CN108314115A - A kind of method of ammonium salt-containing wastewater treatment - Google Patents
A kind of method of ammonium salt-containing wastewater treatment Download PDFInfo
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- CN108314115A CN108314115A CN201710035106.9A CN201710035106A CN108314115A CN 108314115 A CN108314115 A CN 108314115A CN 201710035106 A CN201710035106 A CN 201710035106A CN 108314115 A CN108314115 A CN 108314115A
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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
- C02F1/043—Details
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia 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
- 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
- C02F1/048—Purification of waste water by 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The present invention relates to sewage treatment fields, disclose a kind of method of ammonium salt-containing wastewater treatment, this method includes waste water is passed through MVR vaporising devices carrying out the first evaporation to obtain the first steam containing ammonia and the first concentrate, then first concentrate is each led into progress second in each effect evaporator of multi-effect evaporating device evaporate and obtain the second steam containing ammonia and the second concentrate；Wherein, before the waste water is passed through MVR vaporising devices, the pH value for adjusting the waste water is more than 9；Before the waste water is passed through MVR vaporising devices and multi-effect evaporating device, ammonia steam will be contained and carry out heat exchange with the waste water and obtain ammonium hydroxide；Described first evaporates so that the solid content in first concentrate is 50 mass % or less.The present invention provides treatment method for high-salinity wastewater containing ammonium a kind of at low cost and environmentally friendly, this method can recycle ammonium and salt in waste water, farthest recycle the resource in waste water, and near-zero release may be implemented.
Description
Technical field
The present invention relates to sewage treatment fields, and in particular, to a kind of method of ammonium salt-containing wastewater treatment, more particularly to
A kind for the treatment of method for high-salinity wastewater containing ammonium.
Background technology
In the production process of oil refining catalyst, a large amount of sodium hydroxide, hydrochloric acid, sulfuric acid, ammonium salt, sulfate, salt are needed
The inorganic acids alkali salt such as hydrochlorate generates and largely contains ammonium, sodium sulphate and sodium chloride and alumino-silicate combined sewage.For such
Sewage, common practice is first in the range of adjusting pH value to 6~9, after removing most suspended substances, then to adopt in the prior art
The removing of ammonium ion is carried out with biochemical process, blow-off method or vaporizing extract process, then, by saline sewage through overregulating pH value, the big portion of removing
Divide suspended matter, remove hardness, except silicon and partial organic substances and then by ozone biological activated carbon adsorption and oxidation or other advanced oxygen
Change method oxidation removal major part organic matter, then, after further removing hardness into ion interchange unit, into thickening device
After (such as reverse osmosis and/or electrodialysis) concentration, then using MVR evaporative crystallizations or multiple-effect evaporation crystallization, obtain the sulphur containing a small amount of ammonium salt
Sour sodium and sodium chloride mixing carnallite；Either；First adjust pH value in the range of 6.5~7.5, removing most suspended substances, so
Afterwards, it removes hardness, remove silicon and partial organic substances, gone using ozone biological activated carbon adsorption and oxidation or the oxidation of other advanced oxidation processes
It is (such as reverse osmosis and/or electric into thickening device after further removing hardness into ion interchange unit after most of organic matter
Dialysis) after concentration, then crystallized using MVR evaporative crystallizations or multiple-effect evaporation, sodium sulphate and the sodium chloride mixing for obtaining ammonium salt-containing are miscellaneous
Salt.But these carnallites containing ammonium are difficult to handle at present, or the processing cost is high, also, the process of removing early period ammonium ion,
Add additional the processing cost of waste water.
In addition, biochemical process deamination can only handle the waste water of low ammonium content, and due to COD contents deficiency in Catalyst sewage
Biochemical treatment cannot be directly carried out, machine object, such as glucose or starch are also additionally supplemented with during biochemical treatment, just may be used
To handle ammoniacal nitrogen using biochemical process.Sixty-four dollar question is biochemical process deamination treated waste water often total nitrogen (nitre not up to standard
Acid ion, nitrite ion content are exceeded), it is also necessary to advanced treating, in addition the content of salt is not reduced in waste water
(20000mg/L~30000mg/L), is unable to direct emission, needs further to carry out desalting processing.
Air- extraction deamination needs to add a large amount of adjusting PH with base value, alkaline consumption is very high, due to de- to deviate from the ammoniacal nitrogen in waste water
The alkali in waste water after ammonia cannot recycle, and treated, and pH value of waste water is very high, and the processing cost is high, and air lift rear catalyst is dirty
The not big variation of COD contents in water, the salt content in waste water do not reduce (20000mg/L~30000mg/L), Bu Nengzhi
Running in and put, needs further to carry out desalting processing, wastewater treatment operating cost is high, and a large amount of alkali is remained in treated waste water,
PH value is very high, and waste is big, and processing cost is up to 50 yuan/ton.
Invention content
It is an object of the invention to overcome the problems, such as that the processing cost of high-salt wastewater containing ammonium is high in the prior art, provide it is a kind of at
This low and environmentally friendly treatment method for high-salinity wastewater containing ammonium, this method can recycle ammonium and salt in waste water, farthest sharp again
With the resource in waste water, and near-zero release may be implemented.
To achieve the goals above, the present invention provides a kind of method of ammonium salt-containing wastewater treatment, and this method includes by waste water
It is passed through the first evaporation of MVR vaporising devices progress and obtains the first steam containing ammonia and the first concentrate, then first concentrate is divided
It is not passed through the second evaporation of progress in each effect evaporator of multi-effect evaporating device and obtains the second steam containing ammonia and the second concentrate,
In, before the waste water is passed through MVR vaporising devices, the pH value for adjusting the waste water is more than 9；It is passed through by the waste water
Before MVR vaporising devices, first steam containing ammonia and the waste water are subjected to the first heat exchange and obtain the first ammonium hydroxide；Will before
Carry out the second heat after the second steam containing ammonia that 1st effective evaporator evaporates is sent into 1st effective evaporator with first concentrate
It exchanges and obtains the second ammonium hydroxide；Also, described first evaporates so that the solid content in first concentrate is 50 mass %
Below.
Through the above technical solutions, by waste water being obtained after pH value is adjusted to specific range, MVR being recycled to steam in advance
Transmitting apparatus and multi-effect evaporating device carry out the first evaporation and the second evaporation to waste water, complete the process of separation of ammonia and salt, and adopt
Make waste water heating and steam cooling containing ammonia simultaneously with heat exchange method, be not necessarily to condenser, rationally utilizes the heat in evaporation process,
It is energy saving, cost for wastewater treatment is reduced, the ammonium in waste water is recycled in the form of ammonium hydroxide, and salt is with without ammonium or containing the miscellaneous of a small amount of ammonium
Salt crystal form recycles, and whole process does not have waste residue and liquid generation, realizes the purpose to turn waste into wealth, disregards the resource of recycling
The processing cost of value, waste water per ton is less than steam air lift deamination method.Also, technical scheme of the present invention first carries out waste water
One evaporation carry out the second evaporation again, so as to obtain the higher ammonium hydroxide of concentration in the first evaporation step, convenient for it is subsequent again
It utilizes.
Further, the present invention returns to evaporation process by the waste water during detaching crystal, washing crystal etc., and
It is discharged after the exhaust gas of the processes such as heat exchange is absorbed, so as to realize the near-zero release of processing procedure, to the maximum extent
It reduces environmental pollution.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of the wastewater treatment method of embodiment provided by the invention.
Reference sign
1, multi-effect evaporating device 2, MVR vaporising devices
31, the first heat-exchanger rig 32, the second heat-exchanger rig
33, third heat-exchanger rig 4, vacuum receiver
51, tank used for storing ammonia 52, ammonium hydroxide collecting pit
53, brilliant liquid collecting tank 61, the first pH value measuring device
62, the second pH value measuring device 71, first circulation pump
72, second circulation pump 73, third circulating pump
74, the 4th circulating pump 75, the 5th circulating pump
81, vacuum pump 82, circulating water pool
83, tail gas absorber 9, equipment for separating liquid from solid
10, compressor
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Below in conjunction with Fig. 1, the present invention will be described, and the present invention is not limited by Fig. 1.
The method of ammonium salt-containing wastewater treatment provided by the invention, this method include that waste water is passed through MVR vaporising devices 2 to carry out
First evaporation obtains the first steam containing ammonia and the first concentrate, then first concentrate is each led into multi-effect evaporating device 1
Each effect evaporator in carry out second evaporation obtain the second steam containing ammonia and the second concentrate, wherein be passed through by the waste water
Before MVR vaporising devices 2, the pH value for adjusting the waste water is more than 9；It, will before the waste water is passed through MVR vaporising devices 2
First steam containing ammonia carries out the first heat exchange with the waste water and obtains the first ammonium hydroxide；Also, preceding 1st effective evaporator is steamed
Send out after obtained the second steam containing ammonia is sent into 1st effective evaporator with first concentrate the second heat exchange of progress and obtain the
Two ammonium hydroxide；Also, described first evaporates so that the solid content in first concentrate is 50 mass % or less.
Preferably, before the waste water is passed through MVR vaporising devices 2, the pH value for adjusting the waste water is more than 10.8.
In the present invention, it is to be understood that first steam containing ammonia and second steam containing ammonia are this field
So-called indirect steam.
The present invention is adjusted to strong basicity by the above method, by the pH value of the waste water, and passes through 2 He of MVR vaporising devices
Multi-effect evaporating device 1 carries out the first evaporation and the second evaporation, and the ammonium ion contained in the waste water is converted into ammonia and steams, obtains
The steam that arrives and the waste water carry out heat exchange, and heated waste water while makes steam cool down to obtain ammonium hydroxide, realize ammonia and salt
It recycles simultaneously, and takes full advantage of the heat in evaporation process.
In the present invention, there is no particular limitation for the MVR vaporising devices 2, can be commonly used in the art various
MVR vaporising devices.Such as can be selected from MVR falling film evaporators, MVR forced-circulation evaporators, the evaporation of MVR-FC continuous crystallisations
It is one or more in device, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced-circulation evaporators, MVR-FC connect
Continuous crystallizing evaporator.More preferably falling liquid film+forced circulation two-stage MVR crystallizing evaporators.
In the present invention, there is no particular limitation for the first evaporation conditions of the MVR vaporising devices 2, can be as needed
Appropriate selection.In order to improve the evaporation efficiency of the first evaporation, the condition of preferably described first evaporation includes：Temperature be 30 DEG C with
On, the pressure in terms of gauge pressure is -98kPa or more；More preferably it is described first evaporation condition include：Temperature is 50 DEG C~130 DEG C,
Pressure in terms of gauge pressure is -93kPa~117kPa；Further preferably it is described first evaporation condition include：Temperature be 110 DEG C~
120 DEG C, the pressure in terms of gauge pressure is 11kPa~57kPa.The flow of first evaporation can suitably be selected according to the ability that equipment is handled
It selects, such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
In the present invention, it is evaporated by controlling described first so that the solid content in first concentrate is 50 matter
% or less (preferably 20 mass % are hereinafter, be more preferably free of solid) is measured, the first concentrate does not lose flowability, and can follow
It is sent directly under the action of ring pump in multi-effect evaporating device 1 and carries out the second evaporation.Preferably, first evaporation does not make described the
One concentrate reaches supersaturation (i.e. described first concentrate is free of solid), is not in crystallization in the first concentrate, more just
Just the conveying of the first concentrate.
In the present invention, there is no particular limitation for the degree of first evaporation, in order to obtain the ammonium hydroxide of higher concentration, the
The cycles of concentration of one evaporation is preferably 1.2-1.3 times, more preferably 1.05-1.2 times.It is preferred that by suitably adjusting cycles of concentration,
The concentration of the first ammonium hydroxide made reaches 3 times or more of waste water ammonia density before evaporation, more preferably by suitably adjusting concentration times
Number, so as to get the concentration of the first ammonium hydroxide reach 5-20 times of waste water ammonia density before evaporation.Pass through the adjustment concentration of the first evaporation
Multiple can adjust the concentration of the first ammonium hydroxide in a certain range, and thus, it is possible to the recyclings convenient for ammonium hydroxide.
In the present invention, for the method for pH value adjusting, there is no particular limitation, such as can use additional basic species
The mode of matter adjusts the pH value of the waste water.There is no particular limitation for the alkaline matter, achievees the purpose that above-mentioned adjusting pH value
.In order not to introduce new impurity in waste water, the alkaline matter is preferably positive with the salt metal having the same in waste water
Ion.For example, in the case of containing a large amount of alkali metal cations in waste water, the alkaline matter is preferably the hydrogen-oxygen of alkali metal
Compound (being, for example, NaOH, KOH etc.), specifically, in the case of a large amount of sodium ions are contained in waste water, the alkaline matter is preferred
For NaOH.
Feed postition as the alkaline matter is the feed postition of this field routine, but preferably makes alkaline matter
It is mixed in form of an aqueous solutions with the waste water, such as the aqueous solution containing alkaline matter can be passed into and import the waste water
Pipeline in mixed.For the content of alkaline matter in aqueous solution, there is no particular limitation, as long as can reach above-mentioned
Adjust the purpose of pH value.But in order to reduce the dosage of water, further reduce the cost the saturated water, it is preferable to use alkaline matter
Solution.In order to monitor the pH value of the waste water, the pH value of the waste water can be measured after above-mentioned adjusting pH value.
According to the present invention, before the waste water is passed through MVR vaporising devices 2, by first steam containing ammonia and the waste water
It carries out the first heat exchange and obtains ammonium hydroxide.There is no particular limitation for the mode of first heat exchange, and it is normal that this field may be used
The heat exchange mode of rule carries out.The number of the heat exchange can be more than primary, and preferably 2-4 times, more preferably 2-3 times are special
It You Xuanwei not be 2 times.By the heat exchange, the ammonium hydroxide of output is cooled, and heat utmostly recycles inside processing unit, closes
The energy is utilized in reason, reduces waste.
A preferred embodiment according to the present invention, first heat exchange pass through the first heat-exchanger rig 31 and second
Heat-exchanger rig 32 carries out, specifically, by the first steam containing ammonia evaporated in the MVR vaporising devices 2 respectively by the
Two heat-exchanger rigs 32 and the first heat-exchanger rig 31, and by waste water respectively by the first heat-exchanger rig 31 and the second heat-exchanger rig 32,
First heat exchange is carried out by first steam containing ammonia and the waste water, the waste water heating is made to be convenient for evaporating,
First steam cooling containing ammonia is set to obtain the first ammonium hydroxide simultaneously, first ammonium hydroxide can be stored in tank used for storing ammonia 51.
A preferred embodiment according to the present invention, as shown in Figure 1, first evaporation process can be steamed in MVR
It is carried out in transmitting apparatus 2, before the waste water to be sent into the first heat-exchanger rig 31 and carries out the first heat exchange, by described will give up
Water, which is sent into the pipeline of the first heat-exchanger rig 31, imports the aqueous solution containing alkaline matter and mixing, to carry out first time pH
Value is adjusted；And before the waste water to be sent into the second heat-exchanger rig 32 and carries out the first heat exchange, by being sent by the waste water
Enter and import the aqueous solution containing alkaline matter and mixing in the pipeline of the second heat-exchanger rig 32, to carry out second of pH value tune
Section.It is adjusted by pH value twice, so that pH value of the waste water before being passed through MVR vaporising devices 2 is more than 9, preferably greater than
10.8.Additionally, it is preferred that the adjusting of first time pH value is so that the pH value of the waste water after adjusting is more than 7 (preferably 7-9), for the second time
PH value is adjusted so that pH value is more than 9, preferably greater than 10.8.
The pH value after being adjusted with second of pH value is adjusted in order to detect above-mentioned first time pH value, is preferably sent by the waste water
Enter to be arranged on the pipeline of the first heat-exchanger rig 31 first pH value measuring device 61 measure first time pH value adjust after pH value,
The waste water is sent on the pipeline of the second heat-exchanger rig 32, second pH value measuring device 62 is set to measure second of pH value tune
PH value after section.
In the present invention, in order to improve the salinity of liquid in the MVR vaporising devices 2, the ammonia content in liquid is reduced,
It is preferred that the effluent part evaporated by the MVR vaporising devices 2 is returned in the MVR vaporising devices 2.It is above-mentioned to pass through institute
The process for stating effluent part back to the MVR vaporising devices 2 of the evaporation of MVR vaporising devices 2 is preferably that will pass through the MVR
The effluent part that vaporising device 2 evaporates and the waste water after the adjusting of first time pH value and before being adjusted to second of pH value are mixed
It again returns to after conjunction in MVR vaporising devices 2, will be steamed by the MVR vaporising devices 2 for example, 72 can be pumped by second circulation
The effluent part of hair returns to mixed with waste water in the waste water conveyance conduit between the first heat-exchanger rig 31 and the second heat-exchanger rig 32
It closes, then after being adjusted by second of pH value, carries out heat exchange in the second heat-exchanger rig 32, be re-fed into the MVR
In vaporising device 2.
In the present invention, for first heat-exchanger rig, 31 and second heat-exchanger rig 32, there is no particular limitation, can be with
Using various heat exchangers commonly used in the art, reaches first steam containing ammonia and carry out the first heat friendship with the waste water
The purpose changed.Specifically, can be jacketed type exchanger, plate heat exchanger, shell-and-tube heat exchanger etc., wherein preferably plate
Formula heat exchanger.The material of the heat exchanger can be specifically chosen as needed, such as in order to resist chloride ion corrosion, can be selected
Material is the heat exchanger of two phase stainless steel, titanium or titanium alloy, Hastelloy, can be selected containing plastic material when temperature is relatively low
Heat exchanger.
It is preferably exchanged heat by described first according to the present invention in order to make full use of the thermal energy of the first steam condensate (SC) containing ammonia
After device 31 carries out the first heat exchange, the temperature of the waste water is 30 DEG C or more, preferably 49 DEG C~119 DEG C.
Preferably pass through second heat-exchanger rig 32 according to the present invention in order to make full use of the thermal energy of the first steam containing ammonia
After carrying out the first heat exchange, the temperature of the waste water is 49 DEG C~139 DEG C, preferably 59 DEG C~139 DEG C.
In the case of, according to the invention it is preferred to, the method further include after first steam containing ammonia is compressed again
Carry out first heat exchange.The compression of first steam containing ammonia can be carried out by compressor 10.By to described first
Steam containing ammonia is compressed, to input energy in entire processing system, ensure the process of waste water heating-evaporation-cooling continuously into
Row is needed to input to start steam when MVR evaporation processes start, only be energized by compressor after reaching continuously running state, no longer
It needs to input other energy.The compressor 10 may be used various compressors commonly used in the art, such as centrifugal blower,
Turbocompressor or lobed rotor compressor etc..After the compression of the compressor 10, the temperature of first steam containing ammonia increases 5 DEG C
~20 DEG C.
In the present invention, there is no particular limitation for the multi-effect evaporating device 1, can be commonly used in the art various
Evaporator forms.Such as it can be more selected from downward film evaporator, film-rising evaporator, scraper-type evaporator, standard vertical-tubes
Imitate evaporator, basket evaporator, external heating type evaporator, forced-circulation evaporator and one kind or more in Liewen evaporator
Kind.Wherein, preferably forced-circulation evaporator, external heating type evaporator.Each effect evaporator of the multi-effect evaporating device 1 respectively by
Room and vaporization chamber composition are heated, can also include other evaporation accessories as needed, such as liquid foam is made further to detach
Demister, the vacuum plant the etc. when condenser and decompression operation that make indirect steam all condense.The multi-effect evaporating device
There is no particular limitation for the 1 evaporator quantity contained, can be 2 effects or more, preferably 2-5 effects, more preferably 3-4 effects.
In the present invention, there is no particular limitation for the evaporation conditions of the multi-effect evaporating device 1, can be appropriate as needed
Selection.The evaporation conditions of each effect evaporator of the multi-effect evaporating device 1 can be identical or different, preferably different.In order to carry
High evaporation efficiency, preferably it is described second evaporation condition include：The temperature of evaporation can be 40 DEG C or more, the pressure in terms of gauge pressure
To be more than -97kPa；It is highly preferred that the condition of second evaporation includes：The temperature of evaporation is 50 DEG C~180 DEG C, in terms of gauge pressure
Pressure be -93kPa~750kPa；It is further preferred that it is described second evaporation condition include evaporation temperature be 60 DEG C~
145 DEG C, the pressure in terms of gauge pressure is -87kPa~240kPa.According to the present invention, in the feelings for the condition for meeting above-mentioned second evaporation
Under condition, the evaporation conditions of further preferably each effect evaporator meet：The evaporating temperature of 1st effective evaporator is 100 DEG C~180 DEG C,
1st effective evaporator is 10 DEG C~50 DEG C lower than the evaporating temperature of preceding 1st effective evaporator afterwards；It is highly preferred that the evaporation of 1st effective evaporator
Temperature is 120 DEG C~160 DEG C, and rear 1st effective evaporator is 19 DEG C~41 DEG C lower than the evaporating temperature of preceding 1st effective evaporator.
In addition, in the present invention, each operating pressure for imitating evaporator by evaporation feed liquid saturated vapor pressure.
In addition, respectively the evaporation capacity of effect evaporator can be identical or different, preferably identical, the total evaporation capacity of the second evaporation can
It is suitably selected with the ability and pending wastewater flow rate that are handled according to equipment, such as can be 0.1m3/ h or more (such as 0.1m3/ h~
500m3/h)。
In the present invention, it in order to which the waste water to be passed through to each effect evaporator of multi-effect evaporating device 1 successively, can be steamed in each effect
Circulating pump is set between hair device, the waste water after the evaporation of preceding 1st effective evaporator is passed through next effect by the circulating pump to be evaporated
Device.
In the present invention, the circulating pump between selected each effect evaporator can be various forms commonly used in the art
Pump, generate a large amount of fine grain cores to make material be uniformly evaporated, avoid, prevent crystal grain and impeller high velocity impact in cycle magma
Generate a large amount of secondary nucleus, the circulating pump is preferably the centrifugal pump of the slow-speed of revolution, more preferably big flow, the slow-speed of revolution guide pump
Wheel or big flow, low lift, the slow-speed of revolution axial-flow pump.
In the case of, according to the invention it is preferred to, the last 1st effective evaporator of the multi-effect evaporating device 1 evaporate
Two steam containing ammonia carry out third heat exchange with cooling water in third heat-exchanger rig 33 and obtain ammonium hydroxide.The third heat-exchanger rig
33 there is no particular limitation, can use various heat exchangers commonly used in the art, reach second steam containing ammonia and institute
State the purpose that waste water carries out heat exchange.Specifically, it can be jacketed type exchanger, plate heat exchanger, shell-and-tube heat exchanger
Deng wherein preferably plate heat exchanger.The material of the heat exchanger can be specifically chosen as needed, for example, in order to resist chlorine from
Son corrosion, can select material for two phase stainless steel, the heat exchanger of titanium or titanium alloy, Hastelloy, can be with when temperature is relatively low
Select the heat exchanger containing plastic material.Preferably, the cooling water is the waste water.It is described cold when using conventional cooling water
But water recycles, and when using the waste water as cooling water, the waste water after heat exchange preferably directly returns to processing procedure.
A preferred embodiment according to the present invention will before the waste water is passed through MVR concentration and evaporation devices
The steam containing ammonia that the last 1st effective evaporator of the multi-effect evaporating device 1 evaporates carries out heat exchange with the waste water and obtains
Ammonium hydroxide.
According to the present invention, this method further includes crystallizing second concentrate in crystallization apparatus to obtain magma.It is described
There is no particular limitation for crystallization apparatus, such as can be brilliant liquid collecting tank, brilliant liquid collecting tank, with stirring thickener or without stirring
Thickener etc..The way of the crystallization process can be evaporated each effect evaporator of the multi-effect evaporating device 1 dense
Contracting liquid crystallizes in different crystallization apparatus respectively；Or evaporate each effect evaporator of the multi-effect evaporating device 1
Concentrate crystallizes after merging in a crystallization apparatus, preferably evaporates to obtain by each effect evaporator of the multi-effect evaporating device 1
Concentrate merge after crystallized in a crystallization apparatus.There is no particular limitation for the condition of the crystallization, such as may include：
Crystallization temperature is 20 DEG C~107 DEG C, and crystallization time is 5min~for 24 hours；It preferably includes：Crystallization temperature is 65 DEG C~85 DEG C, crystallization
Time is 10min~30min.
A preferred embodiment according to the present invention, as shown in Figure 1, second evaporation process is filled in multiple-effect evaporation
It is carried out in setting 1, the multi-effect evaporating device 1 is by 1st effective evaporator 1a, 2nd effect evaporator 1b and third effect evaporator 1c groups
At.By the 5th circulating pump 75 by first concentrate each lead into the multi-effect evaporating device 1 1st effective evaporator 1a,
It is evaporated to obtain the second concentrate in 2nd effect evaporator 1b and third effect evaporator 1c.By the multi-effect evaporating device 1
The second steam containing ammonia evaporated in 1st effective evaporator 1a is passed through 2nd effect evaporator 1b and is carried out with first concentrate
Second heat exchange simultaneously obtains ammonium hydroxide, and the second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through third effect evaporator
1c carries out the second heat exchange with first concentrate and obtains the second ammonium hydroxide.Heating steam is passed through in 1st effective evaporator 1a
(life steam i.e. commonly used in the art), the condensate liquid that heating steam obtains after being condensed in 1st effective evaporator 1a can be used for
Configuration washing brine.The second steam containing ammonia evaporated in third effect evaporator 1c in third heat-exchanger rig 33 with cooling water
(it is preferable to use the waste water before being passed through MVR concentration and evaporation devices as cooling water) carries out third heat exchange and obtains ammonia
Water, and stored in ammonium hydroxide collecting tank 52.Waste water is respectively in 1st effective evaporator 1a, 2nd effect evaporator 1b and triple effect evaporation
After being evaporated in device 1c, the second obtained concentrate is respectively in the first brilliant liquid collecting tank 53a, the second crystalline substance liquid collecting tank 53b and third
Crystallization obtains magma or waste water respectively in 1st effective evaporator 1a, 2nd effect evaporator 1b and third in brilliant liquid collecting tank 53c
It imitates after being evaporated in evaporator 1c, the second obtained concentrate is after merging in crystallization apparatus (preferably with stirring thickener or not
Band stirring thickener) in crystallization.
In the present invention, the magma obtains crystal after separation of solid and liquid and is separated by solid-liquid separation obtained liquid.It is described solid
There is no particular limitation for the method for liquid separation, such as can be selected from one or more in centrifugation, filtering, sedimentation.
In the case of in the present invention, it is preferred to, the magma passes through the liquid that separation of solid and liquid obtains, at least part or complete
Portion is back to MVR vaporising devices 2 and carries out the first evaporation again.
Equipment for separating liquid from solid 9 may be used (preferably in a preferred embodiment according to the present invention, the separation of solid and liquid
For centrifuge) it carries out, after the separation of solid and liquid, the liquid that is separated by solid-liquid separation all is back to MVR vaporising devices 2 and carries out again
First evaporation.
In addition, the impurity such as certain free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on the crystal, inhaled to remove
Attached impurity, reduces the peculiar smell of solid salt, reduces corrosivity, improves the purity of the crystal, it is preferable that the crystal water or
Salt water washing and drying.There is no particular limitation for the brine, can suitably select as needed.In order to avoid in washing process
The dissolving of crystal, it is preferable that the type of the salt in the brine is selected according to the salt contained in the waste water, preferably with it is described
Waste water contains identical salt.It is highly preferred that the brine is preferably saturated brine.In order to further decrease processing cost, reduce
The use of salt, the brine are preferably the aqueous solution of the waste water or the crystal, and the saturation of the more preferably described crystal is water-soluble
Liquid.In addition, the cleaning solution for washing the crystal can be recycled to multi-effect evaporating device 1 or MVR enrichment facilities 2, it is preferable that all
It is recycled to multi-effect evaporating device 1.
In the present invention, before the waste water is handled, vacuum outgas is preferably first carried out.The vacuum outgas can be with
It is carried out using vacuum receiver 4.By the vacuum outgas, the gas dissolved in the waste water, such as air, ammonia can be removed
Gas etc. ensures that system is reliable and stable during normal operation, reduces the oxygen corrosion that has of system, extension is set so as to prevent vapour lock
Standby usage time.The condition of the vacuum outgas includes：Vacuum degree can reach -90kPa~-70kPa, vacuum outgas in terms of gauge pressure
Processing speed it is consistent with the fresh feed inlet amount of system, can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
In the case of in the present invention, it is preferred to, tail gas, first steam containing ammonia that the vacuum outgas is obtained pass through
It is remaining by third heat exchange condensation that first heat exchange condenses remaining tail gas and second steam containing ammonia
Tail gas discharges after removing ammonia.The tail gas that the tail gas that the vacuum outgas obtains i.e. vacuum receiver 4 is discharged, described first contains ammonia
Steam condenses the tail gas that i.e. described second heat-exchanger rig 32 of remaining tail gas is discharged by first heat exchange, and described second steams
Vapour condenses the tail gas that remaining tail gas i.e. third heat-exchanger rig 33 is discharged by second heat exchange, by removing above-mentioned tail gas
Ammonia can further decrease the pollutant load in emission so that it can direct emission.
As the mode except ammonia, can be absorbed with tail gas absorber 83.The tail gas absorber 83 is without spy
Other restriction can be various absorption towers commonly used in the art, such as tray absorption columns, packed absorber, falling film absorption
Tower or void tower etc..There is recirculated water in the tail gas absorber 83, the recirculated water is under the action of the 4th circulating pump 74 in tail gas
It is recycled in absorption tower 83, water can also be added to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73, recycled
Pond 82 can add fresh water, while can reduce by the temperature and ammonia content of 81 work water of vacuum pump.The tail gas absorber
The type of flow of 83 inner exhaust gas and recirculated water can adverse current also can cocurrent, preferably adverse current.The recirculated water can be by additional
Fresh water is supplemented.In order to ensure that tail gas fully absorbs, dilute sulfuric acid can also be further added in the tail gas absorber 83,
To absorb a small amount of ammonia in tail gas etc..The recirculated water can be used as ammonium hydroxide or ammonium sulfate to be back to after absorbing tail gas
It produces or sells.As the mode that above-mentioned tail gas is passed through to tail gas absorber 83, can be carried out by vacuum pump 81.
In the present invention, there is no particular limitation for the waste water, as long as the waste water of ammonium salt-containing.In addition, of the invention
Waste water be particularly suitable for the high-salt wastewater containing ammonium processing.As the waste water of the present invention, it is specifically as follows from molecular sieve, aluminium oxide
Or the waste water of oil refining catalyst production process, can also be will be from molecular sieve, aluminium oxide or oil refining catalyst production process
Waste water carries out the waste water after following removal of impurities and concentration.Molecular sieve, aluminium oxide or oil refining catalyst production process will preferably be come from
Waste water carry out it is following removal of impurities and concentration after waste water.
In the present invention, the inorganic ion contained in the waste water is in addition to NH4 +In addition, Na can also be contained+、SO4 2-、
Cl-、NO3 -、NO2 -Plasma.
As the NH in the waste water4 +Can be 8mg/L or more, preferably 300mg/L or more.
As the Na in the waste water+Can be 510mg/L or more, preferably 1000mg/L or more, more preferably
2000mg/L or more, further preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably
16000mg/L or more, further preferably 32000mg/L or more, further preferably 40000mg/L or more, further preferably
For 50000mg/L or more, further preferably 60000mg/L or more.
As the SO in the waste water4 2-Can be 1000mg/L or more, preferably 2000mg/L or more, more preferably
4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, further preferably
32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L or more, further preferably
For 60000mg/L or more, further preferably 70000mg/L or more.
As the Cl in the waste water-Can be 970mg/L or more, more preferably 2000mg/L or more, further preferably
For 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, further preferably
It is further excellent for 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L or more
It is selected as 60000mg/L or more.
The TDS of the waste water can be 1600mg/L or more, preferably 4000mg/L or more, more preferably 8000mg/L with
On, further preferably 16000mg/L or more, further preferably 32000mg/L or more, further preferably 40000mg/L
More than, further preferably 50000mg/L or more, further preferably 60000mg/L or more, further preferably
100000mg/L or more, further preferably 150000mg/L or more, further preferably 200000mg/L or more.
There is no particular limitation for the upper limit of the inorganic ion contained in the waste water, even if contain in the waste water
When inorganic ion is hypersaturated state, method that can also be through the invention is handled.
In the present invention, the pH value of the waste water is preferably 4~7.
In addition, due to the COD of waste water may block up film in concentration, in evaporative crystallization when influence the purity and color and luster etc. of salt,
The fewer the COD of the waste water the better, preferably specifically can be used such as bioanalysis, advanced oxidation by oxidation removal in pretreatment
The progress such as method, when COD contents are very high preferably use it is oxidizing, the oxidant for example can be Fenton reagent.It is excellent
Selection of land, COD contents are 20mg/L hereinafter, more preferably 10mg/L or less.
In addition, Mg can also be contained in the waste water of the present invention2+、Ca2+、K+、Fe3+, rare earth element ion etc. and COD etc. it is miscellaneous
Matter, the content of above-mentioned impurity usually at 3mg/L~50mg/L (preferably 10mg/L is hereinafter, more preferably 5mg/L or less), these
Impurity can be removed by subsequent removal of impurities.
In the present invention, in order to ensure that the continuous-stable of processing procedure carries out, reduction equipment operation maintenance cost is described useless
Water using the processing method of the present invention before being handled preferably through removal of impurities.Preferably, the removal of impurities is heavy selected from separation of solid and liquid, chemistry
It forms sediment, is in absorption, ion exchange and oxidation one or more.
Can be filtering, centrifugation, sedimentation etc. as the separation of solid and liquid；Can be to adjust as the chemical precipitation
PH, carbonate deposition, magnesium salts precipitation etc.；Can be physical absorption and/or chemisorption, specific absorption as the absorption
Agent can select activated carbon, silica gel, aluminium oxide, molecular sieve, natural clay etc.；As the ion exchange, strong acid may be used
Any one in property resin cation, acidulous cation resin；As the oxidation, may be used commonly used in the art
Various oxidants, such as ozone, hydrogen peroxide, ammonium persulfate, Fenton reagent, potassium permanganate etc., it is new miscellaneous in order to avoid introducing
Matter, it is preferred to use ozone, hydrogen peroxide etc..
Specific removal of impurities mode can be specifically chosen according to the dopant species contained in the waste water.It, can for suspended matter
To select solid-liquid isolation method to clean；For inorganic matter and organic matter, chemical precipitation method, ion-exchange, absorption method can be selected
Removal of impurities, such as Subacidity cation exchange process, active carbon adsorption etc.；For organic matter, absorption and/or oxidation may be used
Mode cleans, wherein preferably ozone biological activated carbon adsorption and oxidation method.A preferred embodiment according to the present invention is given up
Water cleans by filtering, Subacidity cation exchange process, ozone biological activated carbon adsorption and oxidation method successively.It is removed by above-mentioned
Miscellaneous process can remove most suspended substances, hardness, silicon and organic matter, reduce device fouling risk, ensure wastewater treatment process
Continuous and steady operation.
It in the present invention, can be before using the processing of the processing method of the present invention (preferably for the lower waste water of salt content
After above-mentioned removal of impurities), so that salt content is reached the range required by the waste water of the present invention by concentrating.Preferably, described dense
Contracting selected from ED films concentration and/or it is reverse osmosis；It is highly preferred that described be concentrated by the concentration of ED films and reverse osmosis progress, the ED films
There is no particular limitation for the sequencing of concentration and reverse osmosis progress.The ED films concentration and reverse osmosis treatment device and condition can
It is carried out, can be specifically chosen according to the case where pending waste water in a manner of conventional using this field.Specifically, as the ED
Film concentrates, and unidirectional electrodialysis system or pole-reversing electroosmosis system can be selected to carry out；As described reverse osmosis, rolling can be selected
Film, plate membrane, dish tubular membrane, vibrating membrane or combinations thereof carry out.The efficiency that wastewater treatment can be improved by the concentration, avoids
Energy waste caused by a large amount of evaporations.
In the preferred embodiment of the present invention, waste water is that the waste water in process of producing molecular sieve is heavy by chemistry
Form sediment, filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method clean, and by the concentration of ED films and
Waste water after reverse osmosis concentration.
Condition as above-mentioned chemical precipitation is preferably：Using sodium carbonate as inorganic agent, relative to 1 mole of calcium in waste water
1.2~1.4 mole of either sodium carbonate are added in ion, and the pH for adjusting waste water is more than 7, and reaction temperature is 20 DEG C~35 DEG C, and the reaction time is
0.5h~4h.
Condition as above-mentioned filtering is preferably：Filter element is situated between more using the double-layer filter material of anthracite and quartz sand composition
Mass filter, anthracite granule size used are 0.7mm~1.7mm, and quartz sand particle size is 0.5mm~1.3mm, filtering velocity 10m/h
~30m/h.Media regeneration is carried out using the regeneration method of " gas backwash-gas and water backwash-water backwashing " after filtrate use,
Regeneration period 10h~15h.
Condition as above-mentioned Subacidity cation exchange process is preferably：PH value range is 6.5~7.5；Temperature≤40 DEG C,
Resin layer height is 1.5m~3.0m, regenerated liquid HCl concentration：4.5~5 mass %；Regenerant consumption (based on 100%), 50kg/
m3~60kg/m3Wet resin；Regenerated liquid HCl flow velocitys are 4.5m/h~5.5m/h, and regeneration time of contact is 35min~45min；Just
It is 18m/h~22m/h to wash flow velocity, and it is 20min~30min just to wash the time；Operation flow velocity is 15m/h~30m/h；Acid cation
Langfang sanat Chemical Co., Ltd., SNT board D113 acid cation exchange resins can be used for example in exchanger resin.
Condition as above-mentioned ozone biological activated carbon adsorption and oxidation method is preferably：The ozone residence time be 50min~
70min, empty bed filtering velocity are 0.5m/h~0.7m/h.
As above-mentioned ED films concentration condition be preferably：Electric current 145A~155A, voltage 45V~65V.For example as ED films
Can be the ED films of A Sitong companies of Japan production.
It is preferably as above-mentioned reverse osmosis condition：Operating pressure 5.4MPa~5.6MPa, 25 DEG C~35 DEG C of inflow temperature,
PH value is 6.5~7.5.It is for example carried out using the sea water desalination membrane TM810C that blue star Toray produces as reverse osmosis membrane.
The present invention will be described in detail by way of examples below.
In following embodiment, waste water is that the waste water in process of producing molecular sieve passes through chemical precipitation, filtering, faintly acid successively
Base exchange method and ozone biological activated carbon adsorption and oxidation method clean, and pass through the concentration of ED films and reverse osmosis successively
Waste water after concentration.
Embodiment 1
As shown in Figure 1, by waste water (110g/L containing NaCl, Na2SO4 100g/L、NH4Cl 25g/L、(NH4)2SO4
It is 23.1g/L) 120m with inlet amount3The speed of/h is passed through the degassing of vacuum receiver 4 (vacuum degree is -70kPa in terms of gauge pressure),
Before waste water after degassing is sent to the first heat-exchanger rig 3 (being specially titanium alloy plate heat exchanger), with equipment for separating liquid from solid
Obtained mother liquor (288.8g/L containing NaCl, Na2SO465.4g/L, NaOH 9.1g/L, flow 29m3/ h) mixing, then
The sodium hydrate aqueous solution that a concentration of 45.16 mass % is imported in pipeline carries out first time pH value adjusting, and passes through the first pH value
Measuring device 61 (pH meter) is monitored (measured value 8.0) to the pH value after adjusting, will be useless after the adjusting of the first pH value
Water is sent into the first heat-exchanger rig 31 by first circulation pump 71, and the first heat exchange is carried out with the first steam condensate containing ammonia of recycling
Waste water is set to be warming up to 93 DEG C；Then, (it is specially titanium the waste water after the first heat exchange is sent to the second heat-exchanger rig 32
Alloy plate type heat exchanger) pipeline in import a concentration of 45.16 mass % sodium hydrate aqueous solution carry out second of pH value tune
Section, and is monitored (measured value 11) by the second pH value measuring device 62 (pH meter) to the pH value after adjusting, will pass through the
Waste water after two pH value are adjusted is sent into the second heat-exchanger rig 32, and carrying out the first heat exchange with the first steam containing ammonia of recycling makes waste water
Be warming up to 124 DEG C, then by the waste water be sent into MVR vaporising devices 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) into
Row first evaporates.Wherein, the condition of the first evaporation includes：Temperature is 117 DEG C, and the pressure in terms of gauge pressure is 41.92kPa, evaporation
Amount is 35.5m3/h.The first steam containing ammonia that first evaporation obtains (12 DEG C of temperature rise) after the compression of compressor 10 leads to successively
The second heat-exchanger rig 32 and the first heat-exchanger rig 31 are crossed, carries out heat exchange with waste water, cooling obtains ammonium hydroxide, and in tank used for storing ammonia 51
Middle storage.In order to improve the salinity of liquid in MVR vaporising devices 2, the part after the first evaporation in MVR vaporising devices 2 is given up
Water returns to second of pH value adjustment process by second circulation pump 72.MVR vaporising devices 2 are concentrated to give 120m per hour3Contain
NaCl 207.1g/L、Na2SO4 140.6g/L、NaOH 2.2g/L、NH3(solid content is the first concentrate of 1.563g/L
0)。
Second evaporation process carries out in multi-effect evaporating device 1 (triple-effect evaporation plant), the multi-effect evaporating device 1
It is made of 1st effective evaporator 1a, 2nd effect evaporator 1b and third effect evaporator 1c.By the 5th circulating pump 75 by above-mentioned
One concentrate be respectively fed to 1st effective evaporator 1a, 2nd effect evaporator 1b and the third effect evaporator 1c of multiple-effect heat-exchanger rig into
The evaporation of row second obtains the second concentrate.Wherein, the evaporation conditions of 1st effective evaporator 1a include：Temperature is 126 DEG C, with gauge pressure
The pressure of meter is 90.96kPa, evaporation capacity 31.6m3/h；The evaporation conditions of 2nd effect evaporator 1b include：Temperature is 107 DEG C,
Pressure in terms of gauge pressure is 0kPa, evaporation capacity 31.5m3/h；The evaporation conditions of third effect evaporator 1c include：Temperature is 66 DEG C,
Pressure in terms of gauge pressure is -82.292kPa, evaporation capacity 31.5m3/h.In the 1st effective evaporator 1a of the multi-effect evaporating device 1
In be passed through heating steam (raw steam), and evaporation will obtain the second steam containing ammonia and be passed through the second effect evaporating in 1st effective evaporator 1a
Device 1b carries out the second heat exchange and obtains ammonium hydroxide, and the second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through third
Effect evaporator 1c carries out the second heat exchange and obtains ammonium hydroxide.The second steam containing ammonia evaporated in third effect evaporator 1c is
Third heat exchange is carried out with the waste water and obtain ammonium hydroxide, obtained ammonium hydroxide in three heat-exchanger rigs 33 (titanium alloy plate heat exchanger)
It is stored in ammonium hydroxide collecting tank 52.The ammonium hydroxide obtained in above-mentioned each step is collected.Waste water is respectively in 1st effective evaporator 1a, second
It imitates after being evaporated in evaporator 1b and third effect evaporator 1c, obtained the second concentrate is respectively in the first brilliant liquid collecting tank 53a, the
Stiff crystallizer (not shown in figure 1) is convergeed to after collecting in two crystalline substance liquid collecting tank 53b and third crystalline substance liquid collecting tank 53c to crystallize
To magma.
Magma is after equipment for separating liquid from solid 9 (centrifuge) is separated by solid-liquid separation, and respectively obtaining crystal, (i.e. salt-mixture crystallizes
Filter cake) and it is separated by solid-liquid separation obtained liquid, after salt-mixture crystalli-zation cake is washed with the saturation mixed salt, partly it is used to modulate full
And mixed salt, 43.69 tons of the salt-mixture crystalli-zation cake that water content is 29 mass % is obtained per hour, it is dry in drying machine,
31.46 tons of the salt-mixture of sodium chloride-containing and sodium sulphate is obtained per hour；Separation of solid and liquid obtains 29m per hour3Containing NaCl
288.8g/L、Na2SO4The liquid that the separation of solid and liquid obtains is back to second by the crystalline mother solution of 65.4g/L, NaOH 9.1g/L
Before secondary pH value is adjusted；The washings that washing filter cake obtains, the concentrate after being evaporated with MVR vaporising devices 2 enter multiple-effect after mixing
Vaporising device 1.
In addition, vacuum receiver 4 and the tail gas of the second heat-exchanger rig 32 discharge introduce tail gas absorber by vacuum pump 81
83 are absorbed, and recirculated water are connected in tail gas absorber, the recirculated water is under the action of the 4th circulating pump 74 in tail gas absorption
It is recycled in tower 83, water, circulating water pool can also be added to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73
82 can add fresh water, while can reduce by the temperature and ammonia content of 81 work water of vacuum pump.In the tail gas absorber into
One step is passed through dilute sulfuric acid, to absorb ammonia in tail gas etc..
In the present embodiment, the ammonium hydroxide 35.5m of a concentration of 4.36 mass % is obtained in tank used for storing ammonia 51 per hour3, multiple-effect
The ammonium hydroxide 94.6m of a concentration of 0.123 mass % is obtained in vaporising device 1 and ammonium hydroxide collecting tank 52 per hour3, ammonium hydroxide can be back to
The production process of molecular sieve.
In addition, the initial period of MVR evaporations, the steam for being 143.3 DEG C by temperature are started.
Embodiment 2
The processing of waste water is carried out according to the method for embodiment 1, unlike, to containing NaCl 248g/L, NH4Cl 35g/L
Waste water handled.First evaporation conditions of MVR vaporising devices 2 include：Temperature is 110 DEG C, and the pressure in terms of gauge pressure is
11.34kPa, evaporation capacity 26.2m3/h.Second evaporation conditions of multi-effect evaporating device 1 include：The steaming of 1st effective evaporator 1a
Clockwork spring part includes：Temperature is 140 DEG C, and the pressure in terms of gauge pressure is 116.77kPa, evaporation capacity 33.8m3/h；Second effect evaporation
The evaporation conditions of device 1b include：Temperature is 120 DEG C, and the pressure in terms of gauge pressure is 56.97kPa, evaporation capacity 33.6m3/h；Third
The evaporation conditions of effect evaporator 1c include：Temperature is 99 DEG C, and the pressure in terms of gauge pressure is -25.7kPa, evaporation capacity 33.6m3/
h。
MVR vaporising devices 2 obtain 131m per hour3Contain NaCl 338.6g/L, NaOH 2.2g/L, NH3 0.917g/L
The first concentrate (solid content 0).The ammonium hydroxide 26.2m of a concentration of 4.6 mass % is obtained in tank used for storing ammonia 51 per hour3。
It is separated by solid-liquid separation 48.38 tons of sodium chloride crystalli-zation cake for obtaining that water content is 28 mass % per hour, is obtained per hour
32m3Crystalline mother solution containing NaCl 312.7g/L, NaOH 9.01g/L finally obtains 34.35 tons of sodium chloride, multiple-effect per hour
Ammonium hydroxide in vaporising device 1 and ammonium hydroxide collecting tank 52 obtains 101m per hour after converging3The ammonium hydroxide of a concentration of 0.118 mass %.
Embodiment 3
The processing of waste water is carried out according to the method for embodiment 1, unlike, to containing Na2SO4 135g/L、(NH4)2SO4
The waste water of 28g/L is handled.First evaporation conditions of MVR vaporising devices 2 include：Temperature is 120 DEG C, the pressure in terms of gauge pressure
For 56.97kPa, evaporation capacity 23.4m3/h.Second evaporation conditions of multi-effect evaporating device 1 include：1st effective evaporator 1a's
Evaporation conditions include：Temperature is 145 DEG C, and the pressure in terms of gauge pressure is 239.9kPa, evaporation capacity 33m3/h；2nd effect evaporator
The evaporation conditions of 1b include：Temperature is 117 DEG C, and the pressure in terms of gauge pressure is 41.92kPa, evaporation capacity 33m3/h；Third effect is steamed
The evaporation conditions of hair device 1c include：Temperature is 90 DEG C, and the pressure in terms of gauge pressure is -47.89kPa, evaporation capacity 32.7m3/h。
MVR vaporising devices 2 obtain 120m per hour3Contain Na2SO4 193.07g/L、NaOH 2.2g/L、NH3
The first concentrate (solid content 0) of 0.649g/L.The ammonia of a concentration of 3.36 mass % is obtained in tank used for storing ammonia 51 per hour
Water 23.4m.
It is separated by solid-liquid separation 27.9 tons of sulfate crystal filter cake for obtaining that water content is 29 mass % per hour, is obtained per hour
8m3Contain Na2SO4 343.24g/L、NaOH 23.23g/L、NH3The crystalline mother solution of 1.4g/L, finally obtains sulfuric acid per hour
19.8 tons of sodium, the ammonium hydroxide in multi-effect evaporating device 1 and ammonium hydroxide collecting tank 52 obtain 98.7m per hour after converging3It is a concentration of
The ammonium hydroxide of 0.0787 mass %.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of method of ammonium salt-containing wastewater treatment, this method includes that waste water is passed through MVR vaporising devices progress first to evaporate
To the first steam containing ammonia and the first concentrate, then first concentrate is each led into each effect evaporator of multi-effect evaporating device
The second evaporation of middle progress obtains the second steam containing ammonia and the second concentrate, which is characterized in that
Before the waste water is passed through MVR vaporising devices, the pH value for adjusting the waste water is more than 9；It is passed through by the waste water
Before MVR vaporising devices, first steam containing ammonia and the waste water are subjected to the first heat exchange and obtain the first ammonium hydroxide；
Also, it is concentrated with described first in 1st effective evaporator after the second steam containing ammonia for evaporating preceding 1st effective evaporator is sent into
Liquid carries out the second heat exchange and obtains the second ammonium hydroxide；
Wherein, described first evaporates so that the solid content in first concentrate is 50 mass % or less.
2. according to the method described in claim 1, wherein, before the waste water is passed through MVR vaporising devices, adjusting described useless
The pH value of water is more than 10.8.
3. according to the method described in claim 1, wherein, described first evaporates the solid content so that in first concentrate
For 20 mass % or less；
Preferably, first evaporation does not make first concentrate reach supersaturation.
4. according to the method described in claim 1, wherein, the condition of first evaporation includes：Temperature is 30 DEG C or more, with table
The pressure of pressure meter is -98kPa or more；
Preferably, the condition of first evaporation includes：Temperature is 50 DEG C~130 DEG C, pressure in terms of gauge pressure be -93kPa~
114kPa；
Preferably, the condition of first evaporation includes：Temperature is 110 DEG C~120 DEG C, pressure in terms of gauge pressure for 11kPa~
57kPa。
5. according to the method described in claim 1, wherein, the condition of second evaporation includes：The temperature of evaporation be 40 DEG C with
On, the pressure in terms of gauge pressure is -97kPa or more；
Preferably, the condition of second evaporation includes：The temperature of evaporation is 50 DEG C~180 DEG C, pressure in terms of gauge pressure is-
93kPa~750kPa；
It is highly preferred that the condition of second evaporation includes：The temperature of evaporation is 60 DEG C~145 DEG C, pressure in terms of gauge pressure is-
87kPa~240kPa.
6. according to the method described in claim 5, wherein, the condition of second evaporation includes：The evaporation of 1st effective evaporator
Temperature is 100 DEG C~180 DEG C, and rear 1st effective evaporator is 10 DEG C~50 DEG C lower than the evaporating temperature of preceding 1st effective evaporator；
It is highly preferred that the condition of second evaporation includes：The evaporating temperature of 1st effective evaporator is 120 DEG C~160 DEG C, latter
It is 19 DEG C~41 DEG C lower than the evaporating temperature of preceding 1st effective evaporator to imitate evaporator.
7. according to the method described in claim 1, wherein, first heat exchange is filled by the first heat-exchanger rig and the second heat exchange
Set progress；
Preferably, after carrying out the first heat exchange by first heat-exchanger rig, the temperature of the waste water is 30 DEG C or more, preferably
It is 49 DEG C~119 DEG C；
Preferably, after carrying out the first heat exchange by second heat-exchanger rig, the temperature of the waste water is 49 DEG C~139 DEG C,
Preferably 69 DEG C~129 DEG C；
Preferably, before the waste water enters the first heat-exchanger rig, the pH value for adjusting the waste water is more than 7.
8. according to the method described in claim 1, wherein, the multi-effect evaporating device is 2 effects or more, preferably 2-5 effects are more excellent
It is selected as 3-4 effects.
9. according to the method described in claim 1, wherein, what the last 1st effective evaporator of the multi-effect evaporating device evaporated
Second steam containing ammonia carries out third heat exchange with cooling water in heat-exchanger rig and obtains ammonium hydroxide；
Preferably, the cooling water is the waste water；
Preferably, before the waste water is passed through MVR concentration and evaporation devices, last effect of the multi-effect evaporating device is steamed
The second steam containing ammonia that hair device evaporates carries out third heat exchange with the waste water and obtains ammonium hydroxide；
Preferably, tail gas, first steam containing the ammonia vacuum outgas obtained condenses remaining by the first heat exchange
Tail gas and second steam containing ammonia condense remaining tail gas by third heat exchange and are discharged after removing ammonia.
10. according to the method described in claim 1, wherein, the method further includes compressing first steam containing ammonia
Carry out first heat exchange again afterwards；
Preferably, before being handled the waste water, vacuum outgas is first carried out.
11. according to the method described in any one of claim 1-10, this method further includes tying second concentrate
Crystallization obtains magma in brilliant device.
12. according to the method for claim 11, wherein the magma obtains crystal and separation of solid and liquid after separation of solid and liquid
At least part for being separated by solid-liquid separation obtained liquid or whole are back to MVR vaporising devices, it is preferable that will by obtained liquid
It is separated by solid-liquid separation obtained liquid and is all back to MVR vaporising devices；
Preferably, the crystal water or salt water washing and drying；
Preferably, the liquid that washing obtains is back to multi-effect evaporating device；
Preferably, the brine is the aqueous solution of the waste water or the crystal；
Preferably, the water in the water or brine is to heat steam after the first effect evaporator condensation of the multi-effect evaporating device
Obtained condensate liquid.
13. according to the method described in any one of claim 1-10, wherein the NH in the waste water4 +For 8mg/L or more,
TDS is 1600mg/L or more；
Preferably, the waste water contains Na+, Na+Content be 510mg/L or more；
Preferably, the waste water contains SO4 2-, SO4 2-Content be 1000mg/L or more；
Preferably, the waste water contains Cl-, Cl-Content be 970mg/L or more.
14. according to the method for claim 13, wherein this method further includes that the waste water is cleaned and concentrated.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108840388A (en) * | 2018-08-22 | 2018-11-20 | 李明 | A kind of residual heat of condensed water utilizes system and method |
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