CN102167482A - Method for extracting Cr3+ and Fe3+ from tannery sludge - Google Patents

Method for extracting Cr3+ and Fe3+ from tannery sludge Download PDF

Info

Publication number
CN102167482A
CN102167482A CN 201110021450 CN201110021450A CN102167482A CN 102167482 A CN102167482 A CN 102167482A CN 201110021450 CN201110021450 CN 201110021450 CN 201110021450 A CN201110021450 A CN 201110021450A CN 102167482 A CN102167482 A CN 102167482A
Authority
CN
China
Prior art keywords
organic phase
leather
making
extracting
mud
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
Application number
CN 201110021450
Other languages
Chinese (zh)
Inventor
马宏瑞
花莉
李蕊
孙永会
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN 201110021450 priority Critical patent/CN102167482A/en
Publication of CN102167482A publication Critical patent/CN102167482A/en
Pending legal-status Critical Current

Links

Landscapes

  • Treatment Of Sludge (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a method for extracting Cr3+ and Fe3+ from tannery sludge. The method comprises the following steps of: during heap leaching, selecting dilute sulphuric acid to regulate the PH to be 1-5, performing static heap leaching for 1 to 7 hours in the solid-to-liquid ratio 1:50, and making metal ions in the sludge enter sulfuric acid solution to form heap leachate; extracting and separating the Fe3+ from the heap leachate by using 5 to 10 percent 2-ethylhexyl phosphoric acid-kerosene extraction system, regulating the pH to be 1.4-4.3, making a volume ratio of an organic phase to an aqueous phase 1:(0.5-2), fully stirring, and standing for demixing, wherein the lower layer is raffinate and the upper layer is a Fe3+-containing organic phase; performing reextraction on the Fe3+-containing organic phase by using 5-8mol/L hydrochloric acid to obtain the Fe3+; and performing selective precipitation separation of the metal ions in the raffinate by using NaOH, making Cr3+ effectively separated from other metal ions, and performing acidification to obtain the Cr3+.

Description

Cr in the leather-making mud 3+With Fe 3+Extracting process
Technical field
The present invention relates to a kind of treatment process of chromium-bearing sludge, Cr in particularly a kind of leather-making mud 3+With Fe 3+Extracting process.
Background technology
Big and the heavy metals exceeding standard of the chromium biochemical sludge amount that contains that tanning industry produces, the method for existing processing process hides chromium-bearing sludge mainly contains: alkaline precipitation, mud outward transport method, the bioleaching method, burning method, safety is filled up method etc.Wherein the alkali precipitation chromium-bearing sludge finally still will emit, and perhaps will carry out complicated neutral salt and remove technology, otherwise can influence chrome tanning reuse effect; Mud outward transport method, is utilized to reach certain year in limited time when it is converted to other raw materials owing to contain chromium in the leather-making mud once more, still can cause secondary pollution; The main process object of bioleaching method is the biochemical sludge that has accumulated a large amount of chromium, and its long processing period is subjected to the restriction of microorganism growth condition, is difficult to realize the industrial treatment Recycle design; The burning method final product is to contain the chromium ashes, and is the same with landfill, be two kinds of methods commonly used, but the recycling rate of mud is low; The security landfill method is not effectively rationally utilized resource, and existing external landfill requires more and more higher, and the difficulty of cost and final-period management thereof also can progressively increase.
In order to solve various metal separation problems, be suggested based on the solvent extraction and separation method of reversible complex reaction.Solvent extraction is the important method of the similar metal ion of separating property.Extraction system in extensive range, extract from the I A family of periodictable to VIIIB family.Along with the development of extraction chemistry at different extracted objects, the extraction agent kind that research is used is also the more.Wherein amine substance, organic phosphine are important complexing agents, comprise acid organic phosphine and neutral organic phosphine extraction agent extraction system, and at present, amine substance extraction agent, organic phosphine extraction agent have begun to be applied to industrial.
The dump leaching method is meant suitable position builds heap with ore on the face of land, adopt certain cloth liquid mode that leaching solution is distributed in the ore deposit heap, make leaching solution useful composition wherein of dissolving leaching selectively in the process of ore deposit heap diafiltration, and collect and soak the effusive leaching rich solution in heap bottom, extract the method that reclaims precious metal by methods such as extraction, electrodeposition.The widespread use in handling the low-grade gold resource of dump leaching technology.China's industrial scale reaches 100,000 t/a, and external year milling of ores amount is more than 1,500,000 t, and its smelting that is used for gold accounts for more than 10% of gold ultimate production.The dump leaching technology has become a major technique in the smelting of uranium ore, copper mine.
Summary of the invention
Technical problem to be solved by this invention provides Cr in a kind of leather-making mud 3+With Fe 3+Extracting process, the metal that will contain in the chromium leather-making mud by dump leaching effectively dissolves, and with organophosphorus solvent is extracted then, removes chrome tanning is produced very big dysgenic Fe 3+, the chromium in the heap leaching solution is carried out resource utilization reclaim, it is used for leather industry once more, make chromium reach the purpose of reuse.
For achieving the above object, the present invention also provides Cr in a kind of leather-making mud 3+With Fe 3+Extracting process, may further comprise the steps:
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 1～5, and the volume that static dump leaching makes dilute sulphuric acid is 1: 50 with the ratio of the quality of leather-making mud, and the time is 1～7h, and the metal ion in this moment mud enters in the dilution heat of sulfuric acid, forms heap leaching solution;
Step 2: 2-ethylhexyl phosphoric acid-kerosene extraction system of using 5-10% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 1.4～4.3, and the volume ratio of organic phase and water is 1: (0.5～2), fully stir the back standing demix, lower floor is a raffinate, the upper strata is for containing Fe 3+Organic phase;
Step 3: the hydrochloric acid of selecting 5～8mol/L for use is to containing Fe 3+Organic phase strip, obtain Fe 3+Use NaOH that the selective precipitation that raffinate carries out metal ion is separated, make Cr 3+Separate effectively with other metal ions, obtain Cr 3+
As the preferred embodiments of the present invention, in the described step 2, described extraction system and heap leaching solution stirred 3～5 minutes with the speed of 120～160r/min;
As the preferred embodiments of the present invention, in the described step 3, the PH of NaOH is 7～12;
As the preferred embodiments of the present invention, the organic phase of described reextraction is 5～6 with sour volume ratio mutually;
As the preferred embodiments of the present invention, the time of described reextraction is 20～60 minutes;
As the preferred embodiments of the present invention, during described reextraction, stirring velocity is 130～140r/min.
Cr in the leather-making mud of the present invention 3+With Fe 3+Extracting process have the following advantages at least:
(1) the present invention is by the method H of dump leaching 2SO 4Make the metal in the mud enter the acidic solution system, the metal ion in the leather-making mud is leached, dump leaching is respond well, Cr in the sludge residue 6+Do not detect Cr 3+Residual quantity be about 120mg/kg, be lower than the regulation of tanning industry mud discharging standard.
(2) the present invention uses chromium and iron and other metal ions in the organophosphorus extraction system separated sludge heap leaching solution with highly selective, and extraction back metal target remnants are low, and percentage extraction can reach 96%, and separation factor is 748, is convenient to Cr 3+Recycle, the chromium-bearing sludge heap leaching solution can satisfy environmental protection and industrial needs fully through two-stage extraction.
(3) raffinate uses NaOH to regulate the pH value, carries out the Metal Ion Selective Electrode precipitate and separate, can be with Cr 3+With Fe 3+, Na +, Ca 2+, K +Effectively separate etc. sulphate component.The resource utilization that helps chromium reclaims, and it is used for leather industry once more, makes chromium reach the purpose of reuse.
Embodiment
Embodiment 1
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 1, and it is 1: 50 that static dump leaching makes solid-to-liquid ratio, and the time is 3h, and the metal ion in the mud enters in the sulphuric acid soln at this moment, forms heap leaching solution.
Step 2: 2-ethylhexyl phosphoric acid (the D2EHPA)-kerosene extraction system with 5% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 2.0, and the volume ratio of organic phase and water is 1, and the control churning time is 3min, and stirring velocity is 130r/min, and settling time is 7.5min, and behind the standing demix, lower floor is a raffinate, and the upper strata is for containing Fe 3+Organic phase.
Step 3: to containing Fe 3+Organic phase strip, strip and to select the hydrochloric acid of 5mol/L for use, stirring velocity is 130r/min, the organic phase of reextraction is 5 with sour volume ratio mutually, the back extraction time is 20min, can obtain Fe after the reextraction 3+, then using PH is that 8.5 NaOH separates the selective precipitation that raffinate carries out metal ion, makes Cr 3+Separate effectively with other metal ions, obtain Cr 3+
Embodiment 2
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 2, and it is 1: 50 that static dump leaching makes solid-to-liquid ratio, and the time is 1h, and the metal ion in the mud enters in the sulphuric acid soln at this moment, forms heap leaching solution.
Step 2: 2-ethylhexyl phosphoric acid (the D2EHPA)-kerosene extraction system with 5% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 3.5, and the volume ratio of organic phase and water is 1: 2, and the control churning time is 5min, and stirring velocity is 140r/min, and settling time is 3min, and behind the standing demix, lower floor is a raffinate, and the upper strata is for containing Fe 3+Organic phase.
Step 3: to containing Fe 3+Organic phase strip, strip and to select the hydrochloric acid of 8mol/L for use, stirring velocity is 130r/min, the organic phase of reextraction and sour volume ratio 6 mutually, the back extraction time is 30min, can obtain Fe after the reextraction 3+, then using PH is that 6.5 NaOH separates the selective precipitation that raffinate carries out metal ion, makes Cr 3+Separate effectively with other metal ions, obtain Cr 3+
Embodiment 3
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 3, and it is 1: 50 that static dump leaching makes solid-to-liquid ratio, and the time is 5h, and the metal ion in the mud enters in the sulphuric acid soln at this moment, forms heap leaching solution.
Step 2: 2-ethylhexyl phosphoric acid (the D2EHPA)-kerosene extraction system with 10% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 1.4, and the volume ratio of organic phase and water is 2: 1, and the control churning time is 5min, and stirring velocity is 120r/min, and settling time is 8min, and behind the standing demix, lower floor is a raffinate, and the upper strata is for containing Fe 3+Organic phase.
Step 3: to containing Fe 3+Organic phase strip, strip and to select the hydrochloric acid of 5mol/L for use, stirring velocity is 140r/min, the reextraction organic phase is 6 with sour volume ratio mutually, the back extraction time is 60min, can obtain Fe after the reextraction 3+, then using PH is that 9.5 NaOH carries out the Metal Ion Selective Electrode precipitate and separate to raffinate, makes Cr 3+Separate effectively with other metal ions, obtain Cr 3+
Embodiment 4
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 5, and it is 1: 50 that static dump leaching makes solid-to-liquid ratio, and the time is 7h, and the metal ion in the mud enters in the sulphuric acid soln at this moment, forms heap leaching solution.
Step 2: 2-ethylhexyl phosphoric acid (the D2EHPA)-kerosene extraction system with 10% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 4.3, and the volume ratio of organic phase and water is 1: 1.5, and the control churning time is 4min, and stirring velocity is 160r/min, and settling time is 5min, and behind the standing demix, lower floor is a raffinate, and the upper strata is for containing Fe 3+Organic phase.
Step 3: to containing Fe 3+Organic phase strip, strip and to select the hydrochloric acid of 6mol/L for use, stirring velocity is 135r/min, the reextraction organic phase is 5.5 with sour volume ratio mutually, the back extraction time is 45min, can obtain Fe after the reextraction 3+, then using PH is that 12 NaOH carries out the Metal Ion Selective Electrode precipitate and separate to raffinate, makes Cr 3+Separate effectively with other metal ions, obtain Cr 3+
Solid in the solid-to-liquid ratio described in the step 1 of the present invention refers to leather-making mud, and liquid refers to sulfuric acid; 2-ethylhexyl phosphoric acid (D2EHPA)-kerosene extraction system of described 5% or 10% refers to that the volume ratio that D2EHPA accounts for kerosene is 5% or 10%.
Utilize dump leaching of the present invention-extracting and separating dump leaching respond well, Cr in the sludge residue 6+Do not detect Cr 3+Residual quantity be about 120mg/kg, be lower than the regulation of tanning industry mud discharging standard.The percentage extraction of heap leaching solution can reach 96%, and separation factor is 748, is convenient to Cr 3+Recycle, the chromium-bearing sludge heap leaching solution can satisfy environmental protection and industrial needs fully through two-stage extraction.
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.

Claims (6)

1. Cr in the leather-making mud 3+With Fe 3+Extracting process, it is characterized in that: may further comprise the steps:
Step 1: select dilute sulphuric acid during dump leaching, regulating its PH is 1～5, and the volume that static dump leaching makes dilute sulphuric acid is 1: 50 with the ratio of the quality of leather-making mud, and the time is 1～7h, and the metal ion in this moment mud enters in the dilution heat of sulfuric acid, forms heap leaching solution;
Step 2: 2-ethylhexyl phosphoric acid-kerosene extraction system of using 5-10% is to the Fe in the heap leaching solution 3+Carry out extracting and separating, regulating PH is 1.4～4.3, and the volume ratio of organic phase and water is 1: (0.5～2), fully stir the back standing demix, lower floor is a raffinate, the upper strata is for containing Fe 3+Organic phase;
Step 3: the hydrochloric acid of selecting 5～8mol/L for use is to containing Fe 3+Organic phase strip, obtain Fe 3+Use NaOH that the selective precipitation that raffinate carries out metal ion is separated, make Cr 3+Separate effectively with other metal ions, obtain Cr 3+
2. Cr in the leather-making mud as claimed in claim 1 3+With Fe 3+Extracting process, it is characterized in that: in the described step 2, described extraction system and heap leaching solution stirred 3～5 minutes with the speed of 120～160r/min.
3. Cr in the leather-making mud as claimed in claim 1 3+With Fe 3+Extracting process, it is characterized in that: in the described step 3, the PH of NaOH is 7～12.
4. as Cr in claim 1 or the 3 described leather-making muds 3+With Fe 3+Extracting process, it is characterized in that: the organic phase of described reextraction is 5～6 with sour volume ratio mutually.
5. Cr in the leather-making mud as claimed in claim 4 3+With Fe 3+Extracting process, it is characterized in that: the time of described reextraction is 20～60 minutes.
6. Cr in the leather-making mud as claimed in claim 4 3+With Fe 3+Extracting process, it is characterized in that: during described reextraction, stirring velocity is 130～140r/min.
CN 201110021450 2011-01-19 2011-01-19 Method for extracting Cr3+ and Fe3+ from tannery sludge Pending CN102167482A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110021450 CN102167482A (en) 2011-01-19 2011-01-19 Method for extracting Cr3+ and Fe3+ from tannery sludge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110021450 CN102167482A (en) 2011-01-19 2011-01-19 Method for extracting Cr3+ and Fe3+ from tannery sludge

Publications (1)

Publication Number Publication Date
CN102167482A true CN102167482A (en) 2011-08-31

Family

ID=44488836

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110021450 Pending CN102167482A (en) 2011-01-19 2011-01-19 Method for extracting Cr3+ and Fe3+ from tannery sludge

Country Status (1)

Country Link
CN (1) CN102167482A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102363820A (en) * 2011-09-22 2012-02-29 兄弟科技股份有限公司 Reutilization method of chromium-containing leather production sludge
CN104944719A (en) * 2015-06-09 2015-09-30 武汉钢铁(集团)公司 Method for extracting and recovering chromium from cold rolling chromium sludge

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497942A (en) * 2009-03-11 2009-08-05 南京农业大学 Biological leaching-solvent extraction-electrodeposition recovering method for heavy metal copper in sludge
CN101643243A (en) * 2009-08-14 2010-02-10 扬州宁达贵金属有限公司 Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497942A (en) * 2009-03-11 2009-08-05 南京农业大学 Biological leaching-solvent extraction-electrodeposition recovering method for heavy metal copper in sludge
CN101643243A (en) * 2009-08-14 2010-02-10 扬州宁达贵金属有限公司 Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《中国皮革》 20080430 孙永会，等人 制革污泥中铁和铬的连续萃取分离工艺研究 第50～53页 1-6 第37卷, 第7期 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102363820A (en) * 2011-09-22 2012-02-29 兄弟科技股份有限公司 Reutilization method of chromium-containing leather production sludge
CN102363820B (en) * 2011-09-22 2013-09-18 兄弟科技股份有限公司 Reutilization method of chromium-containing leather production sludge
CN104944719A (en) * 2015-06-09 2015-09-30 武汉钢铁(集团)公司 Method for extracting and recovering chromium from cold rolling chromium sludge
CN104944719B (en) * 2015-06-09 2017-03-29 武汉钢铁(集团)公司 The method for reclaiming chromium is extracted from cold rolling chromium mud

Similar Documents

Publication Publication Date Title
CN101838736B (en) Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
CN101660054B (en) Method for extracting metal indium from waste residues generated from lead and zinc smelting
AU2013351773B2 (en) Monazite ballast separation and recovery method
CN102191391B (en) Method for extracting germanium from high-impurity low-grade complex zinc oxide powder
CN105274342B (en) A kind of technique for producing monohydrate zinc sulphate using spent acid, zinc slag
CN102244309B (en) Method for recovering lithium from lithium power battery of electric automobile
CN103667720B (en) Method for recovering zinc, indium, iron, and lead from high-iron zinc oxide mixture smelted with zinc
CN102796876B (en) Method for extracting scandium oxide from titanium slag chloride waste
CN102312083A (en) Method for extracting zinc indium and recovering iron from high-iron high indium zinc concentrate
CN102876887B (en) Method for comprehensively recycling metal from laterite-nickel ore leaching agent
CN103468949B (en) A kind for the treatment of process containing scandium nickel hydroxide cobalt
CN102560116B (en) Method for recovering manganese and vanadium from titanium white waste acid, manganese slag and vanadium-containing steel slag
CN101407355B (en) Method for comprehensively utilizing iron vitriol dreg of yellow sodium
CN103468948B (en) Method for comprehensive recycling of metals from scandium-containing cobalt nickel hydroxide
CN106868307A (en) A kind of pyrite cinder arsenic removal is enriched with the comprehensive utilization process of gold and silver
CN104745821B (en) Method for recovering nickel and copper metals in acid pickling sludge
CN103243349A (en) Comprehensive zinc hydrometallurgy recovery system technique
CN108754148A (en) A kind of processing method of cupric, manganese, cobalt, zinc, nickel heavy metal waste slag recycling
CN104046786A (en) Method for recovering metals from vanadium slag
CN103981369B (en) Comprehensive recovery process for multiple metals in arsenic-containing soot
CN103952562A (en) Comprehensive utilization method of iron vitriol slag
CN104928464A (en) Method for extracting valuable metal in vanadium containing material by microwave heating preprocessing
CN103540766B (en) High fluorine, chlorinity zinc oxide material reclaim indium-raffinate fluorine removal, chlorine, arsenic technique
CN109913658A (en) A method of the pickle liquor of smelting smoke dust containing arsenical copper arsenic, copper, Zn-Ca series separation and recycling
CN105110300A (en) Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20110831