CN105948362A - Coal chemical RO strong brine treatment process - Google Patents
Coal chemical RO strong brine treatment process Download PDFInfo
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- CN105948362A CN105948362A CN201610483120.0A CN201610483120A CN105948362A CN 105948362 A CN105948362 A CN 105948362A CN 201610483120 A CN201610483120 A CN 201610483120A CN 105948362 A CN105948362 A CN 105948362A
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- 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
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a coal chemical RO strong brine treatment process. Strong brine enters an activated carbon adsorption tower at first, then bivalent salt and univalent salt are preliminarily separated by virtue of a nanofiltration salt separation system, electrolysis, evaporation and cooling crystallization are performed on a bivalent salt solution to obtain industrial mirabilite, and RO membrane concentration, evaporative crystallization and centrifugal dehydration are performed on a univalent salt solution to obtain industrial sodium chloride crystals. According to the process, the volume of evaporated liquid and energy consumption can be reduced, the purity and quality of the obtained crystal salt can be improved, resources can be recycled, and in addition, solid waste treatment quantity can be reduced.
Description
Technical field
The present invention relates to a kind of Coal Chemical Industry RO strong brine processing technology, belong to environmental protection treatment technical field.
Background technology
Coal chemical industrial waste water Treated sewage reusing technical process is as follows at present, and the waste water after biochemical treatment first passes through height
It is difficult by the Organic substance of biochemical degradation that level oxidation is removed in sewage further；Sand filtration is used to remove the float in sewage and glue afterwards
Body material；Sand filtration water outlet enters back into the processing system that ultrafiltration (UF)+ion exchange (IER)+reverse osmosis (RO) forms, wherein ultrafiltration
Effect be further organics removal and particulate matter, ion exchange resin be used for remove Ca2+, Mg2+ ion in water, soften
After water outlet again by RO concentrating and separating, wherein fresh water carries out reuse, and RO strong brine enters evaporation element, outside crystallizing into after salt
Fortune.
This technological process has carried out reuse to the waste water of 75%, considerably reduces outer discharge capacity, and waste water is after concentrating simultaneously
Relatively reduce the scale of subsequent evaporation device, be an important ring of wastewater zero discharge.But it still has technological deficiency, i.e. vaporizer
Scale is big, power consumption height, additionally, the mixing carnallite that obtains of crystallization is low due to purity, and poor quality, it is difficult to directly carry out commercial recovery profit
With, security landfill need to be carried out as danger is useless, processing cost is expensive.Therefore, develop a kind of process technique for RO strong brine, real
Existing salt separates, and improves purity and the quality of crystalline salt by evaporation so that it is reach industrial reuse requirement, can reduce evaporation body simultaneously
Long-pending, reduce energy consumption, the development to promoting coal chemical industry wastewater zero emission is significant.
Summary of the invention
It is an object of the invention to provide a kind of Coal Chemical Industry RO strong brine processing technology, at existing coal chemical industrial waste water Treated sewage reusing
On the process Process ba-sis of bi-membrane method, Organic substance in RO strong brine is made to remove further, and by degree of depth membrance concentration and salinity
From, reduce evaporated volume and energy consumption, improve purity and the quality of gained crystal salt, be beneficial to the industry recycling to crystal salt,
Fixed-end forces amount is reduced while resource reclaim.
For achieving the above object, the present invention is by the following technical solutions:
A kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that comprise the following steps:
(1), RO strong brine first pass through activated carbon adsorber, reduced the CODcr concentration of former RO strong brine by activated carbon adsorption；
(2) water outlet, after absorption enters two-stage nanofiltration point salt system and carries out nanofiltration and divide salt to obtain two strands of solution, and one is dense for nanofiltration
Water, the dense water of nanofiltration enters electrolytic oxidation pond；One produces water for nanofiltration, and nanofiltration is produced water and entered RO concentration systems；
(3), the dense water of nanofiltration that obtains of step (2) be electrolysed in electrolytic oxidation pond, electrolytic oxidation pond and the first evaporation element phase
Even, the saline after electrolysis enters the first evaporative crystallization unit and is evaporated concentrating, and concentrated solution is centrifugally separating to obtain through decrease temperature crystalline
Industrial sulphuric acid sodium crystal；
(4), the first evaporative crystallization unit and the second evaporative crystallization unit be connected, decrease temperature crystalline in the first evaporative crystallization unit
After the mother solution that obtains be flowed into the second evaporative crystallization unit；
(5), step (2) enter RO concentration systems nanofiltration produce water carry out concentrate nanofiltration, the RO fresh water after nanofiltration is back to middle water
Reuse pool, the dense water of RO, also into the second evaporative crystallization unit, is mixed in the second evaporative crystallization unit with the mother solution of (4)
It is evaporated crystallization, centrifuge dehydration, obtains industrial chlorinations sodium crystal and residue mother solution；
(6), the spray-dried device of residue mother solution of step (5) obtain carnallite after drying, the outward transport security landfill of the carnallite of generation.
Described a kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that: the saliferous rate of described former RO strong brine
For 5%-6%.
Described a kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that: containing of step (2) the dense water of gained nanofiltration
Salt rate is 10%-11%, and main salt component is sodium chloride and sodium sulfate, and the saliferous rate that gained nanofiltration is produced in water is 3%-4%, main salt
Composition is sodium chloride, divides salt by nanofiltration, reduces subsequent sulphuric acid sodium crystallization apparatus scale, reduces energy consumption.
Described a kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that: step (3) crystallizes the aqueous sulfuric acid obtained
The purity of sodium crystal is more than 90%.
Described a kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that: step (5) crystallizes the industrial chlorinations obtained
The purity of sodium crystal is more than 90%.
Described a kind of Coal Chemical Industry RO strong brine processing technology, it is characterised in that: the two-stage nanofiltration described in step (2) divides salt
The NF membrane that system uses can make monovalent ion pass through, and small organic molecule and divalent ion are difficult to by NF membrane, are
The system dense water of gained enters electrolytic oxidation pond, and gained produces water and enters into RO concentration systems..
Currently preferred, the device of the first evaporative crystallization unit and the second evaporative crystallization unit both can individually be selected
MVR or multiple-effect evaporation, it is also possible to Papillary, selection mode carrys out comprehensive consideration according to operational effect, energy consumption.
In sewage water treatment method of the present invention,
Former RO strong brine had been subjected to ion exchange resin treatment, in waste water bivalent cation such as Ca2+ and Mg2+ the most by
Remove, the most former RO strong brine is mainly composed of sodium chloride and sodium sulfate.
Former RO strong brine is after activated carbon adsorption, and CODcr value is reduced to 500-600mg/L by 900-1000mg/L, fall
Low to subsequent film systemic contamination while, also improve the quality of final crystal salt.
The dense water of nanofiltration is after electrolytic oxidation, and CODcr value is reduced to below 100mg/L by 2000mg/L.
Nanofiltration product water is after follow-up RO membranous system, and the response rate of fresh water is 60-70%, and the saliferous rate of the dense water of gained is
10%, it is mainly composed of sodium chloride.
The technique of the present invention, can recycle the salt of 80% in former RO strong brine, can be by RO strong brine
The moisture of 90% recycles.Gained sodium chloride crystal and recycle-water mixed configuration in Treated sewage reusing pond are to finite concentration
After, can be used for regeneration of ion-exchange resin.Gained sodium chloride crystal and Natrii Sulfas purity reach more than 90%, can be used for industry and return
With.
The craft science of the present invention is reasonable, on the basis of tradition Treated sewage reusing technique at present, it is achieved waste water and salinity
Recycling, solid waste achieves resource and minimizing, not only reduces fixed-end forces expense, and alleviates ecological environment
Impact.
Accompanying drawing explanation
Fig. 1 is the process chart of patent of the present invention.
Detailed description of the invention
As it is shown in figure 1, a kind of Coal Chemical Industry RO strong brine processing technology of the present invention, including former RO strong brine pond 1, its
After connect activated carbon adsorber 2, be connected to two-stage nanofiltration system 3 afterwards, the dense water of nanofiltration successively evaporates through electrolyzer 4, first
Unit 5, decrease temperature crystalline unit 6, isolated industry Natrii Sulfas.Nanofiltration is produced water and is entered reverse osmosis (RO) system 7, and gained RO produces water and enters
After reuse pool 8, the dense water of RO and crystallization, mother solution enters the second evaporative crystallization unit 9 after collecting, and separates after centrifuge dehydration 10
Obtaining industrial chlorinations sodium, residue mother solution enters spray dryer 11.
Described sewage water treatment method comprises the following steps,
A) former RO strong brine enters activated carbon adsorber, is removed dirty Organic substance in water further by powder electroless plating.
B) adsorption tower water outlet entrance nanofiltration divides salt system, i.e. water inlet first passes through one-level nanofiltration, and the dense water of its gained leads to two
Level nanofiltration, the product water of firsts and seconds nanofiltration then concentrates further toward reverse osmosis (RO), and two grades of dense water of nanofiltration gained enter electricity
Xie Chi removes dense Organic substance in water.
C) electrolysis water outlet enters the first evaporation element and concentrates, and makes salinity in dense water reach nearly saturated concentration, and evaporation is single
The fresh water that unit generates flows into reuse pool.
D) nearly saturated dense water enters decrease temperature crystalline device, separates out Natrii Sulfas crystal, isolated industry Natrii Sulfas, crystallization residue mother
Liquid enters the second evaporative crystallization unit.
E), after water entrance reverse osmosis (RO) is produced in nanofiltration, produced fresh water entrance reuse pool is to treat reuse, and main salt component is chlorine
The dense water changing sodium then enters the second evaporative crystallization unit.
E) fresh water that the second evaporative crystallization unit generates flows into reuse pool, being centrifuged after the entrance of gained crystal mixed liquor
Dewatering unit.
F) isolated industrial chlorinations sodium after crystal mixed liquor is dehydrated by centrifugation, residue mother solution then enters spray dryer.
G) exsiccator gained carnallite outward transport security landfill.
In step a of the present invention, organic concentration can be reduced to 500-600mg/L by 900-1000mg/L.
In step b of the present invention, the saliferous rate of the dense water of two-stage nanofiltration is up to 10%-11%, and the saliferous rate producing water is 3%-
4%。
In step c of the present invention, the dense water of nanofiltration is after electrolytic oxidation, and CODcr value is reduced to by 2000mg/L
Below 100mg/L.
In step e of the present invention, the saliferous rate of the dense water of reverse osmosis (RO) gained up to 10%, and wherein sodium chloride in salt
Ratio account for more than 95%.
Embodiment 1:
Former RO strong brine is after Powdered Activated Carbon filtration tank internal adsorption 1h, and COD is reduced to 600mg/L by 1000mg/L.Water outlet is entered
Entering two-stage nanofiltration system, it is 3.4% that gained produces the saliferous rate of water, and CODcr value is 300mg/L, and the saliferous rate of the dense water of gained is
10.5%, CODcr value is 2200mg/L.After the dense water of two-stage nanofiltration system gained is by electrolyzer electrolysis 8h, CODcr is reduced to
90mg/L.Electrolysis water outlet after the first evaporation element, the 20% of volume concentration to original volume.Nearly saturated dense water enters cooling knot
Brilliant unit, isolated industry Natrii Sulfas after crystallization.Two-stage nanofiltration system gained produces water and enters reverse osmosis (RO) system, and gained produces water
(fresh water) ion concentration is less than 200ppm, and the saliferous rate of the dense water of gained is 10%, and the purity that sodium chloride is in dense water salt reaches
95%.The dense water of reverse osmosis (RO) and crystalline mother solution enter the second evaporative crystallization unit after collecting, obtaining industry after centrifuge dehydration
Sodium chloride, residue mother solution enters spray dryer.
Concrete operations condition is: the operation pressure of first order nanofiltration is 14 kilograms, and the operation pressure of second level nanofiltration is 28
Kilogram, the overall recovery of two-stage nanofiltration system is 80%.The operation temperature of decrease temperature crystalline unit is-2 DEG C.Reverse osmosis (RO) system
Operation pressure is 85 kilograms, and the response rate is 65%.
Embodiment 2:
Former RO strong brine is after Powdered Activated Carbon filtration tank internal adsorption 1h, and COD is reduced to 600mg/L by 1000mg/L.Water outlet is entered
Entering two-stage nanofiltration system, it is 3.8% that gained produces the saliferous rate of water, and CODcr value is 320mg/L, and the saliferous rate of the dense water of gained is 10
%, CODcr value is 2000mg/L.After the dense water of two-stage nanofiltration system gained is by electrolyzer electrolysis 8h, CODcr is reduced to 85mg/L.
Electrolysis water outlet after the first evaporation element, the 20% of volume concentration to original volume.Nearly saturated dense water enters decrease temperature crystalline unit,
Isolated industry Natrii Sulfas after crystallization.Two-stage nanofiltration system gained produce water enter reverse osmosis (RO) system, gained produce water (fresh water) from
Sub-concentration is less than 200ppm, and the saliferous rate of the dense water of gained is 10%, and the purity that sodium chloride is in dense water salt reaches 95%.Reverse osmosis
The dense water of RO and crystalline mother solution enter the second evaporative crystallization unit after collecting, obtaining industrial chlorinations sodium after centrifuge dehydration, surplus
Remaining mother solution enters spray dryer.
Concrete operations condition is: the operation pressure of first order nanofiltration is 16 kilograms, and the operation pressure of second level nanofiltration is 30
Kilogram, the overall recovery of two-stage nanofiltration system is 80%.The operation temperature of decrease temperature crystalline unit is-2 DEG C.Reverse osmosis (RO) system
Operation pressure is 80 kilograms, and the response rate is 60%.
Claims (6)
1. a Coal Chemical Industry RO strong brine processing technology, it is characterised in that comprise the following steps:
(1), RO strong brine first pass through activated carbon adsorber, reduced the CODcr concentration of former RO strong brine by activated carbon adsorption；
(2) water outlet, after absorption enters two-stage nanofiltration point salt system and carries out nanofiltration and divide salt to obtain two strands of solution, and one is dense for nanofiltration
Water, the dense water of nanofiltration enters electrolytic oxidation pond；One produces water for nanofiltration, and nanofiltration is produced water and entered RO concentration systems；
(3), the dense water of nanofiltration that obtains of step (2) be electrolysed in electrolytic oxidation pond, electrolytic oxidation pond and the first evaporation element phase
Even, the saline after electrolysis enters the first evaporative crystallization unit and is evaporated concentrating, and concentrated solution is centrifugally separating to obtain through decrease temperature crystalline
Industrial sulphuric acid sodium crystal；
(4), the first evaporative crystallization unit and the second evaporative crystallization unit be connected, decrease temperature crystalline in the first evaporative crystallization unit
After the mother solution that obtains be flowed into the second evaporative crystallization unit；
(5), step (2) enter RO concentration systems nanofiltration produce water carry out concentrate nanofiltration, the RO fresh water after nanofiltration is back to middle water
Reuse pool, the dense water of RO, also into the second evaporative crystallization unit, is mixed in the second evaporative crystallization unit with the mother solution of (4)
It is evaporated crystallization, centrifuge dehydration, obtains industrial chlorinations sodium crystal and residue mother solution；
(6), the spray-dried device of residue mother solution of step (5) obtain carnallite after drying, the outward transport security landfill of the carnallite of generation.
A kind of Coal Chemical Industry RO strong brine processing technology the most according to claim 1, it is characterised in that: the described dense salt of former RO
The saliferous rate of water is 5%-6%.
A kind of Coal Chemical Industry RO strong brine processing technology the most according to claim 1, it is characterised in that: step (2) gained is received
The saliferous rate filtering dense water is 10%-11%, and main salt component is sodium chloride and sodium sulfate, and the saliferous rate that gained nanofiltration is produced in water is
3%-4%, main salt component is sodium chloride, divides salt by nanofiltration, reduces subsequent sulphuric acid sodium crystallization apparatus scale, reduces energy
Consumption.
A kind of Coal Chemical Industry RO strong brine processing technology the most according to claim 1, it is characterised in that: step (3) crystallizes
The purity of the aqueous sulfuric acid sodium crystal arrived is more than 90%.
A kind of Coal Chemical Industry RO strong brine processing technology the most according to claim 1, it is characterised in that: step (5) crystallizes
The purity of the industrial chlorinations sodium crystal arrived is more than 90%.
A kind of Coal Chemical Industry RO strong brine processing technology the most according to claim 3, it is characterised in that: described in step (2)
The NF membrane that two-stage nanofiltration point salt system uses can make monovalent ion pass through, and small organic molecule and divalent ion are difficult to logical
Crossing NF membrane, the dense water of system gained enters electrolytic oxidation pond, and gained produces water and enters into RO concentration systems.
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| CN201610483120.0A CN105948362A (en) | 2016-06-24 | 2016-06-24 | Coal chemical RO strong brine treatment process |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106517622A (en) * | 2016-09-23 | 2017-03-22 | 江苏新宇天成环保工程集团有限公司 | Separation and reuse method of sodium sulfate from high salinity wastewater |
| CN106630341A (en) * | 2016-09-23 | 2017-05-10 | 江苏新宇天成环保工程集团有限公司 | Sodium chloride separating and recycling method for high-salinity wastewater |
| CN106746103A (en) * | 2016-09-23 | 2017-05-31 | 江苏新宇天成环保工程集团有限公司 | A kind of separating and recovering method of the sodium chloride of high-salt wastewater and sodium sulphate |
| CN107902677A (en) * | 2016-12-12 | 2018-04-13 | 威立雅水处理技术公司 | The method that potassium sulfate and sodium chloride are produced from waste water |
| CN109081488A (en) * | 2018-08-03 | 2018-12-25 | 北京朗新明环保科技有限公司 | A kind of method and system of industry strong brine resource utilization |
| CN112125457A (en) * | 2020-09-10 | 2020-12-25 | 黄河三角洲京博化工研究院有限公司 | Thermoelectric reverse osmosis concentrated water crystallization salt separation treatment method |
| CN112299634A (en) * | 2020-10-14 | 2021-02-02 | 新疆中泰创新技术研究院有限责任公司 | Method and device for improving quality of PTA high-salt wastewater evaporative crystallization salt separation |
| CN113149346A (en) * | 2021-04-01 | 2021-07-23 | 北京能泰高科环保技术有限公司 | Method for recycling semi-coke wastewater |
| CN114368867A (en) * | 2021-12-29 | 2022-04-19 | 南京工大环境科技有限公司 | Treatment process and method for high-concentration salt aquatic product crystal salt of coal-to-liquid |
| CN117228906A (en) * | 2023-11-15 | 2023-12-15 | 开源环境科技集团有限公司 | Printing and dyeing wastewater treatment process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106517622A (en) * | 2016-09-23 | 2017-03-22 | 江苏新宇天成环保工程集团有限公司 | Separation and reuse method of sodium sulfate from high salinity wastewater |
| CN106630341A (en) * | 2016-09-23 | 2017-05-10 | 江苏新宇天成环保工程集团有限公司 | Sodium chloride separating and recycling method for high-salinity wastewater |
| CN106746103A (en) * | 2016-09-23 | 2017-05-31 | 江苏新宇天成环保工程集团有限公司 | A kind of separating and recovering method of the sodium chloride of high-salt wastewater and sodium sulphate |
| CN107902677A (en) * | 2016-12-12 | 2018-04-13 | 威立雅水处理技术公司 | The method that potassium sulfate and sodium chloride are produced from waste water |
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| CN109081488A (en) * | 2018-08-03 | 2018-12-25 | 北京朗新明环保科技有限公司 | A kind of method and system of industry strong brine resource utilization |
| CN112125457A (en) * | 2020-09-10 | 2020-12-25 | 黄河三角洲京博化工研究院有限公司 | Thermoelectric reverse osmosis concentrated water crystallization salt separation treatment method |
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| CN112299634B (en) * | 2020-10-14 | 2023-12-26 | 新疆中泰创新技术研究院有限责任公司 | Method and device for improving evaporation crystallization salt separation quality of PTA high-salt wastewater |
| CN113149346A (en) * | 2021-04-01 | 2021-07-23 | 北京能泰高科环保技术有限公司 | Method for recycling semi-coke wastewater |
| CN114368867A (en) * | 2021-12-29 | 2022-04-19 | 南京工大环境科技有限公司 | Treatment process and method for high-concentration salt aquatic product crystal salt of coal-to-liquid |
| CN117228906A (en) * | 2023-11-15 | 2023-12-15 | 开源环境科技集团有限公司 | Printing and dyeing wastewater treatment process |
| CN117228906B (en) * | 2023-11-15 | 2024-02-20 | 开源环境科技集团有限公司 | Printing and dyeing wastewater treatment process |
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Application publication date: 20160921 |
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