JP4239801B2 - Method for producing waste acid gypsum - Google Patents
Method for producing waste acid gypsum Download PDFInfo
- Publication number
- JP4239801B2 JP4239801B2 JP2003394874A JP2003394874A JP4239801B2 JP 4239801 B2 JP4239801 B2 JP 4239801B2 JP 2003394874 A JP2003394874 A JP 2003394874A JP 2003394874 A JP2003394874 A JP 2003394874A JP 4239801 B2 JP4239801 B2 JP 4239801B2
- Authority
- JP
- Japan
- Prior art keywords
- waste acid
- gypsum
- heavy metals
- acid
- sodium hydrosulfide
- 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
- 239000002253 acid Substances 0.000 title claims description 56
- 239000002699 waste material Substances 0.000 title claims description 54
- 239000010440 gypsum Substances 0.000 title claims description 41
- 229910052602 gypsum Inorganic materials 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims description 34
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 150000004763 sulfides Chemical class 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000005486 sulfidation Methods 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Landscapes
- Removal Of Specific Substances (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、銅製錬において発生する廃酸から石膏を製造する方法、特に廃酸中の重金属類を効率よく硫化物として除去することができる廃酸石膏の製造方法に関するものである。 The present invention relates to a method for producing gypsum from waste acid generated in copper smelting, and particularly to a method for producing waste acid gypsum that can efficiently remove heavy metals in the waste acid as sulfides.
従来から、銅製錬において発生する亜硫酸ガス（ＳＯ２）は、製錬排ガスとして硫酸工場に送られ、ガス精製工程、乾燥工程、転化工程、吸収工程を通して硫酸が製造されている。この銅製錬で発生する亜硫酸ガスの内の１〜３％程度は、製錬工程においてＳＯ２からＳＯ３に転化されて硫酸工場に送られるため、ガス精製工程の冷却段階で硫酸が生成する。しかし、製錬排ガス中には重金属を含む煙灰やヒュームが存在するため、こうして得られた硫酸には不純物が多く含まれ、製品硫酸とはならない。 Conventionally, sulfurous acid gas (SO 2 ) generated in copper smelting is sent to a sulfuric acid factory as smelting exhaust gas, and sulfuric acid is produced through a gas purification process, a drying process, a conversion process, and an absorption process. Since about 1 to 3% of the sulfurous acid gas generated in this copper smelting process is converted from SO 2 to SO 3 and sent to the sulfuric acid factory in the smelting process, sulfuric acid is generated in the cooling stage of the gas refining process. However, since smelting exhaust gas contains smoke ash and fumes containing heavy metals, the sulfuric acid thus obtained contains a large amount of impurities and does not become product sulfuric acid.
通常、このようにガス精製工程の冷却段階で生成した製品とならない硫酸は、廃酸として、炭酸カルシウム（通常は石灰石を粉砕したもの）を用いて中和することにより、石膏を製造している。このようにして製造された石膏は、粒子内に重金属を含むか又は表面に重金属が付着した状態になり、不純物品位の高い石膏となるため、廃酸石膏と称されている。一方、廃酸石膏を製造した後の濾液は廃水処理工程に送られ、残存する重金属類を除去した後排水される。 Normally, sulfuric acid that does not become a product generated in the cooling stage of the gas purification process is neutralized with calcium carbonate (usually pulverized limestone) as waste acid to produce gypsum. . The gypsum produced in this way is called waste acid gypsum because it contains heavy metal in the particles or has a heavy metal attached to the surface and becomes a gypsum with high impurity quality. On the other hand, the filtrate after producing waste acid gypsum is sent to a wastewater treatment process, and drained after removing the remaining heavy metals.
この廃酸石膏中の重金属類を低減させるためには、中和反応終了時のｐＨを低くして、水酸化物を生成させないようにする必要があるが、その場合石膏の粒子径が小さくなるという弊害があった。また、石膏を製造する前に重金属類を除去すれば、低不純物の廃酸石膏を製造することができ、その重金属類を何らかの製品として利用できるうえ、濾液の廃水処理も簡単になる。 In order to reduce the heavy metals in the waste acid gypsum, it is necessary to lower the pH at the end of the neutralization reaction so as not to generate hydroxide. In that case, the particle size of the gypsum is reduced. There was a harmful effect. Further, if heavy metals are removed before producing gypsum, low-impurity waste acid gypsum can be produced, and the heavy metals can be used as any product, and the wastewater treatment of the filtrate can be simplified.
石膏を製造する前に廃酸から重金属類を除去し、低不純物品位の廃酸石膏を製造するする方法として、特開２００３−１３７５４５号公報には、廃酸に水硫化ソーダ（ＮａＨＳ）を添加して、酸化還元電位が０±１０ｍＶとなるまで硫化を行い、重金属類を硫化物として除去した後、炭酸カルシウムを加えて中和することにより、石膏を製造する方法が記載されている。 As a method for removing heavy metals from waste acid before producing gypsum to produce low-impurity grade waste acid gypsum, JP 2003-137545 A adds sodium hydrosulfide (NaHS) to the waste acid. Thus, a method is described in which gypsum is produced by performing sulfidization until the oxidation-reduction potential becomes 0 ± 10 mV, removing heavy metals as sulfides, and neutralizing by adding calcium carbonate.
上記した特開２００３−１３７５４５号公報に記載の方法においては、水硫化ソーダ（ＮａＨＳ）が重金属類と反応する前に硫化水素（Ｈ２Ｓ）となりやすく、反応に寄与しなくなるため、反応効率が低いという問題があった。また、余剰となった硫化水素を苛性ソーダ等で中和する必要があるため、中和に用いる薬品量が増大して、コスト上昇を招く結果となっていた。 In the method described in JP-A-2003-137545, sodium hydrosulfide (NaHS) tends to be hydrogen sulfide (H 2 S) before reacting with heavy metals and does not contribute to the reaction. There was a problem of being low. Moreover, since it was necessary to neutralize surplus hydrogen sulfide with caustic soda or the like, the amount of chemicals used for neutralization increased, resulting in an increase in cost.
本発明は、このような従来の事情に鑑みてなされたものであり、銅精錬で発生した廃酸から石膏を製造する前に、水硫化ソーダを用いて廃酸中に含まれる重金属類を効率よく除去することができ、余剰の硫化水素の生成を抑制して、中和剤の使用量を削減することができる、低不純物品位の廃酸石膏の製造方法を提供することを目的とする。 The present invention has been made in view of such a conventional situation, and before producing gypsum from waste acid generated in copper refining, the heavy metal contained in the waste acid is efficiently used using sodium hydrosulfide. An object of the present invention is to provide a method for producing low-impurity grade waste acid gypsum that can be removed well, suppress the production of excess hydrogen sulfide, and reduce the amount of neutralizing agent used.
本発明者らは、銅精錬で発生した廃酸に水硫化ソーダを添加して重金属類を硫化する際に、水硫化ソーダが重金属と反応する前に硫化水素となりやすく、反応に寄与しなくなる問題について研究した結果、廃酸中の硫酸濃度が高いことが原因であることを見出した。廃酸中の硫酸濃度は通常１００ｇ／ｌを超え、２００ｇ／ｌ以下であるが、硫酸濃度が１００ｇ/ｌ未満であれば、水硫化ソーダが重金属と効率よく反応し、硫化水素の生成が抑制されることが分った。 When the present inventors sulfidize heavy metals by adding sodium hydrosulfide to waste acid generated in copper refining, the problem is that sodium hydrosulfide tends to become hydrogen sulfide before reacting with heavy metals and does not contribute to the reaction. As a result of research on the above, it was found that the cause was a high sulfuric acid concentration in the waste acid. The concentration of sulfuric acid in waste acid is usually over 100 g / l and 200 g / l or less, but if the sulfuric acid concentration is less than 100 g / l, sodium hydrosulfide reacts with heavy metals efficiently and suppresses the formation of hydrogen sulfide. I found out that it would be.
即ち、本発明が提供する廃酸石膏の製造方法は、銅精錬において発生する廃酸から石膏を製造する方法であって、前記廃酸を硫酸濃度が１００ｇ/ｌ未満となるまで予め水で希釈し、次に水硫化ソーダを用いて酸化還元電位が０±１０ｍＶとなるまで硫化して重金属類を硫化物として除去した後、炭酸カルシウムを加えて石膏を製造することを特徴とするものである。 That is, the method for producing waste acid gypsum provided by the present invention is a method for producing gypsum from waste acid generated in copper refining, wherein the waste acid is diluted with water in advance until the sulfuric acid concentration becomes less than 100 g / l. Then, after sulfurating with sodium hydrosulfide until the oxidation-reduction potential becomes 0 ± 10 mV to remove heavy metals as sulfides, gypsum is produced by adding calcium carbonate. .
本発明によれば、銅精錬で発生した廃酸から石膏を製造する前に、廃酸中の重金属類を硫化する際の水硫化ソーダと重金属の反応効率が上昇し、少ない添加量の水硫化ソーダで重金属類を効率よく除去することができ、低不純物品位の廃酸石膏を製造することができる。また、水硫化ソーダで重金属を硫化する際に、余剰の硫化水素の生成を抑制することができ、硫化水素中和剤の使用量を削減することが可能となる。 According to the present invention, before producing gypsum from waste acid generated in copper refining, the reaction efficiency of sodium hydrosulfide and heavy metal when sulfiding heavy metals in the waste acid is increased, and a small amount of hydrosulfide is added. Heavy metals can be efficiently removed with soda, and low-impurity grade waste acid gypsum can be produced. Moreover, when heavy metal is sulfidized with sodium hydrosulfide, it is possible to suppress the generation of excess hydrogen sulfide and reduce the amount of hydrogen sulfide neutralizing agent used.
本発明の廃酸石膏の製造方法においては、銅精錬において発生する廃酸に炭酸カルシウムを加えて石膏を製造する前に、予め廃酸を水で希釈して、廃酸の硫酸濃度を１００ｇ/ｌ未満、好ましくは５０ｇ/ｌ以上１００ｇ／ｌ未満とする。このような硫酸濃度まで希釈した廃酸の場合、添加した水硫化ソーダと重金属の反応効率が上昇し、且つ硫化水素の生成を抑制できるため、少ない添加量の水硫化ソーダで重金属類を効率よく除去することができる。 In the method for producing waste acid gypsum of the present invention, before adding gypsum by adding calcium carbonate to the waste acid generated in copper refining, the waste acid is diluted with water in advance, and the sulfuric acid concentration of the waste acid is adjusted to 100 g / less than 1, preferably 50 g / l or more and less than 100 g / l. In the case of waste acid diluted to such a sulfuric acid concentration, the reaction efficiency of added sodium hydrosulfide and heavy metal increases, and the generation of hydrogen sulfide can be suppressed, so heavy metals can be efficiently removed with a small amount of sodium hydrosulfide. Can be removed.
実際に操業を実施する前に、廃酸を水で希釈した場合と希釈しない場合について、水硫化ソーダと重金属の反応効率の違いをビーカー試験によって確認した。試験に用いた廃酸溶液は同じものであり、従来例では通常のごとく希釈せずに水硫化ソーダで硫化し、本発明例では硫酸濃度が半分になるまで水で希釈して硫化した。得られた結果を、下記表１に示した。 Before actually carrying out the operation, the difference in reaction efficiency between sodium hydrosulfide and heavy metal was confirmed by a beaker test when the waste acid was diluted with water and when it was not diluted. The waste acid solution used in the test was the same, and in the conventional example, it was not diluted as usual, but was sulfided with sodium hydrosulfide, and in the example of the present invention, it was diluted with water until the sulfuric acid concentration was halved and sulfided. The obtained results are shown in Table 1 below.
次に、本発明の廃酸石膏の製造方法を、図１に示すフローチャートにより説明する。まず、銅精錬において発生した廃酸に、予め工業用水などの水を加えて希釈する。通常、廃酸は１００〜２００ｇ／ｌの硫酸を含むと共に、重金属類として、Ａｓ、Ｃｕ、Ｚｎ、Ｃｄなどを含んでいる。水での希釈により、１００ｇ／ｌを超えている廃酸中の硫酸濃度を、１００ｇ/ｌ未満とし、好ましくは５０ｇ/ｌ以上１００ｇ／ｌ未満とする。 Next, the manufacturing method of the waste acid gypsum of this invention is demonstrated with the flowchart shown in FIG. First, water such as industrial water is added in advance to the waste acid generated in copper refining and diluted. Usually, the waste acid contains 100 to 200 g / l of sulfuric acid and also contains As, Cu, Zn, Cd and the like as heavy metals. By diluting with water, the sulfuric acid concentration in the waste acid exceeding 100 g / l is set to less than 100 g / l, preferably 50 g / l or more and less than 100 g / l.
水で希釈した廃酸は、水硫化ソーダを添加して酸化還元電位（ＯＲＰ）が０±１０ｍＶとなるまで硫化し、重金属類を硫化物として沈澱させる。ＯＲＰが１０ｍＶ以上であると、重金属の除去が不十分であり、特にＣｄの除去が不充分となりやすい。また、ＯＲＰが−１０ｍＶ以下となると、水硫化ソーダが重金属の硫化に寄与することなく、硫化水素となる割合が増えるため好ましくない。この硫化反応は、４０±５℃の温度範囲で行うことが好ましく、また反応槽を２段階にして、滞留時間を２時間以上とすることが望ましい。 Waste acid diluted with water is sulfided by adding sodium hydrosulfide until the oxidation-reduction potential (ORP) becomes 0 ± 10 mV, thereby precipitating heavy metals as sulfides. If the ORP is 10 mV or more, the removal of heavy metals is insufficient, and in particular, the removal of Cd tends to be insufficient. On the other hand, when the ORP is -10 mV or less, sodium hydrosulfide does not contribute to the sulfidation of heavy metals, and the ratio of hydrogen sulfide increases, which is not preferable. This sulfurization reaction is preferably carried out in a temperature range of 40 ± 5 ° C., and it is desirable that the reaction tank has two stages and the residence time is 2 hours or more.
この廃酸を硫化物シックナーに供給し、硫化澱物を沈降させて除去する。硫化澱物の沈降が十分でない場合、オーバーフロー液をフィルタープレスに通して、硫化澱物を更に除去する。フィルタープレスの濾液は石膏反応槽に送り、炭酸カルシウムを添加し、ｐＨが２.０〜３.５の範囲となるように中和して、石膏を製造する。添加する炭酸カルシウムとしては、工業的には、石灰石を粉砕して水に溶かした炭カル乳が使用される。この石膏反応槽では、温度は成り行きとし、滞留時間は２.５時間以上とすることが望ましい。 This waste acid is fed to a sulfide thickener to precipitate and remove the sulfide starch. If the sedimentation of the sulfide starch is not sufficient, the overflow liquid is passed through a filter press to further remove the sulfide starch. The filtrate of the filter press is sent to a gypsum reaction tank, calcium carbonate is added, and neutralized so that the pH is in the range of 2.0 to 3.5 to produce gypsum. As the calcium carbonate to be added, charcoal milk obtained by pulverizing limestone and dissolving in water is used industrially. In this gypsum reaction tank, the temperature is expected and the residence time is preferably 2.5 hours or longer.
石膏反応槽で製造された石膏は、石膏シックナーで分離され、更に遠心分離機で水分を除去して、廃酸石膏として回収される。得られる廃酸石膏は、重金属の含有量を低減させることができ、同時に石膏粒子の粒径を大きくすることができる。しかも、水硫化ソーダと重金属の反応効率が高く、少ない水硫化ソーダで重金属を効率よく除去することができるうえ、硫化水素の生成を抑制することができるため、排水処理での中和剤使用量を削減することができる。 The gypsum produced in the gypsum reaction tank is separated by a gypsum thickener, further removed with a centrifuge, and recovered as waste acid gypsum. The obtained waste acid gypsum can reduce the content of heavy metals, and at the same time can increase the particle size of the gypsum particles. In addition, the reaction efficiency of sodium hydrosulfide and heavy metal is high, and heavy metal can be efficiently removed with a small amount of sodium hydrosulfide, and the generation of hydrogen sulfide can be suppressed, so the amount of neutralizing agent used in wastewater treatment Can be reduced.
実際に、銅製錬の排ガス精製工程から産出される廃酸を用い、石膏を製造する操業を実施した。使用した廃酸について、含まれる主な成分を下記表２に示した。その際、石膏を製造する前に、水硫化ソーダで廃酸中の重金属を硫化して除去する場合に、図１に示すフローチャートに従って廃酸を硫酸濃度が９５ｇ／ｌとなるまで水で希釈した後硫化する本発明例と、廃酸を水で希釈することなく硫化した従来例とを実施した。 Actually, operations were carried out to produce gypsum using waste acid produced from the exhaust gas purification process of copper smelting. The main components contained in the spent acid used are shown in Table 2 below. At that time, before producing gypsum, when removing heavy metals in waste acid by sulfidation with sodium hydrosulfide, the waste acid was diluted with water until the sulfuric acid concentration became 95 g / l according to the flowchart shown in FIG. An example of the present invention that was post-sulfided and a conventional example in which waste acid was sulfurized without diluting with water were carried out.
具体的には、上記の本発明例と従来例において、廃酸をそれぞれ２６０リットル／分の割合で硫化反応槽に供給し、４０±５℃の温度範囲でＯＲＰが０±１０ｍＶとなるまで、水流化ソーダを添加して反応させた。反応槽は１次、２次の２段階とし、２次反応槽の出口で上記ＯＲＰとなるように調整した。また、槽内での滞留時間は２時間以上とした。 Specifically, in the present invention example and the conventional example, waste acid was supplied to the sulfurization reaction tank at a rate of 260 liters / minute, respectively, until the ORP reached 0 ± 10 mV in a temperature range of 40 ± 5 ° C. Water flow soda was added to react. The reaction tank was composed of a primary and a secondary stage, and the ORP was adjusted to the ORP at the outlet of the secondary reaction tank. The residence time in the tank was 2 hours or longer.
希釈せずに硫酸濃度が高いままの廃酸を硫化した従来例と、廃酸を希釈してから硫化した本発明例について、反応終了後の廃酸含まれる主な成分を分析し、その結果を下記表２に示した。また、下記表２には、使用した廃酸原液に含まれる主な成分、並びに組成水硫化ソーダで重金属を硫化させたときの硫化反応の反応効率と、最終的に濾液中に残留する硫化水素の中和に要したＮａＯＨ使用量を併せて示した。 Analysis of the main components contained in the waste acid after completion of the reaction for the conventional example in which the waste acid with high sulfuric acid concentration without dilution was sulfurized and the present invention example in which the waste acid was diluted and then sulfurized Is shown in Table 2 below. Table 2 below shows the main components contained in the spent acid stock solution used, the reaction efficiency of the sulfidation reaction when heavy metal is sulfidized with sodium hydrosulfide, and the hydrogen sulfide finally remaining in the filtrate. The amount of NaOH used for neutralization was also shown.
上記表２から分るように、通常の硫化を実施した従来例、廃酸の希釈後に硫化を実施した本発明例共に、Ｚｎ以外の重金属類は、ほとんどが除去されている。しかし、通常の硫化による従来例では、硫化に使用した水硫化ソーダの反応効率が４５％に過ぎなかったが、希釈後に硫化を行った本発明例では反応効率が７３％にまで向上した。これにより硫化水素の生成が抑制されるため、余剰の硫化水素を中和するための苛性ソーダの使用量も大幅に減少した。 As can be seen from Table 2, most of heavy metals other than Zn have been removed in both the conventional example in which normal sulfidation was performed and the present invention example in which sulfidation was performed after dilution of waste acid. However, the reaction efficiency of sodium hydrosulfide used for sulfidation was only 45% in the conventional example using normal sulfidation, but the reaction efficiency was improved to 73% in the present invention example in which sulfidation was performed after dilution. As a result, the production of hydrogen sulfide was suppressed, and the amount of caustic soda used to neutralize excess hydrogen sulfide was also greatly reduced.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003394874A JP4239801B2 (en) | 2003-11-26 | 2003-11-26 | Method for producing waste acid gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003394874A JP4239801B2 (en) | 2003-11-26 | 2003-11-26 | Method for producing waste acid gypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005154196A JP2005154196A (en) | 2005-06-16 |
| JP4239801B2 true JP4239801B2 (en) | 2009-03-18 |
Family
ID=34720777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003394874A Expired - Lifetime JP4239801B2 (en) | 2003-11-26 | 2003-11-26 | Method for producing waste acid gypsum |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4239801B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445733A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Technology for removing thallium with lead and zinc smelting flue gas washing waste acid water |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101484575B1 (en) * | 2013-03-18 | 2015-01-20 | 그린엔텍 주식회사 | Treating methods of sulfuric acid lyes and apparatus |
| JP6206287B2 (en) * | 2014-03-26 | 2017-10-04 | 住友金属鉱山株式会社 | Treatment method of waste acid generated in copper smelting |
| JP6743491B2 (en) * | 2016-05-31 | 2020-08-19 | 住友金属鉱山株式会社 | Waste acid treatment method |
| JP7031207B2 (en) * | 2017-10-05 | 2022-03-08 | 住友金属鉱山株式会社 | Treatment method of waste acid generated in copper smelting |
| KR102140871B1 (en) * | 2018-11-16 | 2020-08-03 | 주식회사 동명케미칼 | Method for manufacturing desulfurization gypsum |
-
2003
- 2003-11-26 JP JP2003394874A patent/JP4239801B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445733A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Technology for removing thallium with lead and zinc smelting flue gas washing waste acid water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005154196A (en) | 2005-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6743491B2 (en) | Waste acid treatment method | |
| JP5138737B2 (en) | Method for producing waste acid gypsum | |
| JP6364716B2 (en) | Heavy metal removal method | |
| JP4710034B2 (en) | Arsenic-containing material treatment method | |
| KR102556133B1 (en) | Wastewater Treatment Method | |
| JP6206287B2 (en) | Treatment method of waste acid generated in copper smelting | |
| CN111500869A (en) | Copper smelting byproduct co-processing technology | |
| CN104561558A (en) | Method for treating selenium-containing mercury acid mud | |
| JP2019173107A (en) | Method of recovering tellurium | |
| JP5685456B2 (en) | Method for producing polyferric sulfate | |
| JP4239801B2 (en) | Method for producing waste acid gypsum | |
| CN109306408B (en) | Method for removing arsenic from ilmenite smoke dust and recycling valuable metals | |
| JP4529969B2 (en) | Method for removing selenium from selenate-containing liquid | |
| US9555362B2 (en) | Method for separating arsenic and heavy metals in an acidic washing solution | |
| JP2001017939A (en) | Treatment of cement kiln waste gas dust | |
| JP4710033B2 (en) | Arsenic content treatment method | |
| JP3945216B2 (en) | Waste acid gypsum manufacturing method | |
| JP2012082458A (en) | Method for separating and recovering zinc from zinc plating waste liquid | |
| JP6953988B2 (en) | How to remove sulfide | |
| JP5888129B2 (en) | How to recover nickel | |
| JP6233177B2 (en) | Method for producing rhenium sulfide | |
| JP2004285368A (en) | Method for refining cobalt aqueous solution | |
| CN108977672B (en) | Method for preparing iron molybdate by taking molybdenum-removing slag as raw material | |
| JP6962017B2 (en) | Waste acid treatment method | |
| JP2013159822A (en) | Impurity removal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051111 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080717 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081014 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081030 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081202 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081215 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120109 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4239801 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120109 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130109 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130109 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140109 Year of fee payment: 5 |
|
| EXPY | Cancellation because of completion of term |