CN102757142A - Method for recycling and processing nickel in stainless steel pickling waste acid - Google Patents

Method for recycling and processing nickel in stainless steel pickling waste acid Download PDF

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Publication number
CN102757142A
CN102757142A CN2012102770473A CN201210277047A CN102757142A CN 102757142 A CN102757142 A CN 102757142A CN 2012102770473 A CN2012102770473 A CN 2012102770473A CN 201210277047 A CN201210277047 A CN 201210277047A CN 102757142 A CN102757142 A CN 102757142A
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China
Prior art keywords
reaction
nickel
stainless steel
acid
lime
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CN2012102770473A
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Chinese (zh)
Inventor
楼洪海
周杰
李波
刘祥虎
潘辉环
朱斌来
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浙江海拓环境技术有限公司
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Priority to CN2012102770473A priority Critical patent/CN102757142A/en
Publication of CN102757142A publication Critical patent/CN102757142A/en

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Abstract

Disclosed is a method for recycling and processing nickel in a stainless steel pickling waste acid. The potential of hydrogen (pH) value of a mixed waste acid is adjusted to 3.5 to 4.5 by lime, hydrogen peroxide is added, a reaction is performed for 0.5 to 1 hour, then the pH value is adjusted again to 4.0 to 4.5 by the lime, then a flocculating agent is added to enter into a sedimentation tank to obtain a clear liquid and sludges, the clear liquid enters into a second reaction tank, the obtained sludges are subjected to a filter pressing to obtain a filter cake, the filter cake is subjected to a back washing by stainless steel factory workshop ground washing wastewater, and filter pressing water is transferred into the second reaction tank. The lime is added into the second reaction tank to adjust the pH value to 9.0 to 10.0, the flocculating agent is added, a formed solid-liquid mixture is transferred into a second sedimentation tank to be subjected to a solid-liquid separation, solids are subjected to the filter pressing to obtain a nickel mud, a sulfuric acid is added into a filter pressing liquor to adjust the pH of effluent to 7.0 to 8.0, and environmentally acceptable discharge can be achieved. By means of the method, the effective recycling of heavy metal nickel can be achieved, secondary pollutions are reduced, sludge qualities can be improved, and waste acid treatment emission requirements can be met.

Description

The recovery and treatment method of nickel in a kind of waste acid from stainless steel acid washing
Technical field
The present invention relates to the recovery method of heavy metal in a kind of spent acid processing, the recovery and treatment method of nickel in particularly a kind of waste acid from stainless steel acid washing.
Technical background
The source of waste acid from stainless steel acid washing mainly result from the steel members blank before electroplating surface, spraying the pickling of process; Mainly be divided into sulfuric acid waste and nitric acid-hydrofluoric acid mixed waste liquor (hereinafter to be referred as " nitration mixture "), sulfuric acid waste mainly is created in the preparatory acid cleaning process.Pickling is to remove the stainless-steel pipe scale on surface in advance; Adopt sulfuric acid washing solution, sulfuric acid content should be 15% ~ 20%, and ferrous sulfate content is lower than 250g/L; Pickling temperature is 50 ~ 72 ℃ in advance; Through the stainless steel tube of preparatory pickling, the black precipitate that the surface has one deck in sulphuric acid soln, not go out, the i.e. oxide compound of chromium and nickel.Thereby just need carry out albefaction pickling (final pickling), and purpose is exactly to remove the black precipitate that remains in steel pipe after the preparatory pickling, i.e. the oxide compound of chromium and nickel, and the process of albefaction pickling (final pickling) is the main source of nitration mixture waste liquid just.
Waste acid from stainless steel acid washing contains very big acidity; No matter be sulfuric acid or nitration mixture; Acidity all reaches tens0000 and even hundreds of thousands of; The stainless steel spent acid also contains a large amount of heavy metal ion simultaneously, no matter be that acidity or heavy metal ion all have very big harm to environment and mankind itself, must deal carefully with.
Existing people is applied to handle pickling iron and steel spent acid and heavy metal wherein with methods such as electrodialysis, roasting method, distillation method, fluiddized-bed roasting method, spray roastings both at home and abroad at present.The advantage of electroosmose process is that equipment is simple, and organic efficiency is high, can reclaim spent acid and extract iron, and shortcoming is that current consumption is higher.Roasting method, distillation method are because of high-temperature operation, and equipment life is shorter, and acid gas, dust and the air pollution problems inherent of Yin Gaowen generation, make environment be difficult for keeping, and need blowing out maintenance equipment in every month, and maintenance cost is higher.The shortcoming of fluiddized-bed roasting method and spray roasting is that equipment cost is high, the scale restriction is arranged, and air pollutant emission is arranged.Chemical precipitation method has that treatment effect is good, less investment, advantage such as easy and simple to handle, but maximum shortcoming is that sludge quantity is big, the sludge dewatering difficulty, and be difficult to recycle, thereby influenced its application and development.If this difficult point can be resolved; Just it seems at present that chemical process still is one of method that is best suited for spent acid comprehensive treating process utilization; And in the last few years to the improvement of neutralisation technology; The pickling iron and steel spent acid treatment process that makes reaches its maturity, and also is a problem demanding prompt solution and how to improve the sludge heavy-metal quality that generates in the chemical precipitation method.
The amount * 100 of the amount/mud of heavy metal in the quality of mud (%)=mud, therefore improving sewage sludge quality is mainly reflected in two aspects: improve heavy metal content and the amount that reduces mud in the mud.
The amount of heavy metal in the amount/water inlet of heavy metal in the heavy metal recovery (%)=mud, therefore improve heavy metal especially the recovery of nickel be mainly reflected in the content that reduces nickel in the no recovery value mud.
Summary of the invention
The technical problem that the present invention will solve provides a kind ofly can carry out efficient recovery to heavy metal nickel, can reduce secondary pollution,
Can improve the quality of mud and reach the recovery and treatment method that spent acid is handled nickel in the waste acid from stainless steel acid washing of emission request.
For solving this technical problem, the technical scheme that the present invention adopts is:
The recovery and treatment method of nickel in a kind of waste acid from stainless steel acid washing is characterized in that may further comprise the steps:
(a) mixed solution (ratio of sulfuric acid and nitration mixture is roughly at 1:1) of collecting waste acid from stainless steel acid washing is put into first reaction tank, and regulating the pH value to the lime that wherein adds 16.7% (massfraction) is 3.5 ~ 4.5, fully reacts;
(b) after the above-mentioned reaction, add the ydrogen peroxide 50 of 27.5% (massfraction), reacted 0.5 ~ 1 hour by amount of inlet water 1% (volume ratio);
(c) after the above-mentioned reaction, replenish the lime that adds part 16.7% (massfraction) and regulate pH to 4.0 ~ 4.5, add flocculation agent SEPIGEL 305 (PAM) (spent acid water inlet per ton adds 4g PAM) then, carry out abundant flocculation reaction;
(d) will pass through solidliquid mixture that above-mentioned reaction forms and send into settling tank and carry out solid-liquid separation, clear liquid is conveyed into second reaction tank;
(e) mud of settling tank is gone into the autoclave diaphragm plate-and-frame filter press by pump delivery and carry out press filtration, and use stainless steel plant's mill floor flushing waste water that filter cake is carried out back flushing (washing water quantity washes by spent acid amount of inlet water 1:1).The collected press filtration water of this step also is conveyed into second reaction tank to be mixed with the gained clear liquid.The autoclave diaphragm plate-and-frame filter press that this step relates to can be referring to application number: 201210122537.6 patents.
(f) lime that adds 16.7% (massfraction) in second reaction tank is regulated pH to 9.0 ~ 10.0, adds flocculation agent SEPIGEL 305 (PAM) (spent acid water inlet per ton adds 2g PAM), carries out abundant flocculation reaction;
(g) will pass through solidliquid mixture that f reaction forms sends into another settling tank and carries out solid-liquid separation;
(h) solid of settling tank is gone into the autoclave diaphragm plate-and-frame filter press by pump delivery and carry out press filtration, obtain nickel mud, pressing filtering liquid merges with the supernatant that (g) step obtains, and regulates water outlet pH7.0 ~ 8.0 through adding sulfuric acid, realizes qualified discharge.
Step a, f use lime as precipitation agent, and chemical equation is:
2OH -+M 2+→M(OH) 2↓,3OH -+M 3+→M(OH)3↓
Step b uses ydrogen peroxide 50 as oxygenant, and chemical equation is:
2Fe 2++H2O2+2H +=2Fe 3++2H2O
Generally speaking, heavy metal and nonmetal composition and content are relatively stable in sulfuric acid that enterprises of producing stainless steel gave off and the nitration mixture mixing spent acid, and this also is that the technology of enterprises of producing stainless steel self determines.Thereby mainly be the control appropriate condition, heavy metal ion and nonmetallic ion in sulfuric acid and the nitration mixture mixing spent acid are precipitated fully, realize the needs of qualified discharge.In the present invention, except the nickel heavy metal, also contain iron in sulfuric acid and the nitration mixture mixing spent acid, chromium, nonmetallic ion such as heavy metal such as copper and fluorine, wherein iron and fluorine content are very big.For effectively enrichment and recovery heavy metal nickel, the present invention separates useful mud and useless mud through fractional precipitation, and nickel is deposited in the useful mud; Use ydrogen peroxide 50 that the difficult oxidation of divalent of removing among the step a is become ferric iron, be deposited in the lump in the useless mud, realization separates with heavy metal nickel; Loss through filter cake flushing minimizing heavy metal nickel realizes the maximization enrichment of nickel.
In actual production process, it is big that step a, b, c produce the precipitating sludge amount, mud taste not high (being useless mud), therefore; The control of reaction pH should be satisfied lower nickel rate of loss, the iron that makes as much as possible again, and chromium, the fluorine plasma is in useless mud; Be separated with nickel, so controlled step a and step c pH value in reaction all are 4.0, under this pH; The nickel rate of loss is little, and ferric iron, chromium; Remove fully for fluorine-based, and the divalence iron rule becomes ferric iron through hydrogen peroxide oxidation, under this pH value, also is able to effective removal.Step f is transferred to 9.5 with pH, can satisfy the needs of qualified discharge fully, and the relative quantity of getting back simultaneously is less, the useful mud that quality is very high (the nickel taste is very high).Be the face of land, workshop, stainless steel plant flushing waste water to the employed wash-down water of filter cake back flushing in this flow process; Wash-down water source, the face of land, workshop is abundant; And itself be waste water, do not increased the use of new tap water, also improved the recovery of whole flow process nickel simultaneously effectively.
Present method technology is simple, and it is low to reclaim the nickel cost, and it is big to reclaim benefit, and satisfies the requirement that spent acid is handled qualified discharge, is fit to wide popularization and application.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
Certain stainless steel plant's mixing spent acid influent quality such as following table:
Table 1 acid-washing stainless steel mixing spent acid influent quality situation
Referring to Fig. 1, the recovery and treatment method of nickel in a kind of waste acid from stainless steel acid washing may further comprise the steps:
A, above-mentioned sulfuric acid and nitration mixture are mixed the back inject first reaction tank (ratio of sulfuric acid and nitration mixture is roughly at 1:1); The lime adjusting pH value that adds 16.7% (massfraction) through PLC (automatic medicament feeding system) is 4.0; Fully react,, pH is implemented on-line monitoring for reacting fully.This step PH transfers to 3.5 ~ 4.5 can.
After b, above-mentioned reaction accomplish, add the ydrogen peroxide 50 of 27.5% (massfraction), reacted 0.8 hour by amount of inlet water 1% (volume ratio).Through this step, some are about the 4.0 difficult ions of removing in the pH value, and as ferrous, the oxidation formation ferric iron through ydrogen peroxide 50 forms deposition again, thereby effectively removes.0.5 ~ 1 hour this reaction times in step can.
After c, the above-mentioned reaction, replenish the lime that adds part 16.7% (massfraction) through PLC and regulate pH to 4.0, and add flocculation agent SEPIGEL 305 (PAM) (spent acid water inlet per ton adds 4g PAM), carry out abundant flocculation reaction.This step PH transfers to 3.5 ~ 4.5 can.
D, will pass through solidliquid mixture that above-mentioned reaction forms and send into first settling tank and carry out solid-liquid separation, clear liquid is conveyed into second reaction tank.
E, the solid of first settling tank is gone into the autoclave diaphragm plate-and-frame filter press by pump delivery carry out press filtration, and use stainless steel plant's mill floor flushing waste water that filter cake is carried out back flushing (washing water quantity washes by spent acid amount of inlet water 1:1).The collected press filtration water of this step also is conveyed into second reaction tank and mixes (PH is approximately 4.0) with d gained clear liquid.What this step filter press came out is useless mud, and contained liquid uses stainless steel plant's mill floor flushing waste water flushing, can effectively reduce the nickel loss, makes the further enrichment of nickel.
Used face of land wash-down water water quality such as following table:
Table 2 stainless steel plant mill floor flushing waste water water quality situation
Through after this step, the water quality situation such as the following table of second reaction tank institute water sampling:
The table 3 second reaction tank water quality situation
F, the lime that adds 16.7% (massfraction) in second reaction tank through automatic medicament feeding system are regulated pH to 9.5, add flocculation agent SEPIGEL 305 (PAM) (spent acid water inlet per ton adds 2g PAM), carry out abundant flocculation reaction.This step PH transfers to 9.0 ~ 10.0 can.
G, will pass through solidliquid mixture that f reaction forms and send into second settling tank and carry out solid-liquid separation.
H, the solid of second settling tank is gone into the autoclave diaphragm plate-and-frame filter press by pump delivery carry out press filtration; Obtain nickel mud; The heavy 21.11kg/t (referring to convert amount) of mud at over dry mud, the quality of nickel mud reaches 7.34% (over dry shale amount mark), and the recovery of nickel is 75.08%.The supernatant that pressing filtering liquid and g obtain merges, and regulates water outlet pH7.0 ~ 8.0 through adding sulfuric acid, realizes qualified discharge.
Experiment records each index value of water outlet and sees table 2:
Table 4 experiment records each index value of water outlet
The quality of nickel in the quality/water inlet of nickel in nickel recovery=nickel mud
Adopt this technical process, the processing cost of waste water is 79.10 yuan/ton, and processing cost is lower, and recovery value is big, and to this example, ton water reclaims nickel more than 1.5kg, brings benefits nearly 200 yuan.And water outlet each item index meets requirement up to standard fully.

Claims (3)

1. the recovery and treatment method of nickel in the waste acid from stainless steel acid washing is characterized in that may further comprise the steps:
(a) mixed solution of collection waste acid from stainless steel acid washing gets into first reaction tank, and using lime to regulate the pH value is 3.5 ~ 4.5, fully reacts;
(b) after the above-mentioned reaction, add ydrogen peroxide 50, reacted 0.5 ~ 1 hour;
(c) restock adds lime and regulates pH to 4.0 ~ 4.5, adds flocculation agent then and carries out abundant flocculation reaction;
(d) will pass through solidliquid mixture that above-mentioned reaction forms and send into first settling tank and carry out solid-liquid separation, clear liquid is conveyed into second reaction tank;
(e) with the mud process press filtration of first settling tank, with stainless steel plant's mill floor flushing waste water filter cake is carried out back flushing then, press filtration water is conveyed into second reaction tank to be mixed with (d) gained clear liquid;
(f) in second reaction tank, add lime adjusting pH to 9.0 ~ 10.0, add flocculation agent, carry out abundant flocculation reaction;
(g) will pass through solidliquid mixture that f reaction forms sends into second settling tank and carries out solid-liquid separation;
(h) with the solid press filtration of second settling tank, obtain nickel mud, pressing filtering liquid merges with the supernatant that (g) step obtains, and regulates water outlet pH7.0 ~ 8.0 through adding sulfuric acid, realizes qualified discharge.
2. method according to claim 1 is characterized in that: said flocculation agent is a SEPIGEL 305, and (c) add-on is that spent acid water inlet per ton adds the 4g SEPIGEL 305 in the step, and (f) spent acid water inlet per ton adds the 2g SEPIGEL 305 in the step.
3. method according to claim 1 is characterized in that: said press filtration adopts the autoclave diaphragm plate-and-frame filter press to carry out press filtration.
CN2012102770473A 2012-08-06 2012-08-06 Method for recycling and processing nickel in stainless steel pickling waste acid CN102757142A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105254076A (en) * 2015-11-16 2016-01-20 苏州南风优联环保工程有限公司 Simple and efficient nickel-containing wastewater treating process
CN105481145A (en) * 2016-01-11 2016-04-13 上海世渊环保科技有限公司 Stainless steel pickling waste water/liquid waste resourceful treatment method and system
CN106544528A (en) * 2016-10-27 2017-03-29 环境保护部华南环境科学研究所 A kind of method that metallic nickel is reclaimed from pickling waste waters
CN107585912A (en) * 2017-10-09 2018-01-16 中冶南方工程技术有限公司 Stainless steel nitration mixture acid pickle of acid washing pretreatment system and its technique
WO2018166480A1 (en) * 2017-03-14 2018-09-20 福建欣宇卫浴科技股份有限公司 Nickel-containing waste water processing system
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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CN101648757A (en) * 2009-09-01 2010-02-17 浙江大学 Recycling processing method for stainless steel processing process wastewater grading precipitation
CN101875518A (en) * 2010-07-01 2010-11-03 陈启松 Treatment method of stainless steel pickling waste water

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CN101456637A (en) * 2008-11-25 2009-06-17 天津大学 Treatment process and method of electroplating wastewater
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105254076A (en) * 2015-11-16 2016-01-20 苏州南风优联环保工程有限公司 Simple and efficient nickel-containing wastewater treating process
CN105481145A (en) * 2016-01-11 2016-04-13 上海世渊环保科技有限公司 Stainless steel pickling waste water/liquid waste resourceful treatment method and system
CN106544528A (en) * 2016-10-27 2017-03-29 环境保护部华南环境科学研究所 A kind of method that metallic nickel is reclaimed from pickling waste waters
CN106544528B (en) * 2016-10-27 2018-07-03 环境保护部华南环境科学研究所 A kind of method that metallic nickel is recycled from pickling waste waters
WO2018166480A1 (en) * 2017-03-14 2018-09-20 福建欣宇卫浴科技股份有限公司 Nickel-containing waste water processing system
CN107585912A (en) * 2017-10-09 2018-01-16 中冶南方工程技术有限公司 Stainless steel nitration mixture acid pickle of acid washing pretreatment system and its technique
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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