CN110015799A - A kind of processing method of waste water - Google Patents
A kind of processing method of waste water Download PDFInfo
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- CN110015799A CN110015799A CN201910326383.4A CN201910326383A CN110015799A CN 110015799 A CN110015799 A CN 110015799A CN 201910326383 A CN201910326383 A CN 201910326383A CN 110015799 A CN110015799 A CN 110015799A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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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
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
A kind of processing method of waste water, is related to chemical industry and metallurgical environmental protection field.The processing method of waste water the following steps are included: by include ammonium ion, sodium ion and sulfate ion waste water dilution crystallization after be separated by solid-liquid separation, obtain ammonium sulfate and the first mother liquor；By crystallisation by cooling after the first mother liquor concentrations, sodium sulphate is obtained.The processing method of the waste water realizes the separation of ammonium ion and sodium ion by dilution crystallization, in dissolved agent-aqueous systems, with the increase of dissolved agent content, ammonium sulfate is easier to be precipitated than sodium sulphate, after part of sulfuric acid ammonium is precipitated, recycles sodium sulphate from the first mother liquor, compared with existing alkali carries ammonia still process-evaporative crystallization technique, additional liquid alkaline is not needed, the cost of raw materials used in operational process is reduced, while sodium sulphate yield will not be caused to increase because of the introducing of liquid alkaline；In addition the energy consumption during alkali carries ammonia still process is also avoided, operating cost is reduced.
Description
Technical field
This application involves chemical industry and metallurgical environmental protection field, in particular to a kind of processing method of waste water.
Background technique
The polynary electrode material of nickle cobalt lithium manganate [Li (NiCoMn) O2] it is to develop swift and violent new type lithium ion battery in recent years
Positive electrode, it has concentrated cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2) and LiMn2O4 (LiMnO2) three kinds of materials the advantages of,
Have many advantages, such as that discharge capacity height, stable structure, safety is good, has extended cycle life, becomes lithium ion cell positive material in recent years
The hot spot of material research and industrialization.
In precursor of lithium ionic cell positive material such as nickel-cobalt-manganese ternary hydroxide, nickel cobalt binary hydroxide, nickel manganese
In the production processes such as binary hydroxide, ball-shape nickel hydroxide, cobalt hydroxide, mangano-manganic oxide, ammonium hydroxide, liquid alkaline, nickel are used
The mixed solution of cobalt manganese, after the completion of precipitating, mother liquor of precipitation of ammonium is by-product high-salt wastewater (ammonia nitrogen ≈ 10g/L, Na+≈30g/L、
SO4 2-≈100g/L)。
For the high-salt wastewater or with the consistent high-salt wastewater of its ingredient, the recycling of ammonium ion and sodium ion is existing
Method using the method for alkali carries ammonia still process-evaporative crystallization processing byproduct wastewater, that is to say the ammonia still process in ammonia evaporator by this waste water,
The ammonia steamed is ammonium sulfate with retrieval of sulfuric acid or is directly recovered as ammonium hydroxide, and dope is again after the filtering of three-level RO film for distilled ammonia liquid
It is evaporated crystallization recycling sodium sulphate.Wherein, ammonia is being separately recovered using alkali carries ammonia still process-evaporative crystallization process mixed liquor
Before water and sodium sulphate, existing method can also be mixed after concentration with mother liquor using first wash water is concentrated using membrane technology
Pretreatment operation.
But in alkali carries ammonia still process-evaporation technology, need to be firstly added equimolar NaOH before (1) ammonia still process for ammonium ion
Being converted into ammonium hydroxide could deviate from, and while consuming high added value NaOH, increase the amount of cheap chemicals sodium sulphate；(2) process
Complexity, whole equipment energy consumption is high, and the value of the product of recycling is difficult to offset operating cost, and most producer just will under the pressure of environmental pressure
The technology carries out industrialization.
Summary of the invention
The application provides a kind of processing method of waste water, high attached to avoid consumption to efficiently separate ammonium ion, sodium ion
Value added NaOH and simple flow reduce operating cost.
According to a kind of processing method of waste water of the embodiment of the present application comprising following steps:
By include ammonium ion, sodium ion waste water dilution crystallization after be separated by solid-liquid separation, obtain ammonium sulfate and the first mother liquor；
By crystallisation by cooling after the first mother liquor concentrations, sodium sulphate is obtained.
According to the processing method of the waste water of the embodiment of the present application, point of ammonium ion and sodium ion is realized by dilution crystallization
From in dissolved agent-aqueous systems, with the increase of dissolved agent content, ammonium sulfate is easier to be precipitated than sodium sulphate, part of sulfuric acid ammonium
After precipitation, sodium sulphate is recycled from the first mother liquor, compared with existing alkali carries ammonia still process-evaporative crystallization technique, does not need outer liquid feeding
Alkali reduces the cost of raw materials used during operation, while sodium sulphate yield will not be caused to increase because of the introducing of liquid alkaline；Separately
The energy consumption during alkali carries ammonia still process is also avoided outside, and cost for wastewater treatment per ton is reduced to 40 yuan by 75 yuan, operating cost
It substantially reduces.
It should be noted that the sodium sulphate and ammonium sulfate that obtain in the application are major product, it can be containing certain
The impurity of amount, it is not limited here.
In addition, also there is following additional technical characteristic according to the processing method of the waste water of the embodiment of the present application:
In some embodiments shown in the application, the step of dilution crystallization, includes:
Dissolved agent, which is made an addition in waste water, makes ammonium ion crystallize precipitation as ammonium sulphate, until remaining ammonium ion
When mass concentration ratio with sodium ion is 1:5~1:10, stop that dissolved agent is added.
Wherein, when remaining ammonium ion (that is to say in waste water-dissolved agent system, not analyse as ammonium sulphate
Ammonium ion out) it with the mass concentration ratio of sodium ion (in waste water-dissolved agent system, free sodium ion) is 1:5~1:10
When, then dissolved agent is added, it will lead to sodium ion and be largely precipitated in the form of sodium sulphate, mixed with ammonium sulfate, ammonium sulfate is caused to produce
Sodium ion in product is higher.For the degree of purity of the ammonium sulfate guaranteed, at the same in order to efficiently separate ammonium ion and
Sodium ion, therefore stop that dissolved agent is added when the mass concentration ratio of remaining ammonium ion and sodium ion is 1:5~1:10.
Optionally, in order to guarantee the adequacy being precipitated, stop after dissolved agent is added, stir 1-3h.
Optionally, the temperature of dilution crystallization is 0~40 DEG C, is chosen as 20-30 DEG C；Such as the temperature of dilution crystallization be 0 DEG C,
Any in 5 DEG C, 8 DEG C, 10 DEG C, 13 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 27 DEG C, 30 DEG C, 33 DEG C, 36 DEG C, 39 DEG C and 40 DEG C
Range between temperature or any two points.
Optionally, dissolved agent include one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetonitrile, acetone, tetrahydrofuran or
It is a variety of.Optionally, dissolved agent is selected from any one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetonitrile, acetone, tetrahydrofuran.
Since dissolved agent has volatility, in order to guarantee the adequacy and accuracy of dilution crystallization, and also to anti-
The only waste of raw material and pollution environment, optionally, the step of dilution crystallization, carries out in the reaction vessel of sealing.Such as it reacts
Container is crystallization kettle etc..
It further include by before the first mother liquor concentrations in some embodiments shown in the application to reduce operating cost
The distillation of one mother liquor, collects the distillate containing dissolved agent.
The distillate containing dissolved agent is collected, the waste of dissolved agent can be effectively prevent, it should be noted that can be according to specific
Dissolved agent distillate of boiling point (refer to the relevant technologies, do not do specifically the repeat herein) collection containing the dissolved agent.
Optionally, stop distilling when the first mother liquor being distilled to the mass concentration < 1.0% of remaining dissolved agent.
Under this condition, it is equivalent to and has recycled dissolved agent completely, improve the availability of dissolved agent, if the first mother liquor is distilled
Mass concentration to remaining dissolved agent is greater than 1.0% and just stops distillation, and it will cause the recycling of dissolved agent is incomplete, part is molten
Analyse agent waste.It is noted that the mass concentration of remaining dissolved agent herein, refers to and contain in the first mother liquor after distillation
The mass concentration of dissolved agent.
In order to recycle dissolved agent, cost is reduced, is convenient for industrialized production, while also can effectively prevent
It pollutes environment.Optionally, the step of distillate being delivered to dilution crystallization recycles.
Wherein, concentration can for example use film filtering and concentrating, but this mode is at high cost, and film is more easily damaged, inconvenient
In industrialization operate in large scale, therefore optionally, concentration is by the way of being concentrated by evaporation.
Still optionally further, it is concentrated by evaporation and is carried out in the same distillation container with the step of the first mother liquor of distillation.
The step of the step of that is to say, distilling the first mother liquor and evaporation and concentration, is in the same distillation container, such as distillation still
In successively carry out, on the one hand can use the heat that the first mother liquor of distillation generates and be effectively evaporated concentration, reduction energy consumption,
Operating cost is reduced, on the other hand, the new distillation container of additional increase is not needed and increases the process of liquid out and feed liquor,
It is further simplified operating process and reduces operating cost.
Optionally, the steam generated when being concentrated by evaporation is cooling, recycling.Optionally, the water generated in distillation process is steamed
Gas can also carry out cooling recycling.The waste for preventing water resource improves the degree of making full use of of the raw material of entire wastewater treatment method.
Since nickel-cobalt-manganese ternary hydroxide produces the ammonium ion contained in waste water, the variation of sodium ion equal size less,
Generally ammonia nitrogen ≈ 10g/L, Na+≈30g/L、SO4 2-≈ 100g/L, for the ease of macrotechnique, convenient for adding dissolved agent,
Stop being added under the requirement of dissolved agent when the mass concentration ratio of remaining ammonium ion and sodium ion is 1:5~1:10, with dissolved
The additive amount of agent and the volume ratio of waste water are defined.
Optionally, waste water includes the waste water of ammonium hydroxide complex-precipitation process, and the additive amount of dissolved agent and the volume ratio of waste water are
0.2:1~5:1.It is defined with volume ratio, the efficiency of water process can be improved in actual operation convenient for stock.
In some embodiments shown in the application, the step of crystallisation by cooling, includes:
The concentrate obtained after concentration, which is cooled to 20~45 DEG C, is precipitated sodium ion in the form of sodium sulphate, solid-liquid point
From obtaining sodium sulphate and the second mother liquor.
The concentration of the sodium ion in concentrate is improved by being concentrated, cooperation cools, effectively by sodium ion mainly with
The form of sodium sulphate carries out crystallization precipitation.On the basis of evaporation and concentration, due to be concentrated by evaporation after concentrate temperature compared with
The solubility of height, the sodium sulphate contained is big, and by cooling, the solubility of sodium sulphate becomes smaller, and effectively sulfate crystal can be made to analyse
Out.
Optionally, it is by concentrate crystallisation by cooling to its remaining ammonium ion and the mass concentration ratio of remaining sodium ion
It is separated by solid-liquid separation when 10:1~5:1.At this point, remaining ammonium ion refers to the ammonium root contained in the concentrate after crystallisation by cooling
Ion, remaining sodium ion refer to the sodium ion being precipitated in the concentrate after crystallisation by cooling not in the form of sodium salt.
Under this condition, remaining Na ion concentration is small, and the rate of recovery of sodium sulphate is high, meanwhile, remaining ammonium ion with it is residual
The ratio of the sodium ion stayed is suitable, and remaining ammonium ion can be effectively prevent also to crystallize precipitation, influences the degree of purity of sodium sulphate, with
And it is not easy to separate ammonium ion and sodium ion.
Since the second mother liquor contains remaining ammonium ion and remaining sodium ion, in order to as far as possible by ammonium ion with
Sodium ion is kept completely separate, while obtaining whole ammonium ion and sodium ion as far as possible, while realizing the processing to waste water
Waste water is made full use of, optionally, the processing method of waste water further includes that the second mother liquor and waste water are mixed for supplement part to give up
Water.
In other words, by the second mother liquid recycling, the discharge of waste liquid is prevented, improves the whole process of the wastewater treatment method
In the feature of environmental protection, and raw material involved in the processing method of entire waste water makes full use of, and reduces operating cost.
Because of lithium ions such as ball nickel, cobalt hydroxide, mangano-manganic oxide, nickel cobalt binary hydroxide, nickel manganese binary hydroxide
The waste water of by-product and byproduct wastewater ingredient in nickel cobalt manganese production process are almost the same in cell positive material presoma production process,
Be ammonium hydroxide complex-precipitation, so the ingredient of waste water is essentially identical, mainly comprising ammonium ion, sodium ion and sulfate radical from
Son, therefore this method processing can be used.
Therefore, in some embodiments shown in the application, waste water includes nickel-cobalt-manganese ternary hydroxide production waste water, nickel cobalt
Binary hydroxide produces waste water, nickel manganese binary hydroxide produces waste water, ball nickel production waste water, cobalt hydroxide produce waste water,
Mangano-manganic oxide produces one of waste water or a variety of.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the flow diagram of the processing method of waste water in some specific embodiments provided by the present application.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In this application, term " first ", " second " etc. are only used for distinguishing description, are not understood to indicate or imply phase
To importance.
Waste water provided by the present application is ammonium hydroxide complex-precipitation waste water, mainly includes ammonia nitrogen, Na+And SO4 2-, wherein
Nickel cobalt manganese produces in waste water, ammonia nitrogen ≈ 10g/L, Na+≈30g/L、SO4 2-Therefore ≈ 100g/L is based on above-mentioned content, Ke Yili
Volume ratio with the additive amount of dissolved agent and waste water is the configuration that 0.2:1~5:1 carries out dissolved agent.
It should be noted that the waste water in the application include but is not limited to nickel-cobalt-manganese ternary hydroxide production waste water,
Nickel cobalt binary hydroxide produces waste water, nickel manganese binary hydroxide production waste water, ball nickel production waste water, cobalt hydroxide and produces and give up
One of water, mangano-manganic oxide production waste water are a variety of.It can also be to be other mainly including ammonia nitrogen, Na+And SO4 2-
Waste water, wherein ammonia nitrogen, Na+And SO4 2-Concentration can with nickel cobalt manganese produce waste water in the content of each substance it is identical, close
Or it is different, it is not limited here.
It should be noted that other than the processing method for the waste water that the application improves, based at water provided by the present application
Waste water treatment system can also be derived on the basis of reason method, wastewater treatment method provided by the present application is used to carry out waste water
Processing.
Optionally, the processing method of waste water is as shown in Figure 1 in some specific embodiments provided by the present application.
The feature of the application and performance are described in further detail with reference to embodiments.
Embodiment 1
A kind of processing method of nickel-cobalt-manganese ternary hydroxide production waste water comprising following steps:
(1) by 2m3≈ containing ammonia nitrogen 10g/L, Na+≈30g/L、SO4 2-The nickel-cobalt-manganese ternary hydroxide of ≈ 100g/L produces
The volume that waste water is pumped into sealing is 5m3In crystallization kettle, making an addition to dissolved agent in waste water in 20 DEG C makes ammonium ion with ammonium sulfate
Form crystallize and be precipitated, when making the mass concentration ratio 1:10 of remaining ammonium ion and sodium ion, stop that dissolved agent is added, it is total
2m is added3Dissolved agent, stop be added dissolved agent after stir 2h, be separated by solid-liquid separation using centrifuge, respectively obtain ammonium sulfate
Product and the first mother liquor, wherein the direct export trade of ammonium sulfate product that is to say recycling ammonium sulfate product.
Wherein, dissolved agent is ethyl alcohol.
(2) the first mother liquor is pumped into distillation still to distill, it is dense that the first mother liquor is distilled the quality to remaining dissolved agent
Stop distillation when spending 1.0%, collects the distillate containing dissolved agent, and distillate is delivered to the dilution crystallization in step (1)
Step cycle utilizes.
(3) then to distillation still of first mother liquor directly in step (2) for removing the distillate containing dissolved agent after distillation
In be evaporated concentration, obtain the concentrate that density is 1.5g/mL, also, the vapor that by evaporation and concentration and distillation when generates
It is cooling, recycle condensate liquid.
(4) concentrate is cooled to 30 DEG C makes sodium ion crystallize precipitation in the form of sodium sulphate, by concentrate crystallisation by cooling
Mass concentration ratio to remaining ammonium ion and remaining sodium ion is separated by solid-liquid separation when being 10:1, obtain sodium sulphate product with
Second mother liquor, sodium sulphate international sale, the second mother liquor return to the waste water being incorporated in step (1), continue waste water next time
Processing.
The present embodiment, in the dilution crystallization process of step (1), ammonium sulfate crystallization rate is 60%, the percent crystallization in massecuite of sodium sulphate is
1%, Na in dilution crystallization product+Content 1.5%.
In step (4) crystallisation by cooling process, sulfate crystal rate is 70%, the percent crystallization in massecuite of ammonium sulfate is 1.5%, cooling knot
NH in brilliant product4 +Content 0.8%.
Embodiment 2
The processing method of one bulb nickel production waste water comprising following steps:
(1) by 2m3≈ containing ammonia nitrogen 30g/L, Na+≈10g/L、SO4 2-The ball nickel production waste water of ≈ 100g/L is pumped into sealing
Volume is 5m3In crystallization kettle, making an addition to dissolved agent in waste water in 30 DEG C makes ammonium ion crystallize precipitation as ammonium sulphate,
When making the mass concentration ratio 1:5 of remaining ammonium ion and sodium ion, stops that dissolved agent is added, 0.4m is added altogether3Dissolved
Agent is stopped stirring 3h after dissolved agent is added, is separated by solid-liquid separation using centrifuge, respectively obtains ammonium sulfate product and the first mother
Liquid, wherein the direct export trade of ammonium sulfate product that is to say recycling ammonium sulfate product.
Wherein, dissolved agent is propyl alcohol.
(2) the first mother liquor is pumped into distillation still to distill, it is dense that the first mother liquor is distilled the quality to remaining dissolved agent
Stop distillation when spending 0.9%, collects the distillate containing dissolved agent, and distillate is delivered to the dilution crystallization in step (1)
Step cycle utilizes.
(3) then to distillation still of first mother liquor directly in step (2) for removing the distillate containing dissolved agent after distillation
In be evaporated concentration, obtain the concentrate that density is 1.4g/mL, also, the vapor that by evaporation and concentration and distillation when generates
It is cooling, recycle condensate liquid.
(4) concentrate is cooled to 35 DEG C is precipitated sodium ion in the form of sodium sulphate, by concentrate crystallisation by cooling to residual
The ammonium ion stayed and the mass concentration ratio of remaining sodium ion are separated by solid-liquid separation when being 5:1, obtain sodium sulphate product and second
Mother liquor, sodium sulphate international sale, the second mother liquor return to the waste water being incorporated in step (1), continue wastewater treatment next time.
The present embodiment, in the dilution crystallization process of step (1), ammonium sulfate crystallization rate is 65%, the percent crystallization in massecuite of sodium sulphate is
0.5%, Na in dilution crystallization product+Content 0.5%.
In step (4) crystallisation by cooling process, sulfate crystal rate is 65%, the percent crystallization in massecuite of ammonium sulfate is 1.0%, cooling knot
NH in brilliant product4 +Content 0.5%.
Embodiment 3
A kind of processing method of cobalt hydroxide production waste water comprising following steps:
(1) by 2m3≈ containing ammonia nitrogen 20g/L, Na+≈20g/L、SO4 2-The cobalt hydroxide production waste water of ≈ 100g/L is pumped into close
The volume of envelope is 5m3In crystallization kettle, making an addition to dissolved agent in waste water in 25 DEG C crystallizes ammonium ion as ammonium sulphate
It is precipitated, when making the mass concentration ratio 1:7.5 of remaining ammonium ion and sodium ion, stops that dissolved agent is added, 3m is added altogether3's
Dissolved agent is stopped stirring 1h after dissolved agent is added, is separated by solid-liquid separation using centrifuge, respectively obtains ammonium sulfate product and first
Mother liquor, wherein the direct export trade of ammonium sulfate product that is to say recycling ammonium sulfate product.
Wherein, dissolved agent is propyl alcohol.
(2) the first mother liquor is pumped into distillation still to distill, it is dense that the first mother liquor is distilled the quality to remaining dissolved agent
Stop distillation when spending 0.5%, collects the distillate containing dissolved agent, and distillate is delivered to the dilution crystallization in step (1)
Step cycle utilizes.
(3) then to distillation still of first mother liquor directly in step (2) for removing the distillate containing dissolved agent after distillation
In be evaporated concentration, obtain the concentrate that density is 1.4g/mL, also, the vapor that by evaporation and concentration and distillation when generates
It is cooling, recycle condensate liquid.
(4) concentrate is cooled to 20 DEG C is precipitated sodium ion in the form of sodium sulphate, by concentrate crystallisation by cooling to residual
The mass concentration ratio of the ammonium ion stayed and remaining sodium ion is separated by solid-liquid separation when being 7.5:1, obtains sodium sulphate product and the
Two mother liquors, sodium sulphate international sale, the second mother liquor return to the waste water being incorporated in step (1), continue at waste water next time
Reason.
The present embodiment, in the dilution crystallization process of step (1), ammonium sulfate crystallization rate is 80%, the percent crystallization in massecuite of sodium sulphate is
1.5%, Na in dilution crystallization product+Content 2.0%.
In step (4) crystallisation by cooling process, sulfate crystal rate is 80%, the percent crystallization in massecuite of ammonium sulfate is 2.0%, cooling knot
NH in brilliant product4 +Content 1.5%.
Embodiment 4
A kind of processing method of mangano-manganic oxide production waste water comprising following steps:
(1) by 2m3≈ containing ammonia nitrogen 5g/L, Na+≈35g/L、SO4 2-The mangano-manganic oxide production waste water of ≈ 100g/L is pumped into close
The volume of envelope is 15m3In crystallization kettle, making an addition to dissolved agent in waste water in 10 DEG C crystallizes ammonium ion as ammonium sulphate
It is precipitated, when making the mass concentration ratio 1:10 of remaining ammonium ion and sodium ion, stops that dissolved agent is added, 10m is added altogether3's
Dissolved agent is stopped stirring 3h after dissolved agent is added, is separated by solid-liquid separation using centrifuge, respectively obtains ammonium sulfate product and first
Mother liquor, wherein the direct export trade of ammonium sulfate product that is to say recycling ammonium sulfate product.
Wherein, dissolved agent is acetone.
(2) the first mother liquor is pumped into distillation still to distill, it is dense that the first mother liquor is distilled the quality to remaining dissolved agent
Stop distillation when spending 0.9%, collects the distillate containing dissolved agent, and distillate is delivered to the dilution crystallization in step (1)
Step cycle utilizes.
(3) then to distillation still of first mother liquor directly in step (2) for removing the distillate containing dissolved agent after distillation
In be evaporated concentration, obtain the concentrate that density is 1.6g/mL, also, the vapor that by evaporation and concentration and distillation when generates
It is cooling, recycle condensate liquid.
(4) concentrate is cooled to 10 DEG C is precipitated sodium ion in the form of sodium sulphate, by concentrate crystallisation by cooling to residual
The ammonium ion stayed and the mass concentration ratio of remaining sodium ion are separated by solid-liquid separation when being 10:1, obtain sodium sulphate product and second
Mother liquor, sodium sulphate international sale, the second mother liquor return to the waste water being incorporated in step (1), continue wastewater treatment next time.
The present embodiment, in the dilution crystallization process of step (1), ammonium sulfate crystallization rate is 85%, the percent crystallization in massecuite of sodium sulphate is
2%, Na in dilution crystallization product+Content 2.5%.
In step (4) crystallisation by cooling process, sulfate crystal rate is 85%, the percent crystallization in massecuite of ammonium sulfate is 2.5%, cooling knot
NH in brilliant product4 +Content 1.5%.
Embodiment 5
A kind of processing method of nickel manganese binary hydroxide production waste water comprising following steps:
(1) by 2m3≈ containing ammonia nitrogen 10g/L, Na+≈30g/L、SO4 2-The nickel manganese binary hydroxide production of ≈ 100g/L is useless
The volume that water is pumped into sealing is 5m3In crystallization kettle, making an addition to dissolved agent in waste water in 40 DEG C makes ammonium ion with ammonium sulfate
Form, which crystallizes, to be precipitated, and when making the mass concentration ratio 1:5 of remaining ammonium ion and sodium ion, is stopped that dissolved agent is added, is added altogether
Enter 2m3Dissolved agent, stop be added dissolved agent after stir 2h, be separated by solid-liquid separation using centrifuge, respectively obtain ammonium sulfate production
Product and the first mother liquor, wherein the direct export trade of ammonium sulfate product that is to say recycling ammonium sulfate product.
Wherein, dissolved agent is tetrahydrofuran.
(2) the first mother liquor is pumped into distillation still to distill, it is dense that the first mother liquor is distilled the quality to remaining dissolved agent
Stop distillation when spending 0.5%, collects the distillate containing dissolved agent, and distillate is delivered to the dilution crystallization in step (1)
Step cycle utilizes.
(3) then to distillation still of first mother liquor directly in step (2) for removing the distillate containing dissolved agent after distillation
In be evaporated concentration, obtain the concentrate that density is 1.5g/mL, also, the vapor that by evaporation and concentration and distillation when generates
It is cooling, recycle condensate liquid.
(4) concentrate is cooled to 25 DEG C is precipitated sodium ion in the form of sodium sulphate, by concentrate crystallisation by cooling to residual
The ammonium ion stayed and the mass concentration ratio of remaining sodium ion are separated by solid-liquid separation when being 5:1, obtain sodium sulphate product and second
Mother liquor, sodium sulphate international sale, the second mother liquor return to the waste water being incorporated in step (1), continue wastewater treatment next time.
The present embodiment, in the dilution crystallization process of step (1), ammonium sulfate crystallization rate is 63%, the percent crystallization in massecuite of sodium sulphate is
1.2%, Na in dilution crystallization product+Content 1.5%.
In step (4) crystallisation by cooling process, sulfate crystal rate is 69%, the percent crystallization in massecuite of ammonium sulfate is 1.8%, cooling knot
NH in brilliant product4 +Content 1.2%.
To sum up, the processing method of waste water provided by the present application can efficiently separate ammonium sulfate and sodium sulphate in waste water,
Additional liquid alkaline is not needed simultaneously, the cost of raw materials used during operation is reduced, sulphur will not be caused because of the introducing of liquid alkaline
Sour sodium yield increases；And the energy consumption during alkali carries ammonia still process is avoided, operating cost is further decreased.
The above is only the alternative embodiments of the application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of processing method of waste water, which is characterized in that itself the following steps are included:
By include ammonium ion, sodium ion and sulfate ion waste water dilution crystallization after be separated by solid-liquid separation, obtain ammonium sulfate and
First mother liquor；
By crystallisation by cooling after first mother liquor concentrations, sodium sulphate is obtained.
2. processing method according to claim 1, which is characterized in that the step of dilution crystallization includes:
Dissolved agent, which is made an addition in the waste water, makes ammonium ion crystallize precipitation as ammonium sulphate, until remaining ammonium ion
When mass concentration ratio with sodium ion is 1:5~1:10, stop that the dissolved agent is added.
3. processing method according to claim 2, which is characterized in that the temperature of the dilution crystallization is 0~40 DEG C, optional
It is 20-30 DEG C；
Optionally, the dissolved agent include one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetonitrile, acetone, tetrahydrofuran or
It is a variety of；
Optionally, the step of dilution crystallization carries out in the reaction vessel of sealing.
4. processing method according to claim 2, which is characterized in that further include by institute before first mother liquor concentrations
The distillation of the first mother liquor is stated, the distillate for containing the dissolved agent is collected；
Optionally, stop distilling when first mother liquor being distilled to the mass concentration < 1.0% of remaining dissolved agent.
5. processing method according to claim 4, which is characterized in that the distillate is delivered to the step of the dilution crystallization
Suddenly it recycles.
6. processing method according to claim 4, which is characterized in that concentration is by the way of being concentrated by evaporation；
Optionally, the evaporation and concentration carries out in the same distillation container with the step of distilling first mother liquor；
Optionally, the density of the concentrate obtained after concentration is 1.4-1.6g/mL；
Optionally, the steam generated when being concentrated by evaporation is cooling, recycling.
7. processing method according to claim 2, which is characterized in that the waste water includes the useless of ammonium hydroxide complex-precipitation process
Water, the additive amount of the dissolved agent and the volume ratio of the waste water are 0.2:1~5:1.
8. processing method according to claim 1, which is characterized in that the step of crystallisation by cooling includes:
The concentrate obtained after concentration is cooled to 20~45 DEG C so that sodium ion crystallizes precipitation, solid-liquid point in the form of sodium sulphate
From obtaining the sodium sulphate and the second mother liquor；
Optionally, by the mass concentration ratio of concentrate crystallisation by cooling to remaining ammonium ion and remaining sodium ion be 10:1~
It is separated by solid-liquid separation when 5:1.
9. processing method according to claim 8, which is characterized in that the processing method of the waste water further includes by described
Two mother liquors and the waste water mixing circulation utilize.
10. processing method according to claim 1, which is characterized in that the waste water includes nickel-cobalt-manganese ternary hydroxide
It produces waste water, nickel cobalt binary hydroxide production waste water, nickel manganese binary hydroxide production waste water, ball nickel and produces waste water, hydrogen-oxygen
Change one of cobalt production waste water, mangano-manganic oxide production waste water or a variety of.
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| CN111498929A (en) * | 2020-04-20 | 2020-08-07 | 内蒙古久科康瑞环保科技有限公司 | Fractional crystallization system and fractional crystallization method |
| CN111547918A (en) * | 2020-04-15 | 2020-08-18 | 苏州乔发盐化工设备科技有限公司 | Recycling treatment method for sodium sulfate and ammonium sulfate wastewater |
| CN112279273A (en) * | 2019-07-24 | 2021-01-29 | 中国科学院过程工程研究所 | Treatment method for removing COD (chemical oxygen demand) of industrial byproduct salt |
| CN112279274A (en) * | 2019-07-25 | 2021-01-29 | 中国科学院过程工程研究所 | Method for removing COD (chemical oxygen demand) of industrial byproduct salt |
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| CN112279273A (en) * | 2019-07-24 | 2021-01-29 | 中国科学院过程工程研究所 | Treatment method for removing COD (chemical oxygen demand) of industrial byproduct salt |
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