JPS62226805A - Treatment of hydrogen sulfide - Google Patents
Treatment of hydrogen sulfideInfo
- Publication number
- JPS62226805A JPS62226805A JP61069759A JP6975986A JPS62226805A JP S62226805 A JPS62226805 A JP S62226805A JP 61069759 A JP61069759 A JP 61069759A JP 6975986 A JP6975986 A JP 6975986A JP S62226805 A JPS62226805 A JP S62226805A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen sulfide
- chloride
- gas
- aqueous solution
- oxygen
- 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 65
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 65
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 39
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 39
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 229960002089 ferrous chloride Drugs 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 24
- 230000003647 oxidation Effects 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000000706 filtrate Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 3
- 150000001805 chlorine compounds Chemical class 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010959 steel Substances 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〕
本発明は改良された硫化水素の処理方法に関するもので
ある。さらに詳しくいえば、本発明は、塩化鉄の酸化、
還元反応を利用した硫化水素または硫化水素含有ガスの
処理において、硫化水素の吸収により生成した塩化第一
鉄の塩化第二鉄への再生速度を速め、効率よく硫化水素
を処理する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved method for treating hydrogen sulfide. More specifically, the present invention provides oxidation of iron chloride,
This article relates to a method for efficiently treating hydrogen sulfide by accelerating the regeneration rate of ferrous chloride produced by absorption of hydrogen sulfide into ferric chloride in the treatment of hydrogen sulfide or hydrogen sulfide-containing gas using a reduction reaction. be.
硫化水素ガスは、例えば製鉄所において、高温の溶滓に
水をかけて高炉滓から水滓を製造する際に、水蒸気と共
に多量発生し、また、石油精製の際にも多量発生する。Hydrogen sulfide gas is generated in large amounts together with steam when, for example, in steel plants, water is poured over high-temperature slag to produce slag from blast furnace slag, and large amounts of hydrogen sulfide gas are also generated during oil refining.
このような硫化水素ガスは悪臭を発生する上に、腐食性
を有し、かつ人体に対して悪影響を及ぼすなどの問題を
有し、公害防止、設備保全、労働環境衛生上からその処
理対策が要望されている。Such hydrogen sulfide gas not only emits a foul odor, but also has corrosive properties and has a negative effect on the human body. Measures to dispose of it are necessary from the viewpoint of pollution prevention, equipment maintenance, and occupational health. It is requested.
従来、このような水素ガスを処理する方法としては、水
酸化ナトリウム、石灰、アルカリ錯塩などのアルカリに
硫化水素ガスを接触させる方法が知られているが、この
方法は、反応が遅く、かつ硫化物や多硫化物などの生成
物の処理に問題があるなど、実用的に十分に満足しうる
方法とはいえない。Conventionally, a method known to treat such hydrogen gas is to contact hydrogen sulfide gas with an alkali such as sodium hydroxide, lime, or an alkali complex salt, but this method has a slow reaction and This method cannot be said to be fully satisfactory in practical terms, as there are problems with the treatment of products such as polysulfides and polysulfides.
ところで、硫化水素は３価の鉄イオンを含む水溶液に接
触すると、酸化されて容易に硫黄を生成することが知ら
れている。３価の鉄イオンを含む水溶液として、例えば
塩化第二鉄水溶液を用いる場合、次に示す反応式に従っ
て硫化水素から硫黄を生成する。By the way, it is known that when hydrogen sulfide comes into contact with an aqueous solution containing trivalent iron ions, it is oxidized and easily generates sulfur. When using, for example, a ferric chloride aqueous solution as the aqueous solution containing trivalent iron ions, sulfur is produced from hydrogen sulfide according to the reaction formula shown below.
２Ｆｅ（１！ｉ＋ＩＩｚＳ−２ＦｅＣ１ｚ＋２１１（１
＋Ｓ ・・・（１）すなわち、硫化水素は塩化第二鉄に
より酸化されて硫黄を生成し、一方、塩化第二鉄は還元
されて塩化第一鉄となる。2Fe(1!i+IIzS-2FeC1z+211(1
+S... (1) That is, hydrogen sulfide is oxidized by ferric chloride to produce sulfur, while ferric chloride is reduced to become ferrous chloride.
このような３価の鉄イオンと硫化水素との反応を利用し
た硫化水素処理方法としては、例えば硫酸銅と硫酸第二
鉄を含む水溶液を吸収液として用いる方法（特公昭５６
−２３６５０号公報）が提案されている。この方法は、
前記水溶液を用いて硫化水素を吸収させたのち、この液
を酸素加圧下、１２０℃以上の温度で加圧処理して、溶
融硫黄と硫酸銅および硫酸第二鉄を生成させ、溶融硫黄
は回収除去し、硫酸銅と硫酸第二鉄を含む処理液は吸収
液として繰り返し使用するという方法である。As a hydrogen sulfide treatment method using such a reaction between trivalent iron ions and hydrogen sulfide, for example, a method using an aqueous solution containing copper sulfate and ferric sulfate as an absorption liquid (Japanese Patent Publication No. 56
-23650) has been proposed. This method is
After hydrogen sulfide is absorbed using the aqueous solution, this liquid is pressure-treated at a temperature of 120°C or higher under oxygen pressure to produce molten sulfur, copper sulfate, and ferric sulfate, and the molten sulfur is recovered. The treatment solution containing copper sulfate and ferric sulfate is repeatedly used as an absorption solution.
しかしながら、この方法においては、生成した硫黄の存
在下で酸化処理が行われるために、不純物が生成して、
硫黄の分離回収性が悪いなどの欠点がある。However, in this method, since the oxidation treatment is performed in the presence of the generated sulfur, impurities are generated.
There are drawbacks such as poor separation and recovery of sulfur.
また、塩化第二鉄水溶液に硫化水素を吸収させ、生成し
た硫黄を分離したのち、この水溶液中の塩化第一鉄を酸
素酸化して塩化第二鉄に再生し、硫化水素の吸収に再使
用するという硫化水素の処理方法が提案されている（特
開昭５１−１０３０９６号公報、特公昭５５−１６９６
３号公報、米国特許第３０９７９２５号明細書）。しか
しながら、この方法は、硫化水素の吸収速度が比較的速
いものの、塩化第一鉄の酸化速度が十分に満足しうるほ
ど速くないという欠点を有している。In addition, after hydrogen sulfide is absorbed into a ferric chloride aqueous solution and the generated sulfur is separated, the ferrous chloride in this aqueous solution is oxidized with oxygen and regenerated into ferric chloride, which is then reused to absorb hydrogen sulfide. A method for treating hydrogen sulfide has been proposed (Japanese Unexamined Patent Publication No. 103096/1983, Japanese Patent Publication No. 1696/1983).
No. 3, U.S. Pat. No. 3,097,925). However, this method has the disadvantage that although the absorption rate of hydrogen sulfide is relatively fast, the oxidation rate of ferrous chloride is not sufficiently fast.
本発明の目的は、このような従来の硫化水素処理方法が
有する欠点を改良し、硫化水素の吸収速度が比較的速い
塩酸酸性塩化第二鉄水溶液を用いて、硫化水素または硫
化水素含有ガスを処理するとともに、生成した塩化第一
鉄の塩化第二鉄への酸化速度を速めて硫化水素の除去率
を高めるとともに、処理速度を速めた処理方法を提供す
ることにある。The purpose of the present invention is to improve the drawbacks of such conventional hydrogen sulfide treatment methods, and to treat hydrogen sulfide or hydrogen sulfide-containing gas by using a hydrochloric acid acidified ferric chloride aqueous solution, which has a relatively fast hydrogen sulfide absorption rate. It is an object of the present invention to provide a treatment method that increases the rate of oxidation of generated ferrous chloride to ferric chloride, increases the removal rate of hydrogen sulfide, and increases the treatment speed.
本発明者らは、前記目的を達成するために鋭意研究を重
ねた結果、塩酸酸性塩化第二鉄水溶液に硫化水素を吸収
させ、次いで生成した硫黄を分離したのち、この水溶液
に特定の無機塩を添加して、酸素または酸素含有ガスを
吹込むことにより、その目的を達成しうろことを見出し
、この知見にもに基づいて本発明を完成するに至った。As a result of extensive research in order to achieve the above object, the present inventors discovered that hydrogen sulfide was absorbed into a hydrochloric acid acidified ferric chloride aqueous solution, the generated sulfur was separated, and a specific inorganic salt was added to this aqueous solution. It was discovered that the objective could be achieved by adding oxygen and blowing in oxygen or an oxygen-containing gas, and based on this knowledge, the present invention was completed.
すなわち、本発明は、塩酸酸性塩化第二鉄水溶液に硫化
水素または硫化水素含有ガスを接触させて硫化水素を吸
収させ、次いで生成した硫黄を分離したのち、この水溶
液に酸素または酸素台をガスを吹込み、その中の塩化第
一鉄を塩化第二鉄に再生するにあたり、前記硫黄を分離
後の水溶液に、アルカリ金属の塩化物、アルカリ土類金
属の塩化物および塩化アンモニウムの中から選ばれた少
なくとも１種の無機塩を添加して、酸素または酸素含有
ガスを吹込むことを特徴とする硫化水素の処理方法を提
供するものである。That is, in the present invention, hydrogen sulfide or a hydrogen sulfide-containing gas is brought into contact with a hydrochloric acid acidic ferric chloride aqueous solution to absorb hydrogen sulfide, the generated sulfur is then separated, and then oxygen or an oxygen gas is introduced into the aqueous solution. In order to regenerate the ferrous chloride in the ferrous chloride into ferric chloride, the aqueous solution after the sulfur has been separated is injected with a mixture of alkali metal chlorides, alkaline earth metal chlorides and ammonium chloride. The present invention provides a method for treating hydrogen sulfide, which is characterized by adding at least one inorganic salt and blowing oxygen or an oxygen-containing gas.
本発明方法において用いられる被処理ガスとしては、硫
化水素単独であってもよいし、硫化水素と他の気体、例
えば水素、−酸化炭素、二酸化炭素、炭化水素、アンモ
ニアなどとの混合ガスであってもよい。The gas to be treated used in the method of the present invention may be hydrogen sulfide alone, or a mixed gas of hydrogen sulfide and other gases such as hydrogen, carbon oxide, carbon dioxide, hydrocarbons, and ammonia. It's okay.
本発明方法においては、硫化水素の吸収に塩酸酸性塩化
第二鉄水溶液が用いられる。この水溶液中の塩酸含有量
は１ ｋｇ当り０．１〜７モルの範囲が好ましく、また
塩化第二鉄の含有量は通常水Ｌ ｋｇ当り０．５〜５モ
ルの範囲で選ばれる。塩化第一鉄は含有していてもよい
し、含有していなくてもよい。 この塩酸酸性塩化第二
鉄水溶液に前記の硫化水素または硫化水素含有ガスを接
触させる方法としては、通常液体によるガス吸収におい
て慣用されている方法を用いることができる。この際の
温度としては、５０〜９０℃の範囲の温度が好ましく用
いられる。ガス吸収温度がこの範囲を逸脱すると、硫化
水素の吸収速度が遅くなって好ましくなく、また、低い
温度では、生成した硫黄がゴム状になりやすい。In the method of the present invention, a hydrochloric acid acidic ferric chloride aqueous solution is used to absorb hydrogen sulfide. The hydrochloric acid content in this aqueous solution is preferably in the range of 0.1 to 7 mol per kg, and the ferric chloride content is usually selected in the range of 0.5 to 5 mol per kg of water. Ferrous chloride may or may not be contained. As a method for bringing the hydrogen sulfide or hydrogen sulfide-containing gas into contact with this hydrochloric acid acidified ferric chloride aqueous solution, a method commonly used in gas absorption by a liquid can be used. As the temperature at this time, a temperature in the range of 50 to 90°C is preferably used. If the gas absorption temperature is outside this range, the absorption rate of hydrogen sulfide will be undesirably slow, and at low temperatures, the produced sulfur tends to become rubbery.
このようにして、塩酸酸性塩化第二鉄水溶液に硫化水素
が吸収されると、該硫化水素は、前記の反応式（１）に
示されるように、酸化されて硫黄を生成し、一方塩化第
二鉄は還元されて塩化第一鉄となる。When hydrogen sulfide is absorbed into the hydrochloric acid acidified ferric chloride aqueous solution in this way, the hydrogen sulfide is oxidized to produce sulfur as shown in the reaction formula (1) above, while ferric chloride Diiron is reduced to ferrous chloride.
本発明方法においては、硫化水素吸収液中の硫黄を分離
回収したのち、この液に酸化処理を施すが、該硫黄の分
離回収方法としては、固体状の硫黄を遠心分離やろ過な
どの手段で分離する方法を用いてもよいし、所望ならば
１２０〜１５０℃程度に加熱して、溶融状の硫黄を分液
などの手段で分離する方法を用いてもよい。In the method of the present invention, after the sulfur in the hydrogen sulfide absorption liquid is separated and recovered, this liquid is subjected to oxidation treatment. A method of separating the sulfur may be used, or, if desired, a method of heating the sulfur to about 120 to 150° C. and separating the molten sulfur by liquid separation or the like may be used.
次にこのようにして、硫黄が分離回収された塩化第一鉄
を含む水溶液に、塩化カリウム、塩化リチウムおよび塩
化アンモニウムの中から選ばれた少なくとも１種の無機
塩を添加し、酸素または空気などの酸素含有ガスを吹込
み、次の反応式２式％
で示されるように、塩化第一鉄を塩化第二鉄に酸化する
。この際、該塩化第一鉄を含む水溶液中の塩酸含有量は
水１ ｋｇ当り２モル以上が好ましく、また、酸化温度
は好ましくは５０〜９０℃の範囲で選ばれる。Next, to the aqueous solution containing ferrous chloride from which sulfur has been separated and recovered, at least one inorganic salt selected from potassium chloride, lithium chloride, and ammonium chloride is added, and oxygen or air etc. of oxygen-containing gas is blown in to oxidize ferrous chloride to ferric chloride as shown in the following reaction formula 2. At this time, the hydrochloric acid content in the aqueous solution containing ferrous chloride is preferably 2 moles or more per 1 kg of water, and the oxidation temperature is preferably selected within the range of 50 to 90°C.
これらの無機塩のうちでは、塩化カリウム、塩化リチウ
ム、塩化ナトリウム、塩化アンモニウムが好ましく用い
られ、特に酸化速度の点から塩化カリウムが好ましく用
いられる。Among these inorganic salts, potassium chloride, lithium chloride, sodium chloride, and ammonium chloride are preferably used, and potassium chloride is particularly preferably used from the viewpoint of oxidation rate.
前記無機塩の添加量は、塩化第一鉄と塩化第二鉄との合
計１モル当り、好ましくは０．１〜２モルの範囲で選ば
れる。この量が０．１モル未満では本発明の効果が十分
に発揮されず、また２モルを超えると量の割には酸化速
度が向上せず、むしろ、この酸化処理液を硫化水素の吸
収に再使用する場合、その吸収速度に悪影響を及ぼすよ
うになり好ましくない。The amount of the inorganic salt added is preferably selected in the range of 0.1 to 2 mol per 1 mol of ferrous chloride and ferric chloride. If this amount is less than 0.1 mole, the effect of the present invention will not be fully exhibited, and if it exceeds 2 moles, the oxidation rate will not improve in proportion to the amount, but rather the oxidation treatment liquid will not be used to absorb hydrogen sulfide. If it is reused, it is not preferable because it will adversely affect its absorption rate.
前記無機塩を添加することにより、無添加の場合に比べ
て、塩化第一鉄の酸化速度は約１．５〜２倍速くなる。By adding the inorganic salt, the oxidation rate of ferrous chloride becomes about 1.5 to 2 times faster than when no addition is made.
このようにして、酸化処理が施され、再生した塩化第二
鉄を含む水溶液は、硫化水素の吸収に循環使用され、硫
化水素が効率よく処理される。The aqueous solution containing ferric chloride that has been oxidized and regenerated in this manner is recycled to absorb hydrogen sulfide, and the hydrogen sulfide is efficiently treated.
次に、本発明方法の好適な１例を添付図面に従って説明
する。第１図は本発明方法を実施するためのフローシー
トの１例であって、５０〜９０℃の温度に調整された硫
化水素または硫化水素含有ガス１は送風機１４によって
ガス吸収塔２に導入され、この吸収塔の上部１５より供
給される温度５０〜９０℃の該無機塩含有塩酸酸性塩化
第二鉄水溶液と接触したのち、排ガス４として大気へ放
出される。Next, a preferred example of the method of the present invention will be explained with reference to the accompanying drawings. FIG. 1 is an example of a flow sheet for carrying out the method of the present invention, in which hydrogen sulfide or hydrogen sulfide-containing gas 1 adjusted to a temperature of 50 to 90°C is introduced into a gas absorption tower 2 by a blower 14. After coming into contact with the inorganic salt-containing hydrochloric acid acidic ferric chloride aqueous solution at a temperature of 50 to 90° C. supplied from the upper part 15 of this absorption tower, it is released into the atmosphere as exhaust gas 4.
一方、ガス吸収塔２の下部３から排出され硫化水素を吸
収し、スラリー状の硫黄をふくむ該無機塩含有塩化鉄水
溶液７は、ろ過装置５へ供給され、該硫黄６はろ過分離
されて排出される。ろ液８は酸化器１０の上部９に供給
され、一方、この酸化器１０に酸素または酸素含有ガス
１２を導入して、５０〜９０℃の温度でろ液８中の塩化
第一鉄を塩化第二鉄に酸化する。再生された塩化鉄水溶
液１１はガス吸収塔２の上部１５へ供給され、酸素また
は酸素含有ガスは排ガス１３として大気へ放出される。On the other hand, the inorganic salt-containing iron chloride aqueous solution 7 that is discharged from the lower part 3 of the gas absorption tower 2, absorbs hydrogen sulfide, and contains slurry sulfur is supplied to the filtration device 5, and the sulfur 6 is filtered and separated before being discharged. be done. The filtrate 8 is fed to the upper part 9 of an oxidizer 10, while oxygen or an oxygen-containing gas 12 is introduced into the oxidizer 10 to convert the ferrous chloride in the filtrate 8 to ferrous chloride at a temperature of 50 to 90°C. Oxidizes to diiron. The regenerated iron chloride aqueous solution 11 is supplied to the upper part 15 of the gas absorption tower 2, and oxygen or oxygen-containing gas is released to the atmosphere as exhaust gas 13.
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.
実施例１
第１図に示したフローシートに従ってＨｚＳを３１．４
ｖｏ１％含有する脱硫装置排ガス１ （石油精製におけ
る水素化脱硫装置よりの排ガス）を約６０℃に加熱した
のち、送風機１４により、圧力２７５ｍｍ水柱で吸収塔
２に導入し、その上部１５から供給される６０℃の塩化
第二鉄水溶液（ＦｅＣｊ！ Ｚ Ｏ。Example 1 HzS was set to 31.4 according to the flow sheet shown in Figure 1.
After heating the desulfurization equipment exhaust gas 1 (exhaust gas from a hydrodesulfurization equipment in oil refining) containing VO1% to about 60°C, it is introduced into the absorption tower 2 at a pressure of 275 mm water column by the blower 14, and is supplied from the upper part 15. Ferric chloride aqueous solution (FeCj!ZO.
８モル／ ｋｇ １１□０、ＦｅＣｊ！ ３１．２モル
／ ｋｇ ＨｚＯ，ｌＩｃ１５モル／ｋｇＨ，０、＋Ｋ
１１１．５モル／ｋｇＨアＯ）と接触させて、該水溶液
に硫化水素を吸収させた。8 mol/kg 11□0, FeCj! 31.2 mol/kg HzO, lIc15 mol/kgH, 0, +K
The aqueous solution was brought into contact with 111.5 mol/kg H2O) to absorb hydrogen sulfide.
ガス吸収塔２の下部３から排出される硫化水素吸収液７
をろ過装置５に供給し、生成した硫黄をろ過分離した。Hydrogen sulfide absorption liquid 7 discharged from the lower part 3 of the gas absorption tower 2
was supplied to the filtration device 5, and the generated sulfur was separated by filtration.
ろ過機５からは、単体硫黄６を０．０１ｋｇ／時間の割
合で連続的に排出した。硫黄を分離したのち、吸収液中
の塩化第一鉄を塩化第二鉄へ酸化するため、ろ液８を酸
化塔１０に供給し、一方酸素１２を５５０ｍ ｊｌ！
／ｍｉｎの速度で吹込んだ。再生した塩化鉄水溶液１１
は、ガス吸収塔２の上部１５へ供給され再び硫化水素の
吸収に用いた。 このような硫化水素の処理を、連続的
に３時間行ったところ、硫化水素の除去率が９９．４％
と極めて良好な結果が得られた。Elemental sulfur 6 was continuously discharged from the filter 5 at a rate of 0.01 kg/hour. After separating the sulfur, the filtrate 8 is fed to the oxidation tower 10 in order to oxidize the ferrous chloride in the absorption liquid to ferric chloride, while the oxygen 12 is fed at 550 mjl!
It was injected at a speed of /min. Regenerated iron chloride aqueous solution 11
was supplied to the upper part 15 of the gas absorption tower 2 and used again to absorb hydrogen sulfide. When this hydrogen sulfide treatment was carried out continuously for 3 hours, the hydrogen sulfide removal rate was 99.4%.
Very good results were obtained.
実施例２
塩化第一鉄１．５モル／ｋｇｏ２ｏおよび塩酸２モル／
ｋｇＨｚｏを含有する水溶液に、塩化カリウム１．５モ
ル／ ｋｇ ＩＩ ２０を添加した溶液６抛ｌに、温度
７０℃、酸素分圧０．８ａｔ１１１で、ＮＩＩＬ２ガラ
スポールフィルターを用い、酸素を１８０ｍ ＩＩ ／
ｗｉｎの速度で吹込み、塩化第一鉄を塩化第二鉄に酸化
した。反応時間と反応率との関係を第２図にグラフ（○
−Ｏ）で示す。なお無添加の場合も該図にグラフ（・−
・）で示す。Example 2 Ferrous chloride 1.5 mol/kgo2o and hydrochloric acid 2 mol/
To 6 liters of a solution containing 1.5 mol/kg II 20 of potassium chloride added to an aqueous solution containing 1.5 mol/kg II 20 of potassium chloride, 180 m II/kg of oxygen was added using a NIIL2 glass pole filter at a temperature of 70°C and an oxygen partial pressure of 0.8 at 111.
ferrous chloride was oxidized to ferric chloride. The relationship between reaction time and reaction rate is shown in the graph in Figure 2 (○
-O). In addition, the graph (・-
・Indicated by ).
塩化第一鉄から塩化第二鉄への酸化速度は、無極性溶媒
添加の場合に比べて約２倍に増加した。The oxidation rate of ferrous chloride to ferric chloride increased approximately twice compared to the case of nonpolar solvent addition.
実施例３
実施例２において、塩化カリウムの代りに、塩化アンモ
ニウムを用いる以外は、実施例２と全く同様にして塩化
第一鉄を塩化第二鉄に酸化した。Example 3 In Example 2, ferrous chloride was oxidized to ferric chloride in exactly the same manner as in Example 2, except that ammonium chloride was used instead of potassium chloride.
反応時間と反応率との関係を第２図にグラフ（■−■）
で示す。The relationship between reaction time and reaction rate is graphed in Figure 2 (■-■)
Indicated by
塩化第一鉄から塩化第二鉄への酸化速度は、無添加の場
合に比べて約１．５倍に増加した。The oxidation rate of ferrous chloride to ferric chloride increased approximately 1.5 times compared to the case without the addition.
実施例４
実施例２において、塩化カリウムの代りに、塩化リチウ
ムを用いる以外は、実施例２と全く同様にして塩化第一
鉄を塩化第二鉄に酸化した。反応時間と反応率との関係
を第２図にグラフ（Ｇ−〇）で示す。Example 4 In Example 2, ferrous chloride was oxidized to ferric chloride in exactly the same manner as in Example 2, except that lithium chloride was used instead of potassium chloride. The relationship between reaction time and reaction rate is shown in graph (G-○) in FIG.
塩化第一鉄から塩化第二鉄への酸化速度は、無添加の場
合に比べて約１．５倍に増加した。The oxidation rate of ferrous chloride to ferric chloride increased approximately 1.5 times compared to the case without the addition.
実施例５
実施例２において、酸素吹込みの温度を７０℃から９０
℃に変える以外は、実施例２と全く同様にして塩化第一
鉄を塩化第二鉄に酸化した。Example 5 In Example 2, the temperature of oxygen injection was changed from 70°C to 90°C.
Ferrous chloride was oxidized to ferric chloride in exactly the same manner as in Example 2, except that the temperature was changed to °C.
塩化第一鉄から塩化第二鉄への酸化速度は、無添加の場
合に比べて約１．８倍に増加した。The oxidation rate of ferrous chloride to ferric chloride increased approximately 1.8 times compared to the case without the addition.
本発明の硫化水素処理法は、塩化鉄の酸化、還元反応を
利用した硫化水素または硫化水素含有ガスの処理方法で
あって、硫化水素の吸収により生成した塩化第一鉄を十
分に速い酸化速度で塩化第二鉄に再生しうるので、硫化
水素の処理の効率化、酸化塔のコンパクト化などが可能
であり、実用的価値の高い方法といえる。The hydrogen sulfide treatment method of the present invention is a method for treating hydrogen sulfide or hydrogen sulfide-containing gas using the oxidation and reduction reactions of iron chloride, and the ferrous chloride produced by absorption of hydrogen sulfide is oxidized at a sufficiently high rate. Since it can be regenerated into ferric chloride, it is possible to improve the efficiency of hydrogen sulfide treatment and make the oxidation tower more compact, making it a method with high practical value.
第１図は本発明方法を実施するためのフローシ−トの１
例であって、図中符号ｌは硫化水素または硫化水素含有
ガス、２はガス吸収塔、５は硫黄を分離するだめのろ過
装置、１０は酸化塔、１１は再生された吸収液、１２は
酸化または酸素含有ガスである。
第２図は、塩化第一鉄を塩化第二鉄に酸素酸化する際に
、無機塩を添加した場合の効果の１例を示すグラフであ
り、横軸は反応時間、縦軸は反応率を表わす。図におい
て、０−０は塩化カリウム、■−■は塩化アンモニウム
、Ｌ３−〇は塩化リチウムを添加した場合であり、・−
・は無添加の場合である。Figure 1 is a flow sheet for carrying out the method of the present invention.
In the figure, reference numeral 1 indicates hydrogen sulfide or hydrogen sulfide-containing gas, 2 indicates a gas absorption tower, 5 indicates a filtration device for separating sulfur, 10 indicates an oxidation tower, 11 indicates a regenerated absorption liquid, and 12 indicates a filtration device for separating sulfur. It is an oxidizing or oxygen-containing gas. Figure 2 is a graph showing an example of the effect of adding an inorganic salt during the oxygen oxidation of ferrous chloride to ferric chloride, with the horizontal axis representing the reaction time and the vertical axis representing the reaction rate. represent. In the figure, 0-0 is potassium chloride, ■-■ is ammonium chloride, L3-0 is the case where lithium chloride is added, and...
・ is the case without additives.
Claims (1)
水素含有ガスを接触させて硫化水素を吸収させ、次いで
生成した硫黄を分離したのち、この水溶液に酸素または
酸素含有ガスを吹込み、その中の塩化第一鉄を塩化第二
鉄に再生するにあたり、前記硫黄を分離後の水溶液に、
アルカリ金属の塩化物、アルカリ土類金属の塩化物およ
び塩化アンモニウムの中から選ばれた少なくとも１種の
無機塩を添加して、酸素または酸素含有ガスを吹込むこ
とを特徴とする硫化水素の処理方法。 ２、無機塩が塩化カリウム、塩化リチウム、塩化ナトリ
ウムおよび塩化アンモニウムから選ばれた少なくとも１
種である特許請求の範囲第１項記載の硫化水素の処理方
法。 ３、無機塩が塩化カリウムである特許請求の範囲第２項
記載の硫化水素の処理方法。 ４、無機塩の添加量が、塩化第一鉄と塩化第二鉄との合
計１モル当り０．１〜２モルである特許請求の範囲第１
項、第２項または第３項記載の硫化水素の処理方法。[Scope of Claims] 1. Hydrochloric acid acidic ferric chloride aqueous solution is brought into contact with hydrogen sulfide or a hydrogen sulfide-containing gas to absorb hydrogen sulfide, then the generated sulfur is separated, and then oxygen or oxygen-containing aqueous solution is added to the aqueous solution. In injecting gas to regenerate the ferrous chloride in it into ferric chloride, the sulfur is separated into the aqueous solution,
Hydrogen sulfide treatment characterized by adding at least one inorganic salt selected from alkali metal chlorides, alkaline earth metal chlorides, and ammonium chloride and blowing oxygen or oxygen-containing gas Method. 2. At least one inorganic salt selected from potassium chloride, lithium chloride, sodium chloride and ammonium chloride
A method for treating hydrogen sulfide according to claim 1, which is a hydrogen sulfide. 3. The method for treating hydrogen sulfide according to claim 2, wherein the inorganic salt is potassium chloride. 4. Claim 1, wherein the amount of inorganic salt added is 0.1 to 2 moles per 1 mole of ferrous chloride and ferric chloride in total.
The method for treating hydrogen sulfide according to item 2, item 3, or item 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069759A JPS62226805A (en) | 1986-03-29 | 1986-03-29 | Treatment of hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069759A JPS62226805A (en) | 1986-03-29 | 1986-03-29 | Treatment of hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62226805A true JPS62226805A (en) | 1987-10-05 |
| JPH0475764B2 JPH0475764B2 (en) | 1992-12-01 |
Family
ID=13412048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61069759A Granted JPS62226805A (en) | 1986-03-29 | 1986-03-29 | Treatment of hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62226805A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015005762A1 (en) * | 2013-07-12 | 2015-01-15 | Geo Estratos, S.A. De C.V. | Method and apparatus for sequestering hydrogen sulphide in petroleum well gas |
| CN107308793A (en) * | 2017-06-27 | 2017-11-03 | 苏州克莱尔环保科技有限公司 | A kind of device that sulphur is reclaimed from hydrogen sulfide containing industrial tail gas |
| CN107789960A (en) * | 2016-09-02 | 2018-03-13 | 上海新禹固废处理有限公司 | Iron chloride removes hydrogen sulfide technology |
-
1986
- 1986-03-29 JP JP61069759A patent/JPS62226805A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015005762A1 (en) * | 2013-07-12 | 2015-01-15 | Geo Estratos, S.A. De C.V. | Method and apparatus for sequestering hydrogen sulphide in petroleum well gas |
| CN107789960A (en) * | 2016-09-02 | 2018-03-13 | 上海新禹固废处理有限公司 | Iron chloride removes hydrogen sulfide technology |
| CN107308793A (en) * | 2017-06-27 | 2017-11-03 | 苏州克莱尔环保科技有限公司 | A kind of device that sulphur is reclaimed from hydrogen sulfide containing industrial tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0475764B2 (en) | 1992-12-01 |
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