CN113955838B - Co-treatment method for electroplating waste residue and chromium-containing heavy metal ion waste liquid - Google Patents

Co-treatment method for electroplating waste residue and chromium-containing heavy metal ion waste liquid Download PDF

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CN113955838B
CN113955838B CN202111116548.9A CN202111116548A CN113955838B CN 113955838 B CN113955838 B CN 113955838B CN 202111116548 A CN202111116548 A CN 202111116548A CN 113955838 B CN113955838 B CN 113955838B
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electroplating
waste
chromium
waste liquid
waste residue
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CN113955838A (en
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宋宇飞
李佳欣
赵宇飞
李绍泉
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Removal Of Specific Substances (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a co-treatment method of electroplating waste residue and chromium-containing heavy metal ion waste liquid. The invention uses the electroplating waste residue of the electroplating factory as the mineralizer of the chrome tanning waste liquid of the leather factory, and oxides and hydroxides in the electroplating waste residue adsorb chromium ions to be mineralized and converted into chromium-containing hydrotalcite, so that the obtained chromium-containing hydrotalcite has the ultra-stable mineralization effect, does not easily dissolve chromium ions and does not cause secondary pollution. The method of the invention can effectively treat the environmental pollution problem caused by chrome tanning waste liquid and realize the reutilization of electroplating waste residues, the filtered supernatant can be used for the subsequent pickling process of leather, and mineralized solid products can effectively adsorb organic dyes such as congo red, evan blue and the like, thereby realizing a green route for treating waste with waste. The method has the advantages of mild reaction conditions, simple and convenient operation, simple process, no need of adding alkali, atom economy and low cost, and can be applied to electroplating plants and leather plants on a large scale.

Description

Co-treatment method for electroplating waste residue and chromium-containing heavy metal ion waste liquid
Technical Field
The invention belongs to the technical field of waste liquid and waste residue treatment, and particularly relates to a method for co-treating electroplating waste residues and chromium-containing heavy metal ion waste liquid.
Background
Currently, the traditional method for removing trivalent chromium heavy metals is to add alkali (such as NaOH) to form Cr (OH) by chromium ions 3 Precipitating, and filtering to separate. The method has the defects of slower reaction speed, large precipitation amount and high hardness of the effluent. In addition, due to the formation of Cr (OH) 3 The particle size of the particles is small, and the filtering is not easy; and, the pH of the waste liquid after alkali treatment is too high to be directly utilized or discharged, and must be treated again. Therefore, it is important to develop an economical, efficient, convenient and environment-friendly method for treating waste leather-making liquid.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a method for co-processing electroplating waste residues and chromium-containing heavy metal ion waste liquid.
The co-treatment method of the electroplating waste residue and the chromium-containing heavy metal waste liquid comprises the following steps: adding the electroplating waste residue into the chromium-containing heavy metal ion waste liquid, and reacting for 2-48h at 20-80 ℃; and mineralizing and precipitating trivalent chromium ions in the waste liquid by using metal hydroxide and metal oxide in the electroplating waste residue.
After the reaction is finished, filtering, and continuously using the obtained supernatant for tanning production water; the obtained solid precipitate is used for adsorbing and removing the organic dye.
The metal hydroxide and metal oxide in the electroplating waste residue comprise CuO, znO, niO, mgO, cdO, coO, cu (OH) 2 、Mg(OH) 2 、Zn(OH) 2 、Ni(OH) 2 One or more of them.
The chromium-containing heavy metal ion waste liquid is an acidic waste liquid.
The addition amount of the electroplating waste residue is based on that the solution becomes clear and colorless after the reaction and is nearly neutral.
The invention uses the electroplating waste residue of the electroplating factory as the mineralizer of the chrome tanning waste liquid of the leather factory, and oxides and hydroxides in the electroplating waste residue adsorb chromium ions to be mineralized and converted into chromium-containing hydrotalcite, so that the obtained chromium-containing hydrotalcite has the ultra-stable mineralization effect, does not easily dissolve chromium ions and does not cause secondary pollution. The method of the invention can effectively treat the environmental pollution problem caused by chrome tanning waste liquid and realize the reutilization of electroplating waste residues, the filtered supernatant can be used for the subsequent pickling process of leather, and mineralized solid products can effectively adsorb organic dyes such as congo red, evan blue and the like, thereby realizing a green route for treating waste with waste. The method has the advantages of mild reaction conditions, simple and convenient operation, simple process, no need of adding alkali, atom economy and low cost, and can be applied to electroplating plants and leather plants on a large scale.
Drawings
FIG. 1 is an XRD pattern of a solid product obtained after treating chrome tanning waste for 12 hours with Zn plating waste residue in example 1.
FIG. 2 is a graph showing the color change of the supernatant liquid before and after treating chrome tanning waste with Zn plating waste in example 1.
FIG. 3 is a graph showing the performance of solid precipitate obtained after treating chrome tanning waste with Zn plating waste residue as Congo Red (Congo Red) adsorbent in example 1, wherein a is an ultraviolet-visible spectrum-time graph of the residual Congo Red in the solution; b is a concentration-time diagram of the rest Congo red in the solution; c is an adsorption quantity-time chart (Congo red initial concentration 20 mg/L, congo red solution 50mL, adsorbent 20 mg).
Detailed Description
[ example 1 ]
Treatment of Cr in chrome tanning waste liquid by adopting Zn electroplating waste residue 3+ Ion: collecting chrome tanning waste liquid, filtering to remove solid skin slag, wherein Cr 3+ The ion concentration is 1300mg/L, and the pH value of the waste liquid is 5; 1gZn electroplating waste residue is added into 40mL of waste liquid, and the reaction is carried out for 12 hours at 25 ℃.
After the reaction is completed, filtering to obtain supernatant which is clarified, changing from dark green to colorless (shown in figure 2), and testing to obtain supernatant with neutral pH value 3+ Concentration of<The removal efficiency reaches 99.92% at 1mg/L, and the method can be continuously used for tanning production water. The solid precipitate obtained by filtration, the mineralized product obtained by treating chrome tanning waste liquid with Zn electroplating waste residue can be seen from XRD in figure 1, and characteristic peaks such as (003), (006) and (110) of LDH are formed. The solid mineralized product was used for organic dye adsorption removal. As can be seen from fig. 3, the mineralized solid product was excellent in adsorbing the organic dye congo red.
[ example 2 ]
Treatment of Cr in chrome tanning waste liquid by adopting Cu electroplating waste residue 3+ Ion: treatment of Cr in chrome tanning waste liquid by adopting Cu electroplating waste residue 3+ Ion: collecting chrome tanning waste liquid, filtering to remove solid skin slag, wherein Cr 3+ The ion concentration is 1300 and mg/L,the pH value of the waste liquid is 5; adding 1g of Cu electroplating waste residue into 40mL of waste liquid; the reaction was carried out at 35℃for 12h. After the reaction is finished, filtering, and continuously using the obtained supernatant for tanning production water; the obtained solid precipitate is used for adsorbing and removing the organic dye.
[ example 3 ]
Treatment of Cr in chrome tanning waste liquid by adopting Ni electroplating waste residue 3+ Ion: treatment of Cr in chrome tanning waste liquid by adopting Zn electroplating waste residue 3+ Ion: collecting chrome tanning waste liquid, filtering to remove solid skin slag, wherein Cr 3+ The ion concentration is 1300mg/L, and the pH value of the waste liquid is 5; adding 1gNi electroplating waste residues into 40mL of waste liquid; the reaction was carried out at 35℃for 12h. After the reaction is finished, filtering, and continuously using the obtained supernatant for tanning production water; the obtained solid precipitate is used for adsorbing and removing the organic dye.
[ example 4 ]
Treatment of Cr in chrome tanning waste liquid by Co electroplating waste residue 3+ Ion: treatment of Cr in chrome tanning waste liquid by adopting Zn electroplating waste residue 3+ Ion: collecting chrome tanning waste liquid, filtering to remove solid skin slag, wherein Cr 3+ The ion concentration is 1300mg/L, and the pH value of the waste liquid is 5; adding 1g of Co electroplating waste residue into 40mL of waste liquid; the reaction was carried out at 35℃for 12h. After the reaction is finished, filtering, and continuously using the obtained supernatant for tanning production water; the obtained solid precipitate is used for adsorbing and removing the organic dye.
[ example 5 ]
Treatment of Cr in chrome tanning waste liquid by adopting Cd electroplating waste residue 3+ Ion: treatment of Cr in chrome tanning waste liquid by adopting Zn electroplating waste residue 3+ Ion: collecting chrome tanning waste liquid, filtering to remove solid skin slag, wherein Cr 3+ The ion concentration is 1300mg/L, and the pH value of the waste liquid is 5; adding 1g of Cd electroplating waste residue into 40mL of waste liquid; the reaction was carried out at 25℃for 12h. After the reaction is finished, filtering, and continuously using the obtained supernatant for tanning production water; the obtained solid precipitate is used for adsorbing and removing the organic dye.

Claims (5)

1. A method for co-processing electroplating waste residue and chromium-containing heavy metal waste liquid is characterized by comprising the following specific steps: adding the electroplating waste residue into chromium-containing heavy goldReacting in ion waste liquid at 20-80 deg.c for 2-48 hr; mineralizing and precipitating trivalent chromium ions in the waste liquid by using metal hydroxide and metal oxide in the electroplating waste residue; the metal hydroxide and metal oxide in the electroplating waste residue comprise CuO, znO, niO, mgO, cdO, coO, cu (OH) 2 、Mg(OH) 2 、Zn(OH) 2 、Ni(OH) 2 One or more of them.
2. The method according to claim 1, wherein after completion of the reaction, the supernatant obtained is filtered and is further used for tanning process water.
3. The method according to claim 1, wherein after completion of the reaction, the obtained solid precipitate is filtered for adsorption removal of the organic dye.
4. The method of claim 1, wherein the waste solution containing chromium heavy metal ions is an acidic waste solution.
5. The method according to claim 1, wherein the amount of the electroplating waste is based on the fact that the solution becomes clear and colorless after the reaction and is nearly neutral.
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US4204973A (en) * 1974-08-06 1980-05-27 John Cunningham Treatment composition for use in chrome removal and recovery
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US5106508A (en) * 1990-09-26 1992-04-21 Klaus Schwitzgebel Integrated process for cyanide and heavy metal removal from plating process waste streams
CN101407365A (en) * 2007-10-10 2009-04-15 天津科技大学 Method for processing chroming waste liquor
CN103695970A (en) * 2013-12-17 2014-04-02 陕西科技大学 Method for processing chrome-containing tanned wastewater and recycling chrome metal
CN104609683A (en) * 2014-12-12 2015-05-13 浙江工商大学 Chrome tanning sludge heavy metal chromium regeneration method

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JPS605285A (en) * 1983-06-21 1985-01-11 Nikko Guurudo Fuoiru Kk Treatment of copper-containing waste water
US5106508A (en) * 1990-09-26 1992-04-21 Klaus Schwitzgebel Integrated process for cyanide and heavy metal removal from plating process waste streams
CN101407365A (en) * 2007-10-10 2009-04-15 天津科技大学 Method for processing chroming waste liquor
CN103695970A (en) * 2013-12-17 2014-04-02 陕西科技大学 Method for processing chrome-containing tanned wastewater and recycling chrome metal
CN104609683A (en) * 2014-12-12 2015-05-13 浙江工商大学 Chrome tanning sludge heavy metal chromium regeneration method

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