CN1061104C - 一种从不锈钢带酸洗废液中回收硫酸钠电解液的方法 - Google Patents
一种从不锈钢带酸洗废液中回收硫酸钠电解液的方法 Download PDFInfo
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- CN1061104C CN1061104C CN96105924A CN96105924A CN1061104C CN 1061104 C CN1061104 C CN 1061104C CN 96105924 A CN96105924 A CN 96105924A CN 96105924 A CN96105924 A CN 96105924A CN 1061104 C CN1061104 C CN 1061104C
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- Prior art keywords
- stainless steel
- solution
- electrolytes
- pickles
- na2so4
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- 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
- 238000000034 method Methods 0.000 title claims abstract description 25
- 235000021110 pickles Nutrition 0.000 title claims abstract description 12
- 239000003792 electrolyte Substances 0.000 title claims abstract description 10
- 239000010935 stainless steel Substances 0.000 title claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 title abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 title abstract description 11
- 239000002699 waste material Substances 0.000 title abstract description 3
- 239000007832 Na2SO4 Substances 0.000 title abstract 2
- 230000008929 regeneration Effects 0.000 title abstract 2
- 238000011069 regeneration method Methods 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 11
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
- C25F7/02—Regeneration of process liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明涉及一种从不锈钢材,尤其是不锈钢带的废酸洗液中回收电解液,尤其是硫酸钠的方法。其主要特征在于:在酸溶液中添加NaxHySzOv使六价铬离子(Cr6+)还原为三价铬离子(Cr3+),其下标为x=0-2,y=0-2,z=1-6,v=2-6。
Description
本发明涉及一种从不锈钢尤其是不锈钢带酸洗废液中回收电解液,尤其是硫酸钠的方法。
用中性电解液电解酸洗不锈钢带,尤其是冷轧钢带的“neloyte”方法已经得到全世界的广泛认可。该方法通过在硫酸钠溶液中通入电流而对不锈钢带除去氧化皮。在该方法中,金属累积在电解液中,在本发明中即为硫酸钠溶液。金属铬以铬酸盐(Cr6+)的形式溶解,其它金属如铁和镍以氢氧化物的形式存在。
酸洗液中金属含量通过不断从酸洗池中抽出电解液,同时补加新的硫酸钠溶液保持恒定。补加硫酸钠和废电解液的处理都会带来相当高昂的操作费用。
因此,本发明的目的在于降低这两种操作费用,同时也减少所谓“neolyte”酸洗工厂对环境的污染。
根据本发明的方法,本发明的目的通过在一种酸溶液中添加NaxHySzOv使六价铬离子(Cr6+)还原为三价铬离子(Cr3+)而实现,其下标分别为:x=0-2,y=0-2,z=1-6,v=2-6。通过掺入该物质,可在任何反应中生成硫酸钠,并能容易地循环到工艺过程中。
本发明的一个有益设计,其特征在于,溶液中没有引入任何杂质原子,避免了除硫酸钠外其它不希望的反应产物的生成。
本发明的一个改进,其特征在于:发生反应的pH值范围约为2-3。加入硫酸能有利地实现pH值的降低。这同样意味着在溶液中没有引入杂质原子。还原反应在酸性条件下发生有利地加快了反应速度。
本发明的一个另有益设计,其特征在于:所得酸溶液通过添加氢氧化钠中和。在该步骤中,与氢氧化钠中和反应也生成硫酸钠,这样就能容易地循环到工艺过程中去。
本发明的一个另有益改进,其特征在于:中和反应得到的金属氢氧化物从酸洗液(Na2SO4)中分离后,其溶液再循环到酸洗过程中。洗液的回收避免了因使用新的酸洗液而导致的高昂费用。金属氢氧化物从酸洗液中分离出来后,它们能够在高浓度即低剩余酸含量的情况下沉积。
可能发生的反应如下:1) 2) 3)
结果为:
下面通过实例将本发明的方法与公知的“neolyte”法进行比较:
冷轧钢带尺寸1250mm×0.8mm,用钢质为AISI304的钢材制成,以85m/min的速度酸洗。平均酸洗损失量为3g/m2。硫酸钠浓度150gl,六价铬离子浓度5g/l。
比较得到下列数据:
表格中数据表明:酸洗过程中硫酸钠的消耗显著降低。水的消耗也相应减少。废酸洗泥的量约降低一半,且其pH值为中性。上述分析还没有考虑用于中和反应所节约的石灰。
现通过实施例和附图对本方法进行解释。附图显示了含neolyte回收过程的酸洗系统。
附图显示了含电极对2的电解酸洗系统1。金属带3从其中通过,尤其从充满酸洗液的区间4通过。中性电解液如硫酸钠作为酸洗液。该酸洗系统之后是一个清洗系统5,它包括清洗刷6。
中性电解液通过方便可调的泵8、温度可调的换热器9和输送管10从酸洗装置1中的循环罐7输送到酸洗装置1中。这一点可根据要求,最好在多处实现。废的酸洗液因富含从金属带3酸洗下来的氧化皮,以及其中除含铁和镍外,还很大部分是六价铬离子(Cr6+),它通过管路11输送到循环罐7中。富含金属离子的电解液输送到循环罐7中,再进一步输送到反应罐12中。新的硫酸(H2SO4)通过管路13添加以降低pH值。还原剂如Na2S2O5通过管路14添加用以还原六价铬离子(Cr6+)。反应罐12中的pH值在酸性范围内,如pH=2。反应结果根据上述化学式得到硫酸钠。
反应产物如铁和镍的氢氧化物输送到中和反应阶段15中,中和反应的氢氧化钠通过管路16添加。中和反应罐15内pH值在中性范围,即pH=8-9。中和反应阶段15的酸泥液(母液)由泵17抽入到过滤器18中,从中将电解液即纯硫酸钠溶液通过管路19输送到循环罐7中,再回收到流程中。富含金属氧化物的相作为酸泥从过滤器18通过管路20排出,然后沉积。
漂洗水通过泵21和管路22添加到酸洗装置1后的清洗阶段5中,并喷洒在钢带3上。如可在金属带3进行清洗阶段5的入口或刷洗轴6的附近进行清洗。清洗后的污泥通过管道23引入静置罐24中,再由管路25排出并沉淀。漂洗后的水则由管路26输入反应罐12中。本发明并不限于附图显示的方案,它还可以设计成不含清洗系统或配置不同方式的清洗系统。还可以设计成几个酸洗系统按先后顺序排列。
Claims (5)
1.一种从不锈钢带酸洗废液中回收硫酸钠电解液的方法,其特征在于:将NaxHySzOv添加到酸洗溶液中使六价铬离子Cr6+还原为三价铬离子Cr3+,其下标x=0-2,y=0-2,z=1-6,v=2-6。
2.如权利要求1所述的方法,其特征在于:溶液中没有引入任何杂质原子。
3.如权利要求1或2所述的方法,其特征在于:发生反应的pH值范围约为2-3。
4.如权利要求1到3其中之一所述的方法,其特征在于:酸溶液用氢氧化钠中和。
5.如权利要求4所述的方法,其特征在于:将中和反应得到的金属氢氧化物从Na2SO4电解液中分离出来,而电解液再返回酸洗过程中。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA268/95 | 1995-02-15 | ||
ATA268/1995 | 1995-02-15 | ||
AT0026895A AT401183B (de) | 1995-02-15 | 1995-02-15 | Verfahren zur regeneration von elektrolyten, insbesondere na2so4 aus abbeizen von edelstahl, insbesondere edelstahlbändern |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1149086A CN1149086A (zh) | 1997-05-07 |
CN1061104C true CN1061104C (zh) | 2001-01-24 |
Family
ID=3486028
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96105924A Expired - Lifetime CN1061104C (zh) | 1995-02-15 | 1996-02-14 | 一种从不锈钢带酸洗废液中回收硫酸钠电解液的方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6506294B1 (zh) |
KR (1) | KR100209987B1 (zh) |
CN (1) | CN1061104C (zh) |
AT (1) | AT401183B (zh) |
BR (1) | BR9600726A (zh) |
DE (1) | DE19602304A1 (zh) |
ES (1) | ES2125795B1 (zh) |
FI (1) | FI960645A (zh) |
FR (1) | FR2732041B1 (zh) |
TW (1) | TW349076B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT406486B (de) * | 1998-12-22 | 2000-05-25 | Andritz Patentverwaltung | Verfahren zum beizen von edelstahl |
IT1317896B1 (it) * | 2000-08-10 | 2003-07-15 | Ct Sviluppo Materiali Spa | Metodo di decapaggio elettrolitico continuo di prodotti metallici concelle alimentate a corrente alternata. |
CN103484888B (zh) * | 2012-06-14 | 2015-11-04 | 兰州大学 | 一种不锈钢生产中含铬硫酸钠废液及硫酸酸洗废液的处理方法 |
AT517710B1 (de) * | 2016-04-13 | 2017-04-15 | Andritz Ag Maschf | Verfahren zum elektrolytischen beizen von metallbändern |
CN113215646A (zh) * | 2021-05-11 | 2021-08-06 | 山西太钢工程技术有限公司 | 一种电解硫酸钠溶液循环利用智能控制系统 |
CN113637976B (zh) * | 2021-08-20 | 2023-01-13 | 深圳天华机器设备有限公司 | 一种硫酸洗槽药水再生系统 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01184096A (ja) * | 1988-01-18 | 1989-07-21 | Kawasaki Steel Corp | 金属含有廃液の処理装置 |
CN1043535A (zh) * | 1988-12-24 | 1990-07-04 | 由正明 | 硫酸酸洗废液再生的工艺方法 |
CN1084907A (zh) * | 1992-10-14 | 1994-04-06 | 烟台大学 | 硫酸酸洗液闭路循环工艺处理方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5230260A (en) * | 1975-09-03 | 1977-03-07 | Hitachi Seiko Ltd | Treatment process and treatment apparatus for electrolyte |
AT387406B (de) * | 1987-05-07 | 1989-01-25 | Andritz Ag Maschf | Verfahren zum elektrolytischen beizen von chromhaeltigem edelstahl |
-
1995
- 1995-02-15 AT AT0026895A patent/AT401183B/de not_active IP Right Cessation
-
1996
- 1996-01-23 DE DE19602304A patent/DE19602304A1/de not_active Ceased
- 1996-02-01 ES ES009600224A patent/ES2125795B1/es not_active Expired - Fee Related
- 1996-02-09 KR KR1019960003205A patent/KR100209987B1/ko not_active IP Right Cessation
- 1996-02-13 FI FI960645A patent/FI960645A/fi unknown
- 1996-02-14 BR BR9600726A patent/BR9600726A/pt not_active Application Discontinuation
- 1996-02-14 CN CN96105924A patent/CN1061104C/zh not_active Expired - Lifetime
- 1996-02-15 US US08/601,675 patent/US6506294B1/en not_active Expired - Lifetime
- 1996-02-15 FR FR9601854A patent/FR2732041B1/fr not_active Expired - Lifetime
- 1996-03-05 TW TW085102676A patent/TW349076B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01184096A (ja) * | 1988-01-18 | 1989-07-21 | Kawasaki Steel Corp | 金属含有廃液の処理装置 |
CN1043535A (zh) * | 1988-12-24 | 1990-07-04 | 由正明 | 硫酸酸洗废液再生的工艺方法 |
CN1084907A (zh) * | 1992-10-14 | 1994-04-06 | 烟台大学 | 硫酸酸洗液闭路循环工艺处理方法 |
Also Published As
Publication number | Publication date |
---|---|
ATA26895A (de) | 1995-11-15 |
FR2732041B1 (fr) | 1998-06-05 |
US6506294B1 (en) | 2003-01-14 |
ES2125795B1 (es) | 1999-11-16 |
FR2732041A1 (fr) | 1996-09-27 |
KR960031654A (ko) | 1996-09-17 |
FI960645A0 (fi) | 1996-02-13 |
KR100209987B1 (ko) | 1999-07-15 |
TW349076B (en) | 1999-01-01 |
ES2125795A1 (es) | 1999-03-01 |
AT401183B (de) | 1996-07-25 |
DE19602304A1 (de) | 1996-08-22 |
CN1149086A (zh) | 1997-05-07 |
BR9600726A (pt) | 1997-12-23 |
FI960645A (fi) | 1996-08-16 |
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