JP4113369B2 - Method for demetalization from sulfuric acid - Google Patents
Method for demetalization from sulfuric acid Download PDFInfo
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- JP4113369B2 JP4113369B2 JP2002095607A JP2002095607A JP4113369B2 JP 4113369 B2 JP4113369 B2 JP 4113369B2 JP 2002095607 A JP2002095607 A JP 2002095607A JP 2002095607 A JP2002095607 A JP 2002095607A JP 4113369 B2 JP4113369 B2 JP 4113369B2
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- Prior art keywords
- sulfuric acid
- concentrated sulfuric
- activated carbon
- demetalization
- sulfur
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Description
【０００１】
【産業上の利用分野】
本発明は、硫酸中の金属を除去する方法に関する。特に非鉄製錬で生産されている濃硫酸中の金属特にＡｓの除去する方法に関する。
【０００２】
【従来の技術】
最近において、濃硫酸の国内需要が急激に激減し、更に石油プラントから産出されるイオウを原料とする濃硫酸との販売競争が行われている。
この競争の中で非鉄製錬から産出される濃硫酸中には、金属、特にAsが0.01〜1ppm含有されており、Asを含有していない石油プラントからのイオウを原料とした濃硫酸と品質の差がある。原料となる精製SO2ガス中の重金属特にAsを低減するためには、膨大なガス精製設備が必要となり、経済性の面で現実的な対応とはならない。
また、ガス精製工程を改造しないでAsを含有している濃硫酸を精製しようとすれば、濃硫酸を再び揮発し回収するか、発煙硫酸を原料としてSO3を揮発させ濃硫酸を製造する所謂、高純度硫酸を製造する他に良い方法が提案されていなかった。
【０００３】
【発明が解決しようとする課題】
そこで、硫酸（特に非鉄製錬で生産される濃硫酸）中の金属特にAsを如何にして安価に除去できるかが課題である。
【０００４】
【課題を解決するための手段】
本発明者等は、鋭意検討した結果以下の発明をなした。
（１）硫黄を添着した活性炭を用いて濃硫酸中の少なくとも Asを５０〜８
０℃において、吸着除去する濃硫酸からの脱金属方法。
（２）上記（１）の重金属が砒素である濃硫酸からの脱金属方法。
【０００５】
：
【課題を解決するための手段】
（２）上記（１）の方法において、硫黄の添着量が１〜３０mass％である濃硫酸からの脱金属方法。
（３）上記（１）〜（２）の何れかの方法において、活性炭が破砕状活性炭であって、粒径が０．７〜２．４ｍｍである濃硫酸からの脱金属方法。
（４）上記（１）〜（３）の何れかの方法において、活性炭と対象処理濃硫酸とのＳＶ値を1〜10とする濃硫酸からの脱金属方法。
【０００６】
以下本発明について、詳細に説明する。
本発明における硫酸とは、非非鉄製錬から生産される濃硫酸さらには、発煙硫酸等も対象とする。
特に発煙硫酸の製造の際には、前工程である濃硫酸の製造工程である乾燥処理工程後に行われることが好ましい。
以下代表的な濃硫酸に関して本発明に関して詳しく述べる。
濃硫酸製造は、イオウ燃焼ガスや、銅・亜鉛・鉛製錬のように硫化鉱を製錬した時に発生するSO2ガスを原料として製造される。 銅・鉛・亜鉛などの非鉄製錬の場合、これらの原料SO2ガスには、製錬ダストやF・Cl・Asなど揮発性不純物などが含まれるため、これをガス洗浄・冷却・精製し精製SO2ガスとなる。その後、濃硫酸製造設備（転化器・吸収塔設備）でSO2＋１/2 O2→SO3への酸化反応及びH2O＋SO3→H2SO4の吸収反応を行い、濃硫酸を製造する。
前記濃硫酸は、乾燥塔において、精製SO2ガス中の水分除去が行われ、吸収塔で濃硫酸を製造し、本発明の活性炭による金属除去を行う。
【０００７】
非鉄製錬出濃硫酸には、ガス精製後の精製SO2ガスにも微量であるがこれらの不純物が含まれているため、製造された濃硫酸中に極微量であるが残存する元素もある。
本発明において、硫酸からの除去対象金属は、砒素、水銀等である。
非鉄製錬出硫酸中に約0.01〜1ppm程度の砒素が含有されている。
本方法では、吸収塔あるいは乾燥塔から排出される製品硫酸を当該活性炭充填塔に送液して、吸着するものである。
【０００８】
活性炭吸着と硫酸のSV値は、１〜10 望ましくは2〜5である。
SVが早いほうがコンパクトであり、安価に設備製作が可能であるが、流速が早いと活性炭の流動現象による破損や液流れのショートパスによる目的元素の流出の恐れがある。逆にSVが遅い場合には必要設備容量が大きくなり、設備的に高価であり現実的でない。
【０００９】
吸着温度は、常温〜90℃の温度範囲で砒素の吸着が可能であるが、温度が高いほうが吸着し易く、また一般的に吸収塔の塔入口循環酸温度は50〜80℃であるため、吸収塔循環酸の保有熱を有効利用できることから、50〜80℃が望ましい。
吸収塔の塔入口運転温度を９０℃より高く上げると、設備的に腐食が著しくなり現実的ではなく、加熱設備あるいは冷却設備が必要となるからである。
【００１０】
活性炭中にイオウが添着していると、砒素は活性炭表面で捕捉されやすくなる。これは、イオウと反応し、硫化物になるためと考えられる。
【００１１】
【実施例】
（実施例１）武田薬品工業製粒状活性炭白鷺MAC-W8/24（ヤシガラ活性炭に硫黄を主成分として薬剤を添着したもの）２０ｇと濃硫酸３００ｃｃを５００ｃｃのビーカにいれ、室温（２５℃）で３Hr攪拌した。その結果下記表１のデータを得た。
【００１２】
【表１】
【００１３】
（実施例２）
実施例１と同じ活性炭を 20gと濃硫酸300ccを500ccのビーカにいれ、室温(25℃)、50℃で3hr攪拌した。その結果下記の表２のデータを得た。
【００１４】
【表２】
【００１５】
（実施例３）
実施例１と同じ活性炭を図1に示す試験装置を用いて、連続試験を行った。
ガラス製のカラムに20ｇ充填し、充填部50℃に加温して濃硫酸をカラム上部よりSV3で通液した。その結果以下の表３のデータを得た。
【００１６】
【表３】
【００１７】
【発明の効果】
（１）本発明により、安価に重金属の少ない品質の高い濃硫酸が得られる。
（２）本発明により、砒素が0.01ppm以下の濃硫酸が安価に得られる。
【図面の簡単な説明】
【図１】実施例３において使用した試験装置を示す。[0001]
[Industrial application fields]
The present invention relates to a method for removing metals in sulfuric acid. In particular, the present invention relates to a method for removing metals, particularly As, in concentrated sulfuric acid produced by non-ferrous smelting.
[0002]
[Prior art]
Recently, domestic demand for concentrated sulfuric acid has drastically decreased, and sales competition with concentrated sulfuric acid made from sulfur produced from petroleum plants has been conducted.
Concentrated sulfuric acid produced from non-ferrous smelting in this competition contains 0.01 ppm to 1 ppm of metals, especially As. Concentrated sulfuric acid and quality from sulfur from petroleum plants that do not contain As There is a difference. In order to reduce heavy metals, especially As, in the refined SO2 gas used as a raw material, a huge amount of gas purification equipment is required, which is not a realistic measure in terms of economy.
In addition, if the concentrated sulfuric acid containing As is to be purified without remodeling the gas purification process, the concentrated sulfuric acid is volatilized and recovered again, or SO3 is volatilized using fuming sulfuric acid as a raw material to produce concentrated sulfuric acid, No other good method has been proposed for producing high purity sulfuric acid.
[0003]
[Problems to be solved by the invention]
Therefore, how to remove metals, especially As, in sulfuric acid (especially concentrated sulfuric acid produced by non-ferrous smelting) at low cost is an issue.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have made the following invention.
(1) 50-8 at least As dark in sulfuric acid using impregnated activated carbon sulfur
In 0 ° C., demetallization process from concentrated sulfuric acid to remove adsorbed.
(2) demetallization process from concentrated sulfuric acid heavy metal is arsenic above (1).
[0005]
:
[Means for Solving the Problems]
(2) A method for removing metal from concentrated sulfuric acid in which the amount of sulfur added is 1 to 30 mass% in the method of (1).
(3) A method for demetalization from concentrated sulfuric acid in which the activated carbon is crushed activated carbon and the particle size is 0.7 to 2.4 mm in any of the methods (1) to (2).
(4) above (1) In any of the methods to (3), demetallization process of concentrated sulfuric acid to 1 to 10 to SV value of the activated carbon and the target processing concentrated sulfuric acid.
[0006]
The present invention will be described in detail below.
The sulfuric acid in the present invention includes concentrated sulfuric acid produced from non-ferrous smelting and fuming sulfuric acid.
In particular, when producing fuming sulfuric acid, it is preferably carried out after a drying treatment step which is a manufacturing step of concentrated sulfuric acid, which is a preceding step.
Hereinafter, the present invention will be described in detail with respect to typical concentrated sulfuric acid.
Concentrated sulfuric acid is produced using sulfur combustion gas or SO2 gas generated when smelting sulfide ore, such as copper, zinc and lead smelting. In the case of non-ferrous smelting of copper, lead, zinc, etc., these raw material SO2 gas contains smelting dust and volatile impurities such as F, Cl, As, etc., so this is purified by gas cleaning, cooling and refining. It becomes SO2 gas. After that, the concentrated sulfuric acid production equipment (converter / absorption tower equipment) performs oxidation reaction of SO2 + 1/2 O2 → SO3 and absorption reaction of H2O + SO3 → H2SO4 to produce concentrated sulfuric acid.
The concentrated sulfuric acid is subjected to removal of water in the purified SO2 gas in a drying tower, and concentrated sulfuric acid is produced in the absorption tower, and metal is removed by the activated carbon of the present invention.
[0007]
Non-ferrous smelted concentrated sulfuric acid contains trace amounts of these impurities in the purified SO2 gas after gas purification, but there are also trace amounts of residual elements in the concentrated sulfuric acid produced.
In the present invention, the metal to be removed from sulfuric acid is arsenic, mercury or the like.
The non-ferrous smelted sulfuric acid contains about 0.01 to 1 ppm of arsenic.
In this method, the product sulfuric acid discharged from the absorption tower or the drying tower is fed to the activated carbon packed tower and adsorbed.
[0008]
The SV value of activated carbon adsorption and sulfuric acid is 1-10, preferably 2-5.
The faster the SV, the more compact the equipment can be manufactured at a low cost. However, if the flow rate is fast, the activated carbon may be damaged due to the flow phenomenon or the target element may flow out due to a short path of the liquid flow. On the other hand, when SV is slow, the required equipment capacity increases, and the equipment is expensive and unrealistic.
[0009]
The adsorption temperature can adsorb arsenic in the temperature range from room temperature to 90 ° C, but the higher the temperature, the easier it is to adsorb, and generally the column inlet circulating acid temperature of the absorption tower is 50-80 ° C, Since the retained heat of the absorption tower circulating acid can be effectively used, 50 to 80 ° C. is desirable.
This is because if the tower inlet operating temperature of the absorption tower is raised higher than 90 ° C., the equipment becomes corrosive and unrealistic, and heating equipment or cooling equipment is required.
[0010]
When sulfur is impregnated in the activated carbon, arsenic is easily captured on the activated carbon surface. This is considered to react with sulfur and become sulfide.
[0011]
【Example】
(Example 1) Takeda Pharmaceutical's granular activated carbon Hakuho MAC-W8 / 24 (coconut charcoal activated carbon with sulfur as a main component) 20 g and 300 cc of concentrated sulfuric acid are placed in a 500 cc beaker at room temperature (25 ° C). Stir for 3 hours. As a result, data shown in Table 1 below was obtained.
[0012]
[Table 1]
[0013]
(Example 2)
20 g of the same activated carbon as in Example 1 and 300 cc of concentrated sulfuric acid were placed in a 500 cc beaker and stirred at room temperature (25 ° C.) and 50 ° C. for 3 hours. As a result, data shown in Table 2 below was obtained.
[0014]
[Table 2]
[0015]
(Example 3)
A continuous test was performed on the same activated carbon as in Example 1 using the test apparatus shown in FIG.
A glass column was filled with 20 g, heated to a packed portion of 50 ° C., and concentrated sulfuric acid was passed through the column with SV3. As a result, the following data in Table 3 was obtained.
[0016]
[Table 3]
[0017]
【The invention's effect】
(1) According to the present invention, high quality concentrated sulfuric acid with few heavy metals can be obtained at low cost.
(2) According to the present invention, concentrated sulfuric acid containing 0.01 ppm or less of arsenic can be obtained at a low cost.
[Brief description of the drawings]
1 shows a test apparatus used in Example 3. FIG.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002095607A JP4113369B2 (en) | 2002-03-29 | 2002-03-29 | Method for demetalization from sulfuric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002095607A JP4113369B2 (en) | 2002-03-29 | 2002-03-29 | Method for demetalization from sulfuric acid |
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| JP2003292305A JP2003292305A (en) | 2003-10-15 |
| JP4113369B2 true JP4113369B2 (en) | 2008-07-09 |
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| LU100464B1 (en) * | 2017-09-29 | 2019-03-29 | Cppe Carbon Process & Plant Eng S A | Process for the removal of heavy metals from liquids |
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