JP2002322581A - Method for regenerating waste solution of nitric- hydrofluoric acid and method for pickling stainless steel - Google Patents
Method for regenerating waste solution of nitric- hydrofluoric acid and method for pickling stainless steelInfo
- Publication number
- JP2002322581A JP2002322581A JP2001126900A JP2001126900A JP2002322581A JP 2002322581 A JP2002322581 A JP 2002322581A JP 2001126900 A JP2001126900 A JP 2001126900A JP 2001126900 A JP2001126900 A JP 2001126900A JP 2002322581 A JP2002322581 A JP 2002322581A
- Authority
- JP
- Japan
- Prior art keywords
- hydrofluoric acid
- nitric
- waste liquid
- ions
- stainless steel
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 238000005554 pickling Methods 0.000 title claims abstract description 36
- 239000010935 stainless steel Substances 0.000 title claims description 34
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 30
- 230000001172 regenerating effect Effects 0.000 title claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 45
- -1 iron ions Chemical class 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 16
- 150000004692 metal hydroxides Chemical class 0.000 claims description 16
- 229910001430 chromium ion Inorganic materials 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 34
- 239000011651 chromium Substances 0.000 abstract description 17
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052804 chromium Inorganic materials 0.000 abstract description 15
- 150000001455 metallic ions Chemical class 0.000 abstract 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 19
- 229910017604 nitric acid Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 102200110702 rs60261494 Human genes 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100032842 Oryza sativa subsp. japonica RA16 gene Proteins 0.000 description 1
- 101100467533 Oryza sativa subsp. japonica RAG1 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉄イオン、クロム
イオン、ニッケルイオンなどの金属イオンを含有する硝
フッ酸廃液の再生方法、特に、ステンレス鋼の硝フッ酸
酸洗で生じた硝フッ酸廃液の再生方法およびこの再生液
を用いるステンレス鋼の酸洗方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating nitric hydrofluoric acid waste liquid containing metal ions such as iron ions, chromium ions and nickel ions, and more particularly, to nitric hydrofluoric acid produced by pickling nitric hydrofluoric acid of stainless steel. The present invention relates to a method for regenerating waste liquid and a method for pickling stainless steel using the regenerated liquid.
【０００２】ステンレス鋼においては、耐食性や耐熱性
などの機能の他に、とくに表面の美麗さ (光沢、白色度
等) も製品の価値を左右する。このため、ステンレス鋼
を製造する際には、一般に、鋼表面のスケールを除去
(脱スケール）する処理が行われる。ステンレス鋼のス
ケールは、鋼中のFe、Cr等の合金成分が熱間圧延や焼鈍
工程で酸化され、鋼表面に生成したものであって、一般
に、数μｍから数十μｍの厚みのものである。このスケ
ールは、ステンレス鋼表面の美麗さを損なったり、耐食
性や加工性を阻害するので、スケールのこうした悪影響
を脱スケール処理によって排除するのである。[0002] In stainless steel, in addition to functions such as corrosion resistance and heat resistance, the beauty of the surface (gloss, whiteness, etc.), in particular, also determines the value of the product. For this reason, when manufacturing stainless steel, scale on the steel surface is generally removed.
(Descale) is performed. The scale of stainless steel is formed on the steel surface by oxidizing alloy components such as Fe and Cr in the steel in the hot rolling and annealing processes, and generally has a thickness of several μm to several tens μm. is there. Since this scale impairs the beauty of the stainless steel surface and impairs corrosion resistance and workability, such adverse effects of the scale are eliminated by descaling.
【０００３】しかし、ステンレス鋼のスケールは一般の
鋼スケールに比べて緻密であるために、通常の塩酸や硫
酸では酸との反応性が低く、かかる酸のみでステンレス
鋼のスケールを脱スケールすることは困難である。この
ため、一般的には、酸洗処理の前処理として、ブラス
ト、グラインダー、メカニカルブラシによるスケールの
機械的な除去や、ベンディング、テンションレベラー、
スキンパス等によるスケール層へのクラック付与や、塩
浴 (溶融アルカリ塩) 浸漬処理や中性塩電解によるCr系
酸化物の変質等の処理が行われる。その後、これらの前
処理に続いて、硫酸、硝酸および硝フッ酸 (フッ酸と硝
酸の混合液) 等の酸を用いて、酸洗処理が行われる。こ
の酸洗は、多くの場合、脱スケールとともに不動態化の
処理も兼ねて実施される。これらの酸のうち、特に硝フ
ッ酸は、酸洗能力が最も強く、短時間で美麗な表面肌が
得られることから、ステンレス鋼の酸洗で一般的に使用
されている。However, since stainless steel scale is more dense than ordinary steel scale, it has low reactivity with acids in ordinary hydrochloric acid or sulfuric acid. It is difficult. For this reason, generally, as a pretreatment of the pickling treatment, mechanical removal of scale by blast, grinder, mechanical brush, bending, tension leveler,
Cracking is applied to the scale layer by a skin pass or the like, and treatment such as alteration of the Cr-based oxide by salt bath (molten alkali salt) immersion treatment or neutral salt electrolysis is performed. Thereafter, following these pretreatments, an acid washing treatment is performed using an acid such as sulfuric acid, nitric acid, and nitric hydrofluoric acid (a mixed solution of hydrofluoric acid and nitric acid). In many cases, this pickling is performed not only for descaling but also for passivation. Among these acids, nitric hydrofluoric acid is particularly used in pickling stainless steel because it has the strongest pickling ability and can provide a beautiful surface skin in a short time.
【０００４】ところで、ステンレス鋼を硝フッ酸で酸洗
した酸洗廃液は、従来から、水酸化カルシウムを添加し
て処理されてきた。すなわち、この処理方法では、酸洗
廃液に水酸化カルシウムを添加することにより、中和す
ると共に、鉄、クロム、ニッケルなどの金属イオンを金
属水酸化物として、また、フッ素イオンをフッ化カルシ
ウムとして沈殿させる。沈殿した金属水酸化物とフッ化
カルシウムをろ過などで除去すると、ろ液には主に硝酸
が残る。こうして得られた硝酸を再利用することは可能
である。By the way, pickling waste liquid obtained by pickling stainless steel with nitric hydrofluoric acid has been conventionally treated by adding calcium hydroxide. That is, in this treatment method, calcium hydroxide is added to the pickling waste liquid to neutralize it, and metal ions such as iron, chromium, and nickel are converted to metal hydroxides, and fluorine ions are converted to calcium fluoride. Let it settle. When the precipitated metal hydroxide and calcium fluoride are removed by filtration or the like, mainly nitric acid remains in the filtrate. It is possible to reuse the nitric acid thus obtained.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、硝酸の
酸化力は硝フッ酸よりも弱いため、硝フッ酸として回収
して再利用する方が、ステンレス鋼の酸洗液としてより
有効に利用できる。上述した、水酸化カルシウムを用い
る従来の方法を、硝フッ酸の酸洗廃液に利用しても、再
生される酸は、硝酸が主体である。このため、再生した
酸を用いてステンレス鋼の硝フッ酸による酸洗を行うに
は、当然ながら、再生された硝酸にフッ酸を添加する必
要があった。また、得られた沈殿物 (金属水酸化物とフ
ッ化カルシウムの混合物) は、溶融還元などの処理を行
うことにより、金属成分を再生することは可能である。
しかし、溶融還元処理時に生成するスラグ中にフッ素分
が混入してしまい、スラグ処理の問題があった。という
のは、現在フッ素の排出規制が行われているため、スラ
グを安易に廃棄することができず、スラグを保管するな
どの処置を取らざるを得なかったのである。そこで、本
発明は、鉄、クロム、ニッケルなどの金属イオンを含む
硝フッ酸廃液から、金属イオンを除去して硝フッ酸を再
生する方法およびこの方法で得られた硝フッ酸をステン
レス鋼の酸洗液として再利用する方法を提供することを
目的とする。However, since the oxidizing power of nitric acid is weaker than that of nitric hydrofluoric acid, it is more effective to collect and reuse nitric hydrofluoric acid as a pickling solution for stainless steel. Even if the above-mentioned conventional method using calcium hydroxide is used for the pickling waste liquid of nitric hydrofluoric acid, the acid to be regenerated is mainly nitric acid. Therefore, in order to perform pickling of stainless steel with nitric hydrofluoric acid using the regenerated acid, it is necessary to add hydrofluoric acid to the regenerated nitric acid. Further, the obtained precipitate (mixture of metal hydroxide and calcium fluoride) can be subjected to a treatment such as smelting reduction to regenerate a metal component.
However, the slag generated during the smelting reduction process contains fluorine, which causes a problem of the slag treatment. This is because the slag could not be easily disposed of due to the current regulations on the emission of fluorine, and the slag had to be stored and other measures had to be taken. Therefore, the present invention provides a method of regenerating nitric hydrofluoric acid by removing metal ions from a nitric hydrofluoric acid waste liquid containing metal ions such as iron, chromium, and nickel, and converting the nitric hydrofluoric acid obtained by this method into stainless steel. It is an object of the present invention to provide a method for reusing it as a pickling solution.
【０００６】[0006]
【課題を解決するための手段】金属イオンを含む硝フッ
酸廃液から金属イオンを除去する方法として、陽イオン
交換樹脂を充填したカラムに上記硝フッ酸廃液を流通さ
せる方法が考えられる。鉄、クロム、ニッケルなどの金
属イオンは陽イオン交換樹脂に吸着されるため、硝フッ
酸を得ることはできる。しかし、上記の金属イオンが吸
着された陽イオン交換樹脂を再生するには、陽イオン交
換樹脂と上記金属イオンとの親和性が強いために、陽イ
オン交換樹脂の洗浄に多量の酸が必要となる。したがっ
て、この方法は工業的に得策でなく採用しがたい。Means for Solving the Problems As a method for removing metal ions from nitric hydrofluoric acid waste liquid containing metal ions, a method in which the nitric hydrofluoric acid waste liquid is passed through a column filled with a cation exchange resin is considered. Since metal ions such as iron, chromium and nickel are adsorbed on the cation exchange resin, nitric hydrofluoric acid can be obtained. However, in order to regenerate the cation exchange resin on which the metal ions are adsorbed, a large amount of acid is required for washing the cation exchange resin because the affinity between the cation exchange resin and the metal ions is strong. Become. Therefore, this method is not industrially feasible and difficult to employ.
【０００７】また、陰イオン交換樹脂を充填したカラム
に金属イオンを含む硝フッ酸廃液を流通させる方法も考
えられる。この場合は、フッ素イオンと硝酸イオンが陰
イオン交換樹脂に吸着され、金属イオンを含有する液が
排出される。しかし、陰イオン交換樹脂としてＯＨ−型
の陰イオン交換樹脂を用いると、金属水酸化物が析出
し、カラムの閉塞原因となる。ＳＯ４ −型の陰イオン交
換樹脂の場合は、フッ素イオン、硝酸イオンの吸着効率
が悪く、排出液中にこれらのイオンが残留してしまう。
また、Cl−型の陰イオン交換樹脂を用いると、陰イオン
樹脂を再生して、フッ素イオンと硝酸イオンを取り出す
際に、塩素イオンが硝フッ酸中に混入してしまう。塩素
イオンが混入した硝フッ酸をステンレス鋼の酸洗に用い
ると、ステンレス鋼にピットと称される欠陥が生じやす
くなる。[0007] A method of flowing a nitric hydrofluoric acid waste liquid containing metal ions through a column filled with an anion exchange resin is also conceivable. In this case, fluorine ions and nitrate ions are adsorbed on the anion exchange resin, and the liquid containing metal ions is discharged. However, when an OH - type anion exchange resin is used as the anion exchange resin, metal hydroxide precipitates and causes blockage of the column. In the case of the SO 4 − type anion exchange resin, the adsorption efficiency of fluorine ions and nitrate ions is poor, and these ions remain in the discharged liquid.
When a Cl − type anion exchange resin is used, chlorine ions are mixed into hydrofluoric acid when regenerating the anion resin and extracting fluorine ions and nitrate ions. When nitric hydrofluoric acid mixed with chlorine ions is used for pickling stainless steel, defects called pits are likely to occur in the stainless steel.
【０００８】そこで、発明者らは、鉄、クロム、ニッケ
ルなどの金属イオンを含む硝フッ酸廃液に水酸化ナトリ
ウム、水酸化カリウムや炭酸ナトリウムなどのアルカリ
金属の水酸化物および／または炭酸塩を添加し、ｐＨを
8 以上として、予め金属イオンのみを水酸化物として沈
殿、除去した廃液を、Ｈ＋型陽イオン交換樹脂と接触さ
せることにより、硝フッ酸を再生できることを見だし、
本発明に想到したのである。Therefore, the inventors of the present invention have added hydroxides and / or carbonates of alkali metals such as sodium hydroxide, potassium hydroxide and sodium carbonate to waste nitric hydrofluoric acid containing metal ions such as iron, chromium and nickel. And add pH
8 As described above, it was found that nitric hydrofluoric acid can be regenerated by contacting a waste liquid in which only metal ions were precipitated and removed as hydroxide in advance with an H + type cation exchange resin,
The present invention has been made.
【０００９】すなわち、本発明の要旨構成は、以下のと
おりである。 (1)金属イオンを含有する硝フッ酸廃液に、アルカリ金
属の水酸化物および／または炭酸塩を添加して、廃液の
ｐＨを８以上とすることにより、金属水酸化物を生成さ
せ、次いで、生成した金属水酸化物を廃液から分離除去
し、その後、金属水酸化物が除去された廃液をＨ＋型陽
イオン交換樹脂と接触させることにより、この廃液から
アルカリ金属イオンを除去して硝フッ酸を得ることを特
徴とする硝フッ酸廃液の再生方法。That is, the gist of the present invention is as follows. (1) A hydroxide and / or carbonate of an alkali metal is added to a nitric hydrofluoric acid waste liquid containing a metal ion to adjust the pH of the waste liquid to 8 or more, thereby generating a metal hydroxide. Then, the generated metal hydroxide is separated and removed from the waste liquid, and thereafter, the waste liquid from which the metal hydroxide has been removed is brought into contact with an H + type cation exchange resin, thereby removing alkali metal ions from the waste liquid and removing nitric acid. A method for regenerating nitric hydrofluoric acid waste liquid, comprising obtaining hydrofluoric acid.
【００１０】(2) (1)に記載の方法で再生された硝フッ
酸を更に濃縮することを特徴とする硝フッ酸廃液の再生
方法。(2) A method for regenerating nitric hydrofluoric acid waste liquid, further comprising concentrating the nitric hydrofluoric acid regenerated by the method described in (1).
【００１１】(3)上記金属イオンが、鉄イオン、クロム
イオンおよびニッケルイオンの内から選ばれる少なくと
も一種であることを特徴とする (1)または (2)に記載の
硝フッ酸廃液の再生方法。(3) The method for regenerating nitric hydrofluoric acid waste liquid according to (1) or (2), wherein the metal ion is at least one selected from iron ions, chromium ions and nickel ions. .
【００１２】(4)上記硝フッ酸廃液が、ステンレス鋼の
酸洗廃液であることを特徴とする (1)または (2)に記載
の硝フッ酸廃液の再生方法。(4) The method for regenerating nitric hydrofluoric acid waste liquid according to (1) or (2), wherein the nitric hydrofluoric acid waste liquid is a stainless steel pickling waste liquid.
【００１３】(5) (1)〜 (4)のいずれか１つに記載の方
法で再生された硝フッ酸の再生液をステンレス鋼の酸洗
液として使用することを特徴とするステンレス鋼の酸洗
方法。(5) A stainless steel hydrofluoric acid regenerating solution regenerated by the method according to any one of (1) to (4) is used as a pickling solution for stainless steel. Pickling method.
【００１４】[0014]
【発明の実施の形態】図１に、本発明に従うステンレス
鋼酸洗廃液から有価金属（鉄、クロムおよびニッケルな
ど）と硝フッ酸を回収する方法の１態様をフローで示
す。ステンレス鋼の脱スケールには、硝酸(HNO３)およ
びフッ酸(HF)を混合した硝フッ酸の溶液が用いられ、こ
の酸洗廃液には、鉄、ニッケル、クロムがイオンの形態
で存在するとともに、脱スケールに直接関与しなかった
硝酸およびフッ酸も含まれる。この酸洗廃液にNaOH, N
a２CO３, KOHなどのアルカリ金属の水酸化物および／ま
たは炭酸塩を添加し、溶液のｐＨを８以上にすることに
よって、廃液中の上記イオンは、鉄、ニッケル、クロム
の水酸化物（固体）として沈殿する。ここに、金属イオ
ンの溶解度とｐＨの関係は、たとえば「水処理管理便
覧」 (水処理管理便覧編集委員会編、丸善株式会社) に
記載されていて、金属の種類によってその挙動は異な
る。鉄、ニッケル、クロムを含む酸洗廃液から、これら
金属をほぼすべて金属水酸化物として効率良く、経済的
に沈殿させるには、ｐＨを８以上、好ましくは８〜１２
にする必要がある。ｐＨが８に満たないと、鉄、ニッケ
ル、クロムがイオンの形態で廃液中に残存する。ｐＨが
高すぎると、鉄、ニッケル、クロムはほぼすべて金属水
酸化物として沈殿するものの、NaOH, Na２CO３, KOH な
どのアルカリの添加量が多くなるので、経済的ではな
い。FIG. 1 is a flow chart showing one embodiment of a method for recovering valuable metals (such as iron, chromium and nickel) and nitric hydrofluoric acid from a stainless steel pickling wastewater according to the present invention. For descaling stainless steel, a solution of nitric hydrofluoric acid mixed with nitric acid (HNO 3 ) and hydrofluoric acid (HF) is used, and iron, nickel, and chromium are present in the form of ions in this pickling waste liquid. In addition, nitric acid and hydrofluoric acid which were not directly involved in descaling are also included. NaOH, N
a 2 By adding a hydroxide and / or carbonate of an alkali metal such as CO 3 and KOH to adjust the pH of the solution to 8 or more, the ions in the waste liquid are converted to iron, nickel and chromium hydroxides. Precipitates as (solid). Here, the relationship between the solubility and pH of metal ions is described in, for example, “Water Treatment Management Handbook” (edited by the Water Treatment Management Handbook Editing Committee, Maruzen Co., Ltd.), and the behavior differs depending on the type of metal. In order to efficiently and economically precipitate almost all of these metals as metal hydroxides from the pickling waste liquid containing iron, nickel and chromium, the pH should be 8 or more, preferably 8-12.
Need to be If the pH is less than 8, iron, nickel and chromium remain in the waste liquid in the form of ions. If the pH is too high, almost all of iron, nickel and chromium precipitate as metal hydroxides, but the amount of alkalis such as NaOH, Na 2 CO 3 and KOH increases, which is not economical.
【００１５】溶液から固体として沈殿した、鉄、ニッケ
ル、クロムの水酸化物は、ろ過、遠心分離、静置分離な
どの固液分離方法によって、分離除去する。水酸化物を
分離除去したろ液にはNa＋，Ｋ＋のアルカリ金属イオン
とフッ素イオン（Ｆ−) と硝酸イオン(NO３ −) が含ま
れる。このろ液をＨ＋型陽イオン交換樹脂（Ｒ−SO３ −
H＋）と接触させると、例えば次式： Ｒ−SO３ −H＋＋NaF → Ｒ−SO３ −Na＋＋HF Ｒ−SO３ −H＋＋NaNO３ → Ｒ−SO３ −Na＋＋HNO３ の反応によってアルカリ金属とフッ酸および硝酸とは分
離できる。ろ液中のアルカリ金属(Na, K) と酸の分離に
用いた、Ｈ＋型陽イオン交換樹脂は、強酸性陽イオン交
換樹脂と呼ばれ、スルホン酸基(SO３−) の官能基の付
いたものである。上式のように、プロトン(H＋) とアル
カリ金属イオンの交換によって分離が行われる。Iron, nickel precipitated as a solid from solution
And chromium hydroxide can be filtered, centrifuged,
Separation and removal are performed by any solid-liquid separation method. Hydroxide
The filtrate separated and removed contains Na+, K+Alkali metal ions
And fluorine ion (F−) And nitrate ion (NO3 −) Included
It is. This filtrate is H+Type cation exchange resin (R-SO3 −
H+), For example, the following formula: R-SO3 −H++ NaF → R-SO3 −Na++ HF R-SO3 −H++ NaNO3→ R-SO3 −Na++ HNO3 Reaction between alkali metal and hydrofluoric acid and nitric acid
You can release. For separation of alkali metal (Na, K) and acid in filtrate
H used+Type cation exchange resin is strongly acidic cation exchange
Sulfonic acid groups (SO3−) Functional group
It was what was. As shown in the above formula, proton (H+) And al
Separation takes place by exchange of potassium metal ions.
【００１６】ここで、陽イオン交換樹脂と接触させるろ
液は、鉄、クロム、ニッケルの濃度がそれぞれ100 質量
ppm 以下、硝酸イオン濃度は 0.5〜15質量％、フッ素イ
オン濃度は 0.5〜10質量％、アルカリ金属イオン濃度が
0.5〜35質量％であることが望ましい。というのは、
鉄、クロム、ニッケルのうちの少なくとも１種の濃度が
100 質量ppm 超えであると、これらの金属イオンがアル
カリ金属イオンと比較してＨ＋型陽イオン交換樹脂に対
して親和力が大きいために、鉄、クロム、ニッケルイオ
ンが陽イオン交換樹脂に先に吸着されてしまい、Na, Ｋ
が陽イオン交換樹脂に吸着されるのを著しく阻害する。
このため、HF、HNO３の回収の歩留りが悪くなる。ま
た、硝酸イオン濃度が 0.5質量％未満、フッ素イオン濃
度が 0.5質量％未満、アルカリ金属イオン濃度が 0.5質
量％未満であると、回収される酸の濃度が低く、経済的
ではない。一方、硝酸イオン濃度が15質量％超え、フッ
素イオン濃度が10質量％超え、アルカリ金属イオン濃度
が35質量％超えであると、イオン交換樹脂によるプロト
ンとのイオン交換率が悪くなり、結局回収された酸中に
アルカリ金属イオンが残存し、酸の回収が行われない。
アルカリ金属イオンと交換した陽イオン交換樹脂は、塩
酸のような再生液を通して、次式： Ｒ−SO３ −Na＋＋HCl → Ｒ−SO３ −H＋＋NaCl によりプロトンを含む陽イオン交換樹脂として、再び使
用される。Here, the filtrate to be brought into contact with the cation exchange resin has a concentration of iron, chromium and nickel of 100% by mass.
ppm or less, nitrate ion concentration is 0.5 to 15% by mass, fluorine ion concentration is 0.5 to 10% by mass, alkali metal ion concentration is
It is desirably 0.5 to 35% by mass. I mean,
The concentration of at least one of iron, chromium and nickel
If the content exceeds 100 ppm by mass, these metal ions have a higher affinity for the H + type cation exchange resin than the alkali metal ions, so that iron, chromium, and nickel ions are preceded by the cation exchange resin. Adsorbed, Na, K
Significantly inhibits adsorption of cation-exchange resin on the cation exchange resin.
For this reason, the recovery yield of HF and HNO 3 is deteriorated. If the nitrate ion concentration is less than 0.5% by mass, the fluorine ion concentration is less than 0.5% by mass, and the alkali metal ion concentration is less than 0.5% by mass, the concentration of the recovered acid is low, which is not economical. On the other hand, when the nitrate ion concentration exceeds 15% by mass, the fluorine ion concentration exceeds 10% by mass, and the alkali metal ion concentration exceeds 35% by mass, the ion exchange rate with protons by the ion exchange resin deteriorates, and the ion exchange resin is eventually recovered. Alkali metal ions remain in the acid, and the acid is not recovered.
Cation exchange resins exchanged with alkali metal ions, through such regenerant as hydrochloric acid, the formula: R-SO 3 - as H + + cation exchange resin containing a proton by NaCl, - Na + + HCl → R-SO 3 Used again.
【００１７】このようにして回収された硝酸およびフッ
酸は、再びステンレス鋼の酸洗用の硝フッ酸として再利
用することができる。また、回収された硝フッ酸中の硝
酸およびフッ酸の濃度が低い場合には、電気透析法、蒸
留等によって、濃度を高くして再びステンレス鋼の酸洗
用の酸として再利用してもよい。なお、硝フッ酸をステ
ンレス鋼用の酸洗溶液として用いる場合には、硝酸濃度
が５〜１５質量％、フッ酸濃度が１〜7.5 質量％である
ことが望ましい。The nitric acid and hydrofluoric acid thus recovered can be reused as nitric hydrofluoric acid for pickling stainless steel. Further, when the concentration of nitric acid and hydrofluoric acid in the recovered nitric hydrofluoric acid is low, the concentration may be increased by electrodialysis, distillation, etc., and reused again as an acid for pickling stainless steel. Good. When nitric hydrofluoric acid is used as a pickling solution for stainless steel, it is preferable that the concentration of nitric acid is 5 to 15% by mass and the concentration of hydrofluoric acid is 1 to 7.5% by mass.
【００１８】[0018]
【実施例】以下、本発明を実施例にて具体的に説明す
る。 (実施例１)ステンレス304 (18Cr-8Ni)を硝酸とフッ酸の
混合液で、酸洗し、鉄イオン濃度2.2質量％、クロムイ
オン濃度 0.4質量％、ニッケルイオン濃度 0.1質量％、
フッ素イオン濃度 2.0質量％、硝酸イオン濃度 3.2質量
％の酸洗廃液を得た。この廃液に、３規定のNaOH溶液を
pH＝10になるまで添加し、その後30分間、攪拌した。攪
拌終了後、溶液は金属水酸化物を含むスラッジ状とな
り、この溶液を濾過により金属水酸化物とろ液に分離し
た。この濾液には、鉄、クロム、ニッケルが全く含有さ
れず、フッ素イオン濃度 1.0質量％、硝酸イオン濃度
1.7質量％、ナトリウムイオン濃度 4.0質量％であっ
た。陽イオン交換樹脂 (商品名：マラソンＣ、室町化学
社製) を充填したカラム(直径：2.5cm 、長さ50cm)
に、流速10cm３/min でろ液を通し、ナトリウムイオン
を陽イオン交換樹脂に吸着分離させ、フッ酸と硝酸を回
収した。この時、フッ素イオン濃度 0.9質量％、硝酸イ
オン濃度 1.6質量％であり、ナトリウムイオンを全く含
まない硝フッ酸が回収できた。回収した硝フッ酸を電気
透析法により、フッ素イオン濃度 3.6質量％、硝酸イオ
ン濃度 6.4質量％に濃縮してステンレス鋼の酸洗に使用
した。この酸洗液は、ステンレス鋼にピットなどの欠陥
を発生させることもなく、問題なく使用できることを確
認した。The present invention will be specifically described below with reference to examples. (Example 1) Stainless steel 304 (18Cr-8Ni) was pickled with a mixed solution of nitric acid and hydrofluoric acid, and the iron ion concentration was 2.2% by mass, the chromium ion concentration was 0.4% by mass, and the nickel ion concentration was 0.1% by mass.
A pickling waste liquid having a fluorine ion concentration of 2.0% by mass and a nitrate ion concentration of 3.2% by mass was obtained. To this waste liquid, add 3N NaOH solution
It was added until pH = 10 and then stirred for 30 minutes. After completion of the stirring, the solution became a sludge containing a metal hydroxide, and this solution was separated into a metal hydroxide and a filtrate by filtration. This filtrate contains no iron, chromium or nickel, and has a fluorine ion concentration of 1.0% by mass and a nitrate ion concentration of
It was 1.7% by mass and the sodium ion concentration was 4.0% by mass. Column (diameter: 2.5cm, length 50cm) packed with cation exchange resin (trade name: Marathon C, manufactured by Muromachi Chemical Co., Ltd.)
The filtrate was passed through the filtrate at a flow rate of 10 cm 3 / min, and sodium ions were adsorbed and separated on a cation exchange resin to recover hydrofluoric acid and nitric acid. At this time, the concentration of fluorine ions was 0.9% by mass and the concentration of nitrate ions was 1.6% by mass, and nitric hydrofluoric acid containing no sodium ions could be recovered. The recovered nitric hydrofluoric acid was concentrated by electrodialysis to a fluorine ion concentration of 3.6% by mass and a nitrate ion concentration of 6.4% by mass and used for pickling stainless steel. It was confirmed that this pickling liquid can be used without any problem without generating defects such as pits in stainless steel.
【００１９】(実施例２)ステンレス304 (18Cr-8Ni)を硝
酸とフッ酸の混合液で、酸洗し、鉄イオン濃度2.2質量
％、クロムイオン濃度 0.4質量％、ニッケルイオン濃度
0.1質量％、フッ素イオン濃度 3.5質量％、硝酸イオン
濃度 4.2質量％の酸洗廃液を得た。この廃液に３規定の
KOH溶液をpH＝10になるまで添加し、その後30分間、攪
拌した。攪拌終了後、溶液は金属水酸化物を含むスラッ
ジ状となり、この溶液を濾過により金属水酸化物と濾液
に分離した。このろ液には、鉄、クロム、ニッケルが全
く含有されず、フッ素イオン濃度 2.3質量％、硝酸イオ
ン濃度 3.2質量％、カリウムイオン濃度 5.3質量％であ
った。陽イオン交換樹脂 (商品名：マラソンＣ、室町化
学社製) を充填したカラム (直径：2.5cm 、長さ50cm)
に、ろ液流速10cm３/minで通し、カリウムイオンを陽イ
オン交換樹脂に吸着分離させ、フッ酸と硝酸を回収し
た。この時、フッ素イオン濃度 2.0質量％、硝酸イオン
濃度 3.0質量％であり、カリウムイオンを全く含まない
硝フッ酸が回収できた。回収した硝フッ酸を電気透析法
により、フッ素イオン濃度 6.0質量％、硝酸イオン濃度
9.0質量％に濃縮してステンレス鋼の酸洗に使用した。
この酸洗液は、ステンレス鋼にピットなどの欠陥を発生
させることもなく、問題なく使用できることを確認し
た。(Example 2) Stainless steel 304 (18Cr-8Ni) was pickled with a mixture of nitric acid and hydrofluoric acid, and the iron ion concentration was 2.2% by mass, the chromium ion concentration was 0.4% by mass, and the nickel ion concentration was
A pickling waste liquid having a concentration of 0.1% by mass, a concentration of fluorine ions of 3.5% by mass, and a concentration of nitrate ions of 4.2% by mass was obtained. This waste liquid is
KOH solution was added until pH = 10, and then stirred for 30 minutes. After completion of the stirring, the solution became a sludge containing a metal hydroxide, and this solution was separated into a metal hydroxide and a filtrate by filtration. This filtrate did not contain any iron, chromium, and nickel, and had a fluorine ion concentration of 2.3% by mass, a nitrate ion concentration of 3.2% by mass, and a potassium ion concentration of 5.3% by mass. Column (diameter: 2.5 cm, length 50 cm) packed with cation exchange resin (trade name: Marathon C, manufactured by Muromachi Chemical Co., Ltd.)
Then, the filtrate was passed at a flow rate of 10 cm 3 / min, and potassium ions were adsorbed and separated on a cation exchange resin to recover hydrofluoric acid and nitric acid. At this time, the concentration of fluorine ions was 2.0% by mass and the concentration of nitrate ions was 3.0% by mass, and nitric hydrofluoric acid containing no potassium ions could be recovered. The recovered nitric hydrofluoric acid was electrodialyzed using a fluoride ion concentration of 6.0% by mass and a nitrate ion concentration.
It was concentrated to 9.0% by mass and used for pickling stainless steel.
It was confirmed that this pickling liquid can be used without any problem without generating defects such as pits in stainless steel.
【００２０】[0020]
【発明の効果】以上説明したように、本発明によれば、
ステンレスの硝フッ酸酸洗において使用された酸洗廃液
を、アルカリ中和処理とそれに引き続く陽イオン交換樹
脂による処理により、有価金属と硝フッ酸を効果的に回
収でき、再利用することができる。したがって、本発明
は、有価金属と酸の有効利用を可能とするので、ステン
レス製品の製造コスト低下を可能にするだけでなく、地
球環境の保全、循環型社会の形成に大いに寄与する。As described above, according to the present invention,
The pickling waste liquor used in the nitric hydrofluoric acid pickling of stainless steel can be effectively recovered and reused by alkali neutralization treatment and subsequent treatment with a cation exchange resin to recover valuable metals and nitric hydrofluoric acid. . Therefore, the present invention enables effective use of valuable metals and acids, and thus not only enables a reduction in the production cost of stainless steel products, but also greatly contributes to the preservation of the global environment and the formation of a recycling-oriented society.
【図１】本発明による硝フッ酸廃液の再生方法を説明す
るためのフロー図である。FIG. 1 is a flowchart for explaining a method for regenerating a nitric hydrofluoric acid waste liquid according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｇ 1/08 Ｃ２３Ｇ 1/08 (72)発明者 弓立 浩三 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 (72)発明者 安原 久雄 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 Ｆターム(参考） 4D025 AA09 AB18 BA11 BB02 DA10 4D038 AA08 AB65 AB66 AB67 AB79 BA04 BB08 BB17 4K053 PA03 PA04 PA12 QA01 RA16 RA17 YA06 YA10 YA12 YA13──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C23G 1/08 C23G 1/08 (72) Inventor Kozo Yumitate 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Pref. (72) Inventor Hisao Yasuhara 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Prefecture BB17 4K053 PA03 PA04 PA12 QA01 RA16 RA17 YA06 YA10 YA12 YA13
Claims (5)
アルカリ金属の水酸化物および／または炭酸塩を添加し
て、廃液のｐＨを８以上とすることにより、金属水酸化
物を生成させ、次いで、生成した金属水酸化物を廃液か
ら分離除去し、その後、金属水酸化物が除去された廃液
をＨ＋型陽イオン交換樹脂と接触させることにより、こ
の廃液からアルカリ金属イオンを除去して硝フッ酸を得
ることを特徴とする硝フッ酸廃液の再生方法。1. A nitric acid hydrofluoric acid waste liquid containing metal ions,
By adding a hydroxide and / or carbonate of an alkali metal to adjust the pH of the waste liquid to 8 or more, a metal hydroxide is generated, and then the generated metal hydroxide is separated and removed from the waste liquid, Thereafter, the waste liquid from which the metal hydroxide has been removed is brought into contact with an H + -type cation exchange resin, whereby alkali metal ions are removed from the waste liquid to obtain nitric hydrofluoric acid. Playback method.
ッ酸を更に濃縮することを特徴とする硝フッ酸廃液の再
生方法。2. A method for regenerating a nitric hydrofluoric acid waste liquid, wherein the nitric hydrofluoric acid regenerated by the method according to claim 1 is further concentrated.
オンおよびニッケルイオンの内から選ばれる少なくとも
一種であることを特徴とする請求項１または２に記載の
硝フッ酸廃液の再生方法。3. The method according to claim 1, wherein the metal ions are at least one selected from iron ions, chromium ions, and nickel ions.
洗廃液であることを特徴とする請求項１または２に記載
の硝フッ酸廃液の再生方法。4. The method for regenerating nitric hydrofluoric acid waste liquid according to claim 1, wherein the nitric hydrofluoric acid waste liquid is a pickling waste liquid of stainless steel.
法で再生された硝フッ酸の再生液をステンレス鋼の酸洗
液として使用することを特徴とするステンレス鋼の酸洗
方法。5. A method for pickling stainless steel, comprising using a regenerating solution of nitric hydrofluoric acid regenerated by the method according to claim 1 as a pickling solution for stainless steel. .
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| JP2001126900A JP2002322581A (en) | 2001-04-25 | 2001-04-25 | Method for regenerating waste solution of nitric- hydrofluoric acid and method for pickling stainless steel |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553249A (en) * | 2013-10-23 | 2014-02-05 | 长沙赛恩斯环保科技有限公司 | Method for acid separation and heavy metal recovery in electroplating waste liquor |
| CZ305399B6 (en) * | 2014-06-30 | 2015-09-02 | Výzkumný ústav anorganické chemie, a. s. | Neutralization process of waste rinsing water of stainless steel pickling plants |
| CN105293745A (en) * | 2014-05-29 | 2016-02-03 | 宝山钢铁股份有限公司 | Cold rolling and acid pickling wastewater resourceful treatment process system |
| CN108503167A (en) * | 2018-03-30 | 2018-09-07 | 江苏宝钢精密钢丝有限公司 | A method of utilizing iron and steel pickling waste liquid synthesizing new water purification agent |
| CN108624893A (en) * | 2018-05-14 | 2018-10-09 | 北京科技大学 | A kind of high-valued processing method of stainless steel acid cleaning waste water |
| CN109354288A (en) * | 2018-11-09 | 2019-02-19 | 常州润德石墨科技有限公司 | The method for handling stainless steel acid cleaning waste water |
-
2001
- 2001-04-25 JP JP2001126900A patent/JP2002322581A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553249A (en) * | 2013-10-23 | 2014-02-05 | 长沙赛恩斯环保科技有限公司 | Method for acid separation and heavy metal recovery in electroplating waste liquor |
| CN103553249B (en) * | 2013-10-23 | 2016-01-06 | 长沙赛恩斯环保科技有限公司 | In electroplating effluent, acid is separated and heavy metal collection method |
| CN105293745A (en) * | 2014-05-29 | 2016-02-03 | 宝山钢铁股份有限公司 | Cold rolling and acid pickling wastewater resourceful treatment process system |
| CZ305399B6 (en) * | 2014-06-30 | 2015-09-02 | Výzkumný ústav anorganické chemie, a. s. | Neutralization process of waste rinsing water of stainless steel pickling plants |
| CN108503167A (en) * | 2018-03-30 | 2018-09-07 | 江苏宝钢精密钢丝有限公司 | A method of utilizing iron and steel pickling waste liquid synthesizing new water purification agent |
| CN108624893A (en) * | 2018-05-14 | 2018-10-09 | 北京科技大学 | A kind of high-valued processing method of stainless steel acid cleaning waste water |
| CN109354288A (en) * | 2018-11-09 | 2019-02-19 | 常州润德石墨科技有限公司 | The method for handling stainless steel acid cleaning waste water |
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