JPS6016365B2 - Method for removing mercury from exhaust gas - Google Patents
Method for removing mercury from exhaust gasInfo
- Publication number
- JPS6016365B2 JPS6016365B2 JP2352777A JP2352777A JPS6016365B2 JP S6016365 B2 JPS6016365 B2 JP S6016365B2 JP 2352777 A JP2352777 A JP 2352777A JP 2352777 A JP2352777 A JP 2352777A JP S6016365 B2 JPS6016365 B2 JP S6016365B2
- Authority
- JP
- Japan
- Prior art keywords
- mercury
- sulfuric acid
- gas
- ore
- exhaust gas
- 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.)
- Expired
Links
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052753 mercury Inorganic materials 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 description 25
- 239000002994 raw material Substances 0.000 description 8
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 4
- 229910000370 mercury sulfate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 241000269821 Scombridae Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 235000020640 mackerel Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052950 sphalerite Inorganic materials 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 208000001613 Gambling Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- -1 pyrite sulfide Chemical compound 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Description
【発明の詳細な説明】
本発明は、微量の水銀を含む硫化鉱、例えば硫化鉄鉱、
閃亜鉛鉱などを酸化燈凝することにより、亜硫酸ガスを
主要成分として含有する賭競ガスを生成させるに際し、
水銀を実質上随伴しない上記婚暁ガスを生成する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to sulfide ores containing trace amounts of mercury, such as pyrite sulfide,
When producing gambling gas containing sulfur dioxide gas as the main component by oxidizing sphalerite etc.
The present invention relates to a method for producing the above-mentioned mercury gas substantially free of mercury.
硫化鉱には主成分としての金属、ィオウの他に屡々徴量
の水銀が含まれており、このような水銀を含む硫化鉱を
煩擁すると水銀の殆んどが水銀蒸気として焔隣ガス中に
伴って混入してくるので、該焔焼ガス中の亜硫酸ガスを
原料として得られる濃硫酸や発煙硫酸中に水銀が混入し
てくることが避けられない。Sulfide ores often contain large amounts of mercury in addition to the metal sulfur as their main component, and when sulfide ores containing mercury are harvested, most of the mercury is released into the gas as mercury vapor. Therefore, it is inevitable that mercury will be mixed into concentrated sulfuric acid or fuming sulfuric acid, which is obtained using the sulfur dioxide gas in the combustion gas as a raw material.
従来、濃硫酸中に微量に混在している水銀を除去してそ
の濃度を低減させる方法として原料としての亜硫酸ガス
中の水銀を除去する方法と濃硫酸中の水銀を除去する方
法があり、これらの方法について種々の提案がなされて
いるが、それらは水銀の除去効果からみて必ずしも満足
すべきものではない。Conventionally, there are two methods to remove the trace amount of mercury mixed in concentrated sulfuric acid and reduce its concentration. Although various proposals have been made regarding methods for removing mercury, they are not necessarily satisfactory in terms of mercury removal effects.
例えば、亜硫酸ガスからそれに含まれる水銀を除去する
場合には酸の循環精製など可成り大きな装置を既存の硫
酸製造設備に付設しなければならず、しかもこれによる
系内の圧力バランスの変化が硫酸製造設備に与える影響
が大きいなどの不利な点がみられる。本発明者は、亜硫
酸ガスを発生させるための硫化鉱の焔嫁段階において硫
酸を硫化鉱に添加するか、もしくは硫酸を福暁炉へ供給
して、硫化鉱を特定範囲量の硫酸の存在下で酸化婚雛す
ると、生成する樽焼排ガス中に水銀が実質上随伴しなく
なることを見出し、本発明をなすに至った。For example, in order to remove the mercury contained in sulfur dioxide gas, it is necessary to install fairly large equipment such as acid circulation purification equipment to existing sulfuric acid production equipment, and the resulting change in the pressure balance within the system causes sulfuric acid There are disadvantages such as a large impact on manufacturing equipment. The present inventor has proposed to add sulfuric acid to the sulfide ore during the flaming stage of the sulfide ore to generate sulfur dioxide gas, or to supply sulfuric acid to the Fuxiao furnace, to process the sulfide ore in the presence of a specific range of sulfuric acid. The inventors have discovered that when oxidation is carried out, mercury is substantially not included in the resulting barrel-firing exhaust gas, and the present invention has been completed.
したがって、本発明は、排ガス中の水銀除去方法を提供
することを目的とする。Therefore, an object of the present invention is to provide a method for removing mercury from exhaust gas.
以下本発明について詳しく説明する。The present invention will be explained in detail below.
本発明は、亜硫酸ガスを生成するための焔暁原料鉱石を
該鉱石に対して４〜８ｋ９／Ｔの範囲量の硫酸の存在下
で焔擁することを特徴とする。The present invention is characterized in that raw material ore for producing sulfur dioxide gas is heated in the presence of sulfuric acid in an amount ranging from 4 to 8k9/T.
硫化鉱のような原料鉱石中に含まれている水銀化合物は
橋競により分解してＨぜ（夕）となり、上記鉱石中の他
の微豊成分であるＳｅ、ＣＩなどと化合して日がｅ、Ｈ
ｇＣ１２、ＨｇＳ、ＨｇＳ０４を生成するが、上記Ｈｇ
。（夕）の一部はそのままの状態で鱈鱗ガス中に随伴し
て樽競段階から排出される。本発明においては、硫化鉱
のような、酸化婚燐により亜硫酸ガスを発生する原料鉱
石を硫酸の存在下で煩擁すると、硫酸が高温下で分解し
てＳ０３を生成し、このＳ０３が焔椀により発生した亜
硫酸ガス中のＨｇｏ（夕）と反応して最終的に硫酸水銀
を生成するものと推定される。The mercury compounds contained in raw material ores such as sulfide ores are decomposed by Hashiko to become Hze (Yu), which combines with Se, CI, etc., which are other minute components in the ore, and becomes Hze (Yu). e, H
gC12, HgS, HgS04 are generated, but the above Hg
. A part of the (Yu) remains as it is, accompanying the cod scale gas, and is discharged from the barrel race stage. In the present invention, when a raw material ore, such as sulfide ore, which generates sulfur dioxide gas due to oxidized phosphorous is mixed in the presence of sulfuric acid, the sulfuric acid decomposes at high temperature to produce S03, and this S03 is It is presumed that mercury sulfate is ultimately produced by reacting with Hgo in the sulfur dioxide gas generated.
したがって、この硫酸水銀を焔焼ガスの通常の精製設備
で瓶集すると、熔焼段階から排出される悟暁ガス中に随
伴される水銀量は極めて徴量となり実質上水銀を随伴し
ない亜硫酸ガス含有焔暁ガスが得られる。本発明によっ
て、硫酸を焔焼段階に存在させるには、前述したように
、予め硫酸を原料鉱石に添加するか、もしくは鯖暁炉に
硫酸を供給してもよい。この際における硫酸の添加量も
しくは供給量は、原料鉱石に対して４ｋ９／Ｔ乃至８ｋ
９／Ｔの範囲であって、この範囲量の硫酸を用いると各
種原料鉱石に含まれている水銀量に影響されることなく
鉱石中の焔焼により発生するＨｇ。（夕）を硫酸水銀と
して蒲集することができる。本発明によって、硫化鉱を
種々の量の硫酸の存在下で樽擁したときに生成する亜硫
酸含有婦糠中に随伴する水銀量の変化の関係を下記表に
例示する。Therefore, if this mercury sulfate is collected in a bottle using the usual refining equipment for combustion gas, the amount of mercury accompanying the Gogyo gas discharged from the sintering stage will be extremely large, and it will contain sulfur dioxide gas that does not substantially accompany mercury. Obtains Dawn Gas. According to the present invention, in order for sulfuric acid to be present in the flaming stage, sulfuric acid may be added to the raw ore in advance, as described above, or sulfuric acid may be supplied to the Sabayo furnace. The amount of sulfuric acid added or supplied at this time is 4k9/T to 8k relative to the raw ore.
9/T, and when sulfuric acid is used in this range, Hg is generated by flaming in the ore without being affected by the amount of mercury contained in the various raw material ores. (Yu) can be collected as mercury sulfate. According to the present invention, the relationship between changes in the amount of mercury accompanying sulfite-containing bran produced when sulfide ore is barreled in the presence of various amounts of sulfuric acid is illustrated in the table below.
表
硫酸の使用量 焔健ガス中の 濃硫酸中のＫター鉱石ｔ
森夕霧Ｎ膿で享 本ｐ銀ｐ建史０ １．０
３４ ０．３ １
８ ０．１ ０．３〜０．１１６
０．１ ０．３〜０．１注焔暁ガス
（排カス）の温度・・・１０５０℃上記表から、原料鉱
石ｔ当り４ｋ９以上の硫酸を存在させると、樽凝段階か
ら排出される鯖暁ガス中に随伴される水銀量が著しく低
減されることが理解されるであろう。Amount of sulfuric acid used K-tar ore in concentrated sulfuric acid in flame gas
Enjoyed with Mori Yugiri Npus Hon p Gin p Kenshi 0 1.0
34 0.3 1 8 0.1 0.3~0.116
0.1 0.3 to 0.1 Temperature of flaming gas (exhaust scum)...1050℃ From the above table, if 4k9 or more of sulfuric acid is present per ton of raw material ore, the mackerel discharged from the barrel coagulation stage It will be appreciated that the amount of mercury entrained in the morning gas is significantly reduced.
しかし、原料鉱石ｔ当たり８ｋ９を超える硫酸を存在さ
せても上記水銀量には変化がみられないので得策ではな
い。以上述べたように、本発明によると、原料鉱石に特
定範囲量の硫酸を添加するか、もしくは樽競炉へ特定範
囲量の硫酸を供給するのみで、水銀を実質上随伴しない
亜硫酸を主要成分とする煩焼ガスが得られ、該焔焼ガス
中に生成した硫酸水銀は、通常の糟暁ガス精製設備で容
易に捕集されるので、特別な水銀除去設備を設けること
が必要でなくなる。However, even if more than 8k9 of sulfuric acid is present per ton of raw material ore, the above amount of mercury does not change, so it is not a good idea. As described above, according to the present invention, by simply adding sulfuric acid in a specific range of amount to raw material ore or supplying sulfuric acid in a specific range of amount to a barrel furnace, sulfurous acid, which is substantially free of mercury, can be made into a main component. The mercury sulfate produced in the combustible gas is easily collected by ordinary kasuaki gas purification equipment, so there is no need to provide special mercury removal equipment.
したがって、本発明は、水銀含有濃度の極めて低い濃硫
酸もしくは発煙硫酸の製造上益するところが大きい。次
に実施例を例示する。Therefore, the present invention has great advantages in producing concentrated sulfuric acid or fuming sulfuric acid with extremely low mercury content. Next, an example will be illustrated.
なお、本例にあげる跡は重量を基準として示す。実施例
水銀を２０〜３の如含有する閃亜鉛鉱と、該鉱石のｔ当
り８ｋｇの聡％硫酸を流動婚競炉へ供給し１０８０℃の
温度で婿暁する。Note that the marks shown in this example are based on weight. EXAMPLE Sphalerite containing 20 to 3 parts of mercury and 8 kg of sulfuric acid per ton of the ore are supplied to a liquid marriage furnace and boiled at a temperature of 1080°C.
悟競炉から排出される鯖焼排ガスを冷却、除塵後洗浄し
て排ガス中の水銀濃度を測定したところ０．１の夕／Ｎ
〆であり、このガスから得られる濃硫酸の水銀濃度は０
．３〜０．１脚であった。比較例として上記硫酸を使用
しない場合について同様の手順の下で鱈隣ガス中の水銀
濃度を測定したところ１．５倣／Ｎめであり、該ガスか
ら得られる濃硫酸の水銀濃度は３〜１脚であった。When we measured the mercury concentration in the exhaust gas after cooling and removing dust from the mackerel exhaust gas discharged from the Gokeirō, it was 0.1/N.
〆, and the mercury concentration of concentrated sulfuric acid obtained from this gas is 0.
．． It was 3 to 0.1 legs. As a comparative example, when the mercury concentration in the cod admixture gas was measured under the same procedure in the case where sulfuric acid was not used, it was found to be 1.5 mm/N, and the mercury concentration of concentrated sulfuric acid obtained from the gas was 3 to 1. It was a leg.
Claims (1)
ｇ／Ｔの範囲量の硫酸の存在下で焙焼することを特徴と
する上記硫化鉱の焙焼に際して生成する亜硫酸ガス含有
排ガス中の水銀除去方法。1 Add sulfide ore containing mercury to 4 to 8k per ore.
A method for removing mercury from sulfur dioxide gas-containing exhaust gas generated during roasting of the sulfide ore, the method comprising roasting in the presence of sulfuric acid in an amount in the range of g/T.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2352777A JPS6016365B2 (en) | 1977-03-04 | 1977-03-04 | Method for removing mercury from exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2352777A JPS6016365B2 (en) | 1977-03-04 | 1977-03-04 | Method for removing mercury from exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53108092A JPS53108092A (en) | 1978-09-20 |
| JPS6016365B2 true JPS6016365B2 (en) | 1985-04-25 |
Family
ID=12112909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2352777A Expired JPS6016365B2 (en) | 1977-03-04 | 1977-03-04 | Method for removing mercury from exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6016365B2 (en) |
-
1977
- 1977-03-04 JP JP2352777A patent/JPS6016365B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53108092A (en) | 1978-09-20 |
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