなく、再生の必要もなく、
ｔＸ、Ｓを接触酸化により硫黄に転化させるものである
。従って硫化物から転化した硫黄は融点以上の温度に於
いて液体であり、融点以下の温度に於いては固体である
ため、１′ａ元性のガスの系外に容易に除去が可能とな
る。The method of the invention requires no cooling of the gas, no need for regeneration,
tX, S is converted to sulfur by catalytic oxidation. Therefore, since sulfur converted from sulfide is liquid at temperatures above the melting point and solid at temperatures below the melting point, it can be easily removed from the system of the 1'a elemental gas. .
本発明の優位性について実Ｉ血例により、詳細に説明す
る。The advantages of the present invention will be explained in detail using a real blood example.
実施例
石炭を部分燃焼させて得られるガスとして、表１の組成
ＶＣＴＴ□Ｓ ＋ ０００ ｐ、ｐ、ｍ、を添加してデ
ステストに供した触媒けγ−アルミナ１１１体にＣｎＱ
３．８重量％、Ｍ （１０３１４，７＠ ｉｌ ％を担
持してなる市販品を１０〜１４メツシユに破砕したもの
である。Example 111 catalyst γ-alumina bodies were subjected to a death test with the composition VCTT□S + 000 p, p, m shown in Table 1 added as a gas obtained by partially burning coal.
A commercially available product carrying 3.8% by weight, M (10314.7@il%) was crushed into 10 to 14 meshes.
この触媒１０ｍ１を？Ｗ型反応器に充填し反応温度にな
るよう加熱した。10ml of this catalyst? The mixture was filled into a W-type reactor and heated to the reaction temperature.
この触媒層に上記Ｈ７Ｓ＋ ｔｌ ＯＯｐ、ｐ、ｍ、を
含有するテストガスを流通せしめ表−２の反応条件を設
定した・ 表−２
■Ｓ 、 Ｖ 、−”ガスｂｌｆ、量（Ｎ ｍｌ／ Ｈ
ｌ÷触媒充填量ｍｌこの反応条件下において、触媒層の
上流側に８０２を５００ ｐ、ｐ、ｍ、となるよう添加
し、触媒下流側でのＮ２ Ｓ、Ｆ＞ ０２各成分の濃度
分析を実を布し、同時ｖＣＩ−１，Ｓの硫黄への転化率
を算出して表−５に示した。A test gas containing the above H7S+ tl OOp, p, m was passed through this catalyst layer, and the reaction conditions shown in Table 2 were set.
1 ÷ Catalyst loading amount ml Under these reaction conditions, 802 was added to the upstream side of the catalyst layer at a concentration of 500 p, p, m, and the concentration of N2 S, F > 02 components on the downstream side of the catalyst was analyzed. The fruits were washed, and the conversion rate of vCI-1,S to sulfur was calculated and shown in Table 5.
表−５
Ｈ，Ｓの硫黄への転化率は前述したように（１）式のみ
の場合は１４０．の消去の２倍量のｉ−Ｔ、Ｓが消失す
ることになるが実際には（２）式の反応が同時に生ずる
ためにＳＯ２の消失量に比較してＦＴ、 ｓの消失量が
少くない。Table 5: As mentioned above, the conversion rate of H and S to sulfur is 140. This means that twice the amount of i-T, S will be lost, but in reality, the reaction of equation (2) occurs simultaneously, so the amount of FT, s lost is not small compared to the amount of SO2 lost. .
従って硫黄への転化率はここでは次の如くに定義した。Therefore, the conversion rate to sulfur is defined here as follows.
次にＳｏ、 １０００ ｐ、ｐ、ｍ、添加した場合のＮ
２ Ｓへの転化テスト結果も上記の表−５に合せて示し
た。尚このいづれのテスト時にも（Ｏ８の生成は検出で
きなかった。Next, So, 1000 p, p, m, N when added
The results of the conversion test to 2S are also shown in Table 5 above. Furthermore, during both of these tests (no generation of O8 could be detected).
以上の結果還元ガス中のｒ（、Ｓけ触媒の存在下で等量
程度の８０２を反応させると、ト■２ Ｓの大半をいお
うに転化させることが可能である。１４１ちこのいおう
け液状またげ固体状でガス体からの分離は従来法に比較
して容易であり、優れた発明である。As a result of the above, when an equal amount of 802 in the reducing gas is reacted in the presence of a catalyst, it is possible to convert most of the 2S into sulfur. It is an excellent invention because it is in a solid state and can be easily separated from a gaseous body compared to conventional methods.
尚テストでけＳＯ７を別途ト１玉人したが、実プロセス
に於いてはＪｉ：ｉｌ Ｉ［７１，たいおうを燃焼させ
ることにより利用がｒｉＴ能である。In addition, in the test, SO7 was used separately, but in the actual process, it can be used by burning the material.
復代理人 内 １） 明 復代理人 萩 ハχ 亮 − −６１１，−Sub-agent: 1) Akira Sub-agent Hagi Ryo - -611,-
Claims (1)
プロセスに於いて、該ガス光中に二酸化硫黄を混入した
る後に、還元触媒の存在下で硫黄に転化することを特徴
とするガス精製法。In a process for completely removing hydrogen sulfide from reducing gases such as carbon monoxide and hydrogen, gas purification is characterized by mixing sulfur dioxide into the gas light and then converting it to sulfur in the presence of a reducing catalyst. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57176393A JPS5966491A (en) | 1982-10-08 | 1982-10-08 | Gas purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57176393A JPS5966491A (en) | 1982-10-08 | 1982-10-08 | Gas purification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5966491A true JPS5966491A (en) | 1984-04-14 |
Family
ID=16012869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57176393A Pending JPS5966491A (en) | 1982-10-08 | 1982-10-08 | Gas purification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5966491A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4990318A (en) * | 1989-06-07 | 1991-02-05 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a nickel-promoted absorbing composition |
-
1982
- 1982-10-08 JP JP57176393A patent/JPS5966491A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4990318A (en) * | 1989-06-07 | 1991-02-05 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a nickel-promoted absorbing composition |
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