JPS61227905A - Denitration of concentrated sulfuric acid - Google Patents
Denitration of concentrated sulfuric acidInfo
- Publication number
- JPS61227905A JPS61227905A JP6730585A JP6730585A JPS61227905A JP S61227905 A JPS61227905 A JP S61227905A JP 6730585 A JP6730585 A JP 6730585A JP 6730585 A JP6730585 A JP 6730585A JP S61227905 A JPS61227905 A JP S61227905A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- h2so4
- urea
- absorption tower
- nox
- 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
Landscapes
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
（産業分野）
本発明は濃硫酸中に含まれた窒素酸化物を除去する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field) The present invention relates to a method for removing nitrogen oxides contained in concentrated sulfuric acid.
（従来技術とその問題点）
製錬排ガスを原料として濃硫酸を製造する場合、銅製錬
における反射炉などで、鉱石溶解用燃料として粉炭など
を使用すると、得られた濃硫酸中にＮｏｖ −ＮＯｓ
（以下ＮＯｘという）などの窒素酸化物が混入する。窒
素酸化物を多量に含有した濃硫酸は黄色がかつて透光度
が悪いばかりでなく、発煙硫酸などの製造に使用するこ
とはできない。(Prior art and its problems) When producing concentrated sulfuric acid using smelting exhaust gas as a raw material, if pulverized coal is used as a fuel for dissolving ore in a reverberatory furnace in copper smelting, Nov-NOs will be present in the obtained concentrated sulfuric acid.
Nitrogen oxides such as (hereinafter referred to as NOx) are mixed in. Concentrated sulfuric acid, which contains a large amount of nitrogen oxides, has a yellow color and not only poor light transmittance, but also cannot be used to produce fuming sulfuric acid.
従来硫酸中の脱硝剤として使用されているものはほとん
どなく、主として原料排ガス中の窒素酸化物除去方法が
提案されているにすぎない。しかしながら、提案されて
いるような排ガス中のＮＯｘ除去を実施するためには、
大規模な設備が必要となり、また、硫酸中の脱硝剤とし
て提案されているＦｅＳＯ４、金属アルミニウムなどは
硫酸中の強残増加の原因となり、尿素を使用するとして
も固体であるため、取扱いが不便であるなどの欠点かあ
った。ＮＯｘ の窒素酸化物を含む硫酸に尿素を添加し
、加熱すると、次式により反応して窒素酸化物は分解さ
れ、窒素ガスと炭酸ガスになって放出される。Conventionally, there are few denitration agents used in sulfuric acid, and only methods for removing nitrogen oxides from raw material exhaust gas have been proposed. However, in order to remove NOx from exhaust gas as proposed,
Large-scale equipment is required, and FeSO4, metal aluminum, etc., which have been proposed as denitrification agents in sulfuric acid, cause a strong residual increase in sulfuric acid, and even if urea is used, it is inconvenient to handle because it is solid. There were some drawbacks, such as: When urea is added to sulfuric acid containing nitrogen oxides (NOx) and heated, a reaction occurs according to the following equation, and the nitrogen oxides are decomposed and released as nitrogen gas and carbon dioxide gas.
（ＮＨい、Ｃ叶２ＨＮＯｔ→ＣＯｔ＋３Ｈ＊Ｏ＋２Ｎｔ
−−−−−−（１１５（ＮＨｔ）ｔ ＣＯ＋６ＨＮＤｓ
−４６Ｃへ＋１３Ｈｔｏ十８Ｎｔ −−−−（２１（１
１，１２１式で示される反応は公知であるが、常温では
起こりにくく、またＨ２Ｏの生成を伴うため、製品酸を
加熱し、尿素を添加すれば、エネルギーか必要となるば
かりでなく製品酸の＠度が低下する。(NH, C Kano 2HNOt → COt+3H*O+2Nt
-------(115(NHt)t CO+6HNDs
-46C to +13Hto 18Nt -----(21(1
The reaction shown by formula 1,121 is well known, but it does not occur easily at room temperature and involves the production of H2O, so heating the product acid and adding urea not only requires energy but also reduces the production of the product acid. @The degree decreases.
（発明の目的）
本発明者等は上記の従来技術の欠点を解決し、濃硫酸中
のＮω改効率よく除去できる濃硫酸の脱硝方法を提出す
べく検討した結果、尿素の溶解度が大きいことに着目し
、尿素水溶液を吸収塔循環硫酸に添加することによって
上記目的を達成しうることを見出し本発明に到達した。(Purpose of the Invention) The present inventors have investigated to solve the drawbacks of the above-mentioned prior art and propose a denitrification method for concentrated sulfuric acid that can remove Nω from concentrated sulfuric acid with high efficiency. The inventors have focused on this and discovered that the above object can be achieved by adding an aqueous urea solution to the sulfuric acid circulating in the absorption tower, and have arrived at the present invention.
（発明の構成）
すなわち、本発明によれば、９素酸化物を含有する製錬
排ガスを原料として吸収塔方式で得られる濃硫酸の脱硝
方法において、尿素水溶液な蚊吸収塔循環中の硫酸に添
加することを特徴とする濃硫酸の脱硝方法、が得られる
。(Structure of the Invention) That is, according to the present invention, in a method for denitrating concentrated sulfuric acid obtained by an absorption tower method using smelting exhaust gas containing 9 element oxides as a raw material, the sulfuric acid being circulated in the mosquito absorption tower, which is an aqueous urea solution, is A method for denitrifying concentrated sulfuric acid is obtained.
本発明を図面によって説明する。The present invention will be explained with reference to the drawings.
第１図は本発明の基礎的実験を行なった装置、第２図は
本発明の工業的規模の装置である。FIG. 1 shows an apparatus on which basic experiments of the present invention were conducted, and FIG. 2 shows an industrial-scale apparatus of the present invention.
第１図の装置を用いて反応速度に対する温度、尿素添加
量、滞留時間などの影響を試験した。すなわち、グリセ
リンｌを入れた容器内にＮＯｘ含有濃硫酸を３００ｃｃ
入れたビーカーをセットし、ビーカーで一定温度に加熱
保持した。次いでピペット３で規定貴の尿素水溶液を濃
硫酸中に注入して攪拌し、所定時間後に濃硫酸を入れた
ビーカーを取出し、常温まで冷却後Ｎｏ！−ＮＯｘを分
析した各種条件について、測定結果を第１表に示す。な
お、使用した尿素水溶液は尿素：水＝１ ： ２ （重
量比）のものである。第１表の結果から硫酸中のＮｏｘ
ｆｌｋ度は１００℃以上の温度では、反応時間が短くて
も１０ｐｐｍ以下に減少しているが、１００ ’Ｃ以下
では原酸中より増加している。この原因としては、添加
した尿素が硫酸中に残留しているためと考えられる。こ
の実験結果から、反応温度が１００℃以上であれば、短
時間に尿素が硫酸中のＮＯｘと反応し、ＮＯｘをＮ！ガ
スとして放出することが確認できた。The influence of temperature, amount of urea added, residence time, etc. on the reaction rate was tested using the apparatus shown in FIG. In other words, 300cc of NOx-containing concentrated sulfuric acid is placed in a container containing glycerin.
A beaker containing the liquid was set, and the beaker was heated and maintained at a constant temperature. Next, pour a specified aqueous urea solution into concentrated sulfuric acid using pipette 3, stir it, and after a predetermined period of time, take out the beaker containing concentrated sulfuric acid, and after cooling it to room temperature, No! Table 1 shows the measurement results for various conditions under which -NOx was analyzed. The urea aqueous solution used had a ratio of urea:water=1:2 (weight ratio). From the results in Table 1, Nox in sulfuric acid
At temperatures above 100'C, the flk degree decreases to below 10 ppm even if the reaction time is short, but below 100'C, it increases compared to that in the raw acid. The reason for this is thought to be that the added urea remains in the sulfuric acid. From this experimental result, if the reaction temperature is 100°C or higher, urea reacts with NOx in sulfuric acid in a short time, converting NOx into N! It was confirmed that it was released as a gas.
次に、第２図の硫酸製造設備において、吸収塔テフロン
クーラー１３に尿素水溶液を添加した。Next, in the sulfuric acid production facility shown in FIG. 2, an aqueous urea solution was added to the Teflon cooler 13 of the absorption tower.
硫酸工場では９８．５チＨａ Ｓ ０４を製造するため
、吸収塔ポンプタンク１呼にＨ，Ｏを補給し、１１度コ
ントロールを行う。本発明ではこの補給水の一部を尿素
を溶層するために使用した水で代用することとした。こ
の方法であれば、尿素を水溶液として使用できるため、
椴扱いが便利になるだけでなく、製品酸濃イが低下する
こともない。At the sulfuric acid factory, in order to produce 98.5% HaS 04, H and O are supplied to one absorption tower pump tank and controlled 11 times. In the present invention, part of this make-up water is replaced with the water used to dissolve urea. With this method, urea can be used as an aqueous solution, so
Not only is it convenient to handle the bowl, but the acid concentration of the product does not decrease.
また、温度維持は吸収塔テフロンクーラー１３への海水
ｆ調整で吸収塔循環硫酸最も高温となる吸収塔田口酸１
２！ｆｆを１００〜１１０℃番で維持する。In addition, the temperature is maintained by adjusting the seawater f to the absorption tower Teflon cooler 13, and the absorption tower circulating sulfuric acid reaches the highest temperature, the absorption tower Taguchi acid 1.
2! ff is maintained at 100-110°C.
尿素は８１１２図に示したように、塩ビ製容器９に６０
とともに装入し、水ｆＢ液とする。この尿素水溶液をポ
ンプ】０でテフロンクーラー１３の酸入口物［１０轟量
吹込む。As shown in Figure 8112, urea is placed in a PVC container 9 containing 60
This is used as a water fB solution. This urea aqueous solution is pumped into the acid inlet of the Teflon cooler 13 at a pump rate of 10.
（発明の効果）
本発明の脱硝方法によって、１０ｐｐｍ 以下のＮＯ
ｘ含有濃度である透明酸が濃度低下なく生産できるとい
う効果か得られた。(Effect of the invention) By the denitrification method of the present invention, NO of 10 ppm or less can be obtained.
The effect was obtained that a transparent acid having a concentration of x can be produced without a decrease in concentration.
第１図は本発明の基礎的実験を行なった装置、ｇ２図は
工業的スケールの本発明による装置の全体図である。
図において、
１−一一一グリセリン ８−一一一海 水２−−−
４硫酸 ９−−−一尿索溶液タンク３−−−−
ピヘット １０−−−−ポンプ４−−−−１１に
素水溶液 １１−−−−ノズル（テフロンライニン
グ）５−−−４闇討 １２−−−一吸収塔６−
−−−尿 素 １３−−−−テフロ／クー
ラー７−−−−水 １４−−−−ポン
プタンク賽許出願人 三菱金属株式会社FIG. 1 is an apparatus in which basic experiments of the present invention were conducted, and FIG. g2 is an overall diagram of the apparatus according to the present invention on an industrial scale. In the figure, 1-111 glycerin 8-111 seawater 2---
4 Sulfuric acid 9---- Urinary cord solution tank 3---
Pihet 10------Pump 4----11, Hydrogen solution 11----Nozzle (Teflon lining) 5---4 Dark attack 12----1 Absorption tower 6-
--- Urea 13 --- Teflo/Cooler 7 --- Water 14 --- Pump tank license applicant Mitsubishi Metals Corporation
Claims (1)
方式で得られる濃硫酸の脱硝方法において、尿素水溶液
を該吸収塔循環中の硫酸に添加することを特徴とする濃
硫酸の脱硝方法。(1) A method for denitrifying concentrated sulfuric acid obtained by an absorption tower method using smelting exhaust gas containing nitrogen oxides as a raw material, which method is characterized by adding an aqueous urea solution to the sulfuric acid circulating in the absorption tower. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6730585A JPS61227905A (en) | 1985-03-30 | 1985-03-30 | Denitration of concentrated sulfuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6730585A JPS61227905A (en) | 1985-03-30 | 1985-03-30 | Denitration of concentrated sulfuric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61227905A true JPS61227905A (en) | 1986-10-11 |
Family
ID=13341164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6730585A Pending JPS61227905A (en) | 1985-03-30 | 1985-03-30 | Denitration of concentrated sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61227905A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030436A (en) * | 1989-05-03 | 1991-07-09 | Ethyl Corporation | Spent acid purification process |
| US5955050A (en) * | 1994-10-25 | 1999-09-21 | Marsulex Inc. | Nox destruction in sulphuric acid |
-
1985
- 1985-03-30 JP JP6730585A patent/JPS61227905A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030436A (en) * | 1989-05-03 | 1991-07-09 | Ethyl Corporation | Spent acid purification process |
| US5955050A (en) * | 1994-10-25 | 1999-09-21 | Marsulex Inc. | Nox destruction in sulphuric acid |
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