JP3431207B2 - Manufacturing method of granular ammonium sulfate - Google Patents
Manufacturing method of granular ammonium sulfateInfo
- Publication number
- JP3431207B2 JP3431207B2 JP11410193A JP11410193A JP3431207B2 JP 3431207 B2 JP3431207 B2 JP 3431207B2 JP 11410193 A JP11410193 A JP 11410193A JP 11410193 A JP11410193 A JP 11410193A JP 3431207 B2 JP3431207 B2 JP 3431207B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- ammonium sulfate
- hydrazine
- coke oven
- oven 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】この発明は、コークス炉ガス中に
含有されるアンモニアをアンモニア源とするバルクブレ
ンド用に適した粒状硫安の製造方法に関する。
【０００２】
【従来の技術】コークス炉ガス中には、アンモニア６〜
１０ｇ／Ｎｍ3、硫化水素４〜７ｇ／Ｎｍ3、シアン化水
素１〜３ｇ／Ｎｍ3が含有されている。このため、コー
クス炉ガスを湿式脱硫塔に導入して触媒を含むアルカリ
水溶液と接触させ、ガス中の硫化水素、シアン化水素を
吸収除去し、硫化水素、シアン化水素を吸収した吸収液
を再生塔に導入し、空気と触媒の作用により酸化してコ
ロイド状硫黄を生成させ、溶液はもとのアルカリに再生
される。このアルカリ水溶液は、循環使用していると副
反応としてロダン、チオ硫酸塩などが生成し蓄積してく
るので、一部抜き出してコロイド状硫黄を分離したの
ち、廃液処理設備で処理する。硫化水素、シアン化水素
の除去されたコークス炉ガスは、ついで硫安飽和器に導
入され、遊離硫酸を含む母液とコークス炉ガス中のアン
モニアを反応させて硫安母液を生成させ、これを結晶槽
に導入して濃縮し、バルクブレンド用に適した粒状硫安
を製造することは公知である。
【０００３】上記コークス炉ガス中の湿式脱硫工程から
排出される硫黄および脱硫廃液の処理方法の一つである
酸化分解法（コンパックス法）は、硫黄および脱硫廃液
を燃焼させてＳＯ2とし、これをさらにＳＯ3に酸化して
水で吸収し、硫酸として回収している。したがって、湿
式脱硫工程から排出される硫黄および脱硫廃液の処理に
よって回収した製鉄副生硫酸を、コークス炉ガス中のア
ンモニアからの硫安製造における硫酸として使用できれ
ば、極めて合理的で、コスト削減を図ることができる。
【０００４】
【発明が解決しようとする課題】しかしながら、コーク
ス炉ガス中のアンモニアをアルカリ源とするコークス炉
ガス湿式脱硫工程から排出される脱硫硫黄を燃焼させ、
回収した製鉄副生硫酸は、コークス炉ガス中のアンモニ
アからの硫安製造における硫酸として使用すると、母液
が着色して製品硫安に着色が発生すること、また母液中
に黒粉等の異物が発生することが判明した。したがっ
て、製鉄副生硫酸は、そのままではコークス炉ガス中の
アンモニアからの硫安製造における硫酸として精製硫酸
と同等に使用することは困難である。
【０００５】この発明の目的は、上記製鉄副生硫酸をコ
ークス炉ガス中のアンモニアからの硫安製造における硫
酸として使用した場合における母液の着色と黒粉等の異
物が発生を防止し、精製硫酸を使用したと同じ粒状硫安
を製造できる粒状硫安の製造方法を提供することにあ
る。
【０００６】
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意試験研究を行った。その結果、製鉄副
生硫酸にヒドラジン（Ｎ2Ｈ4）を添加するのが有効で、
ヒドラジンを製鉄副生硫酸に添加処理すれば、母液の着
色や黒粉等の異物の発生が防止され、バルクブレンド用
粒状硫安原料として精製硫酸と同等に使用できることを
究明し、この発明に到達した。
【０００７】すなわちこの発明は、コークス炉ガスを遊
離硫酸を含有する母液で洗浄して硫安母液となし、これ
を晶析して粒状硫安を製造する方法において、コークス
炉ガスの湿式脱硫工程から排出される硫黄および脱硫廃
液の処理によって回収した製鉄副生硫酸をヒドラジンで
処理したのち、硫安製造用に使用することを特徴とする
粒状硫安の製造方法である。
【０００８】
【作用】この発明においては、製鉄副生硫酸をヒドラジ
ンで処理したのち、硫安製造用に使用すると、硫安母液
の着色が防止されると共に、黒粉の発生が抑制され、硫
安製造用として使用することができる。
【０００９】製鉄副生硫酸のヒドラジンで処理時のヒド
ラジンの添加量は、ヒドラジン処理後硫安母液に添加し
ても着色が発生しないようにするためには、製鉄副生硫
酸に対し０．０１〜０．１０％の添加が必要である。し
かし、黒粉の発生度合いや着色の程度に応じて適宜増減
するのが実際的である。製鉄副生硫酸のヒドラジン処理
における温度、時間は、２℃以上で１５分あればよい
が、硫酸ヒドラジン（Ｎ2Ｈ4・Ｈ2ＳＯ4）の溶解性から
みて６０℃以上に加温するのが好ましい。使用するヒド
ラジンとしては、硫酸ヒドラジン（Ｎ2Ｈ4・Ｈ2Ｓ
Ｏ4）、水加ヒドラジン（Ｎ2Ｈ4・Ｈ2Ｏ）等ヒドラジン
の水加物や塩を使用することができる。
【００１０】
【実施例】
実施例１
製鉄副生硫酸と精製硫酸のそれぞれについて、遊離硫酸
５％、遊離硫酸２０％に調整して希硫酸となし、遊離硫
酸５％の場合は希硫酸１００ｇにつきコークス炉ガスを
２００ｌ、遊離硫酸２０％の場合は希硫酸１００ｇにつ
きコークス炉ガスを４００ｌバブリングさせてアンモニ
アを吸収させたのち、吸収直後と２４時間室内に放置後
の母液の着色状況を目視判定した。その結果を表１に示
す。なお、目視判定基準は、○が無色透明、×が赤褐色
である。
【００１１】
【表１】
【００１２】表１に示すとおり、精製硫酸の場合は、遊
離硫酸５％、遊離硫酸２０％のいずれの場合も吸収直後
の母液は無色透明で、２４時間放置後にに赤褐色に着色
した。これに対し製鉄副生硫酸の場合は、母液は吸収直
後に既に赤褐色に着色しており、コークス炉ガスからの
硫安製造用には不向きである。
【００１３】実施例２
室温下、ヒドラジンを製鉄副生硫酸に対し０．０３〜
０．１０％添加して１時間撹拌したのち、ヒドラジン処
理した製鉄副生硫酸５ｇに精製硫酸を使用している実操
業の母液１０ｇを添加し、５３５ｎｍで吸光度を測定
し、ヒドラジン添加量と着色減少率との関係を簡易着色
テストにより評価すると共に、黒粉発生量を測定した。
その結果を図１および図２に示す。図１に示すとおり、
ヒドラジンを製鉄副生硫酸に対し０．０５％添加するこ
とによって、母液の着色をほぼ完全に防止することがで
きる。また、図２に示すとおり、ヒドラジンを製鉄副生
硫酸に対し０．０５％添加することによって、黒粉の発
生を大幅に低減することができる。
【００１４】実施例３
精製硫酸、製鉄副生硫酸および製鉄副生硫酸にヒドラジ
ンを０．０４％添加して室温下１時間処理したヒドラジ
ン処理硫酸のそれぞれについて、水１．１０ｋｇに硫酸
１．０ｋｇを添加したのち、アンモニア水１．２９ｋｇ
を添加して中和し、遊離硫酸４．５％に調製した母液中
に、コークス炉ガスを１０ｌ／ｍｉｎの割合で１回当た
り２．６ｍ3吹込んだのち、遊離硫酸２％に低下した母
液中に硫酸を約５０ｇ／回添加して母液中の遊離硫酸を
４．５％に調整し、再度コークス炉ガスを１０ｌ／ｍｉ
ｎの割合で２．６ｍ3／回吹込むことを２０回繰り返し
て結晶約１ｋｇを含む晶析母液約３．２ｋｇを得た。得
られた３種のコークス炉ガス吸収母液の着色ならびに黒
粉発生量を測定した。その結果を表２に示す。なお、コ
ークス炉ガス吸収母液の着色は、目視ならびに５３５ｎ
ｍにおける吸光度を測定した。
【００１５】
【表２】
【００１６】表２に示すとおり、製鉄副生硫酸にヒドラ
ジンを添加して処理したヒドラジン処理硫酸の場合は、
精製硫酸とほぼ同等の着色ならびに黒粉発生であるのに
対し、製鉄副生硫酸の場合は、着色ならびに黒粉発生量
が精製硫酸に比較して非常に悪化している。
【００１７】
【発明の効果】以上述べたとおり、この発明によれば、
製鉄副生硫酸をコークス炉ガスからの粒状硫安製造用に
使用できるから、従来の精製硫酸を使用する場合に比較
し、大幅なコスト低減を図ることができる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing granular ammonium sulfate suitable for bulk blending using ammonia contained in coke oven gas as an ammonia source. [0002] Coke oven gas contains ammonia 6 to
10 g / Nm 3, hydrogen sulfide 4~7g / Nm 3, hydrocyanic 1 to 3 g / Nm 3 is contained. For this reason, coke oven gas is introduced into the wet desulfurization tower and brought into contact with an alkaline aqueous solution containing a catalyst, to absorb and remove hydrogen sulfide and hydrogen cyanide in the gas, and to introduce an absorbing solution absorbing hydrogen sulfide and hydrogen cyanide into the regeneration tower. The solution is oxidized by the action of air and a catalyst to produce colloidal sulfur, and the solution is regenerated to the original alkali. When this alkaline aqueous solution is used in a circulating manner, rodane, thiosulfate and the like are generated and accumulated as a side reaction. Therefore, a part of the alkaline aqueous solution is extracted to separate colloidal sulfur, which is then treated in a waste liquid treatment facility. The coke oven gas from which hydrogen sulfide and hydrogen cyanide have been removed is then introduced into an ammonium sulfate saturator, where the mother liquor containing free sulfuric acid reacts with ammonia in the coke oven gas to produce an ammonium sulfate mother liquor, which is introduced into the crystallization tank. It is known to concentrate and concentrate to produce granular ammonium sulfate suitable for bulk blending. The oxidative decomposition method (Compax method), which is one of the methods for treating sulfur and desulfurization waste liquid discharged from the wet desulfurization step in the coke oven gas, burns sulfur and desulfurization waste liquid to form SO 2 , This is further oxidized to SO 3 , absorbed with water, and recovered as sulfuric acid. Therefore, if it is possible to use sulfuric acid by-product sulfuric acid recovered by the treatment of sulfur discharged from the wet desulfurization process and desulfurization waste liquid as sulfuric acid in the production of ammonium sulfate from ammonia in coke oven gas, it is extremely reasonable to reduce costs. Can be. [0004] However, the desulfurized sulfur discharged from the coke oven gas wet desulfurization process using ammonia in the coke oven gas as an alkali source is burned,
When the recovered by-product sulfuric acid is used as sulfuric acid in the production of ammonium sulfate from ammonia in a coke oven gas, the mother liquor is colored and the product ammonium sulfate is colored, and foreign substances such as black powder are generated in the mother liquor. It has been found. Therefore, it is difficult to use the by-product sulfuric acid as it is as purified sulfuric acid as it is in the production of ammonium sulfate from ammonia in coke oven gas. An object of the present invention is to prevent coloring of a mother liquor and the generation of foreign matter such as black powder when sulfuric acid produced as a by-product of ironmaking is used as sulfuric acid in the production of ammonium sulfate from ammonia in a coke oven gas. An object of the present invention is to provide a method for producing granular ammonium sulfate, which can produce the same granular ammonium sulfate as used. Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object. As a result, it is effective to add hydrazine (N 2 H 4 ) to by-product sulfuric acid,
The addition of hydrazine to the by-product sulfuric acid produced by ironmaking prevents the coloring of the mother liquor and the generation of foreign substances such as black powder, and as a result, it has been clarified that it can be used as a granular ammonium sulfate raw material for bulk blending in the same manner as purified sulfuric acid. . That is, according to the present invention, in a method of washing a coke oven gas with a mother liquor containing free sulfuric acid to form an ammonium sulfate mother liquor and crystallizing the same to produce granular ammonium sulfate, the method comprises the steps of discharging a coke oven gas from a wet desulfurization step. A method for producing granular ammonium sulfate, comprising treating the sulfur and the sulfuric acid by-product sulfuric acid recovered by the treatment of the desulfurization waste liquid with hydrazine, and then using the treated hydrazine for the production of ammonium sulfate. According to the present invention, when sulfuric acid by-produced iron is treated with hydrazine and then used for the production of ammonium sulfate, the coloring of the ammonium sulfate mother liquor is prevented, and the generation of black powder is suppressed. Can be used as The amount of hydrazine added at the time of treatment with hydrazine as a by-product iron-producing sulfuric acid is 0.01 to 0.01% based on the amount of iron-producing by-product sulfuric acid in order to prevent coloring even when added to an ammonium sulfate solution after hydrazine treatment. 0.10% addition is required. However, it is practical to appropriately increase or decrease according to the degree of black powder generation or the degree of coloring. The temperature and time in the hydrazine treatment of the by-product sulfuric acid sulfuric acid may be 2 ° C. or more and 15 minutes. However, in view of the solubility of hydrazine sulfate (N 2 H 4 .H 2 SO 4 ), the temperature is raised to 60 ° C. or more. Is preferred. The hydrazine used is hydrazine sulfate (N 2 H 4 .H 2 S
Hydrazine hydrates and salts such as O 4 ) and hydrated hydrazine (N 2 H 4 .H 2 O) can be used. EXAMPLES Example 1 Dilute sulfuric acid was prepared by adjusting the concentration of free sulfuric acid to 5% and the concentration of free sulfuric acid to 20% for each of the by-product sulfuric acid and purified sulfuric acid. In the case of 200 l of coke oven gas and 20% of free sulfuric acid, ammonia was absorbed by bubbling 400 l of coke oven gas per 100 g of dilute sulfuric acid, and the coloring of the mother liquor immediately after the absorption and after standing in a room for 24 hours was visually determined. . Table 1 shows the results. In addition, as for the visual judgment criteria, が indicates colorless and transparent, and X indicates reddish brown. [Table 1] As shown in Table 1, in the case of purified sulfuric acid, in both cases of free sulfuric acid 5% and free sulfuric acid 20%, the mother liquor immediately after absorption was colorless and transparent, and was colored reddish brown after standing for 24 hours. On the other hand, in the case of sulfuric acid by-produced iron, the mother liquor is already colored reddish brown immediately after absorption, and is not suitable for producing ammonium sulfate from coke oven gas. Example 2 At room temperature, hydrazine was added in an amount of 0.03 to
After adding 0.10% and stirring for 1 hour, 10 g of mother liquor of the actual operation using purified sulfuric acid was added to 5 g of hydrazine-treated iron by-product sulfuric acid, the absorbance was measured at 535 nm, and the amount of hydrazine added and coloring The relationship with the reduction rate was evaluated by a simple coloring test, and the amount of generated black powder was measured.
The results are shown in FIGS. As shown in FIG.
By adding hydrazine to the by-product sulfuric acid by 0.05%, coloring of the mother liquor can be almost completely prevented. Further, as shown in FIG. 2, the generation of black powder can be significantly reduced by adding hydrazine to sulfuric acid by-produced sulfuric acid in an amount of 0.05%. Example 3 For each of purified sulfuric acid, iron-produced sulfuric acid and hydrazine-treated sulfuric acid obtained by adding 0.04% of hydrazine to iron-produced sulfuric acid at room temperature for 1 hour, 1.01 kg of sulfuric acid was added to 1.10 kg of water. 1.29 kg of ammonia water after adding
Was added, and 2.6 m 3 of coke oven gas was blown at a rate of 10 l / min into the mother liquor adjusted to 4.5% of free sulfuric acid at a time, and then reduced to 2% of free sulfuric acid. About 50 g / time of sulfuric acid was added to the mother liquor to adjust the free sulfuric acid in the mother liquor to 4.5%, and the coke oven gas was again supplied at 10 l / mi.
Injection of 2.6 m 3 / times at a ratio of n was repeated 20 times to obtain about 3.2 kg of a crystallization mother liquor containing about 1 kg of crystals. Coloring and black powder generation of the obtained three types of coke oven gas absorbing mother liquors were measured. Table 2 shows the results. The coloring of the coke oven gas absorption mother liquor was visually and 535n.
The absorbance at m was measured. [Table 2] As shown in Table 2, in the case of hydrazine-treated sulfuric acid obtained by adding hydrazine to by-product sulfuric acid for iron production,
Coloring and black powder generation are almost the same as those of purified sulfuric acid, whereas the amount of coloring and generation of black powder are much worse in the case of iron by-product sulfuric acid as compared with purified sulfuric acid. As described above, according to the present invention,
Since by-product sulfuric acid can be used for the production of granular ammonium sulfate from coke oven gas, the cost can be significantly reduced as compared with the case where conventional purified sulfuric acid is used.
【図面の簡単な説明】
【図１】硫酸ヒドラジン添加量と母液の着色減少率との
関係を示すグラフである。
【図２】硫酸ヒドラジン添加量と黒粉発生量との関係を
示すグラフである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the relationship between the amount of hydrazine sulfate added and the rate of reduction in the coloring of a mother liquor. FIG. 2 is a graph showing the relationship between the amount of hydrazine sulfate added and the amount of black powder generated.
フロントページの続き (56)参考文献 特開 昭57−22115（ＪＰ，Ａ) 特開 平３−8786（ＪＰ，Ａ) 特開 昭53−52291（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C05B 1/00 - C05G 5/00 C01B 17/69 - 17/96 C01C 1/24 - 1/249 Continuation of front page (56) References JP-A-57-22115 (JP, A) JP-A-3-8786 (JP, A) JP-A-53-52291 (JP, A) (58) Fields investigated (Int .Cl. 7 , DB name) C05B 1/00-C05G 5/00 C01B 17/69-17/96 C01C 1/24-1/249
Claims (1)
液で洗浄して硫安母液となし、これを晶析して粒状硫安
を製造する方法において、コークス炉ガスの湿式脱硫工
程から排出される硫黄および脱硫廃液の処理によって回
収した製鉄副生硫酸をヒドラジンで処理したのち、硫安
製造用に使用することを特徴とする粒状硫安の製造方
法。(57) Patent Claims 1 A coke oven gas is washed with the mother liquor containing free sulfuric acid ammonium sulfate mother liquor and without a method for producing granular ammonium sulphate by crystallization of this, coke oven gas A method for producing granular ammonium sulfate, comprising treating sulfur produced from the wet desulfurization step and sulfuric acid by-product sulfuric acid recovered by treating the desulfurization waste liquid with hydrazine, and then using it for producing ammonium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11410193A JP3431207B2 (en) | 1993-04-16 | 1993-04-16 | Manufacturing method of granular ammonium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11410193A JP3431207B2 (en) | 1993-04-16 | 1993-04-16 | Manufacturing method of granular ammonium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06305868A JPH06305868A (en) | 1994-11-01 |
| JP3431207B2 true JP3431207B2 (en) | 2003-07-28 |
Family
ID=14629148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11410193A Expired - Lifetime JP3431207B2 (en) | 1993-04-16 | 1993-04-16 | Manufacturing method of granular ammonium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3431207B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482653B (en) * | 2013-09-27 | 2015-10-14 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of flue gas gas washing in SA production ammonium sulfate |
| CN104961141A (en) * | 2015-06-12 | 2015-10-07 | 安徽东至广信农化有限公司 | Production process of ammonium sulfate |
-
1993
- 1993-04-16 JP JP11410193A patent/JP3431207B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06305868A (en) | 1994-11-01 |
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