CN108726756A - The processing method of ammonium salt-containing waste water - Google Patents

The processing method of ammonium salt-containing waste water Download PDF

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Publication number
CN108726756A
CN108726756A CN201710263271.XA CN201710263271A CN108726756A CN 108726756 A CN108726756 A CN 108726756A CN 201710263271 A CN201710263271 A CN 201710263271A CN 108726756 A CN108726756 A CN 108726756A
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China
Prior art keywords
evaporation
waste water
temperature
sodium chloride
sodium
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CN201710263271.XA
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CN108726756B (en
Inventor
殷喜平
李叶
顾松园
王涛
高晋爱
周岩
杨凌
苑志伟
刘夫足
徐淑朋
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
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Application filed by China Petroleum and Chemical Corp, Sinopec Catalyst Co filed Critical China Petroleum and Chemical Corp
Priority to CN201710263271.XA priority Critical patent/CN108726756B/en
Priority to NL2020788A priority patent/NL2020788B1/en
Priority to JP2018081600A priority patent/JP6594478B2/en
Priority to US15/958,986 priority patent/US10815132B2/en
Priority to BE2018/5260A priority patent/BE1025537B1/en
Priority to BR102018008273A priority patent/BR102018008273A8/en
Publication of CN108726756A publication Critical patent/CN108726756A/en
Priority to US17/027,049 priority patent/US11572289B2/en
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Publication of CN108726756B publication Critical patent/CN108726756B/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/0088—Cascade evaporators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/26—Multiple-effect evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B01D3/146—Multiple effect distillation
    • 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
    • C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—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
    • C02F2101/12—Halogens or halogen-containing 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The present invention relates to sewage treatment fields, disclose a kind of processing method of ammonium salt-containing waste water, which contains NH4 +、SO4 2‑、Cl‑And Na+, this approach includes the following steps, 1) and it pending waste water is subjected to the first evaporation obtains the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal, the pending waste water contains the ammonium salt-containing waste water；2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and first is separated by solid-liquid separation obtained the second evaporation of liquid phase progress and obtains the second concentrate of the second steam containing ammonia and sodium chloride-containing crystal；3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation.Ammonium and sodium sulphate, sodium chloride in waste water can be separately recovered in this method, farthest recycle the resource in waste water.

Description

The processing method of ammonium salt-containing waste water
Technical field
The present invention relates to sewage treatment fields, and in particular, to a kind of processing method of ammonium salt-containing waste water, more particularly to One kind containing NH4 +、SO4 2-、Cl-And Na+Ammonium salt-containing waste water processing method.
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
The purpose of the present invention is overcome to contain NH in the prior art4 +、SO4 2-、Cl-And Na+Ammonium salt-containing cost for wastewater treatment Height, and the problem of can only obtain mixing salt crystal provides and a kind of at low cost and environmentally friendly contains NH4 +、SO4 2-、Cl-And Na+'s Ammonium and sodium sulphate, sodium chloride in ammonium salt-containing waste water can be separately recovered in ammonium salt-containing wastewater treatment method, this method, utmostly Ground recycles the resource in ammonium salt-containing waste water.
To achieve the goals above, the present invention provides a kind of processing method of ammonium salt-containing waste water, which contains NH4 +、SO4 2-、Cl-And Na+, this approach includes the following steps,
1) pending waste water is subjected to the first evaporation and obtains the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal, The pending waste water contains the ammonium salt-containing waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and first is separated by solid-liquid separation and is obtained Liquid phase carry out second evaporation obtain the second concentrate of the second steam containing ammonia and sodium chloride-containing crystal；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is carried out the first evaporation, the pH value for adjusting the pending waste water is more than 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；Relative to 1 mole of institute State the SO contained in pending waste water4 2-, the Cl that contains in the pending waste water-It is 14 moles or less.
Through the above technical solutions, for NH is contained4 +、SO4 2-、Cl-And Na+Waste water, by advance by pending waste water After pH value is adjusted to specific range, recycles the isolated sodium sulfate crystal of the first evaporation and compared with concentrated ammonia liquor, then recycle Second evaporation obtains sodium chloride crystal and compared with weak aqua ammonia.This method can respectively obtain the sodium sulphate and sodium chloride of high-purity, keep away Difficulty during having exempted from mixed salt processing and having recycled, is completed at the same time separation of ammonia and the process of salt, and use heat exchange method Make waste water heating and steam cooling containing ammonia simultaneously, is not necessarily to condenser, energy saving rationally using the heat in evaporation process, drop Low cost for wastewater treatment, the ammonium in waste water are recycled in the form of ammonium hydroxide, and sodium chloride and sodium sulphate are recycled with crystal form respectively, whole A process does not have waste residue and liquid generation, realizes the purpose to turn waste into wealth.
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 ammonium salt-containing wastewater treatment method of embodiment provided by the invention.
Fig. 2 is the flow diagram of the ammonium salt-containing wastewater treatment method of another embodiment provided by the invention.
Reference sign
1, the second vaporising device 72, second circulation pump
2, the first vaporising device 73, third circulating pump
31, the first heat-exchanger rig 74, the 4th circulating pump
32, the second heat-exchanger rig 75, the 5th circulating pump
33, third heat-exchanger rig 76, the 6th circulating pump
34, the 4th heat-exchanger rig 77, the 7th circulating pump
4, vacuum receiver 78, the 8th circulating pump
51, the first tank used for storing ammonia 79, the 9th circulating pump
52, the second tank used for storing ammonia 81, vacuum pump
53, the first mother liquor tank 82, circulating water pool
54, the second mother liquor tank 83, tail gas absorber
55, brilliant liquid collecting tank 91, the first equipment for separating liquid from solid
61, the first pH value measuring device 92, the second equipment for separating liquid from solid
62, the second pH value measuring device 101, the first compressor
71, first circulation pumps the 102, second 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. 1-2, the present invention will be described, and the present invention is not limited by Fig. 1-2.
The processing method of ammonium salt-containing waste water provided by the invention, the ammonium salt-containing waste water contain NH4 +、SO4 2-、Cl-And Na+, should Method includes the following steps,
1) pending waste water is subjected to the first evaporation and obtains the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal, The pending waste water contains the ammonium salt-containing waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and first is separated by solid-liquid separation and is obtained Liquid phase carry out second evaporation obtain the second concentrate of the second steam containing ammonia and sodium chloride-containing crystal；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is carried out the first evaporation, the pH value for adjusting the pending waste water is more than 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；Relative to 1 mole of institute State the SO contained in pending waste water4 2-, the Cl that contains in the pending waste water-It is 14 moles or less.
Preferably, the pending waste water is the ammonium salt-containing waste water；Alternatively, the pending waste water contains and described contains ammonium Salt waste water and described second is separated by solid-liquid separation obtained liquid phase.
It is highly preferred that the pending waste water is the ammonium salt-containing waste water is separated by solid-liquid separation obtained liquid phase with described second At least part of mixed liquor.
It is further preferred that the pending waste water is the ammonium salt-containing waste water is separated by solid-liquid separation obtained liquid with described second The mixed liquor of phase.
Preferably, before the pending waste water is carried out the first evaporation, the pH value for adjusting the pending waste water is big In 10.8.In addition, for the pending waste water pH value the upper limit there is no limit, such as can be 14 hereinafter, preferably 13.5 hereinafter, more preferable 13 or less.
Method provided by the invention, which can be directed to, contains NH4 +、SO4 2-、Cl-And Na+Waste water handled, in addition to containing NH4 +、SO4 2-、Cl-And Na+Outside, to the pending waste water, there is no particular limitation.From the angle for the treatment effeciency for improving waste water Consider, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It rubs for 13.8 You hereinafter, preferably 13.75 moles hereinafter, more preferably 13.5 moles hereinafter, more preferably 13 moles hereinafter, further it is excellent 12 moles are selected as hereinafter, being still more preferably 11 moles hereinafter, being still more preferably 10.5 moles hereinafter, preferably 2 rub More than you, more preferably 2.5 moles or more, further preferably 3 moles or more, such as can be 3-10.5 moles.Passing through will SO4 2-And Cl-Molar ratio control in above range and combine aftermentioned evaporation conditions, sodium sulphate can be made to analyse in the first evaporation Go out and sodium chloride is not precipitated, to achieve the purpose that efficiently separate sodium sulphate.In addition, it is as above described below, in the present invention also Can be by the second Recycling Mother Solution obtained in the second evaporation process to the first evaporation, and thus come in pending waste water SO4 2-And Cl-Molar ratio be adjusted, and the balance of sodium hydroxide can be maintained.
In the present invention, first evaporation makes sodium chloride not crystallize precipitation, refers to that the sodium chloride of control mixed system is dense Degree is no more than the solubility under the first evaporation conditions (including but not limited to temperature, pH value etc.), but sulfate crystal is not precluded The sodium chloride of entrainment or adsorption.Since the water content of crystal after separation of solid and liquid is different, in the sodium sulfate crystal generally yielded The content of sodium chloride (preferably 4 mass % or less) below 8 mass %, in the present invention, chlorine in obtained sodium sulfate crystal It can think that sodium chloride does not crystallize precipitation when changing the content of sodium below 8 mass %.
In the present invention, second evaporation makes sodium sulphate not crystallize precipitation, refers to that the sodium sulphate of control mixed system is dense Degree is no more than the solubility under the second evaporation conditions (including but not limited to temperature, pH value etc.), it is not excluded that sodium chloride crystallization folder The sodium sulphate of band or adsorption.Since the water content of crystal after separation of solid and liquid is different, sulphur in the sodium chloride crystal generally yielded The content of sour sodium (preferably 4 mass % or less) below 8 mass %, in the present invention, sulfuric acid in obtained sodium chloride crystal It can think that sodium sulphate does not crystallize precipitation when the content of sodium is below 8 mass %.
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 pressure is the pressure in terms of gauge pressure.
According to the present invention, there is no particular limitation for the mode that first evaporation and second evaporation carry out, and reaches The purpose evaporated under corresponding evaporation conditions can be used for example various vaporising devices commonly used in the art and carry out.Tool Body can be one or more in MVR vaporising devices, multi-effect evaporating device and single-effect evaporating equipment.Wherein, described first steams Hair is preferably carried out by MVR vaporising devices；Second evaporation is preferably carried out by MVR vaporising devices.
As MVR vaporising devices, such as can be selected from MVR falling film evaporators, MVR forced-circulation evaporators, MVR-FC It is one or more in continuous crystallisation evaporator, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced circulations are steamed Send out device, MVR-FC continuous crystallisation evaporators, more preferably falling liquid film+forced circulation two-stage MVR crystallizing evaporators.
As each effect evaporator in single-effect evaporating equipment or multi-effect evaporating device, such as falling film type evaporation can be selected from It is device, film-rising evaporator, scraper-type evaporator, evaporator with central downcomer, basket evaporator, external heating type evaporator, strong It is one or more in circulating evaporator and Liewen evaporator processed.Wherein, preferably forced-circulation evaporator, external-heat evaporation Device.Above-mentioned evaporator is formed by heating room and vaporization chamber respectively, can also include other evaporation accessories as needed, such as The demister for making liquid foam further detach, the vacuum plant when condenser and decompression operation that make indirect steam all condense Deng.When the vaporising device is multi-effect evaporating device, wherein there is no particular limitation for the evaporator quantity contained, it can be according to need The evaporation conditions selection wanted can be 2 effects or more, preferably 2-5 effects, more preferably 2-4 effects.
In the present invention, when carrying out first evaporation and/or the second evaporation using multi-effect evaporating device, liquid to be evaporated Feeding manner can be identical or different, fair current commonly used in the art, adverse current or advection mode may be used.It is described suitable Stream is specially：Liquid to be evaporated is passed through to each effect evaporator of multi-effect evaporating device successively, before the multi-effect evaporating device The steam containing ammonia that 1st effective evaporator evaporates is passed through in rear 1st effective evaporator.The adverse current is specially：By liquid to be evaporated according to The secondary each effect evaporator for being passed through multi-effect evaporating device contains ammonia by what the rear 1st effective evaporator of the multi-effect evaporating device evaporated Before steam is passed through in 1st effective evaporator.The advection is specially：Liquid to be evaporated is individually passed through to each effect of multi-effect evaporating device The steam containing ammonia that the preceding 1st effective evaporator of the multi-effect evaporating device evaporates is passed through in rear 1st effective evaporator by evaporator. Wherein, it is preferred to use forward feed mode.When using fair current or adverse current feeding, the condition of evaporation refers to multi-effect evaporating device most The evaporation conditions of 1st effective evaporator afterwards；When being fed using advection, the condition of evaporation includes each effect evaporator of multi-effect evaporating device Evaporation conditions.
In the present invention, the condition of first evaporation can be selected suitably as needed, reach make sulfate crystal and Make the purpose that sodium chloride is not precipitated.It is described first evaporation condition may include：Temperature be 45 DEG C or more, pressure be- 95kPa or more.In order to improve evaporation efficiency, the condition of preferably described first evaporation includes：Temperature is 45 DEG C~365 DEG C, pressure For -95kPa~18110kPa；In order to further increase evaporation efficiency, it is highly preferred that the condition of first evaporation includes：Temperature Degree is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；From the point of view of reducing equipment cost and energy consumption, more preferably Ground, it is described first evaporation condition include：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；Further preferably Ground, it is described first evaporation condition include：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；It is particularly preferred that It is described first evaporation condition include：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
In the present invention, the operating pressure of the first evaporation is more preferably the saturated vapor pressure of evaporated feed liquid.
In the present invention, the flow of the first evaporation can suitably be selected according to the ability that equipment is handled, such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sulfate crystal by making the first evaporation carry out under these conditions, sodium chloride is not tied Partial crystallization goes out, the purity for the sodium sulfate crystal that thereby may be ensured that.
Contained ammonia in the pending waste water can be evaporated by the condition of the first evaporation of control according to the present invention 90 mass % or more (preferably 95 mass % or more), to obtain higher first ammonium hydroxide of concentration, the first ammonium hydroxide can be direct Be back to the production process of catalyst, either with acid neutralization obtain carrying out after ammonium salt reuse or with water and corresponding ammonium salt or Ammonium hydroxide allotment uses.
According to the present invention, first evaporation is not so that (i.e. chlorination is precipitated in the sodium chloride crystallization in the pending waste water Sodium is not up to supersaturation), it is preferable that first evaporation makes a concentration of X or less of sodium chloride in the first concentrate (preferably 0.999X is hereinafter, more preferably 0.95X-0.999X, further preferred 0.99X-0.9967X).Wherein, X is in the first evaporation Under the conditions of, the concentration of sodium chloride when sodium sulphate and sodium chloride reach saturation in the first concentrate.Pass through the journey evaporated first Degree control within the above range, can be such that sulfate crystal as much as possible is precipitated under conditions of ensureing that sodium chloride is not precipitated. By making sulfate crystal in the first evaporation as possible, waste water treatment efficiency can be improved, energy waste is reduced.
In the present invention, the carry out degree of first evaporation is in such a way that the first evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the first evaporation of control makes the first evaporation not make described in above-mentioned range Sodium chloride crystallization in first concentrate is precipitated.Here first evaporation obtain the concentration of liquid, by way of measuring density into Row monitoring can specifically use densitometer to carry out density measure.
According to the present invention, first evaporation carries out in the first vaporising device 2 (first vaporising device is as described above). By first circulation pump 71 by pending waste water be passed through the first vaporising device 2 carry out first evaporation, obtain the first steam containing ammonia with First concentrate of sulfur acid sodium crystal.
According to the present invention, this method can also include by the first concentrate of the sulfur acid sodium crystal in the first crystallization dress It sets the first crystallization of middle progress and obtains the magma of sulfur acid sodium crystal.At this point, the evaporation conditions of first evaporation need to meet Make sulfate crystal in first crystallization process and purpose that sodium chloride is not precipitated.First crystallization apparatus does not limit particularly It is fixed, such as can be brilliant flow container, brilliant liquid collecting tank, with stirring thickener or without stirring thickener etc..First crystallization Condition can be selected suitably, such as may include：Temperature is 45 DEG C or more；Preferably 85 DEG C~107 DEG C；More preferably 95 DEG C~ 105℃.In order to fully ensure that the effect of crystallization, crystallization time can be 5min~for 24 hours, preferably 5min~30min.According to this Invention, the first crystallization process of the first concentrate of the sulfur acid sodium crystal can also be in the vaporising device with crystallizer It is carried out in (such as forced-circulation evaporation crystallizer), the temperature of the first crystallization is the temperature of corresponding first evaporation at this time.
According to the present invention, when carrying out the first crystallization using individual crystallization apparatus, need to be further ensured that described first steams Hair is not so that sodium chloride crystallizes precipitation in the first crystallization process (i.e. sodium chloride is not up to supersaturation), it is preferable that described first Evaporation makes a concentration of X or less (the preferably 0.9X-0.99X, more preferably 0.95X- of sodium chloride in first concentrate 0.999X, further preferably 0.99X-0.9967X), wherein X is under conditions of first crystallization, in the first concentrate The concentration of sodium chloride when sodium chloride and sodium sulphate reach saturation.
A preferred embodiment according to the present invention will before the pending waste water is carried out the first evaporation The condensation water of first steam containing ammonia or first steam containing ammonia carries out the first heat exchange with the pending waste water and obtains To the first ammonium hydroxide.There is no particular limitation for the mode of first heat exchange, may be used the heat exchange mode of this field routine into Row.The number of first heat exchange can be 1 time or more, preferably 2-4 times, more preferably 2-3 times.Pass through first heat After exchange, the ammonium hydroxide of output is cooled, and heat utmostly recycles inside processing unit, and the energy is rationally utilized, and reduces Waste.
A preferred embodiment according to the present invention, as shown in Figure 1, first heat exchange is filled by the first heat exchange Set 31 and second heat-exchanger rig 32 carry out, specifically, the first steam containing ammonia that will be evaporated in first vaporising device 2 (or condensation water of the first steam containing ammonia) passes sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31, and will be described pending Waste water passes sequentially through the first heat-exchanger rig 31 and the second heat-exchanger rig 32, by first steam containing ammonia with it is described pending useless Water carries out first heat exchange, makes pending waste water heating be convenient for evaporating, while the first steam cooling containing ammonia being made to obtain First ammonium hydroxide, the first ammonium hydroxide can be stored in the first tank used for storing ammonia 51.
Another preferred embodiment according to the present invention, as shown in Figure 1, first heat exchange passes through the first heat exchange Device 31, the second heat-exchanger rig 32 and third heat-exchanger rig 33 carry out, and specifically, will be evaporated in first vaporising device 2 The first obtained steam containing ammonia passes sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31, second that the second evaporation is obtained The condensation water of the steam containing ammonia is (for example, the condensation that the second steam containing ammonia in the 4th heat-exchanger rig 34 obtain after second heat exchange Liquid) it waits locating by third heat-exchanger rig 33, while by another part by third heat-exchanger rig 33, and by the pending waste water in part Waste water is managed by the first heat-exchanger rig 31, is then converged the pending waste water of above-mentioned two parts, and be mixed to get with the second mother liquor After pending waste water, then by the pending waste water by the second heat-exchanger rig 32, completes first steam containing ammonia and wait locating Manage the first heat exchange between waste water.
There is no particular limitation for first heat-exchanger rig 31, the second heat-exchanger rig 32 and third heat-exchanger rig 33, can be with Using various heat exchangers commonly used in the art, reach the condensation water of first steam containing ammonia or first steam containing ammonia The purpose of first heat exchange is carried out with the pending waste water.Specifically, it can be jacketed type exchanger, board-like change Hot device, shell-and-tube heat exchanger etc., wherein preferably plate heat exchanger.The material of the heat exchanger can be selected specifically as needed It selects, such as in order to resist chloride ion corrosion, material can be selected for the heat exchange of two phase stainless steel, titanium or titanium alloy, Hastelloy Device can select the heat exchanger containing plastic material when temperature is relatively low.
According to the present invention, in order to make full use of the first steam containing ammonia or the first steam containing ammonia condensation water thermal energy, preferably After the first heat exchange, the temperature of the pending waste water is 50 DEG C~370 DEG C, more preferably 65 DEG C~370 DEG C, further Preferably 75 DEG C~184 DEG C, be still more preferably 85 DEG C~139 DEG C.
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 pending waste water.There is no particular limitation for the alkaline matter, reaches above-mentioned adjusting pH value Purpose, such as can be the hydroxide such as sodium hydroxide, potassium hydroxide.In order not to be introduced newly in pending waste water Impurity improves the purity of gained crystal, and the alkaline matter is preferably 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 pending waste water, such as the aqueous solution containing alkaline matter can be passed into and import institute It states and is mixed in the pipeline of pending waste water.For the content of alkaline matter in aqueous solution, there is no particular limitation, as long as It can achieve the purpose that above-mentioned adjusting pH value.But it in order to reduce the dosage of water, further reduces the cost, it is preferable to use alkalinity The saturated aqueous solution of substance.In order to monitor the pH value of the pending waste water, can be waited for described in measurement after above-mentioned adjusting pH value Handle the pH value of waste water.
A preferred embodiment according to the present invention, as shown in Figure 1, first evaporation process is in the first evaporation dress It is carried out in setting 2, before the ammonium salt-containing waste water to be sent into the first heat-exchanger rig 31 and carries out the first heat exchange, by will be described Ammonium salt-containing waste 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；Then the ammonium salt-containing waste water and second are separated by solid-liquid separation at least partly being mixed to get for obtained liquid phase Pending waste water, then the pending waste water is sent into the second heat-exchanger rig 32 and carries out the first heat exchange, and wait locating by described It manages waste water and is sent into the aqueous solution containing alkaline matter of importing in the pipeline of the second heat-exchanger rig 32 and mixing, to carry out second Secondary pH value is adjusted.It is adjusted by pH value twice, pH value of the pending waste water before being passed through the first vaporising device 2 is made to be more than 9, preferably greater than 10.8.Preferably, first time pH value is adjusted so that the pH value of the waste water after adjusting is more than 7 (preferably 7-9), second of pH value is adjusted so that the pH value of the pending waste water is more than 9, preferably greater than 10.8.
In order to detect above-mentioned first time pH value adjust and second of pH value adjust after pH value, preferably by the ammonium salt-containing Waste water be sent into the first heat-exchanger rig 31 pipeline on the first pH value measuring device 61 is set measure first time pH value adjust after PH value is arranged the second pH value measuring device 62 and measures the pending waste water to be sent on the pipeline of the second heat-exchanger rig 32 PH value after second of pH value adjusting.
In the present invention, the first heat exchange, the pH value of the adjusting pending waste water and the pending waste water is mixed (the pending waste water contains the ammonium salt-containing waste water and is separated by solid-liquid separation obtained liquid phase with described second as cycle mother conjunction process Liquid needs the mixed process for carrying out the pending waste water) carry out priority there is no particular limitation, can be fitted as needed When selection, carry out first evaporation before complete.
In the present invention, the first concentrate of the sulfur acid sodium crystal obtains sodium sulphate crystalline substance after first is separated by solid-liquid separation Body and the first mother liquor (i.e. first is separated by solid-liquid separation obtained liquid phase).There is no particular limitation for described first method being separated by solid-liquid separation, Such as it can be selected from one or more in centrifugation, filtering, sedimentation.
According to the present invention, first concentrate first be separated by solid-liquid separation may be used the first equipment for separating liquid from solid (such as For centrifuge, band filter, flame filter press etc.) it carries out.As shown in Figure 1, after described first is separated by solid-liquid separation, the first solid-liquid point The first mother liquor obtained from device 91 is temporarily stored into the first mother liquor tank 53, and the second evaporation can be sent by the 6th circulating pump 76 Device 1 carries out the second evaporation.In addition, certain chlorion, free ammonia, hydrogen can be adsorbed by being difficult to avoid that on obtained sodium sulfate crystal The impurity such as oxygen radical ion reduce the peculiar smell of solid salt to remove the impurity of absorption, reduce corrosivity, improve the crystal Purity, it is preferable that sodium sulfate crystal water, the ammonium salt-containing waste water or metabisulfite solution carry out the first washing and drying.
It is separated by solid-liquid separation the mode washed with first as above-mentioned first, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.Preferably, first washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, It can be carried out by the method for this field routine.It is described elutriation and elution number there is no particular limitation, can be 1 time with On, the sodium sulfate crystal of higher purity, preferably 2-4 times in order to obtain.During elutriation, use the ammonium salt-containing waste water as wash in a pan It does not recycle generally when washing lotion, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the first washing recycling.It carries out Before the elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (content liquid of sulfur acid sodium crystal For 35 mass % or less, which preferably carries out in the device well known in the art such as settling tank, settling tank).It eluriated Cheng Zhong, relative to the slurries of 1 parts by weight sulfur acid sodium crystal, it is 1~20 parts by weight to eluriate the liquid used.In addition, elution is excellent Choosing is carried out using aqueous sodium persulfate solution, and the concentration of the aqueous sodium persulfate solution is preferably the temperature corresponding to sodium sulfate crystal to be washed Lower sodium chloride and sodium sulphate reach the concentration of sodium sulphate in the aqueous solution of saturation simultaneously.In order to further increase the effect of elutriation, The higher sodium sulfate crystal of purity is obtained, it is preferable to use the liquid that elution obtains carries out above-mentioned elutriation, it is preferable to use water or sulfuric acid Sodium solution.For the liquid that washing generates, preferably return it to before the completion of the first heat exchange before the first evaporation.
A preferred embodiment according to the present invention contains sodium sulphate by what the evaporation of the first vaporising device 2 obtained The first concentrate, by the way that after settling and be tentatively separated by solid-liquid separation, first time is carried out in eluriating tank with the ammonium salt-containing waste water It eluriates, then reuses the liquid obtained when subsequent wash sodium sulfate crystal and carry out second of elutriation in another elutriation tank, Equipment for separating liquid from solid finally will be sent by the slurries eluriated twice to be separated by solid-liquid separation, the crystal being separated by solid-liquid separation uses sulphur again During acid sodium aqueous solution is eluted, and the liquid that elution is obtained is eluriated back to second.By above-mentioned washing process, not only The purity of the sodium sulfate crystal made improves, and will not be excessive introducing cleaning solution, improve the efficiency of wastewater treatment.
In the present invention, the evaporation conditions of second evaporation can be selected suitably as needed, and reaching makes sodium chloride knot Partial crystallization goes out and purpose that sodium sulphate is not precipitated.It is described second evaporation condition may include：Temperature is 30 DEG C~85 DEG C, pressure Power is -98kPa~-58kPa.In order to improve evaporation efficiency, and from the point of view of reducing equipment cost and energy consumption, it is preferable that It is described second evaporation condition include：Temperature is 35 DEG C~60 DEG C, and pressure is -97.5kPa~-87kPa；Preferably, described Two evaporation condition include：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa~-87kPa；Preferably, it is described second evaporation Condition includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kP；Preferably, the condition of second evaporation includes： Temperature is 45 DEG C~55 DEG C, and pressure is -95kPa~-90kPa.
In the present invention, the operating pressure of the second evaporation is more preferably the saturated vapor pressure of evaporated feed liquid.
In addition, ability and pending wastewater flow rate that the evaporation capacity of the second evaporation can be handled according to equipment suitably select, Such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sodium chloride crystallization by making the second evaporation carry out under these conditions, sodium sulphate is not tied Crystalline substance, the purity for the sodium chloride crystal that thereby may be ensured that.
According to the present invention, second evaporation is not so that (i.e. sulfuric acid is precipitated in the sulfate crystal in second concentrate Sodium is not up to supersaturation), it is preferable that second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate (preferably For 0.9Y-0.99Y, more preferably 0.95Y-0.98Y), wherein Y is the sulfuric acid in the second concentrate under conditions of second evaporates The concentration of sodium sulphate when sodium and sodium chloride reach saturation.By by the extent control of the second evaporation within the above range, can be with It is precipitated sodium chloride crystallization as much as possible under conditions of ensureing that sodium sulphate is not precipitated.By making chlorine in the second evaporation as possible Change sodium crystallization, waste water treatment efficiency can be improved, reduces energy waste.
In the present invention, the carry out degree of second evaporation is in such a way that the second evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the second evaporation of control makes the second evaporation not make described second in above range Sulfate crystal in concentrate is precipitated.Here the second evaporation obtains the concentration of liquid, is supervised by way of measuring density It surveys, can specifically densitometer be used to carry out density measure.
According to the present invention, second evaporation carries out in the second vaporising device 1 (second vaporising device is as described above). First mother liquor is passed through the second evaporation of progress in second vaporising device 1 and obtains the second steam containing ammonia and sodium chloride-containing crystalline substance Second concentrate of body.
According to the present invention, this method can also include by the second concentrate of the sodium chloride-containing crystal in the second crystallization dress It sets the second crystallization of middle progress and obtains the magma of sodium chloride-containing crystal.At this point, the evaporation conditions of second evaporation need to meet Sodium chloride is set to crystallize and purpose that sodium sulphate is not precipitated in second crystallization process.Second crystallization apparatus is not special It limits, such as can be brilliant flow container, brilliant liquid collecting tank, with stirring thickener or without stirring thickener etc., such as can be in crystalline substance It is carried out in liquid collecting tank 55.The condition of second crystallization can be selected suitably, such as may include：Temperature is 30 DEG C or more； Preferably 40 DEG C~60 DEG C；More preferably 45 DEG C~55 DEG C.In order to fully ensure that the effect of crystallization, crystallization time can be 5min ~for 24 hours, preferably 5min~30min.According to the present invention, the second crystallization process of the second concentrate of the sodium chloride-containing crystal It can also be carried out in crystallizer vaporising device (such as forced-circulation evaporation crystallizer), the temperature of the second crystallization is at this time The temperature of corresponding second evaporation.
According to the present invention, when being crystallized using individual crystallization apparatus, need to be further ensured that second evaporation makes It obtains sodium sulphate and does not crystallize precipitation in the second crystallization process (i.e. sodium sulphate is not up to supersaturation), it is preferable that second evaporation Make a concentration of Y or less (preferably 0.9Y-0.99Y, more preferably 0.95Y-0.98Y) of sodium sulphate in second concentrate, Wherein, Y is sodium sulphate when sodium sulphate and sodium chloride reach saturation in the second concentrate under conditions of second crystallization Concentration.
A preferred embodiment according to the present invention, second steam containing ammonia carry out the second heat exchange with cold medium And obtain ammonium hydroxide.The cold medium can be cooling water, glycol water etc..When using conventional cooling water, the cooling Water recycles, and when using the ammonium salt-containing waste water as cooling water, preferably directly return is handled the ammonium salt-containing waste water after heat exchange Process (is such as back to first time pH value adjustment process).There is no particular limitation for the mode of second heat exchange, may be used The heat exchange mode of this field routine carries out.The number of the heat exchange can be 1 time or more, preferably 2-4 times, more preferably 2- 3 times.By the heat exchange, the ammonium hydroxide of output is cooled, and heat utmostly recycles inside processing unit, is rationally utilized The energy reduces waste.
A preferred embodiment according to the present invention fills as shown in Figure 1, second heat exchange is exchanged heat by third Set 33 and the 4th heat-exchanger rig 34 carry out, specifically, the second steam containing ammonia is passed sequentially through into the 4th heat-exchanger rig 34 and third is changed Thermal 33, the second cleaning solution and second circulation liquid are made in the 4th heat-exchanger rig 34, and (passing through the second vaporising device, (MVR steams Transmitting apparatus) partially liq that returns after 2 evaporations) with second steam containing ammonia the second heat exchange of progress, in third heat-exchanger rig So that ammonium salt-containing waste water and the second steam condensation containing ammonia liquid is carried out the second heat exchange in 33, further decreases the second steam condensation containing ammonia The temperature of liquid improves heat utilization rate, obtains the second ammonium hydroxide.
A preferred embodiment according to the present invention, as shown in Fig. 2, the second vaporising device (multi-effect evaporating device) 1 Obtained the second steam containing ammonia of last 1st effective evaporator carry out the second heat exchange simultaneously with cold medium in third heat-exchanger rig 33 Obtain the second ammonium hydroxide.
There is no particular limitation for 33 and the 4th heat-exchanger rig 34 of the third heat-exchanger rig, this field can be used routinely to make Various heat exchangers achieve the purpose that second steam containing ammonia is made to cool down.Specifically, it can be jacket type heat exchange Device, plate heat exchanger, shell-and-tube heat exchanger, screw heat exchange of heat pipe etc..The material of the heat exchanger can have as needed Body selects, such as since indirect steam does not have corrosivity, preferably stainless steel spiral screwed tube heat exchanger to stainless steel.
In the present invention, sodium chloride is made not crystallize precipitation in order to reach first evaporation, second evaporation makes sulfuric acid Sodium does not crystallize the purpose of precipitation, and it (is corresponding crystallization when being crystallized using individual crystallization apparatus preferably to make the condition of twice evaporation Condition) meet：The temperature of first evaporation is at least 5 DEG C higher than the temperature of the second evaporation, preferably 20 DEG C high, more preferably 35 DEG C high It is~70 DEG C, particularly preferably 40 DEG C high~60 DEG C.It is carried out at different temperature by the first evaporation of control and the second evaporation, makes sulphur The crystallization respectively of sour sodium and sodium chloride is precipitated, to improve the purity of obtained sodium sulphate and sodium chloride crystal.
In the present invention, the second concentrate of the sodium chloride-containing crystal obtains sodium chloride crystalline substance after second is separated by solid-liquid separation Body and the second mother liquor (i.e. second is separated by solid-liquid separation obtained liquid phase).There is no particular limitation for described second method being separated by solid-liquid separation, Such as it can be selected from one or more in centrifugation, filtering and sedimentation.
According to the present invention, second separation of solid and liquid can (be, for example, centrifuge, belt by the second equipment for separating liquid from solid Filter, flame filter press etc.) 92 progress.After described second is separated by solid-liquid separation, the second equipment for separating liquid from solid 92 obtains second female Liquid (namely described second is separated by solid-liquid separation obtained liquid phase) returns to the first vaporising device 2 and carries out the first evaporation again, specifically may be used With after second mother liquor is adjusted back to first time pH value by the 8th circulating pump 78 and second pH value adjust before with institute It states ammonium salt-containing waste water and is mixed to get the pending waste water, be then fed into the first vaporising device 2 and carry out the first evaporation.Separately Outside, the impurity such as certain sulfate ion, free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on the sodium chloride crystal obtained, In order to remove the impurity of absorption, the peculiar smell of solid salt is reduced, corrosivity is reduced, improves the purity of the crystal, it is preferable that described Sodium chloride crystal water, the ammonium salt-containing waste water or sodium chloride solution carry out the second washing and drying.In order to avoid washing process The dissolving of middle sodium chloride crystal, it is preferable that the sodium chloride crystal is washed with sodium-chloride water solution.It is highly preferred that described Sodium chloride and sodium sulphate reach full simultaneously at the concentration of the sodium-chloride water solution preferably temperature corresponding to sodium chloride crystal to be washed The concentration of sodium chloride in the aqueous solution of sum.
It is separated by solid-liquid separation the mode washed with second as above-mentioned second, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.Preferably, second washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, It can be carried out by the method for this field routine.It is described elutriation and elution number there is no particular limitation, can be 1 time with On, the sodium chloride crystal of higher purity, preferably 2-4 times in order to obtain.During elutriation, use the ammonium salt-containing waste water as wash in a pan It does not recycle generally when washing lotion, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the second washing recycling.It carries out Before the elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (content liquid of sodium chloride-containing crystal For 35 mass % or less, which preferably carries out in the device well known in the art such as settling tank, settling tank).It eluriated Cheng Zhong, relative to the slurries of 1 parts by weight sodium chloride-containing crystal, it is 1-20 parts by weight to eluriate the liquid used.Elution it is preferable to use Sodium-chloride water solution (concentration of the sodium-chloride water solution be preferably the temperature corresponding to sodium chloride crystal to be washed under sodium chloride and Sodium sulphate reaches the concentration of sodium chloride in the aqueous solution of saturation simultaneously) it carries out.In order to further increase the effect of elutriation, obtain pure Higher sodium chloride crystal is spent, in the case of preferred, the liquid that elution obtains can be used to carry out above-mentioned elutriation.Washing is produced Raw liquid, it is preferable that the ammonium salt-containing waste water is eluriated liquid and is back to before the adjusting completion of the pH value before the first evaporation, Qi Taxi It washs liquid and is back to the second evaporation.Such as the second vaporising device 1 is returned to by the 9th circulating pump 79 in Fig. 1 and carries out the second steaming again Hair.
A preferred embodiment according to the present invention, by the second concentration of the sodium chloride-containing crystal that crystallization obtains Liquid carries out first time elutriation, then again with the ammonium salt-containing waste water after settling progress tentatively separation of solid and liquid in eluriating tank The liquid obtained when using subsequent wash sodium chloride crystal carries out second in another elutriation tank and eluriates, and will finally pass through two The slurries of secondary elutriation are sent into equipment for separating liquid from solid and are separated by solid-liquid separation, and the crystal being separated by solid-liquid separation uses sodium-chloride water solution again (sodium chloride and sodium sulphate reach full simultaneously at a concentration of temperature corresponding to sodium chloride crystal to be washed of the sodium-chloride water solution The concentration of sodium chloride in the aqueous solution of sum) it is eluted, and will elute during obtained liquid is eluriated back to second as naughty Washing lotion.The purity of the washing process combined by above-mentioned elutriation and elution, the sodium chloride crystal not only made improves, and not The excessive introducing cleaning solution of meeting, improves the efficiency of wastewater treatment.
In the present invention, when carrying out the first evaporation and/or the second evaporation using MVR vaporising devices, in order to improve MVR evaporations Solid content in device, reduce liquid in ammonia content, preferably by by MVR vaporising devices evaporation after partially liq ( The liquid being located inside MVR vaporising devices, hereinafter also referred to as circulation fluid) it flows back into MVR vaporising devices after heating and carries out again Evaporation.It is not limited particularly as the ratio that the partially liq after the evaporation of MVR vaporising devices is flowed back into MVR vaporising devices System, for example, the first reflux ratio of first evaporation can be 10-200, preferably 50-100, the second of second evaporation Reflux ratio can be 0.1-50, preferably 7-25.Here, reflux ratio refers to：Regurgitant volume and the liquid being sent into MVR vaporising devices Total amount subtracts the ratio of regurgitant volume.Preferably, the pH before the first circulation liquid in the first evaporation is preferably returned to the first evaporation Before value adjusts completion, the first circulation liquid is filled back to the first heat exchange as shown in Figure 1,72 can be pumped by second circulation It sets in 31 and the second waste water conveyance conduit between heat-exchanger rig 32 and is mixed with pending waste water, then by described second After pH value is adjusted, heat exchange is carried out in the second heat-exchanger rig 32, is finally sent into first vaporising device 2.
In the present invention, using MVR vaporising devices carry out first evaporation and/or second evaporation when, this method further include by First steam containing ammonia and/or the second steam containing ammonia are compressed.The compression can be carried out by compressor, such as the first pressure Contracting machine 101 and the second compressor 102.By being compressed to containing ammonia steam, to input energy in MVR vapo(u)rization systems, ensure useless The process of water heating-evaporation-cooling is carried out continuously, and is needed to input startup steam when MVR evaporation processes start, is reached and continuously run It is only energized by compressor after state, it is no longer necessary to input other energy.The compressor may be used commonly used in the art Various compressors, such as centrifugal blower, turbocompressor or lobed rotor compressor etc..After compressor compresses, steam containing ammonia Temperature increase 5 DEG C~20 DEG C.
A preferred embodiment according to the present invention, first steam containing ammonia is cold by first heat exchange It coagulates remaining tail gas and second steam containing ammonia and condenses remaining tail gas by removing ammonia heel row by second heat exchange It puts.As shown in Figure 1, first steam containing ammonia condenses remaining tail gas, that is, the second heat exchange dress by first heat exchange The tail gas of 32 discharges is set, second steam containing ammonia condenses remaining i.e. the 4th heat-exchanger rig of tail gas by second heat exchange The tail gas of 34 discharges.By by above-mentioned tail gas remove ammonia, the pollutant load in emission can be further decreased 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 ammonium salt-containing waste water, as long as containing NH4 +、SO4 2-、Cl-And Na+It is useless Water.In addition, the method for the present invention is particularly suitable for the processing of high-salt wastewater.As the waste water of the present invention, it is specifically as follows and Can also be that will be urged from molecular sieve, aluminium oxide or oil refining from molecular sieve, the waste water of aluminium oxide or oil refining catalyst production process The waste water of agent production process carries out the waste water after following removal of impurities and concentration.Molecular sieve, aluminium oxide or oil refining will preferably be come from The waste water of catalyst production process carries out the waste water after following removal of impurities and concentration.
As the NH in the ammonium salt-containing waste water4 +Can be 8mg/L or more, preferably 300mg/L or more.
As the Na in the ammonium salt-containing waste water+Can be 510mg/L or more, preferably 1000mg/L or more, more preferably For 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 ammonium salt-containing waste water4 2-Can be 1000mg/L or more, preferably 2000mg/L or more, it is more excellent It is selected as 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, it is further excellent It is selected as 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L or more, further Preferably 60000mg/L or more, further preferably 70000mg/L or more.
As the Cl in the ammonium salt-containing waste water-Can be 970mg/L or more, more preferably 2000mg/L or more, into one Step is preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, into one Step preferably 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L or more, into One step is preferably 60000mg/L or more.
The NH contained in the ammonium salt-containing waste water4 +、SO4 2-、Cl-And Na+The upper limit there is no particular limitation.Hold from waste water From the point of view of easily starting with, SO in waste water4 2-、Cl-And Na+Respectively 200g/L hereinafter, preferably 150g/L hereinafter, more preferably 120g/L or less；NH in waste water4 +For 50g/L hereinafter, preferably 40g/L or less.
From the efficiency for improving the first evaporation, from the point of view of the energy consumption for reducing processing procedure, relative in ammonium salt-containing waste water The SO contained4 2-, the Cl in ammonium salt-containing waste water-The lower content the better, for example, relative to containing in 1 mole of ammonium salt-containing waste water SO4 2-, the Cl that contains in the ammonium salt-containing waste water-For 30 moles hereinafter, preferably 20 moles hereinafter, more preferably 15 moles Hereinafter, further preferably 10 moles or less.And from the point of view of practicability, relative in 1 mole of ammonium salt-containing waste water The SO contained4 2-, the Cl that contains in the ammonium salt-containing waste water-Preferably 0.1 mole or more, more preferably 0.5 mole or more, into One step is preferably 1 mole or more, such as 1-8 moles.Pass through the SO that will contain in the ammonium salt-containing waste water4 2-And Cl-Molar ratio It is limited to above range, most of water can be steamed in the first evaporation, be reduced the circulation fluid scale of construction in system for handling, save The energy keeps processing procedure more economical.
In the present invention, the inorganic ion contained in the ammonium salt-containing waste water is in addition to NH4 +、SO4 2-、Cl-And Na+In addition, Mg can also be contained2+、Ca2+、K+、Fe3+, the inorganic ions such as rare earth element ion, Mg2+、Ca2+、K+、Fe3+, rare earth element from The respective content of the inorganic ions such as son is preferably 100mg/L hereinafter, more preferably 50mg/L is hereinafter, further preferably 10mg/L is not hereinafter, contain other inorganic ions particularly preferably.It, can by controlling other inorganic ions in above range To further increase the purity of finally obtained sodium sulfate crystal and sodium chloride crystal.In order to reduce in the ammonium salt-containing waste water The content of other inorganic ions preferably carries out following removal of impurities.
The TDS of the ammonium salt-containing waste water can be 1600mg/L or more, preferably 4000mg/L or more, more 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 60000mg/L or more, further preferably For 100000mg/L or more, further preferably 150000mg/L or more, further preferably 200000mg/L or more.
In the present invention, the pH value of the ammonium salt-containing waste water is preferably 4~8, and more preferably 6.2~6.8.
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 COD more fewer better (preferably 20mg/L is hereinafter, more preferably 10mg/L or less) of the ammonium salt-containing waste water, is preferably pre-processing When by oxidation removal, such as bioanalysis, advanced oxidation processes progress specifically can be used, preferably used when COD contents are very high Oxidizing, the oxidant for example can be Fenton reagent.
In the present invention, in order to reduce the concentration impurity ion in waste water, ensure that the continuous-stable of processing procedure carries out, drop Low equipment operation maintenance cost, the ammonium salt-containing waste water using the processing method of the present invention before being handled preferably through removal of impurities.It is excellent Selection of land, the removal of impurities are one or more in separation of solid and liquid, chemical precipitation, absorption, ion exchange and oxidation.
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, potassium permanganate, in order to avoid introducing new impurity, it is preferred to use ozone, dioxygen Water etc..
Specific removal of impurities mode can be specifically chosen according to the dopant species contained in the ammonium salt-containing waste water.For suspension Object can select solid-liquid isolation method to clean；For inorganic matter and organic matter, chemical precipitation method, ion-exchange, suction can be selected Attached method removal of impurities, such as Subacidity cation exchange process, active carbon adsorption etc.；For organic matter, absorption and/or oxygen may be used The mode of change cleans, wherein preferably ozone biological activated carbon adsorption and oxidation method.
A preferred embodiment according to the present invention, the ammonium salt-containing waste water successively by filtering, faintly acid sun from Sub- exchange process, ozone biological activated carbon adsorption and oxidation method clean.By above-mentioned dedoping step, most of suspension can be removed Object, hardness, silicon and organic matter reduce device fouling risk, ensure ammonium salt-containing wastewater treatment process continuous and steady operation.
In the present invention, it for the lower ammonium salt-containing waste water of salt content, can be handled using the processing method of the present invention Before (preferably after above-mentioned removal of impurities), by concentrate make salt content reach the present invention waste water required by range.Preferably, It is described concentration 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, institute Stating the concentration of ED films and the sequencing of reverse osmosis progress, there is no particular limitation.ED films concentration and reverse osmosis treatment device and The mode that this field routine may be used in condition carries out, and can be specifically chosen according to the case where pending waste water.Specifically, as The ED films concentration, can select unidirectional electrodialysis system or pole-reversing electroosmosis system to carry out；As described reverse osmosis, Ke Yixuan It is carried out with rolled film, plate membrane, dish tubular membrane, vibrating membrane or combinations thereof.It can be improved at ammonium salt-containing waste water by the concentration The efficiency of reason avoids energy waste caused by largely evaporating.
In the preferred embodiment of the present invention, the ammonium salt-containing waste water is the waste water in process of producing molecular sieve It cleans, and passes through by chemical precipitation, filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method ED films concentrate and the 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.
It according to the present invention, when proceeding by wastewater treatment, can directly be gone into operation using ammonium salt-containing waste water, if ammonium salt-containing is useless The ion concentration of water meets the condition of the present invention, the first evaporation can be first carried out with condition according to the invention and carry out the second steaming again Hair；If the ion concentration of ammonium salt-containing waste water is unsatisfactory for the condition of the present invention, can control the first evaporation makes in the first concentrate Then first concentrate is carried out the second evaporation by the concentration of sodium chloride close to concentration is precipitated, obtain the second concentrate and solid-liquid point It is mixed with the ammonium salt-containing waste water to adjust pending waste water from obtaining sodium chloride crystal and the second mother liquor, then by the second mother liquor Ion concentration obtains sodium sulfate crystal to carry out the first evaporation again after range of the presently claimed invention.Certainly also may be used in the starting stage It is prepared with certain density SO to use4 2-、Cl-Solution the ion concentration in pending waste water is adjusted, only The pending waste water is set to meet in the present invention to SO in pending waste water4 2-、Cl-Requirement.
The present invention will be described in detail by way of examples below.
In following embodiment, ammonium salt-containing waste water be process of producing molecular sieve in waste water successively pass through chemical precipitation, filtering, Subacidity cation exchange process 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 saturating method concentration.
Embodiment 1
As shown in Figure 1, by ammonium salt-containing waste water (80g/L containing NaCl, Na2SO4 82g/L、NH4Cl 50g/L、(NH4)2SO4 52.1g/L, pH 6.8) with inlet amount it is 5m3The speed of/h is sent into vacuum receiver 4 and carries out vacuum outgas, is being sent to first The sodium hydrate aqueous solution that a concentration of 45.16 mass % is imported in the pipeline of heat-exchanger rig 31 (titanium alloy plate heat exchanger) carries out First time pH value is adjusted, and is monitored that (measured value is to the pH value after adjusting by the first pH value measuring device 61 (pH meter) 7.5) the part ammonium salt-containing waste water after the adjusting of the first pH value, is sent into the first heat-exchanger rig 31 by first circulation pump 71, Carrying out the first heat exchange with the first liquid of steam condensation containing ammonia of recycling makes waste water be warming up to 98 DEG C, will be after the adjusting of the first pH value Another part waste water third heat-exchanger rigs 33 are sent by first circulation pump 71, carry out the with the condensation water of the second steam containing ammonia One heat exchange makes waste water be warming up to 48 DEG C, and above-mentioned two parts ammonium salt-containing waste water is converged, and (is sent into speed with the second mother liquor of return Spend 8.75m3/ h) it is mixed to get pending waste water and (measures the SO wherein contained4 2-And Cl-Molar ratio be 1：6.261) it after, is inciting somebody to action Pending waste water is sent into the pipeline of the second heat-exchanger rig 32 the sodium hydrate aqueous solution progress for importing a concentration of 45.16 mass % Second pH value is adjusted, and is monitored that (measured value is to the pH value after adjusting by the second pH value measuring device 62 (pH meter) 10.8) the first steam containing ammonia for, being then fed into the second heat-exchanger rig 32 (titanium alloy plate heat exchanger) and recycling carries out the first heat Exchange makes pending waste water be warming up to 107 DEG C, then the pending waste water after the first heat exchange is sent into the first vaporising device 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) is evaporated, and obtains the first of the first steam containing ammonia and sulfur acid sodium crystal Concentrate.Wherein, the evaporation conditions of the first vaporising device 2 include：Temperature is 100 DEG C, and pressure is -22.82kPa, and evaporation capacity is 3.92m3/h.The first obtained steam containing ammonia (12 DEG C of temperature rise) after the compression of the first compressor 101 is evaporated to pass sequentially through Second heat-exchanger rig 32 and the first heat-exchanger rig 31 carry out heat exchange with pending waste water, cooling to obtain the first ammonium hydroxide, and the It is stored in one tank used for storing ammonia 51.In addition, in order to improve the solid content in the first vaporising device 2, will be steamed in the first vaporising device 2 Partially liq after hair is recycled to the second heat-exchanger rig 32 as first circulation liquid by second circulation pump 72, is then again introduced into First vaporising device 2 carries out the first evaporation (the first reflux ratio is 77.8).Pass through the densitometer pair being arranged on the first vaporising device 2 The degree of first evaporation is monitored, and controls a concentration of 0.9935X (306.2g/L) of sodium chloride in the first concentrate.
The first concentrate that the evaporation of above-mentioned first vaporising device 2 obtains is sent into the first equipment for separating liquid from solid 91 (centrifuge) After carrying out the first separation of solid and liquid, 10.58m is obtained per hour3Contain NaCl 306.2g/L, Na2SO4 54.0g/L、NaOH 1.4g/L、NH3The first mother liquor of 0.27g/L is temporarily stored into the first mother liquor tank 53, is separated by solid-liquid separation gained solid sodium sulfate (per small When obtain the sulfate crystal filter cake 809.7kg of aqueous 15 mass %, wherein the content of sodium chloride is 6.9 mass % or less) use The metabisulfite solution of the 54g/L equal with sulfate crystal filter cake butt quality elutes, and sodium sulphate is obtained per hour after dry 688.25kg (purity is 99.7 weight %), cleaning solution is recycled to by the 5th circulating pump 75 into before the second heat-exchanger rig 32 It is mixed with waste water in pipeline, is then again introduced into the first vaporising device 2 and carries out the first evaporation.
Second evaporation process in the second vaporising device 1 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) into Row.The first mother liquor in above-mentioned first mother liquor tank 53 is sent into the second vaporising device 1 by the 6th circulating pump 76 and carries out the second steaming Hair obtains the second concentrate of sodium chloride-containing crystal.Wherein, the evaporation conditions of the second vaporising device 1 include：Temperature is 50 DEG C, pressure Power is -92.67kPa, evaporation capacity 1.95m3/h.In order to improve the solid content in the second vaporising device 1, the second evaporation is filled Set the first mother liquor of part after being evaporated in 1 as second circulation liquid by the 7th circulating pump 77 be recycled to the 4th heat-exchanger rig 34 and Second steam containing ammonia carries out heat exchange, is then again introduced into the second vaporising device 1 and carries out the second evaporation (the second reflux ratio is 16). It evaporates the second obtained steam containing ammonia (12 DEG C of temperature rise) after the compression of the second compressor 102 and passes sequentially through the 4th heat exchange dress It sets 34 and third heat-exchanger rig 33 carries out heat exchange and cooling obtains the second ammonium hydroxide, and stored in the second tank used for storing ammonia 52.The The first mother liquor of part after being evaporated in cleaning solution and the second vaporising device 1 after two separation of solid and liquid passes through the 9th circulating pump 79 respectively After pumping out with the 7th circulating pump 77 and mixing in the duct hot friendship is carried out with by the second steam containing ammonia of the 4th heat-exchanger rig 34 It changes, the condensation water of the pending waste water in part and the second steam containing ammonia by third heat-exchanger rig 33 of 71 conveying of first circulation pump Carry out heat exchange.The degree evaporated by the densitometer pair second being arranged on the second vaporising device 1 is monitored, and control second is dense A concentration of 0.9702Y (65.3g/L) of sodium sulphate in contracting liquid.After first mother liquor evaporates in the second vaporising device 1, contained Second concentrate of sodium chloride crystal.
The second concentrate containing sodium chloride crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and is separated by solid-liquid separation, Separation of solid and liquid obtains 8.75m per hour3Contain NaCl 293.8g/L, Na2SO4 65.3g/L、NaOH 1.7g/L、NH3 The second mother liquor of 0.013g/L, the second mother liquor are temporarily stored into the second mother liquor tank 54.Second mother liquor is passed through into the 8th circulating pump 78 It is recycled to the waste water import pipe before second of pH value is adjusted and is mixed to get pending waste water with waste water, be separated by solid-liquid separation gained chlorination Sodium solid (obtains the sodium chloride crystalli-zation cake 785.29kg that water content is 14 mass %, the content of wherein sodium sulphate is per hour 7.1 mass % or less) with after the 293.8g/L sodium chloride solutions elution equal with sodium chloride butt quality, it is done in drying machine It is dry, sodium chloride 675.35kg (purity is 99.4 weight %) is obtained per hour, and the second cleaning solution washed is followed by the 9th Ring pump 79 is recycled to the second vaporising device 1.
In addition, the tail gas of vacuum receiver 4, the second heat-exchanger rig 32 and the discharge of the 4th heat-exchanger rig 34 passes through vacuum pump 81 It introduces tail gas absorber 83 to be absorbed, recirculated water is connected in tail gas absorber 83, the recirculated water is in the 4th circulating pump 74 It recycles in tail gas absorber 83 under effect, while being mended to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73 Add water, and add fresh water in circulating water pool 82, reduces by the temperature and ammonia content of 81 work water of vacuum pump.The tail gas It is further passed through dilute sulfuric acid in absorption tower 83, to absorb ammonia in tail gas etc..
In the present embodiment, the ammonium hydroxide 3.92m of a concentration of 3.53 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.95m of a concentration of 0.144 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
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 60g/L, Na2SO4 130g/L、 NH4Cl 15g/L、(NH4)2SO4The waste water that 33.0g/L, pH are 6.8 is handled, and is contained in obtained pending waste water SO4 2-And Cl-Molar ratio be 1：4.462.Temperature by waste water after the progress heat exchange of the first heat-exchanger rig 31 is 67 DEG C, is led to Cross the second heat-exchanger rig 32 carry out heat exchange after pending waste water temperature be 102 DEG C.The evaporation conditions packet of first vaporising device 2 It includes：Temperature is 95 DEG C, and pressure is -36.36kPa, evaporation capacity 4.48m3/h.The evaporation conditions of second vaporising device 1 include：Temperature Degree is 55 DEG C, and pressure is -90.15kPa, evaporation capacity 1.05m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 978.40kg of aqueous 15 mass % per hour, finally Obtain sodium sulphate 831.63kg per hour (purity is 99.3 weight %)；7.25m is obtained per hour3A concentration of NaCl 307.2g/ L、Na2SO4 54.5g/L、NaOH 1.8g/L、NH3The first mother liquor of 0.18g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 444.79kg that water content is 15 mass % per hour, It is final to obtain sodium chloride 378.07kg per hour (purity is 99.5 weight %)；6.30m is obtained per hour3A concentration of NaCl 295.5g/L、Na2SO4 63.1g/L、NaOH 2.1g/L、NH3The second mother liquor of 0.01g/L.
In the present embodiment, the ammonium hydroxide 4.48m of a concentration of 1.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 1.05m of a concentration of 0.11 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
Embodiment 3
The processing of waste water is carried out according to the method for embodiment 1, unlike：To containing NaCl 160g/L, Na2SO4 55g/L、 NH4Cl 32g/L、(NH4)2SO4The waste water that 11.2g/L, pH are 6.2 is handled, and is contained in obtained pending waste water SO4 2-And Cl-Molar ratio be 1：9.249.Temperature by waste water after the progress heat exchange of the first heat-exchanger rig 31 is 73 DEG C, is led to Cross the second heat-exchanger rig 32 carry out heat exchange after pending waste water temperature be 112 DEG C.The evaporation conditions packet of first vaporising device 2 It includes：Temperature is 105 DEG C, and pressure is -7.02kPa, evaporation capacity 2.63m3/h.The evaporation conditions of second vaporising device 1 include：Temperature Degree is 45 DEG C, and pressure is -94.69kPa, evaporation capacity 2.86m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 385.26kg of aqueous 14 mass % per hour, finally Obtain sodium sulphate 331.32kg per hour (purity is 99.4 weight %)；11.98m is obtained per hour3A concentration of NaCl 306.4g/L、Na2SO4 52.5g/L、NaOH 2.6g/L、NH3The first mother liquor of 0.11g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake that water content is 15 mass % per hour 1151.57kg finally obtains sodium chloride 978.83kg per hour (purity is 99.4 weight %)；9.18m is obtained per hour3Concentration For NaCl 291.2g/L, Na2SO4 67.9g/L、NaOH 3.4g/L、NH3The second mother liquor of 0.0084g/L.
In the present embodiment, the ammonium hydroxide 2.63m of a concentration of 2.3 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 2.86m of a concentration of 0.043 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the life of molecular sieve Production process.
Embodiment 4
As shown in Fig. 2, by ammonium salt-containing waste water (156g/L containing NaCl, Na2SO4 50g/L、NH4Cl 60g/L、(NH4)2SO4 19.55g/L, pH 6.3) with inlet amount it is 5m3The speed of/h is sent in the pipeline of processing system, and concentration is imported into pipeline First time pH value adjusting is carried out for the sodium hydrate aqueous solution of 45.16 mass %, and passes through 61 (pH of first time pH value measuring device Meter) (measured value 7.5) is monitored to the pH value after adjusting, by the ammonium salt-containing waste water one after the adjusting of first time pH value Divide (2.5m3/ h) it is sent into the first heat-exchanger rig 31 (plastics plate heat exchanger) and the first liquid of steam condensation containing ammonia progress the first heat friendship Changing makes ammonium salt-containing waste water be warming up to 99 DEG C, and rest part is sent into the 4th heat-exchanger rig 34 (two phase stainless steel plate heat exchanger) and the Two liquid of steam condensation containing ammonia carry out the first heat exchange, so that the ammonium salt-containing waste water of rest part is warming up to 60 DEG C, next by two Waste water is divided to merge, and (feeding speed is 15.31m with the second mother liquor3/ h) it is mixed to get pending waste water and (contains in pending waste water Some SO4 2-And Cl-Molar ratio be 1：10.356).Then, pending waste water is sent into 32 (titanium alloy sheet of the second heat-exchanger rig Formula heat exchanger), carrying out the first heat exchange with the first steam containing ammonia of recycling makes pending waste water be warming up to 113 DEG C, then will wait for Processing waste water be sent in the pipeline of the first vaporising device 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) import it is a concentration of The sodium hydrate aqueous solution of 45.16 mass % carries out second of pH value adjusting, and passes through the second pH value measuring device 62 (pH meter) (measured value 10.8) is monitored to the pH value after adjusting, the pending waste water after the adjusting of the second pH value is sent into first Vaporising device 2 is evaporated, and obtains the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal.Wherein, the first evaporation dress The evaporating temperature for setting 2 is 105 DEG C, and pressure is -7.02kPa, evaporation capacity 2.53m3/h.Evaporate obtained the first steam containing ammonia warp (14 DEG C of temperature rise) passes sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31 after overcompression machine 10 compresses, and pending Waste water carries out heat exchange, and cooling obtains ammonium hydroxide, and is stored in the first tank used for storing ammonia 51.In addition, in order to improve the first evaporation dress The solid content in 2 is set, is followed by second circulation pump 72 using the partially liq after being evaporated in the first vaporising device 2 as circulation fluid Then ring is again introduced into the first vaporising device 2 and carries out the first evaporation (reflux ratio 56.2) to the second heat-exchanger rig 32.Pass through The degree that the densitometer pair first being arranged on one vaporising device 2 evaporates is monitored, and sodium chloride is dense in the first concentrate of control Degree is 0.99352X (307.0g/L).
After above-mentioned first concentrate is sent into the first separation of solid and liquid of the first equipment for separating liquid from solid 91 (centrifuge) progress, per small When obtain 18.43m3Contain NaCl 307.0g/L, Na2SO4 52.7g/L、NaOH 1.67g/L、NH3The first of 0.13g/L is female Liquid is temporarily stored into the first mother liquor tank 53, is separated by solid-liquid separation gained solid sodium sulfate and (is wherein obtained the sulphur of aqueous 14 mass % per hour Sour sodium crystalli-zation cake 407.73kg, the content of sodium chloride are 6.8 mass % or less) with sulfate crystal filter cake butt quality Equal 52.7g/L metabisulfite solutions elution obtains sodium sulphate 350.64kg (purity is 99.4 weight %) per hour after dry, It elutes obtained leacheate and the second heat-exchanger rig 32 is recycled to by the 8th circulating pump 78, be then again introduced into the first vaporising device 2 carry out the first evaporation.
Second evaporation process carries out in the second vaporising device (multi-effect evaporating device) 1, second vaporising device 1 It is made of 1st effective evaporator 1a, 2nd effect evaporator 1b and third effect evaporator 1c (being forced-circulation evaporator).Pass through Above-mentioned first mother liquor is sent into the second vaporising device 1 by the 5th circulating pump 75, after the first mother liquor evaporates in 1st effective evaporator 1a, It is passed through in 2nd effect evaporator 1b and evaporates, then be passed through in third effect evaporator 1c and evaporate, finally obtained sodium chloride-containing crystal Second concentrate.Wherein, the evaporating temperature of 1st effective evaporator 1a is 86 DEG C, and pressure is -55.83kPa, and evaporation capacity is 1.08m3/h；The evaporating temperature of 2nd effect evaporator 1b is 71 DEG C, and pressure is -77.40kPa, evaporation capacity 1.07m3/h；Third The evaporating temperature for imitating evaporator 1c is 56 DEG C, and pressure is -89.56kPa, evaporation capacity 1.06m3/h.By the second evaporation dress The second steam containing ammonia evaporated in 1 1st effective evaporator 1a is set to be passed through 2nd effect evaporator 1b progress heat exchanges and obtain The second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through third effect evaporator 1c and carries out heat exchange by the second ammonium hydroxide And the first ammonium hydroxide is obtained, above-mentioned second ammonium hydroxide is stored up with after ammonium salt-containing wastewater heat exchange in the second ammonium hydroxide by the 4th heat-exchanger rig 34 It is stored in tank 52.It is passed through heating steam (life steam i.e. commonly used in the art) in 1st effective evaporator 1a, heats steam The condensation water obtained after being condensed in 1st effective evaporator 1a is for configuring washing brine.Third effect evaporator 1c evaporates Second steam containing ammonia carries out heat exchange with cold medium in third heat-exchanger rig 33 and obtains the second ammonium hydroxide, and is stored up in the second ammonium hydroxide It is stored in tank 52.The degree evaporated by the densitometer pair second being arranged on the second vaporising device 1 is monitored, and control second is dense A concentration of 0.9693Y (63.1g/L) of sodium sulphate in contracting liquid.After first mother liquor evaporates in the second vaporising device 1, finally obtain The second concentrate of sodium chloride-containing crystal crystallize that (crystallization temperature is 55 DEG C, and crystallization time is in brilliant liquid collecting tank 55 30min) obtain the magma of sodium chloride-containing crystal.
The magma of sodium chloride-containing crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and is separated by solid-liquid separation, and is separated by solid-liquid separation 15.31m is obtained per hour3Contain NaCl 295.6g/L, Na2SO4 63.1g/L、NaOH 2.0g/L、NH3The of 0.13g/L Second mother liquor by the 7th circulating pump 77 is recycled to waste water import pipe and is mixed to get with ammonium salt-containing waste water and waits locating by two mother liquors Waste water is managed, gained solid sodium chloride is separated by solid-liquid separation and (obtains the sodium chloride crystalli-zation cake that water content is 14 mass % per hour 1293.73kg, the wherein content of sodium sulphate are 7.0 mass % or less) with the 295g/L chlorination equal with sodium chloride butt quality It is dry in drying machine after sodium solution elution, sodium chloride 1112.6kg (purity is 99.4 weight %) is obtained per hour, is washed To cleaning solution the second vaporising device 1 is recycled to by the 6th circulating pump 76.
In addition, the tail gas that the second heat-exchanger rig 32 and third heat-exchanger rig 33 are discharged introduces tail gas absorption by vacuum pump 81 Tower 83 is absorbed, and recirculated water is connected in 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, while water is added to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73, and Fresh water is added in circulating water pool 82, reduces by the temperature and ammonia content of 81 work water of vacuum pump.In the tail gas absorber 83 It is further passed through dilute sulfuric acid, to absorb ammonia in tail gas etc..
In the present embodiment, the ammonium hydroxide 2.53m of a concentration of 4.44 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 3.21m of a concentration of 0.072 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
In addition, the initial period of MVR evaporations, the steam for being 143.3 DEG C by temperature are started.
In the present embodiment, the ammonium hydroxide 2.64m of a concentration of 2.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 3.1m of a concentration of 0.084 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
Embodiment 5
The processing of ammonium salt-containing waste water is carried out according to the method for embodiment 4, unlike：To containing NaCl 71g/L, Na2SO4 132g/L、NH4Cl 16g/L、(NH4)2SO4The ammonium salt-containing waste water that 30.24g/L, pH are 7.0 is handled, and what is obtained is pending The SO contained in waste water4 2-And Cl-Molar ratio be 1：4.163.By pending useless after the progress heat exchange of the first heat-exchanger rig 31 The temperature of water is 64 DEG C, and the temperature by pending waste water after the progress heat exchange of the second heat-exchanger rig 32 is 102 DEG C.First evaporation The evaporation conditions of device 2 include：Temperature is 95 DEG C, and pressure is -36.36kPa, evaporation capacity 2.53m3/h.Second vaporising device 1 The evaporation conditions of 1st effective evaporator 1a include：Temperature is 80 DEG C, and pressure is -65.87kPa, evaporation capacity 0.43m3/h；The The evaporation conditions of 2nd effect evaporator 1b include：Temperature is 64 DEG C, and pressure is -84.0kPa, evaporation capacity 0.43m3/h；Third is imitated The evaporation conditions of evaporator 1c include：Temperature is 46 DEG C, and pressure is -94.33kPa, evaporation capacity 0.42m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 970.09kg of aqueous 15 mass % per hour, finally Obtain sodium sulphate 824.57kg per hour (purity is 99.5 weight %)；6.59m is obtained per hour3A concentration of NaCl 305.6g/ L、Na2SO455.15g/L、NaOH 1.15g/L、NH3The first mother liquor of 0.19g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 518.3kg that water content is 15 mass % per hour, It is final to obtain sodium chloride 440.5kg per hour (purity is 99.5 weight %)；5.42m is obtained per hour3A concentration of NaCl 292.6g/L、Na2SO467.4g/L、NaOH 1.4g/L、NH3The second mother liquor of 0.012g/L.
In the present embodiment, the ammonium hydroxide 4.26m of a concentration of 1.46 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.28m of a concentration of 0.095 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
Embodiment 6
The processing of ammonium salt-containing waste water is carried out according to the method for embodiment 4, unlike：To containing NaCl 118g/L, Na2SO4 116g/L、NH4Cl 19g/L、(NH4)2SO4The ammonium salt-containing waste water that 18.99g/L, pH are 6.8 is handled, and what is obtained is pending The SO contained in waste water4 2-And Cl-Molar ratio be 1：6.419.By pending useless after the progress heat exchange of the first heat-exchanger rig 31 The temperature of water is 97 DEG C, and the temperature by pending waste water after the progress heat exchange of the second heat-exchanger rig 32 is 107 DEG C.First evaporation The evaporation conditions of device 2 include：Temperature is 100 DEG C, and pressure is -22.83kPa, evaporation capacity 3.52m3/h.Second vaporising device The evaporation conditions of 1 1st effective evaporator 1a include：Temperature is 86 DEG C, and pressure is -55.83kPa, evaporation capacity 0.667m3/h； The evaporation conditions of 2nd effect evaporator 1b include：Temperature is 71 DEG C, and pressure is -77.4kPa, evaporation capacity 0.666m3/h；Third The evaporation conditions of effect evaporator 1c include：Temperature is 56 DEG C, and pressure is -89.56kPa, evaporation capacity 0.665m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 792.33kg of aqueous 14 mass % per hour, finally Obtain sodium sulphate 681.41kg per hour (purity is 99.5 weight %)；10.95m is obtained per hour3A concentration of NaCl 305.8g/L、Na2SO4 53.84g/L、NaOH 2.2g/L、NH3The first mother liquor of 0.099g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 817.22kg that water content is 14 mass % per hour, It is final to obtain sodium chloride 694.64kg per hour (purity is 99.4 weight %)；9.06m is obtained per hour3A concentration of NaCl 293.3g/L、Na2SO4 65g/L、NaOH 2.656g/L、NH3The second mother liquor of 0.0072g/L.
In the present embodiment, the ammonium hydroxide 3.515m of a concentration of 1.5 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.998m of a concentration of 0.051 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
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 (11)

1. a kind of processing method of ammonium salt-containing waste water, the ammonium salt-containing waste water contain NH4 +、SO4 2-、Cl-And Na+, which is characterized in that it should Method includes the following steps,
1) pending waste water is subjected to the first evaporation and obtains the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal, it is described Pending waste water contains the ammonium salt-containing waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and obtained liquid is separated by solid-liquid separation by first It mutually carries out the second evaporation and obtains the second concentrate of the second steam containing ammonia and sodium chloride-containing crystal；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is carried out the first evaporation, the pH value for adjusting the pending waste water is more than 9；
First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；
Relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 14 moles with Under.
2. according to the method described in claim 1, wherein, the pending waste water is the waste water；Alternatively, described pending useless Water contains the waste water and described second and is separated by solid-liquid separation obtained liquid phase；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 13.8 mole or less；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 4- 10 moles；
Preferably, before the pending waste water is carried out the first evaporation, the pH value for adjusting the pending waste water is more than 10.8；
Preferably, the pH value for adjusting the pending waste water is carried out using NaOH.
3. method according to claim 1 or 2, wherein first evaporation makes the concentration of sodium chloride in the first concentrate For X or less, wherein X is chlorination when sodium sulphate and sodium chloride reach saturation in the first concentrate under conditions of first evaporates The concentration of sodium；
Preferably, second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate, wherein Y is to be steamed second Under conditions of hair, the concentration of sodium sulphate when sodium sulphate and sodium chloride reach saturation in the second concentrate；
Preferably, first evaporation makes a concentration of 0.95X-0.999X of sodium chloride in the first concentrate,
Preferably, second evaporation makes a concentration of 0.9Y-0.99Y of sodium sulphate in second concentrate.
4. according to the method described in any one of claim 1-3, wherein it is described first evaporation condition include：Temperature is 45 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~365 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；
Preferably, the condition of first evaporation includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；
Preferably, the condition of first evaporation includes：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
5. according to the method described in any one of claim 1-3, wherein it is described second evaporation condition include：Temperature is 30 DEG C~85 DEG C, pressure is -98kPa~-58kPa；
Preferably, the condition of second evaporation includes：Temperature is 35 DEG C~60 DEG C, and pressure is -97.5kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~55 DEG C, and pressure is -95kPa~-90kPa.
6. method according to claim 4 or 5, wherein the temperature of first evaporation is 5 DEG C higher than the temperature of the second evaporation More than；
Preferably, temperature high 20 DEG C or more of the temperature of first evaporation than the second evaporation；
Preferably, it is described first evaporation temperature than second evaporation temperature it is 35 DEG C high~70 DEG C；
Preferably, it is described first evaporation temperature than second evaporation temperature it is 40 DEG C high~60 DEG C.
7. according to the method described in any one of claim 1-6, wherein first evaporation and the second evaporation difference Pass through one or more progress in MVR vaporising devices, single-effect evaporating equipment and multi-effect evaporating device；
Preferably, first evaporation is carried out by MVR vaporising devices；
Preferably, second evaporation is carried out by MVR vaporising devices.
8. according to the method described in claim 1, wherein, before carrying out first evaporation, by first steam containing ammonia Or the condensation water of first steam containing ammonia carries out the first heat exchange with the pending waste water and obtains the first ammonium hydroxide；
Preferably, before carrying out first heat exchange, the pH value for adjusting the pending waste water is more than 7.
9. according to the method described in any one of claim 1-8, this method further includes by the of the sulfur acid sodium crystal One concentrate obtains sodium sulfate crystal after first is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium sulfate crystal.
10. according to the method described in any one of claim 1-8, this method further includes by the of the sodium chloride-containing crystal Two concentrates obtain sodium chloride crystal after second is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium chloride crystal.
11. according to the method described in any one of claim 1-8, wherein NH in the ammonium salt-containing waste water4 +For 8mg/L with On, SO4 2-For 1000mg/L or more, Cl-For 970mg/L or more, Na+For 510mg/L or more；
Preferably, the ammonium salt-containing waste water is the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process；
Preferably, this method further includes that the ammonium salt-containing waste water is cleaned and concentrated.
CN201710263271.XA 2017-04-21 2017-04-21 Method for treating ammonium salt-containing wastewater Active CN108726756B (en)

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CN201710263271.XA CN108726756B (en) 2017-04-21 2017-04-21 Method for treating ammonium salt-containing wastewater
NL2020788A NL2020788B1 (en) 2017-04-21 2018-04-19 Apparatus and Method for Treating Waste Water Containing Ammonium Salts
US15/958,986 US10815132B2 (en) 2017-04-21 2018-04-20 Apparatus and method for treating waste water containing ammonium salts
BE2018/5260A BE1025537B1 (en) 2017-04-21 2018-04-20 APPARATUS AND METHOD FOR TREATING WASTE WATER CONTAINING AMMONIUM SALTS
JP2018081600A JP6594478B2 (en) 2017-04-21 2018-04-20 Apparatus and method for treating ammonium salt-containing wastewater
BR102018008273A BR102018008273A8 (en) 2017-04-21 2018-04-24 apparatus and methods for treating water waste containing ammonium salts
US17/027,049 US11572289B2 (en) 2017-04-21 2020-09-21 Apparatus and method for treating waste water containing ammonium salts

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