CN108726608A - A kind of processing method of catalyst production waste water - Google Patents

A kind of processing method of catalyst production waste water Download PDF

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Publication number
CN108726608A
CN108726608A CN201710263296.XA CN201710263296A CN108726608A CN 108726608 A CN108726608 A CN 108726608A CN 201710263296 A CN201710263296 A CN 201710263296A CN 108726608 A CN108726608 A CN 108726608A
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China
Prior art keywords
waste water
evaporation
concentrate
sodium chloride
sodium
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CN201710263296.XA
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CN108726608B (en
Inventor
殷喜平
李叶
苑志伟
周岩
杨凌
刘夫足
高晋爱
安涛
吕伟娇
顾松园
王涛
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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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    • 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
    • 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
    • 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
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (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 catalyst production waste water, which contains NH4 +、SO4 2‑、Cl‑And Na+, this approach includes the following steps 1) by pending waste water be passed through MVR vaporising devices carry out first evaporation obtain the first concentrate of the first steam containing ammonia and sodium chloride-containing crystal, the pending waste water contains the catalyst production waste water；2) the first concentrate of the sodium chloride-containing crystal first is carried out to be separated by solid-liquid separation, and it is separated by solid-liquid separation obtained liquid phase by first and is passed through the second evaporation of progress in each effect evaporator of multi-effect evaporating device successively, the second steam containing ammonia is respectively obtained in each effect evaporator, and obtains the second concentrate of sulfur acid sodium crystal in last 1st effective evaporator；3) the second concentrate of the sulfur acid sodium 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

A kind of processing method of catalyst production waste water
Technical field
The present invention relates to sewage treatment fields, and in particular, to a kind of processing method of catalyst production waste water, especially It is related to a kind of containing NH4 +、SO4 2-、Cl-And Na+Catalyst production 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 chloride and sodium sulphate 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 chlorine containing a small amount of ammonium salt Change sodium and sodium sulphate 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 chloride and the sodium sulphate 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+Cost for wastewater treatment it is high, 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+Catalyst Production wastewater treatment method, this method can be separately recovered ammonium and sodium chloride, sodium sulphate in waste water, farthest recycle Resource in waste water.
To achieve the goals above, the present invention provides a kind of processing method of catalyst production waste water, catalyst production Waste water contains NH4 +、SO4 2-、Cl-And Na+, this approach includes the following steps,
1) pending waste water is passed through the first evaporation of MVR vaporising devices progress and obtains the first steam containing ammonia and sodium chloride-containing crystalline substance First concentrate of body, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sodium chloride-containing 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 be passed through successively in each effect evaporator of multi-effect evaporating device and carry out the second evaporation, the is respectively obtained in each effect evaporator Two steam containing ammonia, and the second concentrate of sulfur acid sodium crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is big In 9；Before the second steam containing ammonia that rear 1st effective evaporator is evaporated is sent into 1st effective evaporator with first concentrate into The second heat exchange of row simultaneously obtains the second ammonium hydroxide, first concentrate and the second steam counter-flow containing ammonia heat exchange；Described One evaporation makes sodium sulphate not crystallize precipitation, and second evaporation makes sodium chloride not crystallize precipitation；It is described pending relative to 1 mole The SO contained in waste water4 2-, the Cl that contains in the pending waste water-It is 9.5 moles or more.
Through the above technical solutions, for NH is contained4 +、SO4 2-、Cl-And Na+Catalyst production waste water, by that will give up in advance After the pH value of water is adjusted to specific range, MVR vaporising devices is recycled to be evaporated isolated sodium chloride crystal and denseer Then ammonium hydroxide recycles multi-effect evaporating device to be evaporated to obtain sodium sulfate crystal and compared with weak aqua ammonia again.This method can divide The sodium chloride and sodium sulphate for not obtaining high-purity, the difficulty during avoiding mixed salt processing and recycling, are completed at the same time separation The process of ammonia and salt, and make waste water heating and steam cooling containing ammonia simultaneously using heat exchange method, it is not necessarily to condenser, rationally profit It is energy saving with the heat in evaporation process, cost for wastewater treatment is reduced, the ammonium in waste water is recycled in the form of ammonium hydroxide, sulfuric acid Sodium and sodium chloride are recycled with crystal form respectively, and whole process does not have waste residue and liquid generation, realize the purpose to turn waste into wealth.
Second evaporation is carried out by using multi-effect evaporating device, so that the second evaporation is carried out at different temperatures, first It carries out, finally evaporates at relatively high temperatures at a lower temperature, improve the eduction rate of sodium sulphate, advantageously ensure that sodium chloride not It is precipitated, while convenient for the control of temperature.
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 catalyst production waste water processing method of embodiment provided by the invention.
Reference sign
1, multi-effect evaporating device 2, MVR vaporising devices
31, the first heat-exchanger rig 32, the second heat-exchanger rig
33, third heat-exchanger rig 34, the 4th heat-exchanger rig
51, the first tank used for storing ammonia 52, the second tank used for storing ammonia
53, crystallizing tank 54, mother liquor tank
61, the first pH value measuring device 62, the second pH value measuring device
71, first circulation pump 72, second circulation pump
73, third circulating pump 74, the 4th circulating pump
75, the 5th circulating pump 76, the 6th circulating pump
77, the 7th circulating pump 78, the 8th circulating pump
79, the 9th circulating pump 80, the tenth circulating pump
81, vacuum pump 82, circulating water pool
83, tail gas absorber 91, the first equipment for separating liquid from solid
92, the second equipment for separating liquid from solid 10, compressor
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Below in conjunction with Fig. 1, the present invention will be described, and the present invention is not limited by Fig. 1.
The processing method of catalyst production waste water provided by the invention, the catalyst production waste water contain NH4 +、SO4 2-、Cl- And Na+, this approach includes the following steps,
1) pending waste water is passed through first evaporation of the progress of MVR vaporising devices 2 and obtains the first steam containing ammonia and sodium chloride-containing First concentrate of crystal, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sodium chloride-containing 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 be passed through successively in each effect evaporator of multi-effect evaporating device 1 carry out second evaporation, respectively obtained in each effect evaporator Second steam containing ammonia, and the second concentrate of sulfur acid sodium crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices 2, the pH value of the pending waste water is adjusted More than 9；The second steam containing ammonia that rear 1st effective evaporator is evaporated is sent into preceding 1st effective evaporator and first concentrate It carries out the second heat exchange and obtains the second ammonium hydroxide, first concentrate and the second steam counter-flow containing ammonia heat exchange；It is described First evaporation makes sodium sulphate not crystallize precipitation, and second evaporation makes sodium chloride not crystallize precipitation；Relative to waiting locating described in 1 mole The SO contained in reason waste water4 2-, the Cl that contains in the pending waste water-It is 9.5 moles or more.
Preferably, the pending waste water is the catalyst production waste water；Alternatively, the pending waste water contain it is described Catalyst production 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 catalyst production waste water is separated by solid-liquid separation obtained liquid with described second At least part of mixed liquor of phase.
It is obtained with second separation of solid and liquid it is further preferred that the pending waste water is the catalyst production waste water Liquid phase mixed liquor.
Preferably, before the pending waste water is passed through MVR vaporising devices 2, the pH of the pending waste water is adjusted Value is more than 10.8.In addition, for the pending waste water pH value the upper limit there is no limit, such as can be 14 hereinafter, it is preferred that For 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+Catalyst production waste water at Reason, in addition to containing NH4 +、SO4 2-、Cl-And Na+Outside, to the catalyst production waste water, there is no particular limitation.It is catalyzed from improving From the point of view of the treatment effeciency of agent production waste water, relative to the SO contained in 1 mole of pending waste water4 2-, described to wait locating The Cl contained in reason waste water-It is 10 moles or more, preferably 50 moles hereinafter, more preferably 40 moles hereinafter, further preferably For 30 moles hereinafter, for example can be 10-20 moles.By by SO4 2-And Cl-Molar ratio control in above range, can make Sodium chloride is precipitated in first evaporation and sodium sulphate is not precipitated, to achieve the purpose that efficiently separate sodium chloride.In addition, such as context It is described, in the present invention can also be by the second Recycling Mother Solution obtained in the second evaporation process to the first evaporation, and thus come To the SO in pending waste water4 2-And Cl-Molar ratio be adjusted, and the balance of sodium hydroxide can be maintained.
In the present invention, first 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 first 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 %) below 8 mass %, in the present invention, sodium sulphate in obtained sodium chloride crystal When content is below 8 mass %, so that it may to think that sodium sulphate does not crystallize precipitation.
In the present invention, second 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 second evaporation conditions (including but not limited to temperature, pH value etc.), it is not excluded that sulfate crystal presss from both sides The sodium chloride of band or adsorption.Since the water content of crystal after separation of solid and liquid is different, chlorine in the sodium sulfate crystal generally yielded Change the content of sodium below 8 mass % (preferably 4 mass %), in the present invention, sodium chloride in obtained sodium sulfate crystal When content is below 8 mass %, so that it may to think that sodium chloride does not crystallize precipitation.
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.First concentrate and the second steam counter-flow containing ammonia heat exchange are referred to using in multiple-effect evaporation Countercurrent flow.The pressure is the pressure in terms of gauge pressure.
In the present invention, there is no particular limitation for the MVR vaporising devices 2, can be commonly used in the art various MVR vaporising devices.Such as can be selected from MVR falling film evaporators, MVR forced-circulation evaporators, the evaporation of MVR-FC continuous crystallisations It is one or more in device, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced-circulation evaporators, MVR-FC connect Continuous crystallizing evaporator, more preferably falling liquid film+forced circulation two-stage MVR crystallizing evaporators.
In the present invention, it is described first evaporation condition can suitably select as needed, reach make sodium chloride crystallize and Make the purpose that sodium sulphate is not precipitated.It is described first evaporation condition may include：Temperature be 30 DEG C~85 DEG C, pressure be- 98kPa~-58kPa.In order to improve evaporation efficiency, it is preferable that it is described first evaporation condition include：Temperature is 35 DEG C~60 DEG C, pressure is -98kPa~-87kPa；It is highly preferred that the condition of first evaporation includes：Temperature is 40 DEG C~60 DEG C, pressure For -97kPa~-87kPa；It is highly preferred that the condition of first evaporation includes：Temperature be 45 DEG C~60 DEG C, pressure be- 95kPa~-87kPa；From the point of view of reducing equipment cost and energy consumption, it is highly preferred that temperature is 45 DEG C~55 DEG C, pressure For -95kPa~-90kPa.
In the present invention, the operating pressure of the first evaporation is 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 sodium chloride crystallization by making the first 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.
It can be evaporated in the pending waste water according to the present invention by controlling the evaporation conditions of MVR vaporising devices 2 The 90 mass % or more (preferably 95 mass % or more) of contained ammonia, the first ammonium hydroxide can be with direct reuse in the production of catalyst Journey carries out reuse or is used with water and the allotment of corresponding ammonium salt or ammonium hydroxide after either obtaining ammonium salt with acid neutralization.
According to the present invention, first evaporation is not so that sulfate crystal precipitation (i.e. sodium sulphate is not up to supersaturation), excellent Selection of land, first evaporation make a concentration of Y or less of sodium sulphate in the first concentrate (be preferably 0.9Y-0.99Y, more preferably 0.95Y-0.98Y), wherein Y is under conditions of first evaporates, and sodium chloride and sodium sulphate reach saturation in the first concentrate When sodium sulphate concentration.By the way that the extent control of the first evaporation within the above range, can ensured what sodium sulphate was not precipitated Under the conditions of so that sodium chloride as much as possible crystallization is precipitated.By making sodium chloride crystallize in the first evaporation as possible, can improve useless Water treatment efficiency reduces energy waste.
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 sulfuric acid in above-mentioned range Sodium crystallization is precipitated.Here the first evaporation obtains the concentration of liquid, is monitored by way of measuring density, can specifically be used Densitometer carries out density measure.
A preferred embodiment according to the present invention will before the pending waste water is passed through MVR vaporising devices 2 First steam containing ammonia carries out the first heat exchange with the pending waste water and obtains the first ammonium hydroxide.First heat exchange There is no particular limitation for mode, and the heat exchange mode that this field routine may be used carries out.The number of the heat exchange can be 1 time More than, preferably 2-4 times, more preferably 2-3 times, particularly preferably 2 times.Pass through first heat exchange, the first ammonia of output Water carries out heat exchange with pending waste water, and the ammonium hydroxide of output is further cooled, and heat utmostly follows inside processing unit The energy is rationally utilized in ring, reduces waste.
A preferred embodiment according to the present invention, first heat exchange pass through the first heat-exchanger rig 31 and second Heat-exchanger rig 32 carries out, and specifically, the first steam containing ammonia evaporated in the MVR vaporising devices 2 is passed sequentially through the Two heat-exchanger rigs 32 and the first heat-exchanger rig 31, and the pending waste water is passed sequentially through into the first heat-exchanger rig 31 and second and is changed Thermal 32 carries out first heat exchange by first steam containing ammonia and the pending waste water, makes described pending Waste water heating is convenient for evaporating, while first steam cooling containing ammonia being made to obtain the first ammonium hydroxide, and first ammonium hydroxide can be with It is stored in the first tank used for storing ammonia 51.
A preferred embodiment according to the present invention, first heat exchange pass through the first heat-exchanger rig 31, second Heat-exchanger rig 32 and the 4th heat-exchanger rig 34 carry out, and specifically, evaporated in the MVR vaporising devices 2 first is contained Ammonia steam passes sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31, by multi-effect evaporating device 1 obtain second containing ammonia steam Vapour condensation water (higher second ammonium hydroxide of temperature) passes through the 4th heat-exchanger rig 4；And by a part for the catalyst production waste water By the first heat-exchanger rig 31, another part passes through the 4th heat-exchanger rig 34；Then by above-mentioned two parts catalyst production waste water Merge, and be mixed to get after pending waste water through the second heat-exchanger rig 32 with the second mother liquor, passes through first steam containing ammonia With the first heat exchange of the pending waste water, the pending waste water heating is set to be convenient for evaporating, while making described first Steam cooling containing ammonia obtains the first ammonium hydroxide.First ammonium hydroxide can be stored in the first tank used for storing ammonia 51.
In the present invention, do not have for first heat-exchanger rig 31, the second heat-exchanger rig 32 and the 4th heat-exchanger rig 34 It is special to limit, various heat exchangers commonly used in the art can be used, reaches first steam containing ammonia and waits locating with described Reason waste water carries out the purpose of first heat exchange.Specifically, it can be jacketed type exchanger, plate heat exchanger, shell Formula heat exchanger etc., wherein preferably plate heat exchanger.The material of the heat exchanger can be specifically chosen as needed, such as in order to Resist chloride ion corrosion, material can be selected for two phase stainless steel, the heat exchanger of titanium or titanium alloy, Hastelloy, temperature compared with The heat exchanger containing plastic material can be selected when low.
It is preferably exchanged heat by described first according to the present invention in order to make full use of the thermal energy of the first liquid of steam condensation containing ammonia After device 31 carries out the first heat exchange, the temperature of the catalyst production waste water is 29 DEG C~84 DEG C, more preferably 39 DEG C~59 DEG C, further preferably 44 DEG C~59 DEG C.
It is preferably exchanged heat by the described 4th according to the present invention in order to make full use of the thermal energy of the second liquid of steam condensation containing ammonia After device 34 carries out the first heat exchange, the temperature of the catalyst production waste water is 44 DEG C~364 DEG C, more preferably 84 DEG C~ 106℃。
Preferably pass through second heat-exchanger rig 32 according to the present invention in order to make full use of the thermal energy of the first steam containing ammonia After carrying out the first heat exchange, the temperature of the pending waste water is 41 DEG C~67 DEG C, more preferably 47 DEG C~62 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, first evaporation process carry out in MVR vaporising devices 2, Before the catalyst production waste water to be sent into the first heat-exchanger rig 31 or the first heat exchange of progress of the 4th heat-exchanger rig 34, lead to It crosses and contains described in it will be imported in the pipeline of the catalyst production waste water the first heat-exchanger rig 31 of feeding or the 4th heat-exchanger rig 34 There are the aqueous solution of alkaline matter and mixing, to carry out first time pH value adjusting；Then by the catalyst production waste water and second Mother liquor is mixed to get pending waste water, and the pending waste water is sent into the second heat-exchanger rig 32 and carries out the first heat exchange, so Afterwards by the way that the pending waste water is being sent into the aqueous solution containing alkaline matter of importing in the pipeline of MVR vaporising devices 2 And mix, to carry out second of pH value adjusting.
It is adjusted by pH value twice, makes pH value of the pending waste water before being passed through MVR vaporising devices 2 more than 9, it is excellent It is selected as being more than 10.8.Preferably, first time pH value is adjusted so that the pH value of the pending waste water after adjusting is more than 7 (preferably For 7-9), second of pH value adjusts so that pH value 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 will be described pending 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 the pending waste water to be sent on the pipeline of MVR vaporising devices 2 PH value after secondary pH value adjusting.
In the present invention, in order to improve the solid content in the MVR vaporising devices 2, the ammonia content in reduction liquid is excellent Choosing will by partially liq that the MVR vaporising devices 2 evaporate (namely the liquid inside MVR vaporising devices 2, hereinafter Referred to as circulation fluid) it flows back into the MVR vaporising devices 2 and evaporates again after heating.The circulation fluid is flowed back into the MVR evaporations The process of device 2 is preferably that will pass through the circulation fluid to adjust with after the adjusting of first time pH value and to second of pH value It is flowed back into again in MVR vaporising devices 2 after pending waste water mixing before, for example, can pump 72 by second circulation will pass through The circulation fluid is returned in the waste water conveyance conduit between the first heat-exchanger rig 31 and the second heat-exchanger rig 32 and is given up with pending Water mixes, and then carries out heat exchange in the second heat-exchanger rig 32, and by described in second of pH value adjusting and then feeding In MVR vaporising devices 2.The MVR vaporising devices 2 are flowed back into as the partially liq that the MVR vaporising devices 2 evaporate will be passed through Ratio be not particularly limited, for example, it is described first evaporation reflux ratio can be appropriately configured as needed, Ke Yiwei 10-200, preferably 40-120.The reflux ratio refers to：Regurgitant volume subtracts back with the total amount of liquid being sent into MVR vaporising devices 2 The ratio of flow.
In the case of, according to the invention it is preferred to, the method further include after first steam containing ammonia is compressed again Carry out first heat exchange.The compression of first steam containing ammonia can be carried out by compressor 10.By to described first Steam containing ammonia is compressed, to input energy in MVR vapo(u)rization systems, ensure the process of waste water heating-evaporation-cooling continuously into Row is needed to input to start steam when MVR evaporation processes start, only be energized by compressor 10 after reaching continuously running state, no It needs to input other energy again.Various compressors commonly used in the art may be used in the compressor 10, such as centrifuge wind Machine, turbocompressor or lobed rotor compressor etc..After the compression of the compressor 10, the temperature of first steam containing ammonia increases 5 DEG C~20 DEG C.
In the present invention, the first concentrate of the sodium chloride-containing crystal obtains sodium chloride crystalline substance after first is separated by solid-liquid separation Body and the first mother liquor (obtaining liquid after the i.e. first separation of solid and liquid).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, the separation of solid and liquid of first concentrate may be used the first equipment for separating liquid from solid (be, for example, from Scheming, band filter, flame filter press etc.) 91 progress.After the separation of solid and liquid, the first equipment for separating liquid from solid 91 obtain One mother liquor is temporarily stored into mother liquor tank 54, and can be sent into multi-effect evaporating device 1 by the 5th circulating pump 75 and be carried out the second evaporation.Separately Outside, the impurity such as certain chlorion, free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on the sodium chloride crystal obtained, in order to The impurity for removing absorption reduces the peculiar smell of solid salt, reduces corrosivity, improves the purity of the crystal, it is preferable that the chlorination Sodium crystal water, the catalyst production waste water or sodium chloride solution carry out the first washing and drying.
Preferably, first washing includes eluriating and/or eluting.It is preferred that the first washing that above-mentioned washing process is obtained Liquid is returned by the 8th circulating pump 78 before second of pH value adjusting before first evaporation；More preferably above-mentioned washing process is obtained The first cleaning solution it is defeated back to waste water between the first heat-exchanger rig 31 and the second heat-exchanger rig 32 by the 8th circulating pump 78 It send in pipeline, then carries out heat exchange in the second heat-exchanger rig 32, after being adjusted using second of pH value, be finally sent into MVR It is evaporated in vaporising device 2.
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.For above-mentioned elutriation and elution, there is no particular limitation, can be carried out by the method for this field routine.The elutriation There is no particular limitation with the number of elution, can be 1 time or more, in order to obtain the sodium chloride crystal of higher purity, preferably 2-4 times.During elutriation, uses the catalyst production waste water as not recycled generally when eluriating liquid, use the first washing The cleaning solution of recycling can be used when doing elutriation liquid with circulated in countercurrent.Before carrying out the elutriation, carried out preferably by way of sedimentation Preliminary be separated by solid-liquid separation obtains the slurries of sodium chloride-containing crystal (content liquid is 35 mass % or less, and the step is preferably heavy It is carried out in the devices well known in the art such as drop pond, settling tank).During elutriation, the slurry relative to 1 parts by weight sodium chloride-containing crystal Liquid, it is 1~20 parts by weight to eluriate the liquid used.It is preferable to use sodium-chloride water solution progress, the sodium-chloride water solutions for elution Concentration be preferably at the temperature corresponding to sodium chloride crystal to be washed sodium sulphate and sodium chloride reach in the aqueous solution of saturation simultaneously The concentration of sodium chloride.In order to further increase the effect of elutriation, the higher sodium chloride crystal of purity is obtained, in the case of preferred, The liquid that elution can be used to obtain is washed, it is preferable to use water or sodium chloride solution.For the liquid that washing generates, preferably It returns it to before second of pH value adjusting before MVR vaporising devices 2 evaporate.
A preferred embodiment according to the present invention, evaporated by MVR vaporising devices 2 obtain containing sodium chloride First concentrate carries out first with the catalyst production waste water after settling progress tentatively separation of solid and liquid in eluriating tank Then secondary elutriation reuses the liquid obtained when subsequent wash sodium chloride crystal and in another elutriation tank wash in a pan for the second time It washes, finally will be sent into equipment for separating liquid from solid by the slurries eluriated twice is separated by solid-liquid separation, and the crystal being separated by solid-liquid separation is again During the liquid for being eluted with sodium-chloride water solution, and elution being obtained is eluriated back to second.By above-mentioned washing process, The purity of the sodium chloride crystal not only made improves, and will not be excessive introducing cleaning solution, improve the efficiency of wastewater treatment.
In the present invention, there is no particular limitation for each effect evaporator of the multi-effect evaporating device 1, can be normal by this field Advise the various evaporators composition used.Such as can selected from downward film evaporator, film-rising evaporator, scraper-type evaporator, in It entreats in circulating tube type multi-effect evaporator, basket evaporator, external heating type evaporator, forced-circulation evaporator and Liewen evaporator It is one or more.Wherein, preferably forced-circulation evaporator, external heating type evaporator.Each effect of the multi-effect evaporating device 1 is steamed Hair device is formed by heating room and vaporization chamber respectively, can also include other evaporation accessories as needed, for example, make liquid foam into The demister of one step separation, the vacuum plant the etc. when condenser and decompression operation that make indirect steam all condense.It is described more There is no particular limitation for the evaporator quantity that effect vaporising device 1 contains, and can be 2 effects or more, preferably 2-5 is imitated, more preferably 3-5 is imitated.
In the present invention, the condition of second evaporation can be selected suitably as needed, reach make sulfate crystal and The purpose that sodium chloride is not precipitated.It is described second evaporation condition may include：Temperature is 45 DEG C or more, and pressure is -95kPa More than.In order to improve evaporation efficiency, energy consumption is reduced, it is preferable that the condition of second evaporation includes：Temperature is 45 DEG C~365 DEG C, pressure is -95kPa~18110kPa；Preferably, the condition of second evaporation includes：Temperature is 60 DEG C~365 DEG C, pressure Power is -87kPa~18110kPa；Preferably, the condition of second evaporation includes：Temperature be 70 DEG C~175 DEG C, pressure be- 79kPa~653kPa；Preferably, the condition of second evaporation includes：Temperature be 70 DEG C~130 DEG C, pressure be -79kPa~ 117kPa；Preferably, the condition of second evaporation includes：Temperature is 90 DEG C~120 DEG C, and pressure is -48kPa~57kPa；It is excellent Selection of land, it is described second evaporation condition include：Temperature is 95 DEG C~115 DEG C, and pressure is -37kPa~33kPa.In the present invention, The condition of second evaporation refers to the evaporation conditions of the last 1st effective evaporator of multi-effect evaporating device.
In the present invention, in the second evaporation, the evaporating temperature of rear 1st effective evaporator is preferably high than previous high 5 DEG C of effect or more It is 10 DEG C or more, more preferably 10 DEG C high~20 DEG C.
In the present invention, the operating pressure of the second evaporation is 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 sulfate crystal by making the second evaporation carry out under these conditions, sodium chloride is not tied Crystalline substance, the purity for the sodium sulfate crystal that thereby may be ensured that.
It in the present invention, can be each in order to which first mother liquor to be passed through to each effect evaporator of multi-effect evaporating device 1 successively Circulating pump is set between effect evaporator, the liquid after the evaporation of preceding 1st effective evaporator is passed through next effect by the circulating pump to be steamed Send out device.
In the present invention, the circulating pump between selected each effect evaporator can be various forms commonly used in the art Pump, generate a large amount of fine grain cores to make material be uniformly evaporated, avoid, prevent crystal grain and impeller high velocity impact in cycle magma Generate a large amount of secondary nucleus, the circulating pump is preferably the centrifugal pump of the slow-speed of revolution, more preferably big flow, the slow-speed of revolution guide pump Wheel or big flow, low lift, the slow-speed of revolution axial-flow pump.
A preferred embodiment according to the present invention, second evaporation process carry out in multi-effect evaporating device 1, The multi-effect evaporating device 1 is made of 1st effective evaporator 1a, 2nd effect evaporator 1b and third effect evaporator 1c.Pass through the 5th The 1st effective evaporator 1a that first mother liquor is passed through the multi-effect evaporating device 1 by circulating pump 75 is evaporated, and passes through the 9th cycle Liquid after 1st effective evaporator 1a evaporations is passed through 2nd effect evaporator 1b and is evaporated by pump 79, will by the tenth circulating pump 80 Liquid after 2nd effect evaporator 1b evaporation, which is passed through in third effect evaporator 1c, to be evaporated, and the of sulfur acid sodium crystal is obtained Two concentrates.The second steam containing ammonia evaporated in third effect evaporator 1c is passed through 2nd effect evaporator 1b and carries out the second heat The second ammonium hydroxide is exchanged and obtained, the second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through 1st effective evaporator 1a It carries out the second heat exchange and obtains the second ammonium hydroxide (i.e..It is highly preferred that second ammonium hydroxide (i.e. the second liquid of steam condensation containing ammonia) is logical It crosses the 4th heat-exchanger rig and carries out the first heat exchange with catalyst production waste water, make full use of energy.In third effect evaporator 1c It is passed through heating steam (life steam i.e. commonly used in the art), heating steam is coagulated after being condensed in third effect evaporator 1c Liquid is tied, condensation water can be used further to prepare washing solution after for preheating the pending waste water into MVR vaporising devices 2. (it is preferable to use be passed through with cooling water in third heat-exchanger rig 33 for the second steam containing ammonia that 1st effective evaporator 1a evaporates The catalyst production waste water before MVR vaporising devices is as cooling water) it carries out third heat exchange and obtains the second ammonium hydroxide, and It is stored in the second tank used for storing ammonia 52.
According to the present invention, second evaporation is not so that sodium chloride crystallization precipitation (i.e. sodium chloride is not up to supersaturation), excellent Selection of land, second evaporation make a concentration of X or less of sodium chloride in second concentrate (be preferably 0.999X hereinafter, more excellent It is selected as 0.95X-0.999X, further preferred 0.99X-0.9967X), wherein X is the second concentration under conditions of second evaporates The concentration of sodium chloride when sodium chloride and sodium sulphate reach saturation in liquid.By by second evaporation extent control in above range It is interior, sulfate crystal as much as possible can be made to be precipitated under conditions of ensureing that sodium chloride is not precipitated.By being steamed as possible second Make sulfate crystal in hair, 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 sodium chloride knot in above range Partial crystallization goes out.Here the second evaporation obtains the concentration of liquid, is monitored by way of measuring density, can specifically use density Meter carries out density measure.
In the present invention, sodium sulphate is made not crystallize precipitation in order to reach first evaporation, second evaporation makes chlorination Sodium does not crystallize the purpose of precipitation, preferably meets the condition of twice evaporation：Temperature of the temperature of first evaporation than the second evaporation Degree is 5 DEG C at least low, 20 DEG C preferably low, more preferably low 35 DEG C~70 DEG C.By the first evaporation of control and the second evaporation different At a temperature of carry out, so that the crystallization respectively of sodium chloride and sodium sulphate is precipitated, to improve obtained sodium chloride and sodium sulfate crystal Purity.
A preferred embodiment according to the present invention, the multi-effect evaporating device 1 evaporate second obtained and are steamed containing ammonia Vapour carries out third heat exchange with cold medium in third heat-exchanger rig 33 and obtains the second ammonium hydroxide.The third heat-exchanger rig 33 does not have There is special restriction, various heat exchangers commonly used in the art can be used, reaching makes the second steam containing ammonia cooling Purpose.Specifically, it can be jacketed type exchanger, plate heat exchanger, shell-and-tube heat exchanger, screw heat exchange of heat pipe Deng.The material of the heat exchanger can be specifically chosen as needed, such as since indirect steam does not have corrosivity to stainless steel, excellent Select stainless steel spiral screwed tube heat exchanger.The cold medium can be cooling water, glycol water etc..Use conventional cooling When water, the cooling water circulation uses, when using the catalyst production waste water as cooling water, the catalyst production after heat exchange Waste water preferably directly returns to processing procedure (being such as back to first time pH value adjustment process).
In the present invention, it is to be understood that second ammonium hydroxide had both included evaporating the previous effect of multi-effect evaporating device The second heat exchange is carried out after the second steam containing ammonia that device evaporates is sent into first concentrate in 1st effective evaporator to obtain The second ammonium hydroxide, also include multi-effect evaporating device 1 last 1st effective evaporator generate the second steam containing ammonia third heat exchange dress Set the second ammonium hydroxide that middle progress third heat exchange obtains.Above two parts ammonium hydroxide is come together in jointly in the second tank used for storing ammonia 52.
According to the present invention, this method can also include the second concentrate by the sulfur acid sodium crystal in crystallization apparatus Crystallization obtains the magma of sulfur acid sodium crystal.There is no particular limitation for the crystallization apparatus, such as can be crystallizing tank, brilliant liquid receipts Collect tank, band stirring thickener or without stirring thickener etc..A preferred embodiment according to the present invention, the crystallization exist It is carried out in crystallizing tank 53.The condition of the crystallization 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 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 crystallization process of the second concentrate of the sulfur acid sodium crystal can also be with crystallizer It is carried out in multi-effect evaporating device (such as forced-circulation evaporation crystallizer), the temperature crystallized at this time is the temperature of corresponding second evaporation Degree.According to the present invention, when being crystallized using individual crystallization apparatus, need to be further ensured that described second evaporates so that chlorination Sodium does not crystallize precipitation in crystallization process (i.e. sodium chloride is not up to supersaturation), it is preferable that second evaporation makes described second A concentration of X or less of sodium chloride in concentrate, wherein X is sodium chloride and sulphur in the second concentrate under conditions of the crystallization The concentration of sodium chloride when sour sodium reaches saturation.
In the present invention, the second concentrate of the sulfur acid sodium crystal (or when being crystallized in individual crystallization apparatus, is The magma of the sulfur acid sodium crystal) by second be separated by solid-liquid separation after obtain sodium sulfate crystal and the second mother liquor (namely second It 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 can be selected from centrifugation, mistake It is one or more in filter 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 returns to MVR vaporising devices 2 and carries out the first evaporation again, specifically can by the 7th circulating pump 77 by the second mother liquor back to the Two heat-exchanger rigs 32.In addition, certain sulfate ion, 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, catalyst production waste water or metabisulfite solution carry out the second washing and drying. In order to avoid the dissolving of sodium sulfate crystal in washing process, it is preferable that the sodium sulfate crystal is washed with aqueous sodium persulfate solution It washs.It is highly preferred that the concentration of the aqueous sodium persulfate solution be preferably the temperature corresponding to sodium sulfate crystal to be washed under sodium sulphate and Sodium chloride reaches the concentration of sodium sulphate in the aqueous solution of saturation simultaneously.
Preferably, second washing includes eluriating and/or eluting.The second cleaning solution that above-mentioned washing process obtains is preferred Multi-effect evaporating device 1, which is returned, by the 6th circulating pump 76 carries out the second evaporation again.
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.For above-mentioned elutriation and elution, there is no particular limitation, can be carried out by the method for this field routine.The elutriation There is no particular limitation with the number of elution, can be 1 time or more, in order to obtain the sodium sulfate crystal of higher purity, preferably 2-4 times.During elutriation, uses the catalyst production waste water as not recycled generally when eluriating liquid, use the second washing The cleaning solution of recycling can be used when doing elutriation liquid with circulated in countercurrent.Before carrying out the elutriation, carried out preferably by way of sedimentation Preliminary be separated by solid-liquid separation obtains the slurries of sulfur acid sodium crystal (content liquid is 35 mass % or less, and the step is preferably heavy It is carried out in the devices well known in the art such as drop pond, settling tank).During elutriation, the slurry relative to 1 parts by weight sulfur acid sodium crystal Liquid, it is 1~20 parts by weight to eluriate the liquid used.Elute it is preferable to use aqueous sodium persulfate solution (aqueous sodium persulfate solution it is dense Degree be preferably at the temperature corresponding to sodium sulfate crystal to be washed sodium sulphate and sodium chloride reach sulfuric acid in the aqueous solution of saturation simultaneously The concentration of sodium) it carries out.In order to further increase the effect of elutriation, the higher sodium sulfate crystal of purity is obtained, in the case of preferred, The liquid that elution can be used to obtain is washed.The liquid generated for washing, it is preferable that the catalyst production waste water is washed in a pan Washing lotion is back to before second of pH value adjusting before MVR vaporising devices 2 evaporate, and other cleaning solutions are back to multi-effect evaporating device 1。
A preferred embodiment according to the present invention, (or sulfur acid sodium is brilliant for the second concentrate of sulfur acid sodium crystal The magma of body) it is carried out after being tentatively separated by solid-liquid separation by sedimentation, it is carried out for the first time in eluriating tank with the catalyst production 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 Acid sodium aqueous solution (sodium sulphate and sodium chloride at a concentration of temperature corresponding to sodium sulfate crystal to be washed of the aqueous sodium persulfate solution Reach the concentration of sodium sulphate in the aqueous solution of saturation simultaneously) it is eluted, and washed in a pan obtained liquid is eluted back to second It washes middle as elutriation liquid.The washing process combined by above-mentioned elutriation and elution, the purity of the sodium sulfate crystal not only made Improve, and will not be excessive introducing cleaning solution, improve the efficiency of wastewater treatment.
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 the third heat exchange It puts.First steam containing ammonia condenses what i.e. described second heat-exchanger rig 32 of remaining tail gas was discharged by first heat exchange Tail gas, second steam containing ammonia condense the tail that remaining tail gas i.e. third heat-exchanger rig 33 is discharged by the third heat exchange Gas.By the way that above-mentioned tail gas is removed 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 catalyst production waste water, as long as containing NH4 +、SO4 2-、Cl-And Na+ Catalyst production waste water.In addition, the method for the present invention is particularly suitable for the processing of high-salt wastewater.Catalysis as the present invention Agent production waste water is specifically as follows the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process, can also be in the future The waste water after following removal of impurities and concentration is carried out from the waste water of molecular sieve, aluminium oxide or oil refining catalyst production process.Preferably will Waste water from molecular sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.
As the NH in the catalyst production waste water4 +Can be 8mg/L or more, preferably 300mg/L or more.
As the Na in the catalyst production waste water+Can be 510mg/L or more, preferably 1000mg/L or more, more Preferably 2000mg/L or more, further preferably 4000mg/L or more, further preferably 8000mg/L or more, it is further excellent It is selected as 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.
As the SO in the catalyst production waste water4 2-Can be 1000mg/L or more, preferably 2000mg/L or more, More preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, 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, further preferably 70000mg/L or more.
As the Cl in the catalyst production waste water-Can be 970mg/L or more, more preferably 2000mg/L or more, Further preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, Further preferably 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L with On, further preferably 60000mg/L or more.
The NH contained in the catalyst production waste water4 +、SO4 2-、Cl-And Na+The upper limit there is no particular limitation.From useless Water is easy from the point of view of starting with, SO in catalyst production waste water4 2-、Cl-And Na+The upper limit be respectively 200g/L hereinafter, it is preferred that For 150g/L or less；NH in catalyst production waste water4 +For 50g/L hereinafter, preferably 20g/L or less.
It is useless relative to catalyst production from the point of view of the energy consumption for reducing processing procedure from the efficiency for improving the first evaporation The SO contained in water4 2-, the Cl in catalyst production waste water-The higher the better for content, for example, useless relative to 1 mole of ammonium salt-containing The SO contained in water4 2-, the Cl that contains in the catalyst production waste water-It is 1 mole or more, preferably 2 moles or more, preferably It is 5 moles or more, more preferably 9.5 moles or more, further preferably 10 moles or more.And from the point of view of practicability, Relative to the SO contained in 1 mole of catalyst production waste water4 2-, the Cl that contains in the catalyst production waste water-Preferably 200 moles hereinafter, more preferably 150 moles hereinafter, further preferably 100 moles hereinafter, still more preferably be 50 moles Hereinafter, still more preferably for 30 moles hereinafter, such as 10-20 moles.Pass through the Cl that will contain in catalyst production waste water-With SO4 2-Molar ratio be limited to above range, most of water can be steamed in the first evaporation, reduce following in system for handling Ring amount of liquid, it is energy saving, keep processing procedure more economical.
In the present invention, the inorganic ion contained in the catalyst production 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 member The respective content of the inorganic ions such as plain ion 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 chloride crystal and sodium sulfate crystal.In order to reduce the catalyst production waste water In other inorganic ions content, preferably carry out following removal of impurities.
The TDS of the catalyst production 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 catalyst production waste water is preferably 4~8, and preferably 6.4~6.9.
In addition, due to catalyst production waste water COD concentration when may block up film, in evaporative crystallization when influence salt purity With color and luster etc., the COD of the catalyst production waste water it is more fewer better (preferably 20mg/L hereinafter, more preferably 10mg/L with Under), such as bioanalysis, advanced oxidation processes progress specifically preferably can be used, in COD contents by oxidation removal in pretreatment When very high preferably use it is oxidizing, the oxidant for example can be Fenton reagent.
In the present invention, in order to reduce the concentration impurity ion in catalyst production waste water, ensure the continuous of processing procedure Stablize and carry out, reduces equipment operation maintenance cost, the catalyst production waste water is before using the processing of the processing method of the present invention Preferably through removal of impurities.Preferably, the one kind of the removal of impurities in separation of solid and liquid, chemical precipitation, absorption, ion exchange and oxidation Or it is a variety of.
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 catalyst production waste water.For Suspended matter can select solid-liquid isolation method to clean；For inorganic matter and organic matter, chemical precipitation method, ion exchange can be selected Method, absorption method removal of impurities, such as Subacidity cation exchange process, active carbon adsorption etc.；For organic matter, absorption may be used And/or the mode of oxidation cleans, wherein preferably ozone biological activated carbon adsorption and oxidation method.One according to the present invention preferred Embodiment, catalyst production waste water is successively by filtering, Subacidity cation exchange process, ozone biological activated carbon adsorption and oxidation Method cleans.By above-mentioned dedoping step, most suspended substances, hardness, silicon and organic matter can be removed, reduces device fouling Risk ensures wastewater treatment process continuous and steady operation.
It in the present invention, can be in the processing method using the present invention for the lower catalyst production waste water of salt content Before processing (preferably after above-mentioned removal of impurities), salt content is set to reach the range required by the waste water of the present invention by concentrating.It is excellent Selection of land, it is described concentration selected from ED films concentration and/or it is reverse osmosis；It is highly preferred that it is described be concentrated by ED films concentration and reverse osmosis penetrate into There is no particular limitation for the sequencing of row, the ED films concentration and reverse osmosis progress.The ED films concentration and reverse-osmosis treated The mode that this field routine may be used in device and condition carries out, and can be specifically chosen according to the case where pending waste water.Specifically Ground is concentrated as the ED films, and unidirectional electrodialysis system or pole-reversing electroosmosis system can be selected to carry out；As the reverse osmosis Thoroughly, rolled film, plate membrane, dish tubular membrane, vibrating membrane or combinations thereof can be selected to carry out.Waste water can be improved by the concentration The efficiency of processing avoids energy waste caused by largely evaporating.
In the preferred embodiment of the present invention, catalyst production 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 catalyst production waste water, if catalysis The ion concentration of agent production waste water meets the condition of the present invention, the first evaporation can be first carried out with condition according to the invention and carried out again Second evaporation；If the ion concentration of catalyst production waste water is unsatisfactory for the condition of the present invention, can control the first evaporation makes the In one concentrate then the first concentrate is carried out the second evaporation, obtains the second concentration by the concentration of sodium sulphate close to concentration is precipitated Liquid is simultaneously separated by solid-liquid separation and obtains sodium sulfate crystal and the second mother liquor, then the second mother liquor is mixed with the catalyst production waste water to adjust It saves the ion concentration of pending waste water and obtains sodium chloride crystal to carry out the first evaporation again after range of the presently claimed invention.Certainly Na can also be used in the starting stage2SO4The ion concentration in pending waste water is adjusted with NaCl, as long as making described wait for Waste water is handled 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, catalyst production 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 ED films successively and concentrate Waste water after being concentrated with reverse osmosis.
Embodiment 1
As shown in Figure 1, by catalyst production waste water (180g/L containing NaCl, Na2SO4 10g/L、NH4Cl48g/L、(NH4)2SO42.71g/L, pH 6.4) by first circulation pump 71 with inlet amount it is 5m3The speed of/h is sent to the pipeline of processing system In, the sodium hydrate aqueous solution that a concentration of 45.16 mass % is imported into pipeline carries out first time pH value adjusting, and passes through first PH value measuring device 61 (pH meter) is monitored (measured value 7.6) to the pH value after adjusting, will be through by first circulation pump 71 Cross a part (4.5m of the catalyst production waste water after first time pH value is adjusted3/ h) it is sent into 31 (plastic plate of the first heat-exchanger rig Formula heat exchanger) with recycling the first ammonium hydroxide carry out the first heat exchange so that catalyst production waste water is warming up to 43 DEG C, rest part is sent Entering the 4th heat-exchanger rig 34 (two phase stainless steel plate heat exchanger) and the second ammonium hydroxide the first heat exchange of progress of recycling makes catalyst Production waste water is warming up to 58 DEG C, next merges two parts catalyst production waste water, and be mixed to get with the second mother liquor and wait locating Manage the waste water (SO wherein contained4 2-And Cl-Molar ratio be 1：19.893) pending waste water, then, is sent into the second heat exchange to fill 32 (titanium alloy plate heat exchangers) are set, carrying out the first heat exchange with the first steam containing ammonia of recycling makes pending waste water be warming up to 52 DEG C, then the pending waste water after the first heat exchange twice is sent in the pipeline of MVR vaporising devices 2 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 MVR Vaporising device 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) is evaporated, and obtains the first steam containing ammonia and sodium chloride-containing First concentrate of crystal.Wherein, the evaporating temperature of MVR vaporising devices 2 is 45 DEG C, and pressure is -94.69Pa, and evaporation capacity is 5.32m3/h.The first steam containing ammonia that evaporation obtains (10 DEG C of temperature rise) after the compression of compressor 10 passes sequentially through second and changes Thermal 32 and the first heat-exchanger rig 31, carry out heat exchange with pending waste water and catalyst production waste water respectively, and cooling obtains First ammonium hydroxide is stored in the first tank used for storing ammonia 51.In addition, in order to improve the solid content in MVR vaporising devices 2, MVR is steamed The pending waste water in part after being evaporated in transmitting apparatus 2 is recycled to the second heat-exchanger rig as circulation fluid by second circulation pump 72 32, it is then again introduced into MVR vaporising devices 2 and carries out the first evaporation (reflux ratio 112).Pass through what is be arranged on MVR vaporising devices 2 The degree that densitometer pair first evaporates is monitored, and controls a concentration of 0.9711Y (67.3g/ of sodium sulphate in the first concentrate L)。
The first concentrate that the evaporation of above-mentioned MVR vaporising devices 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, 4.19m is obtained per hour3Contain NaCl 292.4g/L, Na2SO4 67.3g/L、NaOH 0.1g/ L、NH3The first mother liquor of 0.711g/L, is temporarily stored into mother liquor tank 54, is separated by solid-liquid separation gained solid sodium chloride and (is contained per hour The sodium chloride crystalli-zation cake 1358.18kg of 14 mass % of water, the wherein content of sodium sulphate be 4 mass % or less) use and sodium chloride The equal 292.4g/L sodium chloride solutions elution of crystalli-zation cake butt quality, it is (pure to obtain sodium chloride 1168kg per hour after dry Degree is 99.5 weight %), cleaning solution is recycled to the second heat-exchanger rig 32 by the 8th circulating pump 78, is then again introduced into MVR steamings Transmitting apparatus 2 carries out the first evaporation.
Second evaporation process carries out in multi-effect evaporating device 1, and the multi-effect evaporating device 1 is by 1st effective evaporator 1a, 2nd effect evaporator 1b and third effect evaporator 1c (being forced-circulation evaporator) compositions.Pass through the 5th circulating pump 75, The first mother liquor in above-mentioned mother liquor tank 54 is sequentially sent to each effect of multi-effect evaporating device 1 by nine circulating pumps 79 and the tenth circulating pump 80 Evaporator is evaporated, the second concentrate of finally obtained sulfur acid sodium crystal.Wherein, the evaporation temperature of 1st effective evaporator 1a Degree is 66 DEG C, and pressure is -82.29kPa, evaporation capacity 0.076m3/h；The evaporating temperature of 2nd effect evaporator 1b is 81 DEG C, pressure Power is -64.34kPa, evaporation capacity 0.075m3/h；The evaporating temperature of third effect evaporator 1c be 96 DEG C, pressure be- 33.82kPa, evaporation capacity 0.075m3/h.Evaporated in the third effect evaporator 1c of multi-effect evaporating device 1 second is contained Ammonia steam is passed through 2nd effect evaporator 1b and carries out the second heat exchange and obtain the second ammonium hydroxide, will be evaporated in 2nd effect evaporator 1b To the second steam containing ammonia be passed through 1st effective evaporator 1a and carry out the second heat exchange and obtain the second ammonium hydroxide, from 2nd effect evaporator The second ammonium hydroxide that 1b, 1st effective evaporator 1a are obtained is stored in the second tank used for storing ammonia 52 after exchanging heat by the 4th heat-exchanger rig 34 In.Heating steam (life steam i.e. commonly used in the art) is passed through in third effect evaporator 1c, heating steam is imitated in third The condensation water obtained after being condensed in evaporator 1c, condensation water are used to preheat the pending waste water into MVR vaporising devices 2 Afterwards, it is used to prepare washing solution.The second steam containing ammonia that the 1st effective evaporator 1a of multi-effect evaporating device 1 evaporates is in third Third heat exchange is carried out with cooling water (catalyst production waste water) in heat-exchanger rig 33 and obtain the second ammonium hydroxide, and be stored in second In tank used for storing ammonia 52.The degree evaporated by the densitometer pair second being arranged on multi-effect evaporating device 1 is monitored, control second A concentration of 0.99351X (306.2g/L) of sodium chloride in concentrate.After first mother liquor evaporates in 1st effective evaporator 1a, lead to It crosses the 9th circulating pump 79 and is passed through in 2nd effect evaporator 1b and evaporate, then be passed through in third effect evaporator 1c by the tenth circulating pump 80 Evaporation, the second concentrate of finally obtained sulfur acid sodium crystal crystallizes that (crystallization temperature is 95 DEG C, when crystallization in crystallizing tank 53 Between be 10min) obtain the magma of sulfur acid sodium crystal.
The magma of sulfur acid sodium crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and is separated by solid-liquid separation, per hour To 4.27m3Contain NaCl 306.2g/L, Na2SO4 55.4g/L、NaOH 0.105g/L、NH3The second mother liquor of 0.037g/L, By second mother liquor by the 7th circulating pump 77 be recycled to waste water import pipe be mixed to get with catalyst production waste water it is pending Waste water is separated by solid-liquid separation gained solid sodium sulfate and (obtains the sulfate crystal filter cake that water content is 15 mass % per hour 69.45kg, the wherein content of sodium chloride are 3.9 mass % or less) with the 55.4g/L sodium sulphate equal with sodium sulphate butt quality It is dry in drying machine after solution elution, sodium sulphate 59.03kg (purity is 99.6 weight %) is obtained per hour, and washing obtains The second cleaning solution multi-effect evaporating 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 5.32m of a concentration of 1.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 0.226m of a concentration of 1.3 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.
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 catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl176g/L, Na2SO4 20g/L、NH4Cl 34.6g/L、(NH4)2SO4The catalyst production waste water that 4.0g/L, pH are 6.9 is handled, A middle part (5.0m3/ h) it carries out heat exchange rear catalyst to produce the temperature of waste water being 48 DEG C by the first heat-exchanger rig 31, Remaining part point carries out heat exchange rear catalyst to produce the temperature of waste water being 98 DEG C by the 4th heat-exchanger rig 34, is filled by the second heat exchange The temperature for setting pending waste water after 32 carry out heat exchanges is 57 DEG C, the SO contained in obtained pending waste water4 2-And Cl-Rub You are than being 1：15.307.The evaporating temperature of MVR vaporising devices 2 is 50 DEG C, and pressure is -92.7kPa, evaporation capacity 5.06m3/h。 The evaporating temperature of 1st effective evaporator 1a is 70 DEG C, and pressure is -78.45kPa, evaporation capacity 0.14m3/h；2nd effect evaporator The evaporating temperature of 1b is 85 DEG C, and pressure is -57.66kPa, evaporation capacity 0.14m3/h；The evaporating temperature of third effect evaporator 1c It it is 100 DEG C, pressure is -22.83kPa, evaporation capacity 0.13m3/h.Crystallization temperature is 100 DEG C, crystallization time 5min.
First equipment for separating liquid from solid 91 obtains the sodium chloride crystalli-zation cake 1248.92kg of aqueous 14 mass % per hour, most Obtain sodium chloride 1074.07kg per hour eventually (purity is 99.5 weight %)；8.94m is obtained per hour3A concentration of NaCl 294.7g/L、Na2SO4 65.7g/L、NaOH 0.14g/L、NH3The first mother liquor of 0.067g/L.
Second equipment for separating liquid from solid 92 obtains the sulfate crystal filter cake 135.63kg that water content is 14 mass % per hour, It is final to obtain sodium sulphate 116.65kg per hour (purity is 99.6 weight %)；8.58m is obtained per hour3, a concentration of NaCl 307.1g/L、Na2SO4 54.3g/L、NaOH 0.146g/L、NH3The second mother liquor of 0.0028g/L.
In the present embodiment, the ammonium hydroxide 5.06m of a concentration of 1.1 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 0.41m of a concentration of 0.14 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 catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl98g/L, Na2SO4 102g/L、NH4Cl 20g/L、(NH4)2SO4The catalyst production waste water that 21.16g/L, pH are 6.7 is handled, A middle part (3.0m3/ h) it carries out heat exchange rear catalyst to produce the temperature of waste water being 54 DEG C by the first heat-exchanger rig 31, Remaining part point carries out heat exchange rear catalyst to produce the temperature of waste water being 99 DEG C by the 4th heat-exchanger rig 34, is filled by the second heat exchange The temperature for setting pending waste water after 32 carry out heat exchanges is 62 DEG C, the SO contained in obtained pending waste water4 2-And Cl-Rub You are than being 1：11.779.The evaporating temperature of MVR vaporising devices 2 is 55 DEG C, and pressure is -90.15kPa, evaporation capacity 3.52m3/h。 The evaporating temperature of 1st effective evaporator 1a is 70 DEG C, and pressure is -78.45kPa, evaporation capacity 0.69m3/h；2nd effect evaporator The evaporating temperature of 1b is 90 DEG C, and pressure is -47.89kPa, evaporation capacity 0.69m3/h；The evaporating temperature of third effect evaporator 1c It is 110 DEG C, pressure 11.34kPa, evaporation capacity 0.71m3/h.Crystallization temperature is 105 DEG C, crystallization time 15min.
First equipment for separating liquid from solid 91 obtains the sodium chloride crystalli-zation cake 704.22kg of aqueous 15 mass % per hour, finally Obtain sodium chloride 598.59kg per hour (purity is 99.5 weight %)；49.64m is obtained per hour3A concentration of NaCl 296.6g/L、Na2SO4 63.6g/L、NaOH 0.29g/L、NH3The first mother liquor of 0.059g/L.
Second equipment for separating liquid from solid 92 obtains the sulfate crystal filter cake 726.27kg that water content is 14 mass % per hour, It is final to obtain sodium sulphate 624.59kg per hour (purity is 99.4 weight %)；47.82m is obtained per hour3A concentration of NaCl 307.8g/L、Na2SO4 53g/L、NaOH 0.3g/L、NH3The second mother liquor of 2.09g/L.
In the present embodiment, the ammonium hydroxide 3.52m of a concentration of 1.57 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 2.09m of a concentration of 0.13 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the life of 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 (12)

1. a kind of processing method of catalyst production waste water, the catalyst production waste water contain NH4 +、SO4 2-、Cl-And Na+, special Sign is that this approach includes the following steps,
1) it pending waste water is passed through MVR vaporising devices carries out the first evaporation and obtain the first steam containing ammonia and sodium chloride-containing crystal First concentrate, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sodium chloride-containing crystal is carried out first to be separated by solid-liquid separation, and obtained liquid is separated by solid-liquid separation by first It is mutually passed through successively in each effect evaporator of multi-effect evaporating device and carries out the second evaporation, respectively obtaining second in each effect evaporator contains Ammonia steam, and the second concentrate of sulfur acid sodium crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is more than 9；
Before the second steam containing ammonia that rear 1st effective evaporator is evaporated is sent into 1st effective evaporator with first concentrate into The second heat exchange of row simultaneously obtains the second ammonium hydroxide, first concentrate and the second steam counter-flow containing ammonia heat exchange；
First evaporation makes sodium sulphate not crystallize precipitation, and second evaporation makes sodium chloride 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 9.5 moles with On.
2. according to the method described in claim 1, wherein, the pending waste water is the catalyst production waste water；Alternatively, institute State the liquid phase that pending waste water contains the catalyst production waste water and second separation of solid and liquid obtains；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It is 10 Mole or more, preferably 10-20 moles；
Preferably, before the pending waste water is passed through MVR vaporising devices, 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 sulphate in the first concentrate For Y or less, wherein Y is sulfuric acid when sodium chloride and sodium sulphate reach saturation in the first concentrate under conditions of first evaporates The concentration of sodium；
Preferably, second evaporation makes a concentration of X or less of sodium chloride in second concentrate, wherein X is to be steamed second Under conditions of hair, the concentration of sodium chloride when sodium chloride and sodium sulphate reach saturation in the second concentrate；
Preferably, first evaporation makes a concentration of 0.9Y-0.99Y of sodium sulphate in the first concentrate；
Preferably, second evaporation makes a concentration of 0.95X-0.999X of sodium chloride 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 30 DEG C~85 DEG C, pressure is -98kPa~-58kPa；
Preferably, the condition of first evaporation includes：Temperature is 35 DEG C~60 DEG C, and pressure is -98kPa~-87kPa；
Preferably, the condition of first evaporation includes：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa~-87kPa.
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kPa；
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~55 DEG C, and pressure is -95kPa~-90kPa.
5. according to the method described in any one of claim 1-3, wherein it is described second evaporation condition include：Temperature is 45 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~365 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of second evaporation includes：Temperature is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of second evaporation includes：Temperature is 70 DEG C~175 DEG C, and pressure is -79kPa~653kPa；
Preferably, the condition of second evaporation includes：Temperature is 70 DEG C~130 DEG C, and pressure is -79kPa~117kPa；
Preferably, the condition of second evaporation includes：Temperature is 90 DEG C~120 DEG C, and pressure is -48kPa~57kPa；
Preferably, the condition of second evaporation includes：Temperature is 95 DEG C~115 DEG C, and pressure is -37kPa~33kPa.
6. according to the method described in claim 5, wherein, in the second evaporation, the evaporating temperature of rear 1st effective evaporator is than previous effect High 5 DEG C or more, preferably high 10 DEG C or more.
7. method according to claim 4 or 5, wherein the temperature of first evaporation is 5 DEG C lower than the temperature of the second evaporation More than, preferably low 20 DEG C or more, more preferably low 35 DEG C~70 DEG C.
8. according to the method described in claim 1, wherein, before the pending waste water is passed through MVR vaporising devices, by institute The first steam containing ammonia is stated to carry out the first heat exchange with the pending waste water and obtain the first ammonium hydroxide；
Preferably, before carrying out the first heat exchange, the pH value for adjusting the pending waste water is more than 7.
9. according to the method described in claim 1, wherein, second that the 1st effective evaporator of multi-effect evaporating device generates is steamed containing ammonia Vapour carries out third heat exchange in third heat-exchanger rig and obtains the second ammonium hydroxide；
Preferably, first steam containing ammonia is condensed into remaining tail gas by first heat exchange and multiple-effect evaporation fills The second steam containing ammonia that the last 1st effective evaporator set evaporates condenses remaining tail gas by the third heat exchange to be passed through Except being discharged after ammonia.
10. according to the method described in any one of claim 1-9, this method further includes by the of the sodium chloride-containing crystal One concentrate obtains sodium chloride crystal after first 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 1-9, this method further includes by the of the sulfur acid sodium crystal Two concentrates obtain sodium sulfate crystal after second is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium sulfate crystal.
12. according to the method described in any one of claim 1-9, wherein NH in the catalyst production waste water4 +For 8mg/ L or more, SO4 2-For 1000mg/L or more, Cl-For 970mg/L or more, Na+For 510mg/L or more；
Preferably, the catalyst production waste water is the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process；
Preferably, this method further includes that the catalyst production waste water is cleaned and concentrated.
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