JPS5910343A - Adsorbent for mercury vapor - Google Patents
Adsorbent for mercury vaporInfo
- Publication number
- JPS5910343A JPS5910343A JP57119409A JP11940982A JPS5910343A JP S5910343 A JPS5910343 A JP S5910343A JP 57119409 A JP57119409 A JP 57119409A JP 11940982 A JP11940982 A JP 11940982A JP S5910343 A JPS5910343 A JP S5910343A
- Authority
- JP
- Japan
- Prior art keywords
- mercury vapor
- component
- activated carbon
- adsorbent
- supported
- 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
Abstract
Description
【発明の詳細な説明】 本発明は、ガス中の水銀蒸気吸着剤に関する。[Detailed description of the invention] The present invention relates to mercury vapor adsorbents in gases.
電解水素ガス、天然ガス、焼却炉排ガス、水銀を取扱う
工場の排ガス中には、水銀蒸気が含まれていることが多
い。Mercury vapor is often contained in electrolyzed hydrogen gas, natural gas, incinerator exhaust gas, and exhaust gas from factories that handle mercury.
電解水素は、医薬品９食品、その他の製品を製造するプ
ロセスに使用され、微量の水銀蒸気が触媒毒となったシ
、製品に混入したヤするので問題となることがある。天
然ガス中の水銀蒸気は、ガスの液化プロセスにおけるア
ルミニウム製の熱交換器などを腐食し、大きな事故の原
因となる。また焼却炉排ガスおよび水銀蒸気を取扱う工
場の排ガス中の水銀蒸気は、大気汚染上または作業環境
上、問題となる。Electrolyzed hydrogen is used in the process of manufacturing pharmaceuticals, foods, and other products, and this can pose problems because trace amounts of mercury vapor can poison the catalyst or get mixed into the products. Mercury vapor in natural gas corrodes aluminum heat exchangers during the gas liquefaction process, causing major accidents. Furthermore, mercury vapor in incinerator exhaust gas and exhaust gas from factories that handle mercury vapor poses problems in terms of air pollution and the working environment.
したがってこれらガス中の水銀蒸気は、何らかの処理に
よって除去しなければならない。これまで、ガス中の水
銀を除去する方法として、薬液洗浄法、活性炭やイオン
交換樹脂などの吸着剤を使用する乾式吸着法などが知ら
れているが、前者の薬液洗浄法は、水銀蒸気の除去効率
が不充分でかつ廃液を生じるなどの欠点がある。後者の
乾式吸着法では、水銀蒸気の吸着容量が小さく充分満足
し得るものではない。Therefore, mercury vapor in these gases must be removed by some kind of treatment. Until now, known methods for removing mercury from gas include chemical cleaning methods and dry adsorption methods using adsorbents such as activated carbon and ion exchange resins. There are disadvantages such as insufficient removal efficiency and generation of waste liquid. The latter dry adsorption method has a small adsorption capacity for mercury vapor and is not fully satisfactory.
本発明者らはこのような事情に鑑み種々研究し九結果、
第一成分としてカリウム、ナトリウムま九はアンモニウ
ムのヨウ化物または臭化物および第二成分としてアンモ
ニウム、アルミニウム、バナジウム、鉄、コバルト、ニ
ッケル、銅または亜鉛の硫酸塩ま九は硝酸塩を担持した
活性炭はガス中の水銀蒸気を効率よく吸着し、かつその
吸着賽量が著しく大きいことを見いだした。また上記第
一成分および第二成分に加えて第三成分としてイオウを
担持した活性度は水銀蒸気の除去効率および吸着容量を
さらに高めるということを見いだした。In view of these circumstances, the present inventors conducted various studies and found the following results:
Activated carbon carrying potassium, sodium or ammonium iodide or bromide as the first component and ammonium, aluminum, vanadium, iron, cobalt, nickel, copper or zinc sulfate or nitrate as the second component is used in the gas. It was discovered that mercury vapor can be adsorbed efficiently and the amount of adsorption capacity is extremely large. It has also been found that the activity of supporting sulfur as a third component in addition to the first and second components described above further increases the removal efficiency and adsorption capacity of mercury vapor.
すなわち本発明は、
１、活性炭に■Ｋ 、 Ｎａま九はＮＨ４のヨウ化物ま
たは臭化物（以下第一成分というとともある）と■ＮＨ
４，ＡＩ、 Ｖ、 Ｆｅ、 Ｇｏ、Ｎｉ、 Ｃｕ ま
たはＺｎの硫酸塩または硝酸塩（以下第二成分というこ
と本ある）を担持量しめてなる水銀蒸気吸着剤、λ 活
性炭に■に、ＭＩＬｔた［１１（４のヨウ化物ま□たは
臭化物と■ＮＨ，，ム１． Ｖ、 Ｆ’ｅ、 Ｃｏ、
Ｎｉ、 ＣｕまたはＺｎの硫酸塩または硝酸塩および■
イオウ（以下第三成分ということもある）を担持せしめ
てなる水銀蒸気吸着剤、
である。That is, the present invention has the following features: 1.Activated carbon contains ■K, Nama9 is an iodide or bromide of NH4 (hereinafter also referred to as the first component), and ■NH4.
4. A mercury vapor adsorbent containing a supported amount of AI, V, Fe, Go, Ni, Cu, or Zn sulfate or nitrate (hereinafter referred to as the second component), λ activated carbon, and MILt [11 (Iodide or bromide of 4 and ■NH,,mu1. V, F'e, Co,
Sulfate or nitrate of Ni, Cu or Zn and■
This is a mercury vapor adsorbent that supports sulfur (hereinafter also referred to as the third component).
本発明において使用される活性炭は、木炭、コークス、
ヤシガフ、樹脂などを原料として公知方法により製造さ
れたもので、その比表面積が２０θ〜２０００Ｉａ２／
ｆの本のであれば、いかたるものでもよい。Activated carbon used in the present invention includes charcoal, coke,
It is manufactured by a known method using coconut guff, resin, etc. as raw materials, and its specific surface area is 20θ to 2000Ia2/
Any book will do as long as it is a f book.
本発明において用いられる第一成分の具体例としてはた
とえばＫＩ、Ｎａ工、 ＮＨ４Ｉ、 ＫＩ３． ＫＢｒ
。Specific examples of the first component used in the present invention include KI, Na, NH4I, KI3. KBr
.
ＮａＢｒ、 ＮＨ４Ｂｒ、 Ｎ１（４１ｒ３のほか、Ｋ
ＩＯ３，ＫＩＯ４゜ＮａＩＯ３、ＮａＩＯ４、ＮＨ４工
０３． ＮＨ４ＮＯ４などのヨウ素酸４ 、 ＫＢｒＯ
３、Ｎａ１３ｒ０３ 、 ＮＨ４Ｂｒ０３ などの臭
素酸塩があげられる。また第二成分の具体例としてはた
とえば（ＮＥ［４）２８０４． Ａ１２（ＳＯ２）３．
ｖｏｓｏ４、 Ｆ’ｅＳＯ４，）’６２（８０４）３
． ＣｏＳＯ４，Ｎｉ８０４． Ｃｕ８０４、 Ｚｎ８
０４． ＮＨ４ＮＯ３，１１（ＮＯ３）３． Ｔｏ（Ｎ
Ｏ３）２、 Ｆｅ（ＮＯ３）２． Ｆｅ（ＮＯ３）３．
ｃｏ（ｎｏ３）、、 Ｎ１（ＮＯ３）２． Ｃｕ（Ｎ
Ｏ３）２． Ｚｎ（ＮＯ３）２などがあげられる。活性
炭に対する第一成分、第二成分、第三成分の担持量は、
いずれも活性炭１ｆ当）５〜５００＊、好ましくは１０
〜４００〜である。NaBr, NH4Br, N1 (in addition to 41r3, K
IO3, KIO4゜NaIO3, NaIO4, NH4 Engineering 03. Iodic acid 4 such as NH4NO4, KBrO
3, bromates such as Na13r03 and NH4Br03. Further, as a specific example of the second component, for example, (NE[4)2804. A12(SO2)3.
voso4, F'eSO4,)'62(804)3
．． CoSO4, Ni804. Cu804, Zn8
04. NH4NO3,11(NO3)3. To(N
O3)2, Fe(NO3)2. Fe(NO3)3.
co(no3),, N1(NO3)2. Cu(N
O3)2. Examples include Zn(NO3)2. The amount of the first component, second component, and third component supported on activated carbon is
5 to 500*, preferably 10
~400~.
活性炭に第一成分、第二成分、第三成分を担持するには
、たとえば、これらを共に水または溶媒に溶解するか、
または懸濁し、これを活性炭に含浸または散布し、必要
に応じて乾燥または焼成する方法などが挙げられる。In order to support the first component, second component, and third component on activated carbon, for example, they can be dissolved together in water or a solvent, or
Alternatively, examples include a method of suspending it, impregnating or scattering it on activated carbon, and drying or calcining it if necessary.
また第一成分、第二成分、第三成分を個別に担持せしめ
てもよく、担持せしめる順序は、いずれでもよい。たと
えば、第二成分を担持せしめた伊第−成分または第三成
分を担持せしめる方法、また、第一成分を担持せしめた
後、第二成分または第三成分を担持せしめる方法など、
いずれの方法でもよい。Further, the first component, second component, and third component may be supported individually, and the order in which they are supported may be any. For example, a method in which a second component is supported or a third component is supported, a method in which a second component or a third component is supported after the first component is supported, etc.
Either method may be used.
本発明の水銀蒸気吸着剤は、第一成分および第二成分の
二成分を担持し九ものよ如も第一成分。The mercury vapor adsorbent of the present invention supports two components, a first component and a second component.
第二成分および第三成分の三成分を担持したものの方が
、水銀の除去効率および吸着容量が大である。The one that supports the three components, the second component and the third component, has higher mercury removal efficiency and adsorption capacity.
本発明の水銀蒸気吸着剤を用いてガス中の水銀蒸気を除
去するには、水銀蒸気を含有するガスと本発明の吸着剤
とを接触させればよい。接触温度は、１５０℃以下、好
ましくは一１０〜１２０℃で、接触圧力は５０ ｋｇ
／ｃｍ智下、好ましくは０゜１〜３５ ｋｇＡ＋ｏ３で
、接触時間は２５℃１ ｋｇ／ａｍ３換算でｌ／１０〜
３０秒、好ましくは１１５〜２０秒である。また、本吸
着剤と水銀蒸気含有ガスとの接触は、たとえば固定層、
移動層、流動層などを用いて行なうことができる。In order to remove mercury vapor from a gas using the mercury vapor adsorbent of the present invention, it is sufficient to bring the gas containing mercury vapor into contact with the adsorbent of the present invention. The contact temperature is 150°C or less, preferably -10 to 120°C, and the contact pressure is 50 kg.
/cm depth, preferably 0°1~35 kgA+O3, contact time at 25°C 1 kg/am3 converted to l/10~
30 seconds, preferably 115-20 seconds. In addition, the contact between the present adsorbent and the mercury vapor-containing gas can be carried out, for example, by using a fixed layer,
This can be carried out using a moving bed, fluidized bed, etc.
実施例
ＢｌＴ比表面積１２３０ ｍ２／ｆの１６〜２４ｍθ８
ｈの活性炭ム０に所定量の臭化物ｉ九はヨウ化物（第一
成分）および所定量の硫酸塩または硝酸塩（第二成分）
を溶解した水溶液を均一に散布し、担持し九後１１０′
ｃで乾燥した。（吸着剤Ｂ〜２）
なお、対照として活性炭Ａｏに第一成分単独。Example BIT specific surface area 1230 m2/f 16-24 mθ8
A predetermined amount of bromide, i, i9, iodide (first component) and a predetermined amount of sulfate or nitrate (second component) are added to the activated carbon of h.
After dissolving an aqueous solution of
It was dried at c. (Adsorbent B-2) In addition, as a control, the first component was used alone on activated carbon Ao.
第二成分単独を前記と同様に所定量担持し、１１０℃で
乾燥した。（吸着剤ム１〜Ａよ、）このようにして得ら
れ六吸着剤Ａ。〜ム、２．Ｂ〜Ｚの各６１１ｊを１．６
ｃｎφのガフス製カフムに充填し、水銀蒸気９ Ｗ／ｍ
３ 含有の２５℃の窒素ガスを線流速４０ ｃｍ／ｓｅ
ａ で流通し、水銀蒸気の破過吸着テストを行なった。A predetermined amount of the second component alone was supported in the same manner as above and dried at 110°C. (Adsorbents M1-A) Six adsorbents A were thus obtained. ~mu, 2. 1.6 for each 611j of B to Z
Filled cnφ gaffs cuff with mercury vapor 9 W/m
3 containing nitrogen gas at 25°C at a linear flow rate of 40 cm/sec.
It was distributed under a.A and a breakthrough adsorption test for mercury vapor was conducted.
結果は第１表の通シである。The results are shown in Table 1.
この結果から活性度に第一成分単独、または第二成分単
独を担持しても水銀蒸気を吸着する能力が著しく悪く、
第一成分と第二成分との複合成分を担持してはじめてす
ぐれた水銀蒸気吸着能力を発揮することがわかる。This result shows that the ability to adsorb mercury vapor is extremely poor even when the first component alone or the second component alone is supported in terms of activity.
It can be seen that excellent mercury vapor adsorption ability is exhibited only when a composite component of the first component and the second component is supported.
実施例コ
実施例１の吸着剤Ａｌ、 Ａ３． Ａ５．ム８．Ａｌｏ
ｔ Ｂ、Ｄ、Ｇ、Ｊ、Ｎ、Ｐ、ＲおよびＵの各６−を１
．６ｃｍφのガラス製カフ五に、充填し、水銀蓋９に１
ｗｑＩ／ｍ３含有の２５℃の水素ガスを線流速４０ｃｖ
ｏ／ｓｅａで流通し、水銀蒸気の破過吸着テストを行な
い、結果を第２表に示した。Example co Adsorbent Al of Example 1, A3. A5. M8. Alo
t Each 6- of B, D, G, J, N, P, R and U is 1
．． Fill the 6cmφ glass cuff 5, and fill the mercury lid 9 with 1
25℃ hydrogen gas containing wqI/m3 at a linear flow rate of 40cv
It was distributed at o/sea and subjected to a breakthrough adsorption test for mercury vapor, and the results are shown in Table 2.
実施例３
実施例／の吸着剤ム０．ム３．ム５＋ Ａ８．Ａｌ０１
Ｂ、Ｄ、Ｇ、、Ｔ、Ｎ、Ｐ、ＲおよびＵの各６Ｉｔを１
．６Ｃ１ｌφのガラス製カフムに充填し、水銀蒸気９１
ｑ／ ７ｍ ３含有の２５℃（Ｄｌｆス（Ｍ２．−８４
．８ｖＯ１＊ 、０２−１４．５ｖＯ１＊、 Ｈ２Ｏ−
０＋ ７ｖｏｌｆ！６） ヲ線流速４Ｑｃｒｍ／ｓｓｃ
で流通し、水銀蒸気の破過吸着テストを行なつ九。結果
は、第３表の通シである。Example 3 Adsorbent of Example 0. Mu3. M5+ A8. Al01
6 It each of B, D, G, , T, N, P, R and U to 1
．． Fill a 6C1lφ glass cuff with 91% mercury vapor.
q/7m3 at 25℃ (Dlfs(M2.-84
．． 8vO1*, 02-14.5vO1*, H2O-
0+ 7vol! 6) Line flow rate 4Qcrm/ssc
9, which will be distributed in Japan and will undergo a breakthrough adsorption test for mercury vapor. The results are shown in Table 3.
実施例
ＢＩＴ比表面積１０５０♂レリの１６〜２４ｍｅａｈの
活性＃！ａ□に所定量の臭化物またはロウ第２表
第３表
二成分）および所定量のイオウ（第三成分）の水溶液（
ただし、イオウの場合は、懸鴻液）を均一に散布し、担
持した後１２０℃で乾燥した。（吸着剤ｂ−ｍ）
なお、対照として前記と同様に活性炭α０に第一成分、
第二成分、第三成分のうち第一成分を九は第二成分のい
ずれかを含まない水溶液（ただし、イオウＯ場合、懸濁
液）を均一に散布し、担持した後１２０℃で乾燥した。Example BIT specific surface area 1050♂Reli's activity # of 16-24mah! In a□, add a predetermined amount of bromide or wax (Table 2, Table 3, second component) and a predetermined amount of sulfur (third component) aqueous solution (
However, in the case of sulfur, a suspension solution) was uniformly dispersed, supported, and then dried at 120°C. (Adsorbent b-m) As a control, the first component,
Among the second and third components, the first component was uniformly sprayed with an aqueous solution (in the case of sulfur O, a suspension) that did not contain any of the second components, and dried at 120°C after being supported. .
（吸着剤＆１−唯４ ）とのようにして得られ九吸着剤
＆。〜ａ４．ｂ−ｍの各６−を１．６ｃ＊φのガラス製
カフ五に充填し、水銀蒸気９１１ｖ／ｍ３含有の２５℃
の窒素ガスを線流速４０ ｃｒａ／ｓｅａで流通し、水
銀蒸気の破過吸着テスＦを行ない、結果を第４表に示し
九。(adsorbent &1 - only 4) and nine adsorbent &. ~a4. Each 6- of b-m was filled into a 1.6 c*φ glass cuff 5, and heated at 25°C containing 911 v/m3 of mercury vapor.
A breakthrough adsorption test of mercury vapor was conducted by flowing nitrogen gas at a linear flow rate of 40 cra/sea, and the results are shown in Table 4.
（以下余白） １１− １２−(Margin below) 11- 12-
Claims (1)
物または臭化物と■ＮＨ４，Ａｌ、Ｖ、 ｒｅ、Ｃｏ、
Ｍｉ、ＣｕまたはＺｌｌ（Ｄ硫酸塩または硝酸塩を担持
せしめてなる水銀蒸気吸着剤。 ２、活性炭に■Ｋ 、 ＨａまたはＮＨ４のヨウ化物ま
九は臭化物と■ＮＢ４ 、ム１． Ｖ、 ！”ｅ、 Ｃ
ｏ、 Ｎｉ、ＣｕまたはＺｎの硫酸塩ま九は硝酸塩およ
び■イオウを担持せしめてなる水銀蒸気吸着剤。[Claims] t activated carbon with ■x, Ni with iodide or bromide of 11H4 and ■NH4, Al, V, re, Co,
A mercury vapor adsorbent made by supporting Mi, Cu or Zll (D sulfate or nitrate. 2. Iodide of K, Ha or NH4 on activated carbon, bromide and ■NB4, Mu1. V,!"e , C
(1) A mercury vapor adsorbent containing a sulfate of Ni, Cu or Zn; (1) a nitrate; and (2) sulfur.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57119409A JPS5910343A (en) | 1982-07-08 | 1982-07-08 | Adsorbent for mercury vapor |
| AU15801/83A AU559284B2 (en) | 1982-07-08 | 1983-06-15 | Adsorption of mercury vapour |
| GB08316616A GB2122916B (en) | 1982-07-08 | 1983-06-17 | Mercury vapour separation |
| US06/509,232 US4500327A (en) | 1982-07-08 | 1983-06-28 | Process for removal of mercury vapor and adsorbent therefor |
| NLAANVRAGE8302430,A NL190104C (en) | 1982-07-08 | 1983-07-07 | METHOD FOR REMOVING MERCURY VAPOR FROM A GAS AND ADDRESSING PRINCIPLE THEREFOR. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57119409A JPS5910343A (en) | 1982-07-08 | 1982-07-08 | Adsorbent for mercury vapor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5910343A true JPS5910343A (en) | 1984-01-19 |
| JPH0211300B2 JPH0211300B2 (en) | 1990-03-13 |
Family
ID=14760749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57119409A Granted JPS5910343A (en) | 1982-07-08 | 1982-07-08 | Adsorbent for mercury vapor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5910343A (en) |
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| US6953494B2 (en) | 2002-05-06 | 2005-10-11 | Nelson Jr Sidney G | Sorbents and methods for the removal of mercury from combustion gases |
| JP2008238163A (en) * | 2007-03-01 | 2008-10-09 | Japan Enviro Chemicals Ltd | Removal method of mercury vapor in gas |
| JP2009226254A (en) * | 2008-03-19 | 2009-10-08 | Chiyoda Kako Kensetsu Kk | Mercury adsorbent and method of treating gas using the same |
| GB2484301A (en) * | 2010-10-05 | 2012-04-11 | Univ Belfast | Process for removing metals from hydrocarbons |
| JP2012532754A (en) * | 2009-07-13 | 2012-12-20 | ソシエテ アノニム ロワ ルシェルシュ エ ディベロプマン | Solid inorganic composition for reducing dioxins and heavy metals in combustion exhaust gas, its production method and its utilization |
| JP2013539413A (en) * | 2010-08-30 | 2013-10-24 | アルベマール・コーポレーシヨン | Improved adsorbent for removing mercury from emissions generated during fuel combustion |
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| US9884286B2 (en) | 2010-02-04 | 2018-02-06 | ADA-ES, Inc. | Method and system for controlling mercury emissions from coal-fired thermal processes |
| US9889405B2 (en) | 2012-04-11 | 2018-02-13 | ADA-ES, Inc. | Control of wet scrubber oxidation inhibitor and byproduct recovery |
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-
1982
- 1982-07-08 JP JP57119409A patent/JPS5910343A/en active Granted
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| Publication number | Publication date |
|---|---|
| JPH0211300B2 (en) | 1990-03-13 |
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