CN104609683A - Chrome tanning sludge heavy metal chromium regeneration method - Google Patents

Chrome tanning sludge heavy metal chromium regeneration method Download PDF

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CN104609683A
CN104609683A CN201410766191.2A CN201410766191A CN104609683A CN 104609683 A CN104609683 A CN 104609683A CN 201410766191 A CN201410766191 A CN 201410766191A CN 104609683 A CN104609683 A CN 104609683A
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chromium
chrome tanning
hydrochloric acid
mud
leach liquor
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CN104609683B (en
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何闪英
张熹
杨春平
吕黎
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Zhejiang Gongshang University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The invention discloses a chrome tanning sludge heavy metal chromium regeneration method, and the method includes extraction of chrome tanning sludge with hydrochloric acid, reduction of Cr<6 +> in the leaching solution by use of sodium bisulfate, adsorption of Cr<3 +> by use of 732 sodium type cation exchange resin, and desorption of the Cr<3 +> on the resin by use of hydrochloric acid or sulfuric acid. According to the method, the hydrochloric acid as an acid leaching extraction agent is cheap, and can effectively leach metal chromium in the chrome tanning sludge, the chromium efficiency is more than 80%; the sodium 732 type cation exchange resin as an adsorbent can preferentially adsorb the Cr<3 +> in the leaching solution, the adsorption and recovery rate can reach up to 96.1%, and the efficient chromium separation and purification can be realized. At the same time, the resin can be recycled by regeneration, the processing cost can be effectively reduced; by desorption of the Cr<3 +> by use of hydrochloric acid or sulfuric acid, corresponding chromium chloride solution and chromic sulfate solution products can be obtained, and the chromium chloride solution and chromic sulfate solution products can be can used in trivalent chromium electroplating industry.

Description

A kind of renovation process of chrome tanning Heavy Metals in Sludge chromium
Technical field
The present invention relates to environmental technology field, particularly relate to a kind of renovation process of chrome tanning Heavy Metals in Sludge chromium.
Background technology
Leather making process be mainly divided into tan before beam house, tanning process and wet processing workshop section, wherein leather tanning becomes operation steps main in leather making process, possess and effectively avoid environmental factors, as features such as microbiological deterioration, heat effect and moistures, material impact is caused to the quality of leather, and a large amount of chromic salts and basic chromium sulfate are exactly most important raw material in leather tanning process.Chrome tanning mud is the mud that the waste water of process hides tanning process generation is formed through alkali precipitation, and in tannery, the specific absorption of rawhide to chrome tanning agent only has about 55% usually, and remaining chrome tanning agent is arranged outward with waste water, and therefore chrome tanning mud has the feature of high-chromium amount.
Heavy metal chromium has the feature of high stable, difficult degradation, not easily removes from environment, can produce toxic action to organism.Chromium is a kind of toxic metal, is one of dangerous pollutant of EPA confirmation; China will be classified as Hazardous Waste List containing chromium refuse, and chromium mainly contains the two kinds of state of oxidation: Cr 3+and Cr 6+.Cr 3+the essential element in the metabolic process of glucose, lipid and protein, and Cr 6+then be considered to, to biosystem, there is toxic action.If there is strong oxidizer in soil and water, Cr 3+very easily be oxidized to Cr 6+.
In traditional treatment process, be process together with the waste that waste and other workshop sections that tanning process produces produced, treatment process mainly comprises: landfill, Ocean dumping, burning or immobilization.But the process of traditional method certainly will cause a large amount of heavy metal Crs to enter in physical environment, and then enters food chain, threaten the life and health of people.In addition, if the mud mixing of each workshop section to be carried out the resource utilization of chromium-bearing sludge, then also can increase the total amount of lignin-sludge and the chromium concn reduced in mud, thus cause the decline of resource utilization efficiency and the raising of cost, therefore, the present invention is directed in leather making process the regeneration that the chrome tanning mud that can produce Cr pollution carries out heavy metal.
At present, the conventional recovery method of chromate waste water comprises: extraction process, electrowinning method, chemical precipitation method, bioleaching and ion exchange method etc.
Solvent extraction utilizes component in system to have different solubleness to carry out the unit operation of separating mixture in a solvent, namely utilize the difference of compound solubleness or partition ratio in the solvent of two kinds immiscible (or slightly solubles), make compound in a kind of solvent, transfer to method another kind of solvent.El-Hefny (Comparison of liquid-liquid extraction of Cr (VI) from acidic and alkaline solutions by two different amine extractants [J] .Separation and Purification Technology, 2009,67 (1): 44-49) utilize amine extractant Aliquat 336 and Alamine 336 from H 2sO 4cr is extracted with in alkaline media 6+, investigate extractant concentration, acid/alkaline media concentration, the factors such as metallic solution concentration, the aqueous solution and organic solution volume ratio that are extracted to the impact of extraction efficiency, result shows, in the medium of bronsted lowry acids and bases bronsted lowry, and Cr 6+extraction efficiency reaches 95% and 98% respectively.But extraction process requires very high to the selectivity of extraction agent, both needed to possess good selectivity and be easy to again reclaim and regeneration, also require that it has certain thermal stability and chemical stability, in addition, toxicity and viscosity also have certain requirement simultaneously.
Electrowinning by galvanic action, the precious metal ion in waste liquid is reduced to metal under certain condition, is deposited on the method that negative electrode reclaims.The electromotive force that metal ion in usual solution is separated out is different, because can, by changing the size of impressed voltage, make metal ion substep separate out with the object reaching separation.But electrowinning method is high to voltage request, consume electric power simultaneously.
Chemical precipitation method first by carrying out pre-treatment to leather-making mud, makes Cr enter in solution usually, and now, Cr is mainly with Cr 3+form exist, the pH value of regulator solution subsequently, makes alkali and Cr 3+there is chemical reaction, form Cr (OH) 3precipitation, thus reach Cr 3+the object be separated with other interfering ions.But chemical precipitation method needs at substantial acid, alkali, easily to environment.
Bioleaching is the direct effect of some microorganisms utilizing occurring in nature or the indirect action of its meta-bolites, produce oxidation, reduction, complexing, absorption or solvency action, some insoluble composition in solid phase (as heavy metal, sulphur and other metal) is separated lixiviate a kind of technology out.But the method needs acclimation sludge, experimental period is long, there is unstable, and needs post-order process to carry out the extraction of chromium slag.
Authorization Notice No. be CN103011537B patent document discloses a kind of process containing trivalent chromium mud and reclaim the method for heavy metal, the method is analyzed component concentration in chromium-bearing sludge, and then dilution chromium-bearing sludge, and after ammonium salt and ammonia treatment, alkaline purification, acid treatment, obtain pigment-level chromic oxide, metal simple-substance or product.The chromium that the method reclaims may be used in the industries such as iron and steel, plating and tanning.
Authorization Notice No. be CN102363820B patent document discloses a kind of reutilization method of chromium-containing leather production sludge, the method comprises process hides chromium-bearing sludge acid dissolve, then is hydrolyzed, then filter and by filtrate for the production of each tanning agent; Also comprise by filter residue for the production of containing chromium retanning agent, the problem of the filter residue produced during to solve the reuse of process hides chromium-bearing sludge contaminate environment again.
Application publication number is that patent document discloses of CN103351089A a kind ofly utilizes the rich chromium mud preparation of process hides from the method for alkalization chrome tanning agent, the method carries out acidifying, filtration, composite and dust to rich chromium mud, add again after basifier mixing for the production of the chrome tanning powder that certainly alkalizes, the method achieve the recycle of heavy metal chromium at leather industry, thus eliminate the pollution of secondary chromium.But aforesaid method still exists the low problem of chromium regeneration rate, especially for the chrome tanning mud of chromium rich content, how to improve the regeneration rate of chromium in mud, still require study and solve.
At present, chromium is widely used in process hides, electrodeposited chromium, printing and dyeing industry, and the recycling realizing chromium can not only alleviate the problem of chromium resource scarcity, and is conducive to solving heavy metal pollution problem.
In prior art, the solid-to-liquid ratio of electroplating sludge and hydrochloric acid need up to 200g/L, the chromium leaching yield that guarantee is higher.And because organic content is higher in chrome tanning mud of the present invention, sludge density is little, during with acid-respons, if solid-to-liquid ratio is too high, solution is easily in cement shape, and not easily realize solid-liquid separation, mud dissolution rate can reduce.During HCl extract, the solid-to-liquid ratio of chrome tanning mud and hydrochloric acid is 2 ~ 20g/L, is preferably 5 ~ 15g/L, more preferably, and 10g/L.
The temperature and time of lixiviate is conducive to the leaching yield improving chromium metal.As preferably, the temperature of described lixiviate is 20 ~ 80 DEG C, and the time is 0.5 ~ 8h, and more preferably, temperature is 30 ~ 50 DEG C, and the time is 0.5 ~ 1.5h.
In HCl extract process, the concentration of described hydrochloric acid is 0.5 ~ 7mol/L, preferably 4.5 ~ 5.5mol/L, more preferably 5mol/L.When concentration of hydrochloric acid is increased to 7mol/L by 0.5mol/L, hydrochloric acid improves constantly to 85% by 80% the leaching yield of chromium, and is tending towards constant.
For improving the leaching yield of chromium metal, also chrome tanning mud can be carried out secondary lixiviate, merge the leach liquor obtained, the leaching efficiency of final chromium metal can up to 91%.
Except Cr in the vat liquor obtained in step (1) 3+also there is a certain amount of Cr 6+, can Cr be affected 3+regeneration, so reductive agent need be added in vat liquor, by the Cr in leach liquor 6+be reduced to Cr 3+; Described reductive agent also can adopt Na 2s 2o 3or Fe 2+, but in order to not add metallic cation outside reaction system or reductive agent, the present invention selects NaHSO 3, reaction formula is as follows:
3HSO 3 -+Cr 2O 7 2-+5H +→2Cr 3++38O 4 2-+4H 2O
As preferably, Cr in described sodium bisulfite and leach liquor 6+mass ratio be 3 ~ 6: 1; Preferably 5: 1, now, Cr in leach liquor 6+concentration be less than 0.2mg/L, meet the requirement of " process hides and fur manufacturing industrial water pollution thing emission standard GB 30486-2013 ".
Along with the increase of 732 sodium form Zeo-karb quality, this resin can not only provide more active adsorption site to adsorb Cr in leach liquor 3+, the particle total surface area of resin can also be expanded; But along with the increase of resin quality, resin starts adsorbing contaminant metal ion gradually, as Ca 2+, Mg 2+, so, as preferably, Cr in described 732 sodium form Zeo-karbs and leach liquor 3+mass ratio be 10 ~ 70: 1.
As preferably, in step (3), the temperature of adsorption process is 30 ~ 50 DEG C, and the time is 5 ~ 120min.In adsorption process, the pH value of leach liquor is 0.4 ~ 3.When the pH value of leach liquor is less than 3, the chromium in leach liquor is mainly with Cr 3+form exists, and easily by resin absorption, the main reaction occurred is: as pH>4, the chromium in leach liquor starts to form Cr (OH) 2 +, Cr 3(OH) 4 5+, Cr 2(OH) 2 4+, relative to Cr 3+, these ions, not easily by resin absorption, can affect resin to Cr 3+the absorption rate of recovery.
The desorption process of step (3) carries out at normal temperatures, with 200rpm oscillatory reaction 0.5 ~ 2h.What obtain contains Cr 3+hydrochloric acid or sulphuric acid soln can through evaporation, the concentrated Cr obtained needed for electrodeposited chromium 3+concentration range, thus plating industry can be applied to.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention forms " acidleach-ion-exchange-chromic salts product preparation " technology, the regeneration of effective implemention chrome tanning Heavy Metals in Sludge chromium, simple to operate, with low cost, realizes the recycle of chromium between industry.
(2) the present invention adopts hydrochloric acid as acid leaching extraction agent, low price, can chromium metal effectively in lixiviate chrome tanning mud, and chromium leaching efficiency is more than 80%;
(3) the present invention selects 732 sodium form Zeo-karbs as sorbent material, and this sorbent material can Cr in Preferential adsorption vat liquor 3+, the absorption rate of recovery, up to 96.1%, achieves high efficiency separation and the purification of chromium, and meanwhile, this resin realizes recycle by regeneration, effectively reduces processing cost;
(4) the present invention utilizes sulfuric acid, hydrochloric acid desorb load C r 3+resin, can prepare the corresponding product of chromium chloride solution and chromium sulfate solution, this product can be applied to trivalent chromium plating industry.
Summary of the invention
The invention provides a kind of renovation process of chrome tanning Heavy Metals in Sludge chromium, the heavy metal chromium in the method energy highly efficient regeneration chrome tanning mud, technique be simple, environmental protection.
A renovation process for chrome tanning Heavy Metals in Sludge chromium, comprising:
(1) chrome tanning mud is placed in hydrochloric acid lixiviate, obtains leach liquor;
(2) take sodium bisulfite as reductive agent, by the Cr in leach liquor 6+be reduced to Cr 3+;
(3) 732 sodium form cationic exchange resin adsorption Cr are adopted 3+, add hydrochloric acid or sulfuric acid desorb Cr 3+after, obtain containing Cr 3+hydrochloric acid or sulphuric acid soln.
Through experimental verification, adopt the chromium in pickling process extraction chrome tanning mud, leaching yield can be subject to the impact of sour kind, and wherein, the extracting effect of hydrochloric acid is best.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of Sludge Surface before and after chrome tanning mud HCl extract of the present invention;
Chrome tanning Sludge Surface before (a) HCl extract, the chrome tanning Sludge Surface after (b) HCl extract.
Embodiment
One, mud sample pre-treatment
Take from the chrome tanning mud of Wenzhou tannery sewage treatment station, dewatered sludge, light weight, in block.Dewatered sludge fragmentation is removed wherein impurity also again to mix.Utilize " quartering " (HJ/T 20-1998) sampling, obtain mud homogeneous sample.Get partial sludge to grind to form fine particulate and mix, store for future use with sealing bag encapsulation.
Two, the mensuration of heavy metal content
Adopt clear up-atomic absorption spectrophotometer method measures heavy metal content in mud; With reference to " the sample pre-treatments alkali degestion that GB5085.3-2007 annex T solid waste sexavalent chrome is analyzed ", alkali degestion is adopted to obtain Cr in mud 6+leach liquor; According to " the chromic mensuration diphenyl carbazide spectrophotometry of GB/T 15555.4-1995 solid waste ", measure Cr in chrome tanning mud sample 6+content; Cr 3+content is total Cr and Cr 6+the difference of content.
Three, the regeneration of resin
Through the resin deionized water drip washing repeatedly of desorb, until neutral, filter, dry resin.Resin regeneration is made to be Na by saturated NaCl solution +type.Adopt desorption mode of the present invention to verify, obviously do not reduce compared with the absorption rate of recovery that the acquisition absorption rate of recovery is first with resin.Show thus, it is feasible that resin regeneration utilizes, and recycling effectively can improve resin utilization rate, has more economy.
Embodiment 1
A renovation process for chrome tanning Heavy Metals in Sludge chromium, comprising:
(1) chrome tanning mud being added concentration is in the hydrochloric acid of 5mol/L, the solid-to-liquid ratio of chrome tanning mud and hydrochloric acid is made to be 10g/L, under 50 DEG C of conditions, with 500rpm rotating speed stirring reaction 1.5h, by the mixed solution of gained through 0.22 μm of membrane filtration, obtain leach liquor, repeat above-mentioned steps and carry out secondary lixiviate;
(2) take sodium bisulfite as reductive agent, by the Cr in leach liquor 6+be reduced to Cr 3+, sodium bisulfite and Cr 6+mass ratio be 5: 1;
(3) Cr is contained with in deionized water dilution step (2) 3+leach liquor, get 30mL containing Cr 3+concentration is the leach liquor of 500mg/L, adds 0.7g 732 sodium form cationic exchange resin adsorption, under 30 DEG C of conditions, with 200rpm oscillatory reaction 60min;
(4) hydrochloric acid and the middle load C r of step (3) that 30mL mass concentration is 8% is got 3+mixed with resin, under 30 DEG C of conditions, with 200rpm oscillatory reaction 1.5h, leave standstill, filter, obtain chromium chloride solution.
In above-mentioned renovation process, containing chromium metal, calcium, magnesium and sodium in initial chrome tanning mud, its mass percent is followed successively by 20.1%, 2.0%, 1.9%, 1.5%; In pickling process, chromium leaching yield is 84.9%, and the chromium leaching yield after secondary lixiviate is increased to 91.0%; Cr 6+reduction transformation efficiency be 98%; Resin is to Cr 3+, Ca 2+, Mg 2+the absorption rate of recovery be respectively 96.1%, 40.04%, 33.92%; Cr in chromium chloride solution after desorb 3+, Ca 2+, Mg 2+concentration be respectively: 478.6mg/L, 19.7mg/L and 15.5mg/L.
As shown in Figure 1, when magnification is 500 times, Sludge Surface structural form is high-visible.Before hydrochloric acid acidleach, original chrome tanning mud is surface irregularity, irregular form, and granular size differs, and densely distributed.And filter residue after hydrochloric acid acidleach is larger than primary sludge particle, and distribution loosely, and part is main to be existed with strip, and part then exists with bulk, surperficial relative smooth.
Embodiment 2
A renovation process for chrome tanning Heavy Metals in Sludge chromium, comprising:
(1) chrome tanning mud being added concentration is in the hydrochloric acid of 1mol/L, makes the solid-to-liquid ratio of chrome tanning mud and hydrochloric acid be 5g/L, under 40 DEG C of conditions, with 500rpm rotating speed stirring reaction 1h, by the mixed solution of gained through 0.22 μm of membrane filtration, obtains leach liquor;
(2) take sodium bisulfite as reductive agent, by the Cr in leach liquor 6+be reduced to Cr 3+, sodium bisulfite and Cr 6+mass ratio be 4: 1;
(3) Cr is contained with in deionized water dilution step (2) 3+leach liquor, get 30mL containing Cr 3+concentration is the leach liquor of 500mg/L, adds 0.6g 732 sodium form cationic exchange resin adsorption, under 30 DEG C of conditions, with 200rpm oscillatory reaction 60min;
(4) sulfuric acid and the middle load C r of step (3) that 30mL mass concentration is 8% is got 3+mixed with resin, under 30 DEG C of conditions, with 200rpm oscillatory reaction 1.5h, leave standstill, filter, obtain chromium sulfate solution.
In above-mentioned renovation process, containing chromium metal, calcium, magnesium and sodium in initial chrome tanning mud, its mass percent is followed successively by 20.1%, 2.0%, 1.9%, 1.5%; In pickling process, chromium leaching yield is 82.6%; Cr 6+reduction transformation efficiency be 97.5%; Resin is to Cr 3+, Ca 2+, Mg 2+the absorption rate of recovery be respectively 91.3%, 34.0%, 27.1%; Cr in chromium sulfate solution after desorb 3+, Ca 2+, Mg 2+concentration be respectively: 428.4mg/L, 5.2mg/L and 9.0mg/L.
Comparative example 1
A renovation process for chrome tanning Heavy Metals in Sludge chromium, comprising:
(1) chrome tanning mud being added concentration is in the sulfuric acid of 1mol/L, makes the solid-to-liquid ratio of chrome tanning mud and hydrochloric acid be 10g/L, under 40 DEG C of conditions, with 500rpm rotating speed stirring reaction 1h, by the mixed solution of gained through 0.22 μm of membrane filtration, obtain leach liquor, now chromium leaching yield is 82.98%;
(2) take sodium bisulfite as reductive agent, by the Cr in leach liquor 6+be reduced to Cr 3+, sodium bisulfite and Cr 6+mass ratio be 5: 1, Cr 6+reduction efficiency more than 98%;
(3) Cr is contained with in deionized water dilution step (2) 3+leach liquor, get 30mL containing Cr 3+concentration is the leach liquor of 500mg/L, adds 0.7g 732 sodium form cationic exchange resin adsorption, and under 30 DEG C of conditions, with 200rpm oscillatory reaction 60min, different from embodiment 1, now leach liquor Cr concentration has almost no change, and shows that resin is to Cr 3+produce adsorption effect hardly;
In above-mentioned renovation process, containing chromium metal, calcium, magnesium and sodium in initial chrome tanning mud, its mass percent is followed successively by 20.1%, 2.0%, 1.9%, 1.5%.

Claims (9)

1. a renovation process for chrome tanning Heavy Metals in Sludge chromium, is characterized in that, comprising:
(1) chrome tanning mud is placed in hydrochloric acid lixiviate, obtains leach liquor;
(2) take sodium bisulfite as reductive agent, by the Cr in leach liquor 6+be reduced to Cr 3+;
(3) 732 sodium form cationic exchange resin adsorption Cr are adopted 3+, add hydrochloric acid or sulfuric acid desorb Cr 3+after, obtain containing Cr 3+hydrochloric acid or sulphuric acid soln.
2. renovation process as claimed in claim 1, it is characterized in that, the solid-to-liquid ratio of described chrome tanning mud and hydrochloric acid is 2 ~ 20g/L.
3. renovation process as claimed in claim 1, it is characterized in that, the temperature of described lixiviate is 20 ~ 80 DEG C, and the time is 0.5 ~ 8h.
4. renovation process as claimed in claim 1, it is characterized in that, the concentration of described hydrochloric acid is 0.5 ~ 7mol/L.
5. renovation process as claimed in claim 1, is characterized in that, chrome tanning mud is carried out secondary lixiviate, and what merge acquisition contains Cr 6+leach liquor.
6. renovation process as claimed in claim 1, is characterized in that, Cr in described sodium bisulfite and leach liquor 6+mass ratio be 3 ~ 6: 1.
7. renovation process as claimed in claim 1, is characterized in that, Cr in described 732 sodium form Zeo-karbs and leach liquor 3+mass ratio be 10 ~ 70: 1.
8. renovation process as claimed in claim 1, it is characterized in that, in step (3), the temperature of adsorption process is 30 ~ 50 DEG C, and the time is 5 ~ 120min.
9. renovation process as claimed in claim 1, it is characterized in that, in adsorption process, the initial pH value of leach liquor is 0.4 ~ 3.
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CN106929698A (en) * 2015-12-30 2017-07-07 核工业北京化工冶金研究院 A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome
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CN106435198A (en) * 2016-12-09 2017-02-22 武汉工程大学 Method for dynamically separating and recovering copper in metallurgical sludge by adopting acid leaching associated biological adsorption method
CN112299602A (en) * 2020-10-14 2021-02-02 广东益诺欧环保股份有限公司 Purification system and method for separating nickel and chromium in water
CN113955838A (en) * 2021-09-23 2022-01-21 北京化工大学 Method for co-processing electroplating waste residue and chromium-containing heavy metal ion waste liquid
CN113955838B (en) * 2021-09-23 2023-05-26 北京化工大学 Co-treatment method for electroplating waste residue and chromium-containing heavy metal ion waste liquid

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