CN107522370A - A kind of chrome tanning sludge waste liqouor Application way - Google Patents
A kind of chrome tanning sludge waste liqouor Application way Download PDFInfo
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- CN107522370A CN107522370A CN201710809919.9A CN201710809919A CN107522370A CN 107522370 A CN107522370 A CN 107522370A CN 201710809919 A CN201710809919 A CN 201710809919A CN 107522370 A CN107522370 A CN 107522370A
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- chrome tanning
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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
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
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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
- 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
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention belongs to field of Environment Protection, is related to a kind of chrome tanning sludge waste liqouor Application way, this method is reclaimed from the chromium in acid-hatching of young eggs extraction sludge, then with the efficient precipitation method, then using H2O2Precipitated after oxidation, last H2S04Acidifying, establishes " a H2S04Leach NaOH precipitations H2O2Aoxidize H2S04The chromium-bearing sludge process for reclaiming system of acidifying ", thoroughly solve chromium-bearing sludge environmental pollution problem, while prepare the chromic salts with economic value.
Description
Technical field：
The invention belongs to environmentally friendly production field, and in particular to the clearer production technology in a kind of leather industry, specifically
Be related to a kind of chrome tanning sludge waste liqouor Application way.
Background technology：
Chromium containing high concentration in leather production industry Chrome Tanning Wastewater, it is desirable to pre-processed to it, make chromium concn reach state
It is jointly processed by after could being mixed after the discharge standard that family requires with waste water caused by other production technology sections.Caused by Leather Industry
Chrome Tanning Wastewater is mainly pre-processed by alkaline chemical precipitation means, and this process result in substantial amounts of chromium-bearing sludge and produce.Metal
Chromium is the major pollutant in industrial discharge waste water and sludge, the random discharge of Chrome Tanning Wastewater, chromic salts can be made in soil, planted
Gathered in thing, aquatic organism, huge pollution can be caused to environment.If crome metal enters human body by food chain, can also endanger
Human body health.Therefore how extraction recovery is carried out to caused chromium-bearing sludge in leather industry, pollution of chromium is reduced to most
Low degree, realizing the recycling and reuse of chromium resource turns into one of this area urgent problem to be solved.
The content of the invention
For many weak points existing for prior art, present invention firstly provides a kind of utilization of chrome tanning sludge waste liqouor
Method, this method is reclaimed from the chromium in acid-hatching of young eggs extraction sludge, then with the efficient precipitation method, then using H2O2Sunk after oxidation
Form sediment, last H2S04Acidifying, establishes " a H2S04Leaching-NaOH precipitations-H2O2Oxidation-H2S04The chromium-bearing sludge recycling of acidifying "
Process system, thoroughly solve chromium-bearing sludge environmental pollution problem, while prepare the chromic salts with economic value.
The present invention is achieved through the following technical solutions：
A kind of chrome tanning sludge waste liqouor Application way, is comprised the following steps that：
(1) chrome tanning Treatment of Sludge：Dewatered sludge is ground into fine particulate, is well mixed after crossing 10 mesh sieves, is dried to constant weight,
It is stand-by；
(2) acidleach：In sulfuric acid concentration 0.5-1.25mol/L；Solid-to-liquid ratio 5-30g/L；40 DEG C of temperature, shake time 60min
Under conditions of leach four times, merge leachate enter rear portion processing；
(3) reduce：NaHSO is added into the leachate after above-mentioned merging3Solution, NaHSO3With Cr6+Mol ratio is 1.5:
1-7:1,10min is stirred, then stands 30min；
(4) precipitate：The solution after reduction is taken, NaOH is added and pH value is adjusted to 8.5-9.0, is placed in oscillator fully anti-
Should, solution is filtered to be precipitated；
(5)H2O2Oxidation：NaOH solution is added into sediment, regulation pH is 10, after 60 DEG C of heating water bath 10min of constant temperature,
Add the H of mass fraction 30%2O2, H2O2With Cr3+Mol ratio is 5:1-40:1, by Cr3+It is oxidizing to Cr6+；By being continuously replenished
Sodium hydroxide, pH value of solution is maintained at 10, cooled down again after heating 2h；
(6)H2SO4Acidifying：Upwards H is added in step oxidation resulting solution2SO4Solution, by pH value control 3.5, make
Na2CrO4It is changed into Na2Cr2O7。
The specific Leaching way of wherein described step (2) is：
The steeping tank of 4 series connection of design, four leachings are carried out with the series connection of identical condition, the condition leached every time is homogeneous
Together：
Particle obtained by step (1) is immersed in the sulfuric acid solution in the first immersion shop with solid-to-liquid ratio 5-30g/L ratio,
Sulfuric acid concentration 0.5-1.25mol/L in described sulfuric acid solution, system temperature are 40 DEG C, reaction time 60min, whole system
Reacted in a manner of concussion, in addition, whole reactor concussion, to abundant haptoreaction；Tandem sequence repeats operate 3 times, altogether
Immersion 4 times, finally by leachate merging treatment in 4 steeping tanks, and determines Cr in mixed acid solution6+Content to determine to walk
Suddenly the NaHSO in (3)3Addition；Solid slag Leaching after four leachings meets the Leaching standard of country's restriction, can fill
Processing；
Each condition optimizing is by further inventor：
Acidleach condition is in step (2)：Optimum condition is defined as sulfuric acid concentration 0.75mol/L, solid-to-liquid ratio 15g/L, shake
Swing the time be 60min, temperature be 40 DEG C；
NaHSO in step (3)3With Cr6+Mol ratio is defined as 7:Percent reduction highest when 1, Cr typically can be achieved6+It is reduced to
Cr3+Percent reduction reach 97.8%；
It is optimum value to be added in step (4) when pH is adjusted to 9 by NaOH；
H in step (5)2O2With Cr3+Mol ratio is defined as 40:1；
Solution ph is 3.5 in step (6), by not stopping to add sulfuric acid and stirring adjustment to obtain.
On the basis of above-mentioned processing step, heating evaporation step (6) feed liquid filters to there is sulfate crystal precipitation, uses
90 DEG C or so distillation water washings, carry out double evaporation-cooling to filtrate, also pass through the steps such as filter, washing, now a large amount of sodium sulphate have been
Crystallization separates out, and obtains purer sodium dichromate solution.
In above-mentioned handling process, by four Ore Leachings of step (2), the chromium in solid sludges can be leached big
Part, the Leaching of total chromium is 5.125mg/L in the solid slag that obtains after four immersions, and the Leaching of Cr VI is
0.075mg/L.According to《Leaching characteristic identification (GB5085.3-2007)》Regulation, the Leaching of total chromium is not above 15mg/
L, the Leaching of Cr VI is not above 5mg/L, therefore the Leaching of solid slag meets the leaching poison of country's restriction after four leachings
Property standard, the solid slag of leaching can do landfill disposal, solve harm of the chromium to environment in filter residue；
By obtaining substantial amounts of acid leaching liquor after Ore Leaching, here containing substantial amounts of chromium, inventor by this
Part solution NaHSO3Solution reduction is simultaneously prepared for Cr (OH)3Precipitation, its Cr rate of deposition are 99.97%, and the chromium in filtrate meets
Discharge standard requirement, so that Cr3+Element is changed into solid-state again and realizes separation of solid and liquid, the chromium content in liquid portion
It is very low, therefore can be with qualified discharge, and for Cr (OH)3Precipitation then recycles H2O2Aoxidize Cr3+To Cr6+, the oxygen in step (5)
Rate can reach 98.92%；Invention recycles sulfuric acid to be acidified above-mentioned solution afterwards, so that CrO4 2-It is fully converted into
Cr2O7 2-, obtain Na2Cr2O7Solution, and this is obtained Na2Cr2O7Solution can be back to use in process hides industry and prepare
Chrome tanning agent, so as to realize the recycling of chrome tanning sludge, the chromium content of outer row is greatly reduced, realizes environment and effect
The bumper harvests of benefit；Sulfate crystal is separated out using the difference of solubility, heating evaporation feed liquid simultaneously, obtains purer dichromic acid
Sodium solution.
Therefore handling process provided by the present invention, by reasonably combining, utilize the mode for adding chemical agent
The comprehensive utilization to chromium in chrome tanning sludge is realized, whole process does not need special equipment to complete, than present
Conventional electrochemical process processing substantially reduces time and cost, and handles the various materials obtained and remove and can largely recycle
Outside, remaining with qualified discharge, can be adapted to the process modification of existing various chrome tanning Treatment of Sludge, have high promotional value,
Preferable treatment effect can be reached within the extremely short time.
Embodiment
A kind of chrome tanning sludge waste liqouor Application way, is comprised the following steps that：
(1) chrome tanning Treatment of Sludge：
Dewatered sludge is ground into fine particulate, is well mixed after crossing 10 mesh sieves, is dried to constant weight, uses and divides after full dose is cleared up
Light photometer measures, 170mg containing chromium in every gram of sludge, wherein Cr3+：169.4631mg, Cr6+：0.5369mg；
(2) acidleach：
Different sulfuric acid solution volumes, chromium-bearing sludge dosage, temperature and leaching time are used as variable, designs orthogonal test
Single acidleach condition is optimized, as a result several groups of conditional combinations of chromium leaching rate highest are respectively：Sulfuric acid concentration 0.75mol/
L, solid-to-liquid ratio 15g/L, 40 DEG C of temperature, shake chromium leaching rate 79.10% under conditions of time 60min；Sulfuric acid concentration 1.25mol/
L, solid-to-liquid ratio 20g/L, temperature 60 C, shake chromium leaching rate 76.23% under conditions of time 90min；Sulfuric acid concentration 0.6mol/L,
Solid-to-liquid ratio 10g/L, temperature 50 C, shake chromium leaching rate 69.61% under conditions of time 75min.
It is sulfuric acid concentration 0.75mol/L in optimal acidleach condition, solid-to-liquid ratio 15g/L, 40 DEG C of temperature, shakes time 60min
Under conditions of leach four times.After first acidleach filtering, 201.71mg chromium can be leached per 1.5g grams of sludge, by filter residue through 105 DEG C of bakings
Do to constant weight, with above-mentioned identical leaching condition, secondary pickling is carried out to filter residue, quadratic acid immersion liquid total chrome content is 34.32mg/
L；Three immersion liquid total chrome contents are 1.3212mg/L, and the total chromium concn of four immersion liquid is 1.456mg/L；It is total in the mixed liquor of four leachates
Chromium content is 238.8072mg, wherein Cr3+：238.0108mg, Cr6+：0.7964mg.At leachate mixing after four leachings
Manage, the Leaching of total chromium is 5.125mg/L in the solid slag after four leachings, and the Leaching of Cr VI is 0.075mg/L.According to
《Leaching characteristic identification (GB5085.3-2007)》Regulation, the Leaching of total chromium is not above 15mg/L, the leaching of Cr VI
Toxicity is not above 5mg/L, therefore the Leaching of solid slag meets the Leaching standard of country's restriction after four leachings, and leaching is consolidated
Slag can do landfill disposal, solve harm of the chromium to environment in filter residue.
(3) reduce：
NaHSO is added into the leachate after above-mentioned merging3Solution, to verify optimum value, inventor sets NaHSO3With
Cr6+Mol ratio is respectively 1.5:1,3:Isosorbide-5-Nitrae .5:1,6:1,7:1,10min is stirred, then stands 30min；Percent reduction is respectively
51.6%, 70.2%, 93.1%, 96.7%, 97.8%, finally determine NaHSO3With Cr6+Mol ratio is 7:When 1, percent reduction is
97.8%, when mol ratio continues to become big, percent reduction change is little, therefore chooses NaHSO3With Cr6+Optimum mole ratio is 7:1, this
When, Cr in the solution after reduction3+：238.7899mg, Cr6+：0.01752mg.
(4) precipitate：
The solution after reduction is taken, pH value is adjusted to 9.0 by the NaOH solution for adding 4mol/L, is placed in oscillator fully anti-
Should, solution is filtered to be precipitated；The total cr content in filtrate is 0.070314mg after measured, and Cr rates of deposition are 99.97%, are sunk
The chromium content in shallow lake is 238.73688mg.Chromium in filtrate meets discharge standard and requires 1.5mg/L.
(5)H2O2Oxidation：
Sediment (the Cr (OH) obtained to step (4)3Precipitation) in add sodium hydroxide, with sodium hydroxide regulation pH be
After 10,60 DEG C of heating water bath 10min of constant temperature, 30wt%H is added2O2, H is set2O2With Cr3+Mol ratio is 5:1、20:1、30:1、
40:1、50:1.It is a small amount of every time to add H2O2To prevent from being slopped over out by thermal decomposition punching under its high temperature, pH is determined in course of reaction, with adding
NaOH solution, pH value of solution is maintained at 10, heat 2h, cool down, filtering.Oxygenation efficiency is respectively 59.56%, 78.63%,
89.88%th, 98.92%, 95.78%.It is final to determine to select H2O2With Cr3+Optimum mole ratio is 40:1, oxygenation efficiency can reach most
Good value 98.92%, Cr in the solution after oxidation6+：236.15852mg.
(6)H2SO4Acidifying：Upwards H is added in step oxidation resulting solution2SO4Solution, regulation pH value of solution is 3.5, makes CrO4 2-
It is fully converted into Cr2O7 2-, obtain Na2Cr2O7Solution.Heating evaporation feed liquid is filtered, used to there is a certain amount of sulfate crystal to separate out
90 DEG C or so distillation water washings, carry out double evaporation-cooling to filtrate, also pass through the steps such as filter, washing, now a large amount of sodium sulphate have been
Crystallization separates out, and obtains purer sodium dichromate solution, chromium content 235.0958mg.Chromium recovery ratio 92.2%.
The sodium dichromate solution of above-mentioned acquisition can be prepared chrome tanning agent, used after carbohydrate (mainly cerelose) reduction
In the tanning of each leather-like, various fur；
It can be seen that method provided by the present invention realizes the comprehensive utilization to chromium in chrome tanning sludge, whole process is not required to
Want special equipment to complete, substantially reduce time and cost than existing frequently-used electrochemical process processing, and processing obtains
For the various materials obtained in addition to it can largely recycle, remaining can be adapted to existing various chrome tanning Treatment of Sludge with qualified discharge
Process modification, there is high promotional value, preferable treatment effect can be reached within the extremely short time.
Claims (4)
- A kind of 1. chrome tanning sludge waste liqouor Application way, it is characterised in that：Comprise the following steps that：(1) chrome tanning Treatment of Sludge：Dewatered sludge is ground into fine particulate, is well mixed after crossing 10 mesh sieves, is dried to constant weight, treats With；(2) acidleach：In sulfuric acid concentration 0.5-1.25mol/L；Solid-to-liquid ratio 5-30g/L；40 DEG C of temperature, shake the bar of time 60min Leached four times under part, merge leachate and handled into rear portion；(3) reduce：NaHSO is added into the leachate after above-mentioned merging3Solution, NaHSO3With Cr6+Mol ratio is 1.5:1-7:1, 10min is stirred, then stands 30min；(4) precipitate：The solution after reduction is taken, NaOH is added and pH value is adjusted to 8.5-9.0, be placed in oscillator and fully react, Solution is filtered to be precipitated；(5)H2O2Oxidation：NaOH solution is added into sediment, regulation pH is 10, after 60 DEG C of heating water bath 10min of constant temperature, is added The H of mass fraction 30%2O2, H2O2With Cr3+Mol ratio is 5:1-40:1, by Cr3+It is oxidizing to Cr6+；By the way that hydrogen-oxygen is continuously replenished Change sodium, pH value of solution is maintained at 10, cooled down again after heating 2h；(6)H2SO4Acidifying：Upwards H is added in step oxidation resulting solution2SO4Solution, by pH value control 3.5, make Na2CrO4Turn It is changed into Na2Cr2O7。
- 2. chrome tanning sludge waste liqouor Application way according to claim 1, it is characterised in that：The specific Leaching way of the step (2) is：The steeping tank of 4 series connection of design, four leachings, the condition all same leached every time are carried out with the series connection of identical condition：Particle obtained by step (1) is immersed in the sulfuric acid solution in the first immersion shop with solid-to-liquid ratio 5-30g/L ratio, it is described Sulfuric acid solution in sulfuric acid concentration 0.5-1.25mol/L, system temperature is 40 DEG C, reaction time 60min, and whole system is to shake The mode swung reacts；Tandem sequence repeats are operated 3 times, and total immersion is steeped 4 times, finally by leachate merging treatment in 4 steeping tanks, and Determine Cr in mixed acid solution6+Content to determine the NaHSO in step (3)3Addition.
- 3. chrome tanning sludge waste liqouor Application way according to claim 1, it is characterised in that：Acidleach condition is in step (1)：Sulfuric acid concentration 0.75mol/L, solid-to-liquid ratio 15g/L, concussion the time be 60min, temperature For 40 DEG C；NaHSO in step (2)3With Cr6+Mol ratio is defined as 7:1；In step (3)；Add NaOH and pH is adjusted to 9；H in step (4)2O2With Cr3+Mol ratio is defined as 40:1；Solution ph is defined as 3.5 in step (5).
- 4. chrome tanning sludge waste liqouor Application way according to claim 1, it is characterised in that：The final gained feed liquid of heating evaporation step (6) filters to there is sulfate crystal precipitation, distills water washings with 90 DEG C or so, Double evaporation-cooling is carried out to filtrate, also passes through filter, washing, now a large amount of sodium sulphate have crystallized precipitation, obtain purer dichromic acid Sodium solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824219A (en) * | 2019-04-01 | 2019-05-31 | 陕西科技大学 | A kind of system for processing chrome-containing wastewater and its method |
| CN110436522A (en) * | 2019-09-02 | 2019-11-12 | 宝武集团环境资源科技有限公司 | A kind of recycling processing method of chromium-bearing sludge |
| CN115385507A (en) * | 2022-09-01 | 2022-11-25 | 大连东泰产业废弃物处理有限公司 | Pretreatment method for co-processing of waste etching liquid of sulfuric acid system and water treatment chromium-containing sludge |
| IT202100023831A1 (en) * | 2021-09-16 | 2023-03-16 | Giorgio Boschi | Chrome recovery process from tanning sludge and a plant. |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824219A (en) * | 2019-04-01 | 2019-05-31 | 陕西科技大学 | A kind of system for processing chrome-containing wastewater and its method |
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| CN115385507A (en) * | 2022-09-01 | 2022-11-25 | 大连东泰产业废弃物处理有限公司 | Pretreatment method for co-processing of waste etching liquid of sulfuric acid system and water treatment chromium-containing sludge |
| CN115385507B (en) * | 2022-09-01 | 2024-03-15 | 大连东泰产业废弃物处理有限公司 | Pretreatment method for co-treatment of sulfuric acid system waste etching solution and water treatment chromium-containing sludge |
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