CN108726607A - 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
CN108726607A
CN108726607A CN201710263284.7A CN201710263284A CN108726607A CN 108726607 A CN108726607 A CN 108726607A CN 201710263284 A CN201710263284 A CN 201710263284A CN 108726607 A CN108726607 A CN 108726607A
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China
Prior art keywords
waste water
evaporation
concentrate
sodium chloride
crystal
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CN201710263284.7A
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Chinese (zh)
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CN108726607B (en
Inventor
殷喜平
李叶
顾松园
王涛
周岩
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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
    • C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16—Purification
    • 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
    • C02F1/08—Thin film evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/007—Modular design

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The present invention relates to sewage treatment fields, disclose a kind of processing method of catalyst production waste water, which contains NH4 +、SO4 2‑、Cl‑And Na+, this approach includes the following steps, 1) and it pending waste water is passed through MVR vaporising devices carries out the first evaporation and obtain the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal；2) the first concentrate of the sulfur acid sodium 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 sodium chloride-containing crystal in last 1st effective evaporator；3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation.Ammonium and sodium sulphate, sodium chloride in waste water can be separately recovered in this method, farthest recycle the resource in waste water.

Description

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 sulphate and sodium chloride and alumino-silicate combined sewage.For such Sewage, common practice is first in the range of adjusting pH value to 6~9, after removing most suspended substances, then to adopt in the prior art The removing of ammonium ion is carried out with biochemical process, blow-off method or vaporizing extract process, then, by saline sewage through overregulating pH value, the big portion of removing Divide suspended matter, remove hardness, except silicon and partial organic substances and then by ozone biological activated carbon adsorption and oxidation or other advanced oxygen Change method oxidation removal major part organic matter, then, after further removing hardness into ion interchange unit, into thickening device After (such as reverse osmosis and/or electrodialysis) concentration, then using MVR evaporative crystallizations or multiple-effect evaporation crystallization, obtain the sulphur containing a small amount of ammonium salt Sour sodium and sodium chloride mixing carnallite；Either；First adjust pH value in the range of 6.5~7.5, removing most suspended substances, so Afterwards, it removes hardness, remove silicon and partial organic substances, gone using ozone biological activated carbon adsorption and oxidation or the oxidation of other advanced oxidation processes It is (such as reverse osmosis and/or electric into thickening device after further removing hardness into ion interchange unit after most of organic matter Dialysis) after concentration, then crystallized using MVR evaporative crystallizations or multiple-effect evaporation, sodium sulphate and the sodium chloride mixing for obtaining ammonium salt-containing are miscellaneous Salt.But these carnallites containing ammonium are difficult to handle at present, or the processing cost is high, also, the process of removing early period ammonium ion, Add additional the processing cost of waste water.
In addition, biochemical process deamination can only handle the waste water of low ammonium content, and due to COD contents deficiency in Catalyst sewage Biochemical treatment cannot be directly carried out, machine object, such as glucose or starch are also additionally supplemented with during biochemical treatment, just may be used To handle ammoniacal nitrogen using biochemical process.Sixty-four dollar question is biochemical process deamination treated waste water often total nitrogen (nitre not up to standard Acid ion, nitrite ion content are exceeded), it is also necessary to advanced treating, in addition the content of salt is not reduced in waste water (20000mg/L~30000mg/L), is unable to direct emission, needs further to carry out desalting processing.
Air- extraction deamination needs to add a large amount of adjusting PH with base value, alkaline consumption is very high, due to de- to deviate from the ammoniacal nitrogen in waste water The alkali in waste water after ammonia cannot recycle, and treated, and pH value of waste water is very high, and the processing cost is high, and air lift rear catalyst is dirty The not big variation of COD contents in water, the salt content in waste water do not reduce (20000mg/L~30000mg/L), Bu Nengzhi Running in and put, needs further to carry out desalting processing, wastewater treatment operating cost is high, and a large amount of alkali is remained in treated waste water, PH value is very high, and waste is big, and processing cost is up to 50 yuan/ton.
Invention content
The purpose of the present invention is overcome to contain NH in the prior art4 +、SO4 2-、Cl-And Na+Catalyst production waste water be processed into This height, and the problem of can only obtain mixing salt crystal provides and a kind of at low cost and environmentally friendly contains NH4 +、SO4 2-、Cl-And Na+ Catalyst production waste water processing method, ammonium and sodium sulphate, chlorination in catalyst production waste water can be separately recovered in this method Sodium farthest recycles the resource in catalyst production 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 sulfur acid sodium crystalline substance First concentrate of body, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and first is separated by solid-liquid separation and is obtained Liquid phase 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 sodium chloride-containing crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is big In 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；Relative to 1 mole The SO contained in the pending waste water4 2-, the Cl that contains in the pending waste water-It is 14 moles or less.
Through the above technical solutions, for NH is contained4 +、SO4 2-、Cl-And Na+Waste water, by advance by pending waste water After pH value is adjusted to specific range, MVR vaporising devices are recycled to be evaporated isolated sodium sulfate crystal and concentrated ammonia liquor, so Multi-effect evaporating device is recycled to be evaporated to obtain sodium chloride crystal and weak aqua ammonia again afterwards.This method can respectively obtain high-purity The sodium sulphate and sodium chloride of degree, the difficulty during avoiding mixed salt processing and recycling, are completed at the same time separation of ammonia and the mistake of salt Journey, and make waste water heating and steam cooling containing ammonia simultaneously using heat exchange method, it is not necessarily to condenser, rationally utilizes evaporation process In heat, it is energy saving, reduce cost for wastewater treatment, the ammonium in waste water is recycled in the form of ammonium hydroxide, sodium chloride and sodium sulphate It is recycled respectively with crystal form, whole process does not have waste residue and liquid generation, realizes 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 at relatively high temperatures, improves evaporation efficiency, finally evaporate at a lower temperature, ensure that sodium sulphate is not precipitated, be convenient for simultaneously 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 wastewater treatment method of embodiment provided by the invention.
Reference sign
1, multi-effect evaporating device 2, MVR vaporising devices
31, the first heat-exchanger rig 32, the second heat-exchanger rig
33, third heat-exchanger rig 34, the 4th heat-exchanger rig
51, the first tank used for storing ammonia 52, the second tank used for storing ammonia
53, brilliant liquid collecting 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
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 sulfur acid sodium First concentrate of crystal, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and first is separated by solid-liquid separation and is obtained Liquid phase 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 sodium chloride-containing crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices 2, the pH value of the pending waste water is adjusted More than 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；It rubs relative to 1 The SO contained in your the pending waste water4 2-, the Cl that contains in the pending waste water-It is 14 moles or less.
Preferably, the pending waste water is the 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+Waste water handled, in addition to containing NH4 +、SO4 2-、Cl-And Na+Outside, to the pending waste water, there is no particular limitation.From the angle for the treatment effeciency for improving waste water Consider, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It rubs for 13.8 You hereinafter, more preferably 13.75 moles hereinafter, further preferably 13.5 moles hereinafter, still more preferably be 13 moles with Under, still more preferably for 12 moles hereinafter, be still more preferably 11 moles hereinafter, be still more preferably 10 moles with Under, still more preferably for 9 moles hereinafter, being still more preferably 8 moles hereinafter, being still more preferably 7 moles or less；It is excellent 2 moles or more, more preferably 2.5 moles or more, further preferably 3 moles or more are selected as, such as can be 4-11 moles.It is logical It crosses SO4 2-And Cl-Molar ratio control in above range, can make in the first evaporation that sodium sulphate is precipitated and sodium chloride is not precipitated, To achieve the purpose that efficiently separate sodium sulphate.In addition, it is as above described below, it can also will be evaporated in the present invention second Thus the second Recycling Mother Solution obtained in journey is come to the first evaporation to the SO in pending waste water4 2-And Cl-Molar ratio into Row is adjusted, and can maintain the balance of sodium hydroxide.
In the present invention, first evaporation makes sodium chloride not crystallize precipitation, refers to that the sodium chloride of control mixed system is dense Degree is no more than the solubility under the first evaporation conditions (including but not limited to temperature, pH value etc.), but sulfate crystal is not precluded The sodium chloride of entrainment or adsorption.Since the water content of crystal after separation of solid and liquid is different, in the sodium sulfate crystal generally yielded The content of sodium chloride (preferably 4 mass %) below 8 mass %, in the present invention, sodium chloride in obtained sodium sulfate crystal Content below 8 mass % when can think that sodium chloride does not crystallize precipitation.
In the present invention, second evaporation makes sodium sulphate not crystallize precipitation, refers to that the sodium sulphate of control mixed system is dense Degree is no more than the solubility under the second evaporation conditions (including but not limited to temperature, pH value etc.), it is not excluded that sodium chloride crystallization folder The sodium sulphate of band or adsorption.Since the water content of crystal after separation of solid and liquid is different, sulphur in the sodium chloride crystal generally yielded The content of sour sodium (preferably 4 mass %) below 8 mass %, in the present invention, sodium sulphate in obtained sodium chloride crystal It can think that sodium sulphate does not crystallize precipitation when content is below 8 mass %.
In the present invention, it is to be understood that first steam containing ammonia and second steam containing ammonia are this field So-called indirect steam.First concentrate and the second steam containing ammonia cocurrent heat exchange are referred to using in multiple-effect evaporation Forward flow process.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, the condition of first evaporation can be selected suitably as needed, reach make sulfate crystal and Make the purpose that sodium chloride is not precipitated.It is described first evaporation condition may include：Temperature be 45 DEG C or more, pressure be- 95kPa or more.In order to improve evaporation efficiency, the condition of preferably described first evaporation includes：Temperature is 45 DEG C~365 DEG C, pressure For -95kPa~18110kPa；In order to further increase evaporation efficiency, it is highly preferred that the condition of first evaporation includes：Temperature Degree is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；From the point of view of reducing equipment cost and energy consumption, more preferably The temperature on ground, evaporation is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；It is further preferred that the item of first evaporation Part includes：The temperature of evaporation is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；It is particularly preferred that first evaporation Condition includes：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
In the present invention, the operating pressure of the first evaporation is preferably the saturated vapor pressure of evaporated feed liquid.
In the present invention, the flow of the first evaporation can suitably be selected according to the ability that equipment is handled, such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sulfate crystal by making the first evaporation carry out under these conditions, sodium chloride is not tied Partial crystallization goes out, the purity for the sodium sulfate crystal that thereby may be ensured that.
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 (i.e. chlorination is precipitated in the sodium chloride crystallization in the pending waste water Sodium is not up to supersaturation), it is preferable that first evaporation makes a concentration of X or less of sodium chloride in the first concentrate (preferably 0.999X is hereinafter, more preferably 0.95X-0.999X, further preferred 0.99X-0.9967X), wherein X is in the first evaporation Under the conditions of, the concentration of sodium chloride when sodium sulphate and sodium chloride reach saturation in the first concentrate.Pass through the journey evaporated first Degree control within the above range, can be such that sulfate crystal as much as possible is precipitated under conditions of ensureing that sodium chloride is not precipitated. By making sulfate crystal in the first evaporation as possible, waste water treatment efficiency can be improved, energy waste is reduced.
In the present invention, the carry out degree of first evaporation is in such a way that the first evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the first evaporation of control makes the first evaporation not make described in above-mentioned range Sodium chloride crystallization in first concentrate is precipitated.Here first evaporation obtain the concentration of liquid, by way of measuring density into Row monitoring can specifically use densitometer to carry out density measure.
In the present invention, the first heat exchange, adjust the pH value of the pending waste water and the tune of the pending waste water With process, (the pending waste water contains the case where catalyst production waste water is separated by solid-liquid separation obtained liquid phase with described second Under, need the allocation process for carrying out the pending waste water) carry out priority there is no particular limitation, can be fitted as needed When selection, before the pending waste water is passed through the first MVR vaporising devices complete.
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.After first heat exchange, the ammonium hydroxide of output Cooled, heat utmostly recycles inside processing unit, and the energy is rationally utilized, and 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 pending waste water is passed sequentially through into the first heat-exchanger rig 31 and second heat exchange dress 32 are set, first heat exchange is carried out by first steam containing ammonia and the pending waste water, makes the 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 store In the first tank used for storing ammonia 51.
Another preferred embodiment according to the present invention, first heat exchange pass through the first heat-exchanger rig 31, Two heat-exchanger rigs 32 and the 4th heat-exchanger rig 34 carry out, specifically, first will evaporated in the MVR vaporising devices 2 Steam containing ammonia passes sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31, by multi-effect evaporating device 1 obtain second contain ammonia Steam condensation liquid (higher second ammonium hydroxide of temperature) passes through the 4th heat-exchanger rig 4；And by one of the catalyst production waste water Divide through the first heat-exchanger rig 31, another part passes through the 4th heat-exchanger rig 34；Then above-mentioned two parts waste water is merged, and with At least partly being mixed to get after pending waste water through the second heat-exchanger rig 32 for the liquid phase that second separation of solid and liquid obtains, leads to The first heat exchange for crossing first steam containing ammonia and the catalyst production waste water and the pending waste water makes described to wait locating Reason waste water heating is convenient for evaporating, while first steam cooling containing ammonia being made to obtain the first ammonium hydroxide.First ammonium hydroxide can To 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 pending waste water is 40 DEG C~364 DEG C, more preferably 55 DEG C~364 DEG C, Further preferably 65 DEG C~174 DEG C, be still more preferably 79 DEG C~129 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 29 DEG C~84 DEG C, more preferably 44 DEG C~65 ℃。
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 50 DEG C~370 DEG C, more preferably 65 DEG C~370 DEG C, further Preferably 75 DEG C~184 DEG C, be still more preferably 85 DEG C~139 DEG C.
In the present invention, for the method for pH value adjusting, there is no particular limitation, such as can use additional basic species The mode of matter adjusts the pH value of the pending waste water.There is no particular limitation for the alkaline matter, reaches above-mentioned adjusting pH value Purpose, such as can be the hydroxide such as sodium hydroxide, potassium hydroxide.In order not to be introduced newly in pending waste water Impurity improves the purity of gained crystal, and the alkaline matter is preferably NaOH.
Feed postition as the alkaline matter is the feed postition of this field routine, but preferably makes alkaline matter It is mixed in form of an aqueous solutions with the pending waste water, such as the aqueous solution containing alkaline matter can be passed into and import institute It states and is mixed in the pipeline of pending waste water.For the content of alkaline matter in aqueous solution, there is no particular limitation, as long as It can achieve the purpose that above-mentioned adjusting pH value.But it in order to reduce the dosage of water, further reduces the cost, it is preferable to use alkalinity The saturated aqueous solution of substance.In order to monitor the pH value of the pending waste water, can be waited for described in measurement after above-mentioned adjusting pH value Handle the pH value of waste water.
A preferred embodiment according to the present invention, 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 with it is described The liquid phase that second separation of solid and liquid obtains at least partly is mixed to get pending waste water, and the pending waste water is sent into second Heat-exchanger rig 32 carries out the first heat exchange, then by will led in the pipeline of the pending waste water feeding MVR vaporising devices 2 Enter the aqueous solution containing alkaline matter and mixing, to carry out second of pH value adjusting.It is adjusted, is made described by pH value twice PH value of the pending waste water before being passed through MVR vaporising devices 2 is more than 9, preferably greater than 10.8.Preferably, for the first time PH value is adjusted so that the pH value of the catalyst production waste water after adjusting is more than 7 (preferably 7-9), and second of pH value is adjusted so that waiting for The pH value for handling waste water is more than 9, preferably greater than 10.8.
In order to detect above-mentioned first time pH value adjust and second of pH value adjust after pH value, preferably 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 by after the MVR vaporising devices 2 evaporation partially liq (namely the liquid inside MVR vaporising devices, hereinafter Referred to as circulation fluid) it flows back into the MVR vaporising devices 2 and evaporates again after heating.It is above-mentioned to be steamed by the MVR vaporising devices 2 The process that partially liq after hair flows back into the MVR vaporising devices 2 is preferably, by the circulation fluid and in first time pH value tune It is re-fed into MVR vaporising devices 2 after section and after the pending waste water mixing before being adjusted to second of pH value, for example, 72 can be pumped by second circulation will pass through the circulation fluid back between the first heat-exchanger rig 31 and the second heat-exchanger rig 32 Waste water conveyance conduit in mixed with pending waste water, then by second of pH value adjust after, second heat exchange Device 32 carries out heat exchange, is re-fed into the MVR vaporising devices 2.As will by the MVR vaporising devices 2 evaporation after The ratio that partially liq flows back into the MVR vaporising devices 2 is not particularly limited, for example, the reflux ratio of first evaporation Can be 10-200, preferably 50-100.Here, the reflux ratio refers to：Regurgitant volume and the liquid being sent into MVR vaporising devices 2 Body total amount subtracts the ratio of the amount after regurgitant volume.
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 sulfur acid sodium crystal obtains sodium sulphate crystalline substance after first is separated by solid-liquid separation Body and the first mother liquor.There is no particular limitation for described first method being separated by solid-liquid separation, such as can be selected from centrifugation, filtering, sedimentation In it is one or more.
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 sulfate 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 sulfuric acid Sodium crystal water, the waste water or metabisulfite solution carry out the first washing and drying.First washing includes elution and/or washes in a pan It washes.Additionally, it is preferred that the first cleaning solution that above-mentioned washing process is obtained returns to the second heat-exchanger rig 32 by the 8th circulating pump 78.
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 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 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 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.In addition, it is preferable to use aqueous sodium persulfate solution progress for elution.Preferably, described Sodium chloride and sodium sulphate reach full simultaneously at the concentration of the aqueous sodium persulfate solution preferably temperature corresponding to sodium sulfate crystal to be washed The concentration of sodium sulphate in the aqueous solution of sum.In order to further increase the effect of elutriation, the higher sodium sulfate crystal of purity is obtained, it is excellent In the case of choosing, the liquid that elution obtains can be used to carry out above-mentioned elutriation, more preferably use water or metabisulfite solution.For washing The liquid of generation is washed, before second of the pH value preferably returned it to before the evaporation of MVR vaporising devices is adjusted.
A preferred embodiment according to the present invention, evaporated by MVR vaporising devices 2 obtain containing sodium sulphate 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 sulfate 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 aqueous sodium persulfate solution, and elution being obtained is eluriated back to second.By above-mentioned washing process, The purity of the sodium sulfate 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 2-3 is imitated.
In the present invention, the evaporation conditions of second evaporation can be selected suitably as needed, and reaching makes sodium chloride knot Brilliant and purpose that sodium sulphate is not precipitated.It is described second evaporation condition may include：Temperature is 30 DEG C~85 DEG C, pressure For -98kPa~-58kPa；Preferably, the condition of second evaporation includes：Temperature be 35 DEG C~60 DEG C, pressure be- 97.5kPa~-87kPa；Preferably, the condition of second evaporation includes：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa ~-87kPa；Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kPa； Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~56 DEG C, and pressure is -95kPa~-89kPa.In the present invention In, the condition of second evaporation refers to the evaporation conditions of the last 1st effective evaporator of multi-effect evaporating device.
Wherein, in order to make full use of the heat in evaporation process, it is preferable that the evaporating temperature of preceding 1st effective evaporator is than latter High 5 DEG C of evaporator or more is imitated, it is preferably 5 DEG C high~30 DEG C, it is 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 100L/h or more (such as 0.1m3/ h~500m3/h).By making the second evaporation carry out under these conditions, Ke Yi While ensureing sodium chloride crystallization, sodium sulphate does not crystallize, the purity for the sodium chloride 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 waste water 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 First mother liquor is passed through the 1st effective evaporator 1a of the multi-effect evaporating device 1,2nd effect evaporator by circulating pump 75 successively It is evaporated to obtain the second concentrate of sodium chloride-containing crystal in 1b and third effect evaporator 1c.By the multi-effect evaporating device 1 1st effective evaporator 1a in the second steam containing ammonia for evaporating be passed through 2nd effect evaporator 1b and first concentrate into The second heat exchange of row simultaneously obtains the second ammonium hydroxide, and the second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through third effect Evaporator 1c carries out the second heat exchange with first concentrate and obtains the second ammonium hydroxide.It is highly preferred that the second ammonium hydroxide warp 4th heat-exchanger rig carries out the first heat exchange with pending waste water, makes full use of energy.It is passed through and adds in 1st effective evaporator 1a Hot steam (life steam i.e. commonly used in the art), the condensation that heating steam obtains after being condensed in 1st effective evaporator 1a Liquid, condensation water is used to preheat into after the pending waste water or the catalyst production waste water of MVR vaporising devices 2, then uses Solution is washed in preparing sodium sulphate.The second steam containing ammonia that third effect evaporator 1c evaporates in third heat-exchanger rig 33 with Cooling water (it is preferable to use the catalyst production waste waters before being passed through MVR concentration and evaporation devices as cooling water) carries out third Heat exchange simultaneously obtains ammonium hydroxide, and is stored in the second tank used for storing ammonia 52.After first mother liquor evaporates in 1st effective evaporator 1a, lead to Enter and evaporated in 2nd effect evaporator 1b, then is passed through in third effect evaporator 1c and evaporates, the of finally obtained sodium chloride-containing crystal Two concentrates crystallize in brilliant liquid collecting tank 53 and obtain magma.
According to the present invention, second evaporation is not so that (i.e. sulfuric acid is precipitated in the sulfate crystal in second concentrate Sodium is not up to supersaturation), it is preferable that second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate (preferably For 0.9Y-0.99Y, more preferably 0.95Y-0.98Y)), wherein Y is the sulphur in the second concentrate under conditions of second evaporates The concentration of sodium sulphate when sour sodium and sodium chloride reach saturation.By by second evaporation extent control within the above range, can Be precipitated sodium chloride crystallization as much as possible under conditions of ensureing that sodium sulphate is not precipitated.By making in the second evaporation as possible Sodium chloride crystallizes, and can improve waste water treatment efficiency, reduces energy waste.
In the present invention, the carry out degree of second evaporation is in such a way that the second evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the second evaporation of control makes the second evaporation not make described second in above range Sulfate crystal in concentrate is precipitated.Here the second evaporation obtains the concentration of liquid, is supervised by way of measuring density It surveys, can specifically densitometer be used to carry out density measure.
In the present invention, sodium chloride is made not crystallize precipitation in order to reach first evaporation, second evaporation makes sulfuric acid Sodium does not crystallize the purpose of precipitation, preferably meets the condition of twice evaporation：The temperature of first evaporation is than the second evaporation (with most The evaporation thermometer of 1st effective evaporator afterwards) temperature it is at least 5 DEG C high, it is preferably 20 DEG C high, more preferably it is 35-70 DEG C high, particularly preferably It is 50-60 DEG C high.It is carried out at different temperature by the first evaporation of control and the second evaporation, makes the difference of sodium sulphate and sodium chloride Crystallization is precipitated, to improve the purity of obtained sodium sulphate and sodium chloride crystal.
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 with first concentrate and obtain after the second steam containing ammonia that device evaporates is sent into 1st effective evaporator To the second ammonium hydroxide, also include multi-effect evaporating device last 1st effective evaporator generate steam containing ammonia in third heat-exchanger rig into The heat exchange of row third simultaneously obtains the second ammonium hydroxide.Above two parts ammonium hydroxide is come together in jointly in the second tank used for storing ammonia 52.
A preferred embodiment according to the present invention, second evaporation process carry out in multi-effect evaporating device 1. First mother liquor is passed through the second evaporation of progress in the multi-effect evaporating device 1 by the 5th circulating pump 75 and obtains second containing ammonia Second concentrate of steam and sodium chloride-containing crystal.
According to the present invention, this method can also include the second concentrate by the sodium chloride-containing crystal in crystallization apparatus Crystallization obtains the magma of sodium chloride-containing crystal.Make in crystallization apparatus at this point, the evaporation conditions of second evaporation need to meet Sodium chloride crystallizes and purpose that sodium sulphate is not precipitated.There is no particular limitation for the crystallization apparatus, such as can be brilliant flow container, crystalline substance Liquid collecting tank, band stir thickener or without stirring thickeners etc..A preferred embodiment according to the present invention, the knot Crystalline substance carries out in brilliant liquid collecting tank 53.There is no particular limitation for the condition of the crystallization, such as may include：Temperature be 30 DEG C with On；Preferably 40 DEG C~60 DEG C；More preferably 45 DEG C~55 DEG C.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 sodium chloride-containing 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 second evaporation not so that institute (i.e. sodium sulphate is not up to supersaturation) is precipitated in the sulfate crystal stated in the second concentrate, it is preferable that second evaporation makes institute State a concentration of Y or less of sodium sulphate in the second concentrate, wherein Y is the chlorination in the second concentrate under conditions of the crystallization The concentration of sodium sulphate when sodium and sodium sulphate reach saturation.
In the present invention, the second concentrate of the sodium chloride-containing crystal (or when being crystallized in individual crystallization apparatus, is The magma of the sodium chloride-containing crystal) sodium chloride crystal and the second mother liquor are obtained after second is separated by solid-liquid separation (described in namely Second is separated by solid-liquid separation obtained liquid phase).It is described second be separated by solid-liquid separation method there is no particular limitation, such as can be selected from from It is one or more in the heart, filtering and sedimentation.
According to the present invention, second separation of solid and liquid can (be, for example, centrifuge, belt by the second equipment for separating liquid from solid Filter, flame filter press etc.) 92 progress.After described second is separated by solid-liquid separation, the second equipment for separating liquid from solid 92 obtains second female Liquid (i.e. described second is separated by solid-liquid separation obtained liquid phase) returns to MVR vaporising devices 2 and carries out the first evaporation again, can specifically pass through Second mother liquor is mixed to get institute by the 7th circulating pump 77 back to first time pH value adjustment process with the catalyst production waste water Pending waste water is stated, is then fed into MVR vaporising devices 2 and carries out the first evaporation.In addition, being difficult on obtained sodium chloride crystal It avoids that the impurity such as certain sulfate ion, free ammonia, hydroxide ion can be adsorbed, in order to remove the impurity of absorption, reduces solid The peculiar smell of body salt reduces corrosivity, improves the purity of the crystal, it is preferable that the sodium chloride crystal water, the catalyst It produces waste water or sodium chloride solution carries out the second washing and drying.It is excellent in order to avoid the dissolving of sodium chloride crystal in washing process Selection of land, the sodium chloride crystal are washed with sodium-chloride water solution.It is highly preferred that the concentration of the sodium-chloride water solution is preferred Reach the dense of sodium chloride in the aqueous solution of saturation simultaneously for sodium chloride at the temperature corresponding to sodium chloride crystal to be washed and sodium sulphate Degree.
Preferably, second washing includes elution and/or eluriates.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 chloride crystal of higher purity, preferably 2-4 times.During elutriation, do not recycled generally when using the catalyst production waste water as elutriation liquid, and preferably returned It is back to before second of pH value adjusting before the evaporation of MVR vaporising devices；Using second washing recycling cleaning solution (namely elution production Raw cleaning solution) it can be used with circulated in countercurrent when doing elutriation liquid.Before carrying out the elutriation, carried out preferably by way of sedimentation just Step be separated by solid-liquid separation obtain sodium chloride-containing crystal slurries (content liquid be 35 mass % or less, which is preferably settling It is carried out in the device well known in the art such as 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.In addition, it is preferable to use the sodium-chloride water solution (sodium-chloride water solutions for elution Concentration be preferably at the temperature corresponding to sodium chloride crystal to be washed sodium chloride and sodium sulphate reach in the aqueous solution of saturation simultaneously The concentration of sodium chloride) it carries out.In order to further increase the effect of elutriation, the higher sodium chloride crystal of purity, preferred feelings are obtained Under condition, the liquid that elution obtains can be used to carry out above-mentioned elutriation.The liquid generated for washing, it is preferable that the waste water is washed in a pan Washing lotion is back to before second of pH value adjusting before the evaporation of MVR vaporising devices, and other cleaning solutions are back to multiple-effect evaporation dress It sets and is evaporated.
A preferred embodiment according to the present invention passes through by the magma for the sodium chloride-containing crystal that crystallization obtains Sedimentation carries out after being tentatively separated by solid-liquid separation, and carries out first time elutriation in eluriating tank with the catalyst production waste water, then makes again The liquid obtained when with subsequent wash sodium chloride crystal carries out second in another elutriation tank and eluriates, and will finally pass through twice The slurries of elutriation are sent into equipment for separating liquid from solid and are separated by solid-liquid separation, and the crystal being separated by solid-liquid separation uses sodium-chloride water solution (institute again It states sodium chloride and sodium sulphate at a concentration of temperature corresponding to sodium chloride crystal to be washed of sodium-chloride water solution while reaching saturation Aqueous solution in sodium chloride concentration) eluted, and will the obtained liquid of elution eluriated back to second in as eluriating Liquid.The purity of the washing process combined by above-mentioned elutriation and elution, the sodium chloride crystal not only made improves, and will not Excessive introducing cleaning solution, improves 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 second 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 second 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+ Waste water.In addition, the method for the present invention is particularly suitable for the processing of high-salt wastewater.Catalyst production as the present invention is useless Water is specifically as follows the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process, and can also be will be from molecule The waste water of sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.It will preferably come from and divide The waste water of son 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 urging Change agent production waste water to be 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, preferably 150g/L or less；NH in catalyst production waste water4 +For 50g/L hereinafter, preferably 30g/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 lower content the better, for example, relative to 1 mole of catalyst life The SO contained in production waste water4 2-, the Cl that contains in the catalyst production waste water-For 30 moles hereinafter, preferably 20 moles with Under, more preferably 15 moles hereinafter, further preferably 10 moles or less.And from the point of view of practicability, relative to 1 mole The SO contained in the catalyst production waste water4 2-, the Cl that contains in the catalyst production waste water-Preferably 0.1 mole with On, more preferably 0.5 mole or more, further preferably 1 mole or more, such as 1-8 moles.By the way that the catalyst is produced The SO contained in waste water4 2-And Cl-Molar ratio be limited to above range, most of water can be steamed in the first evaporation, be subtracted The circulation fluid scale of construction in few system for handling, 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 sulfate crystal and sodium chloride 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 more preferably 6.3~7.
In addition, due to the COD of waste water may block up film in concentration, in evaporative crystallization when influence the purity and color and luster etc. of salt, The COD more fewer better (preferably 20mg/L is hereinafter, more preferably 10mg/L or less) of the catalyst production waste water, preferably pre- By oxidation removal when processing, such as bioanalysis, advanced oxidation processes progress specifically can be used, it is preferred when COD contents are very high Using oxidizing, the oxidant for example can be Fenton reagent.
In the present invention, in order to reduce the concentration impurity ion in waste water, ensure that the continuous-stable of processing procedure carries out, drop Low equipment operation maintenance cost, the catalyst production waste water using the present invention processing method handle before preferably through except It is miscellaneous.Preferably, the removal of impurities is one or more in separation of solid and liquid, chemical precipitation, absorption, ion exchange and oxidation.
Can be filtering, centrifugation, sedimentation etc. as the separation of solid and liquid；Can be to adjust as the chemical precipitation PH, carbonate deposition, magnesium salts precipitation etc.；Can be physical absorption and/or chemisorption, specific absorption as the absorption Agent can select activated carbon, silica gel, aluminium oxide, molecular sieve, natural clay etc.；As the ion exchange, strong acid may be used Any one in property resin cation, acidulous cation resin；As the oxidation, may be used commonly used in the art Various oxidants, such as ozone, hydrogen peroxide, potassium permanganate, in order to avoid introducing new impurity, it is preferred to use ozone, dioxygen Water etc..
Specific removal of impurities mode can be specifically chosen according to the dopant species contained in the 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.
A preferred embodiment according to the present invention, the catalyst production waste water is successively by filtering, faintly acid Base exchange method, ozone biological activated carbon adsorption and oxidation method clean.By above-mentioned dedoping step, major part can be removed Suspended matter, hardness, silicon and organic matter reduce device fouling risk, ensure catalyst production waste water processing procedure continuous-stable fortune Row.
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.Catalysis can be improved by the concentration The efficiency of agent production waste water processing avoids energy waste caused by largely evaporating.
In the preferred embodiment of the present invention, the catalyst production waste water is in process of producing molecular sieve Waste water cleans by chemical precipitation, filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method, and Waste water after the concentration of ED films and 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 chloride close to concentration is precipitated Liquid is simultaneously separated by solid-liquid separation and obtains sodium chloride 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 sulfate crystal to carry out the first evaporation again after range of the presently claimed invention；When So, it can also use sodium sulphate or sodium chloride that the ion concentration in pending waste water is adjusted in the starting stage, as long as making The pending waste water meets 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 (156g/L containing NaCl, Na2SO4 50g/L、NH4Cl60g/L、(NH4)2SO419.55g/L, pH 6.3) with inlet amount it is 5m3The speed of/h is sent in the pipeline of processing system, is imported into pipeline The sodium hydrate aqueous solution of a concentration of 45.16 mass % carries out first time pH value adjusting, and passes through first time pH value measuring device 61 (pH meters) are monitored (measured value 7.5) to the pH value after adjusting, and the catalyst after the adjusting of first time pH value is given birth to Produce a waste water part (2.5m3/ h) be sent into the first heat-exchanger rig 31 (plastics plate heat exchanger) and the first liquid of steam condensation containing ammonia into The first heat exchange of row makes catalyst production waste water be warming up to 99 DEG C, and rest part is sent into 34 (two phase stainless steel of the 4th heat-exchanger rig Plate heat exchanger) and the first heat exchange of progress of the second liquid of steam condensation containing ammonia, so that the catalyst production waste water of rest part is heated up To 60 DEG C, next two parts waste water is merged, and (feeding speed is 15.31m with the second mother liquor3/ h) be mixed to get it is pending Waste water (the SO contained in pending waste water4 2-And Cl-Molar ratio be 1：10.356).Then, pending waste water is sent into second Heat-exchanger rig 32 (titanium alloy plate heat exchanger), carrying out the first heat exchange with the first steam containing ammonia of recycling makes pending waste water liter Temperature is to 113 DEG C, then pending waste water is being sent to MVR vaporising devices 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) Pipeline in import the sodium hydrate aqueous solution of a concentration of 45.16 mass % and carry out second of pH value adjusting, and pass through the 2nd pH Value measurement mechanism 62 (pH meter) is monitored (measured value 10.8) to the pH value after adjusting, will be after the adjusting of the second pH value Pending waste water is sent into MVR vaporising devices 2 and is evaporated, and the first concentration of the first steam containing ammonia and sulfur acid sodium crystal is obtained Liquid.Wherein, the evaporation conditions of MVR vaporising devices 2 include：Temperature is 105 DEG C, and pressure is -7.02kPa, evaporation capacity 2.53m3/ h.It evaporates the first obtained steam containing ammonia (14 DEG C of temperature rise) after the compression of compressor 10 and passes sequentially through the second heat-exchanger rig 32 and first heat-exchanger rig 31, heat exchange is carried out with pending waste water, cooling obtains ammonium hydroxide, and is deposited in the first tank used for storing ammonia 51 Storage.In addition, in order to improve the solid content in MVR vaporising devices 2, using the partially liq after being evaporated in MVR vaporising devices 2 as Circulation fluid is recycled to the second heat-exchanger rig 32 by second circulation pump 72, is then again introduced into MVR vaporising devices 2 and carries out the first steaming It sends out (reflux ratio 56.2).The degree evaporated by the densitometer pair first being arranged on MVR vaporising devices 2 is monitored, and is controlled A concentration of 0.99352X (307.0g/L) of sodium chloride in first concentrate.
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, 18.43m is obtained per hour3Contain NaCl 307.0g/L, Na2SO4 52.7g/L、NaOH 1.67g/L、NH3The first mother liquor of 0.13g/L, is temporarily stored into mother liquor tank 54, and it is (wherein every to be separated by solid-liquid separation gained solid sodium sulfate Hour obtains the sulfate crystal filter cake 407.73kg of aqueous 14 mass %, and the content of sodium chloride is 6.8 mass % or less) it uses The 52.7g/L metabisulfite solution elution equal with sulfate crystal filter cake butt quality, sodium sulphate is obtained after dry per hour 350.64kg (purity is 99.4 weight %), the leacheate eluted is recycled to the second heat-exchanger rig by the 8th circulating pump 78 32, it is then again introduced into MVR vaporising devices 2 and 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.It will by the 5th circulating pump 75 The first mother liquor in above-mentioned mother liquor tank 54 is sent into multi-effect evaporating device 1, after the first mother liquor evaporates in 1st effective evaporator 1a, leads to Enter and evaporated in 2nd effect evaporator 1b, then is passed through in third effect evaporator 1c and evaporates, the of finally obtained sodium chloride-containing crystal Two concentrates.Wherein, the evaporating temperature of 1st effective evaporator 1a is 86 DEG C, and pressure is -55.83kPa, evaporation capacity 1.08m3/ h；The evaporating temperature of 2nd effect evaporator 1b is 71 DEG C, and pressure is -77.40kPa, evaporation capacity 1.07m3/h；Triple effect evaporation The evaporating temperature of device 1c is 56 DEG C, and pressure is -89.56kPa, evaporation capacity 1.06m3/h.By the of the multi-effect evaporating device 1 The second steam containing ammonia evaporated in 1st effective evaporator 1a is passed through 2nd effect evaporator 1b and carries out heat exchange and obtain the second ammonia The second steam containing ammonia evaporated in 2nd effect evaporator 1b is passed through third effect evaporator 1c progress heat exchanges and obtained by water First ammonium hydroxide, in the second tank used for storing ammonia after above-mentioned second ammonium hydroxide is exchanged heat by the 4th heat-exchanger rig 34 with catalyst production waste water It is stored in 52.Heating steam (life steam i.e. commonly used in the art) is passed through in 1st effective evaporator 1a, heating steam exists The condensation water obtained after being condensed in 1st effective evaporator 1a is for configuring washing brine.Third effect evaporator 1c evaporate Two steam containing ammonia carry out third heat exchange with cold medium in third heat-exchanger rig 33 and obtain the second ammonium hydroxide, and in the second ammonium hydroxide It is stored in storage tank 52.The degree evaporated by the densitometer pair second being arranged on multi-effect evaporating device 1 is monitored, control second A concentration of 0.9693Y (63.1g/L) of sodium sulphate in concentrate.After first mother liquor evaporates in multi-effect evaporating device 1, final To the second concentrate of sodium chloride-containing crystal crystallize that (crystallization temperature is 55 DEG C, and crystallization time is in brilliant liquid collecting tank 53 30min) obtain the magma of sodium chloride-containing crystal.
The magma of sodium chloride-containing crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and is separated by solid-liquid separation, and is separated by solid-liquid separation 15.31m is obtained per hour3Contain NaCl 295.6g/L, Na2SO4 63.1g/L、NaOH2.0g/L、NH3The second of 0.13g/L Second mother liquor by the 7th circulating pump 77 is recycled to waste water import pipe and is mixed to get with catalyst production waste water and waited for by mother liquor Waste water is handled, gained solid sodium chloride is separated by solid-liquid separation and (obtains the sodium chloride crystalli-zation cake that water content is 14 mass % per hour 1293.73kg, the wherein content of sodium sulphate are 7.0 mass % or less) with the 295g/L chlorination equal with sodium chloride butt quality It is dry in drying machine after sodium solution elution, sodium chloride 1112.6kg (purity is 99.4 weight %) is obtained per hour, is washed To cleaning solution 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 2.53m of a concentration of 4.44 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 3.21m of a concentration of 0.072 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
In addition, the initial period of MVR evaporations, the steam for being 143.3 DEG C by temperature are started.
Embodiment 2
The processing of catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl71g/L, Na2SO4 132g/L、NH4Cl 16g/L、(NH4)2SO4The catalyst production waste water that 30.24g/L, pH are 7.0 is handled, and is obtained To pending waste water in the SO that contains4 2-And Cl-Molar ratio be 1：4.163.Heat exchange is carried out by the first heat-exchanger rig 31 The temperature of pending waste water is 64 DEG C afterwards, and the temperature by pending waste water after the progress heat exchange of the second heat-exchanger rig 32 is 102 ℃.The evaporation conditions of MVR vaporising devices 2 include：Temperature is 95 DEG C, and pressure is -36.36kPa, evaporation capacity 2.53m3/h.The The evaporation conditions of 1st effective evaporator 1a include：Temperature is 80 DEG C, and pressure is -65.87kPa, evaporation capacity 0.43m3/h；Second effect The evaporation conditions of evaporator 1b include：Temperature is 64 DEG C, and pressure is -84.0kPa, evaporation capacity 0.43m3/h；Triple effect evaporation The evaporation conditions of device 1c include：Temperature is 46 DEG C, and pressure is -94.33kPa, evaporation capacity 0.42m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 970.09kg of aqueous 15 mass % per hour, finally Obtain sodium sulphate 824.57kg per hour (purity is 99.5 weight %)；6.59m is obtained per hour3A concentration of NaCl 305.6g/ L、Na2SO455.15g/L、NaOH 1.15g/L、NH3The first mother liquor of 0.19g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 518.3kg that water content is 15 mass % per hour, It is final to obtain sodium chloride 440.5kg per hour (purity is 99.5 weight %)；5.42m is obtained per hour3A concentration of NaCl 292.6g/L、Na2SO467.4g/L、NaOH 1.4g/L、NH3The second mother liquor of 0.012g/L.
In the present embodiment, the ammonium hydroxide 4.26m of a concentration of 1.46 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.28m of a concentration of 0.095 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
Embodiment 3
The processing of catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl118g/L, Na2SO4 116g/L、NH4Cl 19g/L、(NH4)2SO4The catalyst production waste water that 18.99g/L, pH are 6.8 is handled, and is obtained To pending waste water in the SO that contains4 2-And Cl-Molar ratio be 1：6.419.Heat exchange is carried out by the first heat-exchanger rig 31 The temperature of pending waste water is 97 DEG C afterwards, and the temperature by pending waste water after the progress heat exchange of the second heat-exchanger rig 32 is 107 ℃.The evaporation conditions of MVR vaporising devices 2 include：Temperature is 100 DEG C, and pressure is -22.83kPa, evaporation capacity 3.52m3/h.The The evaporation conditions of 1st effective evaporator 1a include：Temperature is 86 DEG C, and pressure is -55.83kPa, evaporation capacity 0.667m3/h；Second The evaporation conditions of effect evaporator 1b include：Temperature is 71 DEG C, and pressure is -77.4kPa, evaporation capacity 0.666m3/h；Third effect is steamed The evaporation conditions of hair device 1c include：Temperature is 56 DEG C, and pressure is -89.56kPa, evaporation capacity 0.665m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 792.33kg of aqueous 14 mass % per hour, finally Obtain sodium sulphate 681.41kg per hour (purity is 99.5 weight %)；10.95m is obtained per hour3A concentration of NaCl 305.8g/L、Na2SO4 53.84g/L、NaOH 2.2g/L、NH3The first mother liquor of 0.099g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 817.22kg that water content is 14 mass % per hour, It is final to obtain sodium chloride 694.64kg per hour (purity is 99.4 weight %)；9.06m is obtained per hour3A concentration of NaCl 293.3g/L、Na2SO4 65g/L、NaOH 2.656g/L、NH3The second mother liquor of 0.0072g/L.
In the present embodiment, the ammonium hydroxide 3.515m of a concentration of 1.5 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.998m of a concentration of 0.051 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (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 sulfur acid sodium crystal First concentrate, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and obtained liquid is separated by solid-liquid separation by first It 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 sodium chloride-containing crystal is obtained in last 1st effective evaporator；
3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is more than 9；
First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；
Relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 14 moles with Under.
2. according to the method described in claim 1, wherein, the pending waste water is the catalyst production waste water；Alternatively, institute It is that the catalyst production waste water is mixed at least part of of liquid phase that second separation of solid and liquid obtains to state pending waste water Liquid；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 13.8 mole or less；
Preferably, 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 chloride in the first concentrate For X or less, wherein X is chlorination when sodium sulphate and sodium chloride reach saturation in the first concentrate under conditions of first evaporates The concentration of sodium；
Second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate, wherein Y is the item in the second evaporation Under part, the concentration of sodium sulphate when sodium sulphate and sodium chloride reach saturation in the second concentrate；
Preferably, first evaporation makes a concentration of 0.95X-0.999X of sodium chloride in the first concentrate；
Preferably, second evaporation makes a concentration of 0.9Y-0.99Y of sodium sulphate in second concentrate.
4. according to the method described in any one of claim 1-3, wherein it is described first evaporation condition include：Temperature is 45 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~365 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；
Preferably, the condition of first evaporation includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；
Preferably, the condition of first evaporation includes：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
5. according to the method described in any one of claim 1-3, wherein it is described second evaporation condition include：Temperature is 30 DEG C~85 DEG C, pressure is -98kPa~-58kPa；
Preferably, the condition of second evaporation includes：Temperature is 35 DEG C~60 DEG C, and pressure is -97.5kPa~-87kPa.
Preferably, the condition of second evaporation includes：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~56 DEG C, and pressure is -95kPa~-89kPa.
6. according to the method described in claim 5, wherein, in the second evaporation, the evaporating temperature of preceding 1st effective evaporator is than latter effect High 5 DEG C of evaporator or more is preferably 5 DEG C high~30 DEG C.
7. method according to claim 4 or 5, wherein the temperature of first evaporation is 5 DEG C higher than the temperature of the second evaporation More than, it is preferably high 20 DEG C or more, more preferably 35 DEG C high~70 DEG C.
8. according to the method described in claim 1, wherein, after the second steam containing ammonia that preceding 1st effective evaporator is evaporated is sent into The second heat exchange is carried out with first concentrate and obtain the second ammonium hydroxide in 1st effective evaporator, first concentrate and described The second cocurrent heat exchange of steam containing ammonia；
Preferably, before the pending waste water is passed through MVR vaporising devices, first steam containing ammonia is waited locating with described Reason waste water carries out the first heat exchange and obtains the first ammonium hydroxide；
Preferably, before 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, the steam containing ammonia that last 1st effective evaporator generates is in third heat-exchanger rig Middle progress third heat exchange simultaneously obtains the second ammonium hydroxide；
Preferably, first steam containing ammonia is condensed into remaining tail gas by first heat exchange and last effect is steamed The second steam containing ammonia that hair device evaporates condenses remaining tail gas by the third heat exchange and is discharged after removing ammonia.
10. according to the method described in any one of claim 1-9, this method further includes by the of the sulfur acid sodium crystal One concentrate obtains sodium sulfate crystal after first is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium sulfate crystal.
11. according to the method described in any one of claim 1-9, this method further includes crystallizing second concentrate Crystallization obtains the magma of sodium chloride-containing crystal in device, and by the magma of the sodium chloride-containing crystal after second is separated by solid-liquid separation Obtain sodium chloride crystal；
Preferably, this method further includes being washed to obtaining sodium chloride 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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