CN108164051A - A kind of leather industry chromate waste water recycling treatment process system - Google Patents
A kind of leather industry chromate waste water recycling treatment process system Download PDFInfo
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- CN108164051A CN108164051A CN201711463147.4A CN201711463147A CN108164051A CN 108164051 A CN108164051 A CN 108164051A CN 201711463147 A CN201711463147 A CN 201711463147A CN 108164051 A CN108164051 A CN 108164051A
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- waste water
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of leather industry chromate waste water recycling treatment process system, including the pretreatment system, film separation system and waste liqouor system being sequentially communicated；Pretreatment system is used to carry out leather chromate waste water the pretreatment before UF membrane；Film separation system carries out fresh water separation and chrome liquor concentration to the chromate waste water of preprocessed mistake；Waste liqouor system carries out the dense chrome liquor concentrated through film separation system the recovery processing of chromium, obtains the chromium powder that chromium content is more than 5%.By the chromate waste water of leather leather tan workshop discharge after pretreatment system obtains filtering and refined filtration, fresh water direct reuse is produced to obtain into the film separation system being made of nanofiltration device and electrodialysis plant, for obtained concentrated water after strong brine is made in electrodialysis desalination, remaining dense chrome liquor enters back into that waste liqouor system is spray-dried to obtain chromium powder.While valuable water resource is greatly saved in the present invention, the recycling of chromium resource is also realized, so as to reach the recycling treatment of leather industry chromate waste water.
Description
Technical field
The invention belongs to work field of waste water treatment, are related to a kind of leather industry chromate waste water recycling treatment process system.
Background technology
Leather products production process more than China, 85% is needed using a large amount of chrome tanning agent, in leather retanning process
In be inevitably generated a large amount of chromate waste water.If these chromate waste waters cannot efficiently use and handle disposition, not only
Environment and the health of the mankind can be seriously endangered, can also cause a large amount of wastes of chromium resource.What newest publication was implemented《Process hides and
Fur processing industry pollutant emission standard》In GB30486-2013 total chromium concentration of emission requirement control in 1.5mg/L hereinafter,
Great pressure is brought to the sustainable development of enterprise or even leather industry.Therefore, it to the efficient process of chromate waste water and follows
Ring utilizes, it has also become restricts the technical barrier and critical issue of leather industry sustainable development.
Patent CN205838738U proposes that chromate waste water first is carried out two-stage reductive oxidation, then it is carried out plus alkali sinks
It forms sediment, supernatant is by direct emission after tube microfiltration membrane separating and filtering, but the process needs to consume a large amount of chemical reagent, processing
Water water quality afterwards is not high, and generates chromium mud and cause secondary pollution.
Patent CN206635167U proposes to filter after chromate waste water is adjusted pH3.0~7.0, and filtrate passes through cation exchange
Resin is purified by ion exchange, is then carried out redox reaction and alkaline chemical precipitation reaction successively, is obtained supernatant again
It is discharged after nanofiltration-micro-filtration processing, but the process generates chromium mud and is difficult to handle, and also needs to carry out the elution and again of resin
It is raw, complex steps.
Patent CN205603375U proposes a kind of continous way chromate waste water processing unit, including the electrolysis dress being sequentially communicated
Put, elevator pump, ion interchange unit, thickener and circulating slot, finally generate chromic acid reuse, but the program need to carry out it is multiple
Exchange operations it is complicated, and the power consumption and very big to the consumption of electrode when handling a large amount of waste water.
Patent CN206204047U proposes a kind of novel chromate waste water processing unit, and chromate waste water is passed through acidity tune successively
Pond, the first reduction reaction pond, the second reduction reaction pond and sedimentation basin are saved, filtrate is using by mechanical filter and activated carbon filtering
It is discharged after the filter device of device composition, but total chrome content is difficult to up to standard in the program treated water, and can not carry out water
Regeneration.
Patent CN206051727U proposes a kind of chromate waste water processing unit, including sequentially connected chromate waste water pond, acid
Alkali regulating reservoir, redox reaction pond, active carbon filter and nano-filtration membrane filter, but the program needs repeated measurement with throwing
Acid adding base reagent, the pretreatment of NF membrane front end are not enough difficult to long-term continuous operation, and inorganic salts in chromate waste water and chromium obtain not
To being effectively treated and reuse.
Invention content
The present invention is difficult for current leather industry chromate waste water process demand and processing water water quality of the existing technology
With up to standard, lead to the problem of the secondary pollution of chromium mud and the regeneration of water and inorganic salts can not be carried out, propose a kind of leather industry
Chromate waste water recycling treatment process system.
For this purpose, the present invention provides following solution：
A kind of leather industry chromate waste water recycling treatment process system, including pretreatment system, film separation system and chromium
Recovery system is sequentially arranged；It is 10~35mg/L by Cr contents, the preprocessed system of chromate waste water of TDS2000~4000mg/L
After processing, production water enters film separation system and carries out chrome liquor concentration, and the three-level nanofiltration rate of recovery is respectively 80%, 50%, 50%,
The concentrated water Cr contents that nanofiltration system generates are 190mg/L~600mg/L, and the fresh water Cr contents that nanofiltration system generates are less than 0.5mg/
L.Nanofiltration system concentrated water enters electrodialysis system and carries out desalination, obtains strong brine total dissolved solid more than 18%, and mainly into
It is divided into sodium chloride and sodium sulphate.It obtains the relatively low dense chrome liquor of salt content and enters precipitation unit, precipitation unit is by adding lye to adjust
Dense chrome liquor pH obtains being deposited in by the way that sulfate moieties is added to dissolve in dissolving unit, it is dense chromium to add in sulfuric acid volume 9.2~9.8
The supernatant for dissolving precipitation is entered spray drying system and chromium powder is made by liquid product 1.3%~1.7%, and wherein main component is
Chromium sulfate basic.The wherein chromium content of chromium powder is more than 5%, and the total dissolved solid in strong brine is more than 18%, system water recycling
Utilization rate reaches 90%~95%.
The pretreatment system includes hydraulic screen, plate compression system and ultrafiltration system, wherein, waterpower mesh size 0.3~
0.5mm, ultrafiltration system use antipollution tubular ultra-filtration membrane.
The film separation system includes nanofiltration system and electrodialysis system.
The nanofiltration system is combined by level-one nanofiltration, two level nanofiltration and three-level nanofiltration, and nanofiltration system obtains dense chrome liquor and enters
Electrodialysis system, obtaining fresh water can be with direct reuse.
The electrodialysis system uses homogeneous membrane, and main body membrane stack is using 1-1 Monovalent selectivities cation-exchange membrane and commonly
The assembling form that anion-exchange membrane is alternately arranged.
Strong brine total dissolved solid is more than 18% in the electrodialysis system, and main component is sodium chloride and sulfuric acid
Sodium.
The waste liqouor system includes precipitation unit, dissolving unit and spray drying system.
The precipitation unit is obtained being deposited in dissolving unit and passed through by the way that lye is added to adjust dense chrome liquor pH 9.2~9.8
Sulfate moieties is added to dissolve, add in 1.3%~1.7% of sulfuric acid volume for dense chrome liquor volume.
Chromium powder is obtained after the spray drying system processing, wherein chromium content is more than 5%.
Compared with prior art, the beneficial effects of the invention are as follows：This work is directed to the characteristics of leather industry chromate waste water, utilizes
The water quality into before NF membrane can be effectively ensured for the pretreatment system of core for tubular ultra-filtration membrane, it can be ensured that nano filter membrance device
Long-term continuous and steady operation, fresh water, inorganic salts and chromium three can effectively be realized by nanofiltration and electrodialytic coupled system
High separation, water total chrome content up to standard are less than 0.5mg/L, and fresh-water recovery rate can reach 90%, and strong brine total dissolved solid is big
In 18%, dense chrome liquor obtains chromium powder after being spray-dried as the processing of core waste liqouor system, and chromium content is not less than 5%.And
In whole process other than adding in appropriate amount of acid alkaline agent, do not need to add in any other chemical reagent, therefore the present invention has flow
Easy to operate, obvious processing effect can realize the advantages such as resource circulation utilization, and process conditions are easy to control, equipment and materials legibility
Certainly.
Description of the drawings
Fig. 1 is a kind of schematic diagram of leather industry chromate waste water recycling treatment process system provided by the present invention.
Specific embodiment
With reference to the drawings and specific embodiments, the present invention is further described in detail.
The present invention provides a kind of leather industry chromate waste water recycling treatment process system, by the workshop discharge of leather leather tan
Chromate waste water pass through pretreatment system, after hydraulic screen and plate compression system coarse filtration, obtain filtrate enter ultrafiltration system into
Row refined filtration.Water is produced after refined filtration and enters film separation system, produces to obtain fresh water direct reuse by three-level nanofiltration processing, obtained concentrated water is again
After strong brine is made into electrodialysis system, remaining dense chrome liquor enters back into that waste liqouor system is spray-dried to obtain chromium powder.Wherein
The chromium content of chromium powder is more than 5%, and the total dissolved solid in strong brine is more than 18%, and system water recovery utilization rate reaches 90%~
95%.It is handed over since electricity drives main body membrane stack in ionic membrane system using 1-1 Monovalent selectivities cation-exchange membrane and common anion
The assembling form that film is alternately arranged is changed, hardness will not be concentrated and all stay in desalted water substantially in water, and system operation is influenced
It is smaller.The processing technological flow is simple and convenient to operate, and meets current leather industry to the urgent of waste water discharge-reducing and recycling
Demand has good promotion prospect.
Embodiment 1：
Certain enterprise leather tan workshop discharge chromate waste water Cr contents are 30mg/L, TDS 3507mg/L, Ca2+Content is 24mg/L,
Mg2+Content is 27mg/L, Cl-Content is 515mg/L, SO4 2-Content is 1039mg/L, Na+Content is 712mg/L.
Chromate waste water through 0.5mm hydraulic screens remove tags after, with 5.0m3/ h flows enter plate compression system and carry out coarse filtration,
Filtrate, through row refined filtration, produces water and enters three-level nanofiltration device, level-one nanofiltration, two level nanofiltration and three-level nanofiltration by tubular ultra-filtration membrane
The rate of recovery is respectively 80%, 50%, 50%, and the ultimate output of nanofiltration system concentrated water is 0.25m3/ h, Cr content are 595mg/L,
The fresh water yield 4.75m that nanofiltration system generates3/ h, Cr content are 0.24mg/L, available for industrial reuse water.Nanofiltration system generates
Concentrated water enter electrodialysis system and carry out desalination, obtain strong brine total dissolved solid content as 206g/L, and main component is
Sodium chloride and sodium sulphate.Since main body membrane stack is using 1-1 Monovalent selectivities cation-exchange membrane and the friendship of common anion exchange membrane
For the assembling form of arrangement, so the Cr in concentrated water will not be migrated and remain in desalting chamber, so as to obtain salt content compared with
Low dense chrome liquor, precipitation unit obtain being deposited in dissolving unit by adding sulfuric acid by the way that lye is added to adjust dense chrome liquor pH 9.5
It is partly dissolved, adds in 1.5% of sulfuric acid volume for dense chrome liquor volume, the supernatant for dissolving precipitation is entered into spray drying system system
Chromium powder, wherein main component is chromium sulfate basic, and chromium content is up to 7%.
Embodiment 2：
Certain enterprise leather tan workshop discharge chromate waste water Cr contents are 16mg/L, TDS 2715mg/L, Ca2+Content is 20mg/L,
Mg2+Content is 46mg/L, Cl-Content is 760mg/L, SO4 2-Content is 888mg/L, Na+Content is 785mg/L.
Chromate waste water through 0.5mm hydraulic screens remove tags after, with 5.0m3/ h flows enter plate compression system and carry out coarse filtration,
Filtrate, through row refined filtration, produces water and enters three-level nanofiltration device, level-one nanofiltration, two level nanofiltration and three-level nanofiltration by tubular ultra-filtration membrane
The rate of recovery is respectively 80%, 50%, 50%, and the ultimate output of nanofiltration system concentrated water is 0.25m3/ h, Cr content are 317mg/L,
The fresh water yield 4.75m that nanofiltration system generates3/ h, Cr content are 0.15mg/L, available for industrial reuse water.Nanofiltration system generates
Concentrated water enter electrodialysis system and carry out desalination, obtain strong brine total dissolved solid as 191g/L, and main component is chlorination
Sodium and sodium sulphate.Since main body membrane stack is using 1-1 Monovalent selectivities cation-exchange membrane and common anion exchange membrane alternating row
The assembling form of row, so the Cr in concentrated water will not be migrated and remain in desalting chamber, it is relatively low so as to obtain salt content
Dense chrome liquor, precipitation unit obtain being deposited in dissolving unit by adding sulfate moieties by the way that lye is added to adjust dense chrome liquor pH 9.3
Dissolving adds in 1.6% of sulfuric acid volume for dense chrome liquor volume, and the supernatant for dissolving precipitation is entered to the chromium of spray drying system
Powder, wherein main component are chromium sulfate basic, and chromium content is up to 5.8%.
Above-mentioned specific embodiment is used for illustrating the present invention, only preferred embodiment of the invention rather than to this hair
It is bright to be limited, in the claims of the present invention, to any modification, equivalent substitution and improvements of the invention made
Deng both falling within protection scope of the present invention.
Claims (8)
1. a kind of leather industry chromate waste water recycling treatment process system, it is characterised in that：Including pretreatment system, UF membrane
System and waste liqouor system are sequentially arranged；By Cr contents be 10~35mg/L, the chromate waste water of TDS2000~4000mg/L is through pre-
After processing system processing, production water enters film separation system and carries out chrome liquor concentration, the three-level nanofiltration rate of recovery is respectively 80%,
50%th, 50%, the concentrated water Cr contents that nanofiltration system generates is 190mg/L~600mg/L, fresh water Cr contents that nanofiltration system generates
Less than 0.5mg/L；Nanofiltration system concentrated water enters electrodialysis system and carries out desalination, obtains strong brine total dissolved solid and is more than
18%, and main component is sodium chloride and sodium sulphate.It obtains the relatively low dense chrome liquor of salt content and enters precipitation unit, precipitation unit is led to
It crosses plus lye adjusts dense chrome liquor pH 9.2~9.8, obtain being deposited in dissolving unit by the way that sulfate moieties is added to dissolve, add in sulphur
Sour volume is dense chrome liquor volume 1.3%~1.7%, and the supernatant for dissolving precipitation is entered spray drying system is made chromium powder,
Middle main component is chromium sulfate basic, and chromium content is not less than 5%.
A kind of 2. leather industry chromate waste water recycling treatment process system according to claim 1, which is characterized in that institute
It states pretreatment system and includes hydraulic screen, plate compression system and ultrafiltration system, wherein, waterpower mesh size is 0.3~0.5mm, is surpassed
Filter system uses antipollution tubular ultra-filtration membrane, and the production water of the pretreatment system enters film separation system.
A kind of 3. leather industry chromate waste water recycling treatment process system according to claim 2, which is characterized in that institute
It states film separation system and includes nanofiltration system and electrodialysis system.
A kind of 4. leather industry chromate waste water recycling treatment process system according to claim 3, which is characterized in that institute
Nanofiltration system to be stated to be combined by level-one nanofiltration, two level nanofiltration and three-level nanofiltration, nanofiltration system obtains dense chrome liquor and enters electrodialysis system,
Obtaining fresh water can be with direct reuse.
A kind of 5. leather industry chromate waste water recycling treatment process system according to claim 4, which is characterized in that institute
Electrodialysis system is stated using homogeneous membrane, main body membrane stack is exchanged using 1-1 Monovalent selectivities cation-exchange membrane and common anion
The assembling form that film is alternately arranged.
A kind of 6. leather industry chromate waste water recycling treatment process system according to claim 4, which is characterized in that institute
It states strong brine total dissolved solid in electrodialysis system and is more than 18%, and main component is sodium chloride and sodium sulphate.
A kind of 7. leather industry chromate waste water recycling treatment process system according to claim 1, which is characterized in that institute
It states waste liqouor system and includes precipitation unit, dissolving unit and spray drying system, the precipitation unit is dense by the way that lye is added to adjust
Chrome liquor pH adds in 1.3%~1.7% that sulfuric acid volume is dense chrome liquor volume in 9.2~9.8, dissolving unit.
A kind of 8. leather industry chromate waste water recycling treatment process system according to claim 7, which is characterized in that institute
Chromium powder is obtained after stating spray drying system processing, wherein chromium content is more than 5%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793517A (en) * | 2018-06-26 | 2018-11-13 | 泉州师范学院 | A kind for the treatment of process of high COD leather-making waste waters with high salt |
| CN108796223A (en) * | 2018-06-26 | 2018-11-13 | 泉州师范学院 | The recovery method of chromium in a kind of high-concentration chromium-containing wastewater |
| CN109133408A (en) * | 2018-08-07 | 2019-01-04 | 泉州师范学院 | The minimizing technology of heavy metal chromium in a kind of process hides chromate waste water |
| CN109502698A (en) * | 2018-12-12 | 2019-03-22 | 天津北方食品有限公司 | A kind of preprocess method of saccharin sodium production waste water |
| CN110655239A (en) * | 2018-06-29 | 2020-01-07 | 宝山钢铁股份有限公司 | Method for treating chromium-containing wastewater |
| CN115259103A (en) * | 2022-08-17 | 2022-11-01 | 四川省银河化学股份有限公司 | Process for preparing acid-base from chromium-containing sodium sulfate solution |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793517A (en) * | 2018-06-26 | 2018-11-13 | 泉州师范学院 | A kind for the treatment of process of high COD leather-making waste waters with high salt |
| CN108796223A (en) * | 2018-06-26 | 2018-11-13 | 泉州师范学院 | The recovery method of chromium in a kind of high-concentration chromium-containing wastewater |
| CN110655239A (en) * | 2018-06-29 | 2020-01-07 | 宝山钢铁股份有限公司 | Method for treating chromium-containing wastewater |
| CN109133408A (en) * | 2018-08-07 | 2019-01-04 | 泉州师范学院 | The minimizing technology of heavy metal chromium in a kind of process hides chromate waste water |
| CN109502698A (en) * | 2018-12-12 | 2019-03-22 | 天津北方食品有限公司 | A kind of preprocess method of saccharin sodium production waste water |
| CN115259103A (en) * | 2022-08-17 | 2022-11-01 | 四川省银河化学股份有限公司 | Process for preparing acid-base from chromium-containing sodium sulfate solution |
| CN115259103B (en) * | 2022-08-17 | 2023-11-10 | 四川省银河化学股份有限公司 | Acid-base preparation process for chromium-containing sodium sulfate solution |
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Application publication date: 20180615 |