CN108726755A - 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
CN108726755A
CN108726755A CN201710263235.3A CN201710263235A CN108726755A CN 108726755 A CN108726755 A CN 108726755A CN 201710263235 A CN201710263235 A CN 201710263235A CN 108726755 A CN108726755 A CN 108726755A
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China
Prior art keywords
waste water
evaporation
temperature
sodium chloride
sodium
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CN201710263235.3A
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Chinese (zh)
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CN108726755B (en
Inventor
殷喜平
李叶
苑志伟
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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

Abstract

The present invention relates to sewage treatment fields, disclose a kind of processing method of 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 the first MVR vaporising devices carries out the first evaporation and obtain the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal, the pending waste water contains 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 the liquid phase that the first separation of solid and liquid obtains is passed through the second evaporation of progress in the 2nd MVR vaporising devices and obtains the second concentrate of the second steam containing ammonia and sodium chloride-containing crystal；3) the second concentrate of the sodium chloride-containing crystal second is carried out to be separated by solid-liquid separation.Ammonium and sodium sulphate, sodium chloride in waste water can be separately recovered in this method, farthest recycle the resource in waste water.

Description

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 the first MVR vaporising devices progress and obtains the first steam containing ammonia and sulfur acid First concentrate of sodium 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 in the 2nd MVR vaporising devices and carry out the second evaporation and obtain the second steam containing ammonia and the second of sodium chloride-containing crystal dense Contracting liquid；
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 the first MVR vaporising devices, the pH of the pending waste water is adjusted Value is more than 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；Relative to 1 The SO contained in mole 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, the first MVR vaporising devices is recycled to be evaporated isolated sodium sulfate crystal and dense ammonia Then water recycles the 2nd MVR vaporising devices to be evaporated to obtain sodium chloride crystal and weak aqua ammonia again.This method can be distinguished The sodium sulphate and sodium chloride of high-purity are obtained, the difficulty during avoiding mixed salt processing and recycling is completed at the same time separation of ammonia With the process of salt, and using heat exchange method simultaneously make waste water heat up and steam cooling containing ammonia, be not necessarily to condenser, rationally utilization Heat in evaporation process, it is energy saving, cost for wastewater treatment is reduced, the ammonium in waste water is recycled in the form of ammonium hydroxide, sodium chloride It is recycled respectively with crystal form with sodium sulphate, whole process does not have waste residue and liquid generation, realizes the purpose to turn waste into wealth.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of the wastewater treatment method of embodiment provided by the invention.
Reference sign
1, the 2nd MVR vaporising devices 2, the first 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
4, vacuum receiver 51, the first tank used for storing ammonia
52, the second tank used for storing ammonia 53, the first mother liquor tank
54, the second mother liquor tank 61, the first pH value measuring device
62, the second pH value measuring device 71, first circulation pump
72, second circulation pump 73, third circulating pump
74, the 4th circulating pump 75, the 5th circulating pump
76, the 6th circulating pump 77, the 7th circulating pump
78, the 8th circulating pump 79, the 9th circulating pump
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 101, the first compressor
102, the second compressor
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Below in conjunction with Fig. 1, 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 the first evaporation of the first MVR vaporising devices progress and obtains the first steam containing ammonia and sulfur acid First concentrate of sodium 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 in the 2nd MVR vaporising devices and carry out the second evaporation and obtain the second steam containing ammonia and the second of sodium chloride-containing crystal dense Contracting liquid；
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 the first MVR vaporising devices, the pH of the pending waste water is adjusted Value is more than 9；First evaporation makes sodium chloride not crystallize precipitation, and second evaporation makes sodium sulphate not crystallize precipitation；Relative to 1 The SO contained in mole 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 the first MVR vaporising devices 2, the pending waste water is adjusted PH value be 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, Preferably 13.5 hereinafter, more preferable 13 or less.
Method provided by the invention, which can be directed to, contains NH4 +、SO4 2-、Cl-And Na+Waste water handled, in addition to containing NH4 +、SO4 2-、Cl-And Na+Outside, to the pending waste water, there is no particular limitation.From the angle for the treatment effeciency for improving waste water Consider, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It rubs for 13.8 You hereinafter, 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 4-10 moles.It is logical It crosses SO4 2-And Cl-Molar ratio control above range and combine aftermentioned evaporation conditions, sulfuric acid in the first evaporation can be made Sodium 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, in the present invention In and can also thus come in pending waste water by the second Recycling Mother Solution obtained in the second evaporation process to the first evaporation SO4 2-And Cl-Molar ratio be adjusted, and the balance of sodium hydroxide can be maintained.
In the present invention, first evaporation makes sodium chloride not crystallize precipitation, refers to that the sodium chloride of control mixed system is dense Degree is no more than the solubility under the first evaporation conditions (including but not limited to temperature, pH value etc.), but sulfate crystal is not precluded The sodium chloride of entrainment or adsorption.Since the water content of crystal after separation of solid and liquid is different, in the sodium sulfate crystal generally yielded The content of sodium chloride (preferably 4 mass % or less) below 8 mass %, in the present invention, chlorine in obtained sodium sulfate crystal It can think that sodium chloride does not crystallize precipitation when changing the content of sodium below 8 mass %.
In the present invention, second evaporation makes sodium sulphate not crystallize precipitation, refers to that the sodium sulphate of control mixed system is dense Degree is no more than the solubility under the second evaporation conditions (including but not limited to temperature, pH value etc.), it is not excluded that sodium chloride crystallization folder The sodium sulphate of band or adsorption.Since the water content of crystal after separation of solid and liquid is different, sulphur in the sodium chloride crystal generally yielded The content of sour sodium (preferably 4 mass % or less) below 8 mass %, in the present invention, sulfuric acid in obtained sodium chloride crystal It can think that sodium sulphate does not crystallize precipitation when the content of sodium is below 8 mass %.
In the present invention, it is to be understood that first steam containing ammonia and second steam containing ammonia are this field So-called indirect steam.The pressure is the pressure in terms of gauge pressure.
In the present invention, there is no particular limitation for the first 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, MVR-FC continuous crystallisations It is one or more in evaporator, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced-circulation evaporators, MVR- FC continuous crystallisation evaporators, 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 Ground, it is described first evaporation condition include：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；Further preferably Ground, it is described first evaporation condition include：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；It is particularly preferred that It is described first evaporation condition include：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
In the present invention, the operating pressure of the first evaporation is more preferably the saturated vapor pressure of evaporated feed liquid.
In the present invention, the flow of the first evaporation can suitably be selected according to the ability that equipment is handled, such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sulfate crystal by making the first evaporation carry out under these conditions, sodium chloride is not tied Partial crystallization goes out, the purity for the sodium sulfate crystal that thereby may be ensured that.
It can be evaporated described pending useless according to the present invention by controlling the evaporation conditions of the first MVR vaporising devices 2 The 90 mass % or more (preferably 95 mass % or more) of contained ammonia in water, the first ammonium hydroxide can be with direct reuse in the life of catalyst Production process 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 MVR vaporising devices complete.
The pending waste water is passed through the first MVR vaporising devices 2 by a preferred embodiment according to the present invention Before, first steam containing ammonia is subjected to the first heat exchange with the pending waste water and obtains the first ammonium hydroxide.First heat There is no particular limitation for the mode of exchange, and the heat exchange mode that this field routine may be used carries out.Time of first heat exchange Number can be 1 time or more, preferably 2-4 times, more preferably 2-3 times.After first heat exchange, the ammonium hydroxide of output is cold But, 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 first MVR vaporising devices 2 is led to successively The second heat-exchanger rig 32 and the first heat-exchanger rig 31 are crossed, and the pending waste water is passed sequentially through into the first heat-exchanger rig 31 and Two heat-exchanger rigs 32 carry out first heat exchange by first steam containing ammonia and the pending waste water, make pending Waste water heating is convenient for evaporating, while the first steam cooling containing ammonia being made to obtain the first ammonium hydroxide, and the first ammonium hydroxide can be stored in the In one tank used for storing ammonia 51.
In the present invention, for first heat-exchanger rig, 31 and second heat-exchanger rig 32, there is no particular limitation, can be with Using various heat exchangers commonly used in the art, reaches first steam containing ammonia and the pending waste water and carry out described the The purpose of one heat exchange.Specifically, can be jacketed type exchanger, plate heat exchanger, shell-and-tube heat exchanger etc., wherein excellent It is selected as plate heat exchanger.The material of the heat exchanger can be specifically chosen as needed, such as in order to resist chloride ion corrosion, can To select material as two phase stainless steel, the heat exchanger of titanium or titanium alloy, Hastelloy, can be selected containing plastics when temperature is relatively low The heat exchanger of material.
A preferred embodiment according to the present invention, by first steam containing ammonia in the first heat-exchanger rig 31 Condensation water carries out the first heat exchange with the pending waste water, by first steam containing ammonia and institute in the second heat-exchanger rig 32 It states pending waste water and carries out the first heat exchange.
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.
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 in the first MVR vaporising devices 2 into Row, before the catalyst production waste water to be sent into the first heat-exchanger rig 31 and carries out the first heat exchange, by being urged by described Change agent production waste water and is sent into the aqueous solution containing alkaline matter of importing in the pipeline of the first heat-exchanger rig 31 and mixing, into Row first time pH value is adjusted；Then the catalyst production waste water and second are separated by solid-liquid separation at least partly mixed of obtained liquid phase Conjunction obtains pending waste water, then the pending waste water is sent into the second heat-exchanger rig 32 and carries out the first heat exchange, and by institute It states pending waste water and is sent into the aqueous solution containing alkaline matter of importing in the pipeline of the second heat-exchanger rig 32 and mixing, into Second of pH value of row is adjusted.It is adjusted by pH value twice, makes the pending waste water before being passed through the first MVR vaporising devices 2 PH value be more than 9, preferably greater than 10.8.Preferably, first time pH value is adjusted so that the pH value of the waste water after adjusting is big In 7 (preferably 7-9), second of pH value adjusts so that the pH value of the pending waste water is more than 9, preferably greater than 10.8 It can.
In order to detect above-mentioned first time pH value adjust and second of pH value adjust after pH value, preferably by the catalyst Production waste water, which is sent on the pipeline of the first heat-exchanger rig 31, is arranged the first pH value measuring device 61 to measure the adjusting of first time pH value The second pH value measuring device 62 is arranged the pending waste water to be sent on the pipeline of the second heat-exchanger rig 32 in pH value afterwards Measure the pH value after second of pH value is adjusted.
In the present invention, in order to improve the solid content in the first MVR vaporising devices 2, the ammonia reduced in liquid contains Amount, preferably by the partially liq after the first MVR vaporising devices 2 evaporation (namely inside the first MVR vaporising devices Liquid, also referred to as first circulation liquid hereinafter) flow back into the first MVR vaporising devices 2 after heating and evaporate again.It is above-mentioned will The process that partially liq after the first MVR vaporising devices 2 evaporation flows back into the first MVR vaporising devices 2 is preferred For by the first circulation liquid and the pending waste water after the adjusting of first time pH value and before being adjusted to second of pH value It is re-fed into after mixing into the first MVR vaporising devices 2, returns the first circulation liquid for example, 72 can be pumped by second circulation It mixes with pending waste water in the waste water conveyance conduit returned between the first heat-exchanger rig 31 and the second heat-exchanger rig 32, then exists After being adjusted by second of pH value, heat exchange is carried out in the second heat-exchanger rig 32, is finally sent into the first MVR evaporations In device 2.The MVR vaporising devices 2 are flowed back into as by the partially liq after the first MVR vaporising devices 2 evaporation Ratio be not particularly limited, for example, it is described first evaporation the first reflux ratio can be 10-200, preferably 50-100. Here, first reflux ratio refers to：Regurgitant volume subtracts regurgitant volume with the total amount of liquid being sent into the first MVR vaporising devices 2 Ratio.
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 the first compressor 101.By to described First steam containing ammonia is compressed, and to input energy in MVR vapo(u)rization systems, ensures that the process of waste water heating-evaporation-cooling is continuous It carries out, needs to input when MVR evaporation processes start and start steam, reach after continuously running state only by the first compressor 101 Energy supply, it is no longer necessary to input other energy.Various compressions commonly used in the art may be used in first compressor 101 Machine, such as centrifugal blower, turbocompressor or lobed rotor compressor etc..After first compressor 101 compression, described first The temperature of the 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 (i.e. first is separated by solid-liquid separation obtained liquid phase).There is no particular limitation for described first method being separated by solid-liquid separation, Such as it can be selected from one or more in centrifugation, filtering, sedimentation.
According to the present invention, 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 the first mother liquor tank 53, and can be sent into the 2nd MVR vaporising devices 1 by the 6th circulating pump 76 and be carried out second Evaporation.In addition, being difficult to avoid that adsorb certain chlorion, free ammonia, hydroxide ion etc. miscellaneous on obtained sodium sulfate crystal Matter reduces the peculiar smell of solid salt to remove the impurity of absorption, reduces corrosivity, improves the purity of the crystal, it is preferable that Sodium sulfate crystal water, the catalyst production waste water or metabisulfite solution carry out the first washing and drying.
It is separated by solid-liquid separation the mode washed with first as above-mentioned first, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.First washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, Ke Yitong The method for crossing this field routine carries out.There is no particular limitation for the number of the elutriation and elution, can be 1 time or more, in order to Obtain the sodium sulfate crystal of higher purity, preferably 2-4 times.During elutriation, use the catalyst production waste water as elutriation It does not recycle generally when liquid, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the first washing recycling.Carry out institute Before stating elutriation, carry out tentatively being separated by solid-liquid separation the slurries for obtaining sulfur acid sodium crystal that (content liquid is preferably by way of sedimentation 35 mass % or less, the step preferably carry out in the device well known in the art such as settling tank, settling tank).Elutriation process In, relative to the slurries of 1 parts by weight sulfur acid sodium crystal, it is 1~20 parts by weight to eluriate the liquid used.In addition, elution is preferred It is carried out using aqueous sodium persulfate solution.Preferably, the concentration of the aqueous sodium persulfate solution is preferably right in sodium sulfate crystal to be washed institute Sodium chloride and sodium sulphate while reaching the concentration of sodium sulphate in the aqueous solution of saturation at a temperature of answering.In order to further increase elutriation Effect obtains the higher sodium sulfate crystal of purity, in the case of preferred, the liquid that elution obtains can be used to carry out above-mentioned wash in a pan It washes, it is preferable to use water or metabisulfite solution.For the liquid that washing generates, the steaming of the first MVR vaporising devices is preferably returned it to Before second of pH value before hair is adjusted, such as pass through the 5th circulating pump 75 the second heat-exchanger rig 32 of return.
A preferred embodiment according to the present invention contains sulfuric acid by what the evaporation of the first MVR vaporising devices 2 obtained First concentrate of sodium is carried out with the catalyst production waste water in eluriating tank after settling progress tentatively separation of solid and liquid It eluriates for the first time, then reuses the liquid obtained when subsequent wash sodium sulfate crystal and carried out second in another elutriation tank It eluriates, finally will be sent into equipment for separating liquid from solid by the slurries eluriated twice is separated by solid-liquid separation, the crystal being separated by solid-liquid separation During the liquid for being eluted again with aqueous sodium persulfate solution, and elution being obtained is eluriated back to second.By above-mentioned washed Journey, the purity of the sodium sulfate crystal not only made improve, and will not be excessive introducing cleaning solution, improve the effect of wastewater treatment Rate.
In the present invention, there is no particular limitation for the 2nd MVR vaporising devices 1, 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, MVR-FC continuous crystallisations It is one or more in evaporator, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced-circulation evaporators, MVR- FC continuous crystallisation evaporators, more preferably falling liquid film+forced circulation two-stage MVR crystallizing evaporators.
In the present invention, the evaporation conditions of second evaporation can be selected suitably as needed, and reaching makes sodium chloride knot Partial crystallization goes out and purpose that sodium sulphate is not precipitated.It is described second evaporation condition may include：Temperature is 30 DEG C~85 DEG C, pressure Power is -98kPa~-58kPa.In order to improve evaporation efficiency, it is preferable that it is described second evaporation condition include：Temperature is 35 DEG C ~60 DEG C, pressure is -97.5kPa~-87kPa；Preferably, the condition of second evaporation includes：Temperature is 40 DEG C~60 DEG C, Pressure is -97kPa~-87kPa；Preferably, the condition of second evaporation includes：Temperature be 45 DEG C~60 DEG C, pressure be- 95kPa~-87kP；Preferably, the condition of second evaporation includes：Temperature be 45 DEG C~55 DEG C, pressure be -95kPa~- 90kPa。
In the present invention, the operating pressure of the second evaporation is more preferably the saturated vapor pressure of evaporated feed liquid.
In addition, ability and pending wastewater flow rate that the evaporation capacity of the second evaporation can be handled according to equipment suitably select, Such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sodium chloride crystallization by making the second evaporation carry out under these conditions, sodium sulphate is not tied Crystalline substance, the purity for the sodium chloride crystal that thereby may be ensured that.
According to the present invention, second evaporation is not so that (i.e. sulfuric acid is precipitated in the sulfate crystal in second concentrate Sodium is not up to supersaturation), it is preferable that second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate (preferably For 0.9Y-0.99Y, more preferably 0.95Y-0.98Y), wherein Y is the sulfuric acid in the second concentrate under conditions of second evaporates The concentration of sodium sulphate when sodium and sodium chloride reach saturation.By by the extent control of the second evaporation within the above range, can be with It is precipitated sodium chloride crystallization as much as possible under conditions of ensureing that sodium sulphate is not precipitated.By making chlorine in the second evaporation as possible Change sodium crystallization, waste water treatment efficiency can be improved, reduces energy waste.
In the present invention, the carry out degree of second evaporation is in such a way that the second evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the second evaporation of control makes the second evaporation not make described second in above range Sulfate crystal in concentrate is precipitated.Here the second evaporation obtains the concentration of liquid, is supervised by way of measuring density It surveys, can specifically densitometer be used to carry out density measure.
According to the present invention, the second steam containing ammonia that the 2nd MVR vaporising devices 1 evaporation obtains is produced with the catalyst Waste water carries out the second heat exchange and obtains the second ammonium hydroxide；Preferably, the 2nd MVR vaporising devices 1 evaporate second obtained and contain Ammonia steam carries out the second heat exchange with cleaning solution, the catalyst production waste water after the second separation of solid and liquid successively and obtains second Ammonium hydroxide.There is no particular limitation for the mode of second heat exchange, and the heat exchange mode that this field routine may be used carries out.It is described The number of heat exchange can be preferably 2-4 times, more preferably 2-3 times, particularly preferably 2 times more than primary.Pass through the heat It exchanges, the ammonium hydroxide of output is cooled, and heat utmostly recycles inside processing unit, and the energy is rationally utilized, and reduces wave Take.It is mixed to be separated by solid-liquid separation obtained liquid phase with first after second heat exchange for cleaning solution after second separation of solid and liquid Close, mixed fluid temperature be 35 DEG C~92 DEG C, more preferably 40 DEG C~67 DEG C, further preferably 45 DEG C~67 DEG C, more Further preferably 50 DEG C~67 DEG C.
A preferred embodiment according to the present invention, second heat exchange pass through third heat-exchanger rig 33 and the 4th Heat-exchanger rig 34 carries out, and specifically, the second steam containing ammonia is passed sequentially through the 4th heat-exchanger rig 34 and third heat-exchanger rig 33, Make in 4th heat-exchanger rig 34 cleaning solution after second separation of solid and liquid and aftermentioned second circulation liquid and second steam containing ammonia into The second heat exchange of row makes the part catalyst production waste water and the second steam containing ammonia pass through the 4th in third heat-exchanger rig 33 Heat-exchanger rig 34 condenses the second obtained liquid of steam condensation containing ammonia and carries out the second heat exchange, and it is solidifying to further decrease the second steam containing ammonia The temperature of liquid is tied, heat utilization rate is improved, obtains the second ammonium hydroxide, second ammonium hydroxide can be stored in the second tank used for storing ammonia 52 In.
In the present invention, in order to improve the solid content in the 2nd MVR vaporising devices 1, the ammonia reduced in liquid contains Amount, preferably by the partially liq after the 2nd MVR vaporising devices 1 evaporation (namely in the 2nd MVR vaporising devices 1 The liquid in portion, also referred to as second circulation liquid) it flows back into the 2nd MVR vaporising devices 1.It is above-mentioned to pass through the 2nd MVR It is preferably the first mother liquor and institute that partially liq after the evaporation of vaporising device 1, which flows back into the process of the 2nd MVR vaporising devices 1, Second circulation liquid and the mixing of the second leacheate are stated, then the second heat exchange is carried out with the second steam containing ammonia.For example, can pass through respectively The second circulation liquid and the second cleaning solution are sent into the 4th by the 7th circulating pump 77 and the 9th circulating pump 79 after mixing in the duct Heat-exchanger rig 34 carries out the second heat exchange, is then mixed and fed into the 2nd MVR vaporising devices 1 with the first mother liquor.As will pass through The ratio that the partially liq of 2nd MVR vaporising devices 1 evaporation flows back into the 2nd MVR vaporising devices 1 is not special Limitation, for example, the second reflux ratio of second evaporation can be 0.1-50, preferably 7-25.Here, second reflux ratio Refer to：Regurgitant volume subtracts the ratio of regurgitant volume with the total amount of liquid being sent into the 2nd MVR vaporising devices 1.
In the case of, according to the invention it is preferred to, the method further include after second steam containing ammonia is compressed again Carry out second heat exchange.The compression of second steam containing ammonia can be carried out by the second compressor 102.By to described Second steam containing ammonia is compressed, and to input energy in MVR vapo(u)rization systems, ensures that the process of waste water heating-evaporation-cooling is continuous It carries out, needs to input when MVR evaporation processes start and start steam, reach after continuously running state only by the second compressor 102 Energy supply, it is no longer necessary to input other energy.Various compressions commonly used in the art may be used in second compressor 102 Machine, such as centrifugal blower, turbocompressor or lobed rotor compressor etc..After second compressor 102 compression, described second The temperature of the steam containing ammonia increases 5 DEG C~20 DEG C.
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：Temperature of the temperature of first evaporation than the second evaporation Degree is at least 5 DEG C high, preferably 20 DEG C high, more preferably 35 DEG C high~70 DEG C, particularly preferably 40 DEG C high~60 DEG C.It is steamed by control first It sends out and the second evaporation carries out at different temperature, so that the crystallization respectively of sodium sulphate and sodium chloride is precipitated, obtained to raising The purity of sodium sulphate and sodium chloride crystal.
A preferred embodiment according to the present invention, second evaporation process in the 2nd MVR vaporising devices 1 into Row.First mother liquor is passed through in the 2nd MVR vaporising devices 1 by the 6th circulating pump 76 and carries out the second evaporation and obtains the Second concentrate of two steam containing ammonia and sodium chloride-containing crystal.
In the present invention, the second concentrate of the sodium chloride-containing crystal obtains sodium chloride crystalline substance after second is separated by solid-liquid separation Body and the second mother liquor (namely described second is separated by solid-liquid separation obtained liquid phase).The method of second separation of solid and liquid is not special Restriction, such as can be selected from one or more in centrifugation, filtering and sedimentation.
According to the present invention, second separation of solid and liquid can (be, for example, centrifuge, belt by the second equipment for separating liquid from solid Filter, flame filter press etc.) 92 progress.After described second is separated by solid-liquid separation, the second equipment for separating liquid from solid 92 obtains second female Liquid (namely described second is separated by solid-liquid separation obtained liquid phase) returns to the first MVR vaporising devices 2 and carries out the first evaporation again, specifically After second mother liquor being adjusted back to first time pH value by the 8th circulating pump 78 and second pH value adjust before with The catalyst production waste water is mixed to get the pending waste water, is then fed into and carries out first into the first MVR vaporising devices 2 Evaporation.In addition, certain sulfate ion, free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on obtained sodium chloride crystal Equal impurity reduce the peculiar smell of solid salt to remove the impurity of absorption, reduce corrosivity, improve the purity of the crystal, preferably Ground, sodium chloride crystal water, the catalyst production waste water or sodium chloride solution carry out the second washing and drying.In order to keep away It is disposable wash during sodium chloride crystal dissolving, it is preferable that the sodium chloride crystal is washed with sodium-chloride water solution.It is more excellent Selection of land, the concentration of the sodium-chloride water solution be preferably at the temperature corresponding to sodium chloride crystal to be washed sodium chloride and sodium sulphate it is same When reach the concentration of sodium chloride in the aqueous solution of saturation.
It is separated by solid-liquid separation the mode washed with second as above-mentioned second, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.Preferably, second washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, It can be carried out by the method for this field routine.It is described elutriation and elution number there is no particular limitation, can be 1 time with On, the sodium chloride crystal of higher purity, preferably 2-4 times in order to obtain.During elutriation, made with the catalyst production waste water It does not recycle generally when liquid to eluriate, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the second washing recycling. Before carrying out the elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (liquid of sodium chloride-containing crystal Content is 35 mass % or less, which preferably carries out in the device well known in the art such as settling tank, settling tank).It washes in a pan During washing, relative to the slurries of 1 parts by weight sodium chloride-containing crystal, it is 1-20 parts by weight to eluriate the liquid used.Elution is preferred Using sodium-chloride water solution, (concentration of the sodium-chloride water solution is preferably chlorination at the temperature corresponding to sodium chloride crystal to be washed Sodium and sodium sulphate reach the concentration of sodium chloride in the aqueous solution of saturation simultaneously) it carries out.In order to further increase the effect of elutriation, obtain To the higher sodium chloride crystal of purity, in the case of preferred, the liquid that elution obtains can be used to carry out above-mentioned elutriation.For washing Wash the liquid of generation, it is preferable that the catalyst production waste water eluriates that liquid is back to before the evaporation of the first MVR vaporising devices 2 Before secondary pH value is adjusted, other cleaning solutions are back to the 2nd MVR vaporising devices 1, such as return to the by the 9th circulating pump 79 Two MVR vaporising devices 1 carry out the second evaporation again.
A preferred embodiment according to the present invention, by the second concentration of the sodium chloride-containing crystal that crystallization obtains Liquid carries out first time elutriation, so with the catalyst production waste water after settling progress tentatively separation of solid and liquid in eluriating tank The liquid that is obtained when subsequent wash sodium chloride crystal is reused afterwards carry out second in another elutriation tank eluriate, it finally will be through Equipment for separating liquid from solid is sent into after the slurries eluriated twice to be separated by solid-liquid separation, the crystal being separated by solid-liquid separation uses aqueous sodium chloride again (sodium chloride and sodium sulphate reach liquid simultaneously at a concentration of temperature corresponding to sodium chloride crystal to be washed of the sodium-chloride water solution The concentration of sodium chloride in the aqueous solution of saturation) it is eluted, and conduct during obtained liquid is eluriated back to second will be eluted Eluriate liquid.The purity of the washing process combined by above-mentioned elutriation and elution, the sodium chloride crystal not only made improves, and Introducing cleaning solution that will not be excessive, 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 of remaining tail gas i.e. the 4th heat-exchanger rig 34 discharge 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.It, specifically can be with as the waste water of the present invention For the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process, can also be will be from molecular sieve, aluminium oxide or refining The waste water of oily catalyst production process carries out the waste water after following removal of impurities and concentration.Preferably will come from molecular sieve, aluminium oxide or The waste water of oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.
As the NH in the catalyst production waste water4 +Can be 8mg/L or more, preferably 300mg/L or more.
As the Na in the catalyst production waste water+Can be 510mg/L or more, preferably 1000mg/L or more, more Preferably 2000mg/L or more, further preferably 4000mg/L or more, further preferably 8000mg/L or more, it is further excellent It is selected as 16000mg/L or more, further preferably 32000mg/L or more, further preferably 40000mg/L or more, further Preferably 50000mg/L or more, further preferably 60000mg/L or more.
As the SO in the catalyst production waste water4 2-Can be 1000mg/L or more, preferably 2000mg/L or more, More preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, into one Step preferably 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L or more, into One step is preferably 60000mg/L or more, further preferably 70000mg/L or more.
As the Cl in the catalyst production waste water-Can be 970mg/L or more, more preferably 2000mg/L or more, Further preferably 4000mg/L or more, further preferably 8000mg/L or more, further preferably 16000mg/L or more, Further preferably 32000mg/L or more, further preferably 40000mg/L or more, further preferably 50000mg/L with On, further preferably 60000mg/L or more.
The NH contained in the catalyst production waste water4 +、SO4 2-、Cl-And Na+The upper limit there is no particular limitation.From useless Water is easy from the point of view of starting with, SO in waste water4 2-、Cl-And Na+Respectively 200g/L hereinafter, preferably 150g/L hereinafter, more excellent It is selected as 120g/L or less；NH in waste water4 +For 50g/L hereinafter, preferably 40g/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 6.2~6.8.
In addition, due to the COD of waste water may block up film in concentration, in evaporative crystallization when influence the purity and color and luster etc. of salt, The COD more fewer better (preferably 20mg/L is hereinafter, more preferably 10mg/L or less) of the 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.Certainly 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 described 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 (80g/L containing NaCl, Na2SO4 82g/L、NH4Cl 50g/L、(NH4)2SO452.1g/L, pH 6.8) with inlet amount it is 5m3The speed of/h is sent into vacuum receiver 4 and carries out vacuum outgas, is being sent to The sodium hydrate aqueous solution of a concentration of 45.16 mass % is imported in the pipeline of first heat-exchanger rig 31 (titanium alloy plate heat exchanger) First time pH value adjusting is carried out, and the pH value after adjusting is monitored by the first pH value measuring device 61 (pH meter) and (is measured Value is 7.5), the effluent part after the adjusting of the first pH value to be sent into the first heat-exchanger rigs 31 by first circulation pump 71, with First liquid of steam condensation containing ammonia of recycling, which carries out the first heat exchange, makes waste water be warming up to 98 DEG C, will be after the adjusting of the first pH value Another part waste water is sent into third heat-exchanger rig 33 by first circulation pump 71, and first is carried out with the condensation water of the second steam containing ammonia Heat exchange makes waste water be warming up to 48 DEG C, and above-mentioned two parts waste water is converged, and (is sent into speed with the second mother liquor of return 8.75m3/ h) it is mixed to get pending waste water and (measures the SO wherein contained4 2-And Cl-Molar ratio be 1：6.261) it after, will wait for Processing waste water, which is sent into the pipeline of the second heat-exchanger rig 32, to be imported the sodium hydrate aqueous solution of a concentration of 45.16 mass % and carries out the Secondary pH value is adjusted, and is monitored that (measured value is to the pH value after adjusting by the second pH value measuring device 62 (pH meter) 10.8) the first steam containing ammonia for, being then fed into the second heat-exchanger rig 32 (titanium alloy plate heat exchanger) and recycling carries out the first heat Exchange makes pending waste water be warming up to 107 DEG C, then the pending waste water after the first heat exchange is sent into the first MVR evaporation dresses It sets 2 (falling liquid films+forced circulation two-stage MVR crystallizing evaporators) to be evaporated, obtains the first steam containing ammonia and sulfur acid sodium crystal First concentrate.Wherein, the evaporation conditions of the first MVR vaporising devices 2 include：Temperature is 100 DEG C, and pressure is -22.82kPa, is steamed Hair amount is 3.92m3/h.Evaporate obtained the first steam containing ammonia after the first compressor 101 compresses (12 DEG C of temperature rise) according to Secondary to carry out heat exchange with pending waste water by the second heat-exchanger rig 32 and the first heat-exchanger rig 31, cooling obtains the first ammonium hydroxide, And it is stored in the first tank used for storing ammonia 51.In addition, in order to improve the solid content in the first MVR vaporising devices 2, by the first MVR Partially liq after being evaporated in vaporising device 2 is recycled to the second heat-exchanger rig as first circulation liquid by second circulation pump 72 32, it is then again introduced into the first MVR vaporising devices 2 and carries out the first evaporation (the first reflux ratio is 77.8).It is evaporated by the first MVR The degree that the densitometer pair first being arranged on device 2 evaporates is monitored, and sodium chloride is a concentration of in the first concentrate of control 0.9935X(306.2g/L)。
The first concentrate that the evaporation of above-mentioned first MVR vaporising devices 2 obtains is sent into the 91 (centrifugation of the first equipment for separating liquid from solid Machine) carry out first be separated by solid-liquid separation after, obtain 10.58m per hour3Contain NaCl 306.2g/L, Na2SO4 54.0g/L、NaOH 1.4g/L、NH3The first mother liquor of 0.27g/L is temporarily stored into the first mother liquor tank 53, is separated by solid-liquid separation gained solid sodium sulfate (per small When obtain the sulfate crystal filter cake 809.7kg of aqueous 15 mass %, wherein the content of sodium chloride is 6.9 mass % or less) use The metabisulfite solution of the 54g/L equal with sulfate crystal filter cake butt quality elutes, and sodium sulphate is obtained per hour after dry 688.25kg (purity is 99.7 weight %), cleaning solution is recycled to by the 5th circulating pump 75 into before the second heat-exchanger rig 32 It is mixed with waste water in pipeline, is then again introduced into the first MVR vaporising devices 2 and carries out the first evaporation.
Second evaporation process is in the 2nd MVR vaporising devices 1 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) It carries out.The first mother liquor in above-mentioned first mother liquor tank 53 is sent into the 2nd MVR vaporising devices 1 by the 6th circulating pump 76 and carries out the Two evaporations obtain the second concentrate of sodium chloride-containing crystal.Wherein, the evaporation conditions of the 2nd MVR vaporising devices 1 include：Temperature is 50 DEG C, pressure is -92.67kPa, evaporation capacity 1.95m3/h.It, will in order to improve the solid content in the 2nd MVR vaporising devices 1 The first mother liquor of part after being evaporated in 2nd MVR vaporising devices 1 is recycled to the as second circulation liquid by the 7th circulating pump 77 Four heat-exchanger rigs 34 and the second steam containing ammonia carry out heat exchange, are then again introduced into the 2nd MVR vaporising devices 1 and carry out the second evaporation (the second reflux ratio is 17.8).Evaporate the second obtained steam containing ammonia (temperature rise 12 after the compression of the second compressor 102 DEG C) pass sequentially through the 4th heat-exchanger rig 34 and third heat-exchanger rig 33 carry out heat exchange and it is cooling obtain the second ammonium hydroxide, and the It is stored in two tank used for storing ammonia 52.Part first after being evaporated in cleaning solution and the 2nd MVR vaporising devices 1 after second separation of solid and liquid After mother liquor is pumped out by the 9th circulating pump 79 and the 7th circulating pump 77 and is mixed in the duct respectively and by the 4th heat-exchanger rig 34 the second steam containing ammonia carries out heat exchange, the pending waste water in part and pass through third heat-exchanger rig that first circulation pump 71 conveys The condensation water of 33 the second steam containing ammonia carries out heat exchange.It is steamed by the densitometer pair second being arranged on the 2nd MVR vaporising devices 1 The degree of hair is monitored, and controls a concentration of 0.9702Y (65.3g/L) of sodium sulphate in the second concentrate.First mother liquor is After being evaporated in two MVR vaporising devices 1, the second concentrate containing sodium chloride crystal is obtained.
The second concentrate containing sodium chloride crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and is separated by solid-liquid separation, 8.75m is obtained per hour3Contain NaCl 293.8g/L, Na2SO4 65.3g/L、NaOH 1.7g/L、NH3The of 0.013g/L Two mother liquors, the second mother liquor are temporarily stored into the second mother liquor tank 54.Second mother liquor is recycled to second by the 8th circulating pump 78 Waste water import pipe before pH value is adjusted is mixed to get pending waste water with waste water, is separated by solid-liquid separation gained solid sodium chloride (per small When obtain water content be 14 mass % sodium chloride crystalli-zation cake 785.29kg, wherein the content of sodium sulphate be 7.1 mass % with Under) with after the 293.8g/L sodium chloride solutions elution equal with sodium chloride butt quality, drying, obtains per hour in drying machine Sodium chloride 675.35kg (purity be 99.4 weight %), the second cleaning solution washed are recycled to the by the 9th circulating pump 79 Two MVR vaporising devices 1.
In addition, the tail gas of vacuum receiver 4, the second heat-exchanger rig 32 and the discharge of the 4th heat-exchanger rig 34 passes through vacuum pump 81 It introduces tail gas absorber 83 to be absorbed, recirculated water is connected in tail gas absorber 83, the recirculated water is in the 4th circulating pump 74 It recycles in tail gas absorber 83 under effect, while being mended to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73 Add water, and add fresh water in circulating water pool 82, reduces by the temperature and ammonia content of 81 work water of vacuum pump.The tail gas It is further passed through dilute sulfuric acid in absorption tower 83, to absorb ammonia in tail gas etc..
In the present embodiment, the ammonium hydroxide 3.92m of a concentration of 3.53 mass % is obtained in the first tank used for storing ammonia 51 per hour3, The ammonium hydroxide 1.95m of a concentration of 0.144 mass % is obtained in second tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to molecular sieve Production process.
In addition, the initial period of MVR evaporations, the steam for being 143.3 DEG C by temperature are started.
Embodiment 2
The processing of waste water is carried out according to the method for embodiment 1, unlike：To containing NaCl 60g/L, Na2SO4 130g/L、 NH4Cl 15g/L、(NH4)2SO4The waste water that 33.0g/L, pH are 6.8 is handled, and is contained in obtained pending waste water SO4 2-And Cl-Molar ratio be 1：4.462.Temperature by waste water after the progress heat exchange of the first heat-exchanger rig 31 is 67 DEG C, is led to Cross the second heat-exchanger rig 32 carry out heat exchange after pending waste water temperature be 102 DEG C.The evaporation article of first MVR vaporising devices 2 Part includes：Temperature is 95 DEG C, and pressure is -36.36kPa, evaporation capacity 4.48m3/h.The evaporation conditions of 2nd MVR vaporising devices 1 Including：Temperature is 55 DEG C, and pressure is -90.15kPa, evaporation capacity 1.05m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 978.40kg of aqueous 15 mass % per hour, finally Obtain sodium sulphate 831.63kg per hour (purity is 99.3 weight %)；7.25m is obtained per hour3A concentration of NaCl 307.2g/ L、Na2SO4 54.5g/L、NaOH 1.8g/L、NH3The first mother liquor of 0.18g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake 444.79kg that water content is 15 mass % per hour, It is final to obtain sodium chloride 378.07kg per hour (purity is 99.5 weight %)；6.30m is obtained per hour3A concentration of NaCl 295.5g/L、Na2SO4 63.1g/L、NaOH 2.1g/L、NH3The second mother liquor of 0.01g/L.
In the present embodiment, the ammonium hydroxide 4.48m of a concentration of 1.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 1.05m of a concentration of 0.11 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
Embodiment 3
The processing of waste water is carried out according to the method for embodiment 1, unlike：To containing NaCl 160g/L, Na2SO4 55g/L、 NH4Cl 32g/L、(NH4)2SO4The waste water that 11.2g/L, pH are 6.2 is handled, and is contained in obtained pending waste water SO4 2-And Cl-Molar ratio be 1：9.249.Temperature by waste water after the progress heat exchange of the first heat-exchanger rig 31 is 73 DEG C, is led to Cross the second heat-exchanger rig 32 carry out heat exchange after pending waste water temperature be 112 DEG C.The evaporation article of first MVR vaporising devices 2 Part includes：Temperature is 105 DEG C, and pressure is -7.02kPa, evaporation capacity 2.63m3/h.The evaporation conditions of 2nd MVR vaporising devices 1 Including：Temperature is 45 DEG C, and pressure is -94.69kPa, evaporation capacity 2.86m3/h。
First equipment for separating liquid from solid 91 obtains the sulfate crystal filter cake 385.26kg of aqueous 14 mass % per hour, finally Obtain sodium sulphate 331.32kg per hour (purity is 99.4 weight %)；11.98m is obtained per hour3A concentration of NaCl 306.4g/L、Na2SO4 52.5g/L、NaOH 2.6g/L、NH3The first mother liquor of 0.11g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake that water content is 15 mass % per hour 1151.57kg finally obtains sodium chloride 978.83kg per hour (purity is 99.4 weight %)；9.18m is obtained per hour3Concentration For NaCl 291.2g/L, Na2SO4 67.9g/L、NaOH 3.4g/L、NH3The second mother liquor of 0.0084g/L.
In the present embodiment, the ammonium hydroxide 2.63m of a concentration of 2.3 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 2.86m of a concentration of 0.043 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the life of molecular sieve Production process.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (11)

1. a kind of processing method of 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) pending waste water is passed through the first evaporation of the first 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 obtained liquid is separated by solid-liquid separation by first It is mutually passed through the second evaporation of progress in the 2nd MVR vaporising devices and obtains the second concentration of the second steam containing ammonia and sodium chloride-containing crystal Liquid；
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 the first 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 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 State the liquid phase that pending waste water contains the catalyst production waste water and second separation of solid and liquid obtains；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 13.8 mole or less；
Preferably, before the pending waste water is passed through the first MVR vaporising devices, the pH value of the pending waste water is adjusted More than 10.8；
Preferably, the pH value for adjusting the pending waste water is carried out using NaOH.
3. method according to claim 1 or 2, wherein first evaporation makes the concentration of sodium chloride in the first concentrate For X or less, wherein X is chlorination when sodium sulphate and sodium chloride reach saturation in the first concentrate under conditions of first evaporates The concentration of sodium；
Preferably, second evaporation makes a concentration of Y or less of sodium sulphate in second concentrate, wherein Y is to be steamed second Under conditions of hair, the concentration of sodium sulphate when sodium sulphate and sodium chloride reach saturation in the second concentrate；
Preferably, first evaporation makes a concentration of 0.95X-0.999X of sodium chloride in the first concentrate,
Preferably, second evaporation makes a concentration of 0.9Y-0.99Y of sodium sulphate in second concentrate.
4. according to the method described in any one of claim 1-3, wherein it is described first evaporation condition include：Temperature is 45 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~365 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；
Preferably, the condition of first evaporation includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；
Preferably, the condition of first evaporation includes：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.
5. according to the method described in any one of claim 1-3, wherein it is described second evaporation condition include：Temperature is 30 DEG C~85 DEG C, pressure is -98kPa~-58kPa；
Preferably, the condition of second evaporation includes：Temperature is 35 DEG C~60 DEG C, and pressure is -97.5kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 40 DEG C~60 DEG C, and pressure is -97kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~60 DEG C, and pressure is -95kPa~-87kPa；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~55 DEG C, and pressure is -95kPa~-90kPa.
6. method according to claim 4 or 5, wherein the temperature of first evaporation is 5 DEG C higher than the temperature of the second evaporation More than；
Preferably, temperature high 20 DEG C or more of the temperature of first evaporation than the second evaporation；
Preferably, it is described first evaporation temperature than second evaporation temperature it is 35 DEG C high~70 DEG C；
Preferably, it is described first evaporation temperature than second evaporation temperature it is 40 DEG C high~60 DEG C.
7. according to the method described in claim 1, wherein, before the pending waste water is passed through the first MVR vaporising devices, First steam containing ammonia is subjected to the first heat exchange with the pending waste water and obtains the first ammonium hydroxide；
Preferably, before carrying out first heat exchange, the pH value for adjusting the pending waste water is more than 7.
8. according to the method described in claim 1, wherein, second steam containing ammonia and the pending waste water are carried out second Heat exchange simultaneously obtains the second ammonium hydroxide.
9. according to the method described in any one of claim 1-8, this method further includes by the of the sulfur acid sodium crystal One concentrate obtains sodium sulfate crystal after first is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium sulfate crystal.
10. according to the method described in any one of claim 1-8, this method further includes by the of the sodium chloride-containing crystal Two concentrates obtain sodium chloride crystal after second is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtaining sodium chloride crystal.
11. according to the method described in any one of claim 1-8, wherein NH in the 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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CN103172088A (en) * 2013-04-11 2013-06-26 南风化工集团股份有限公司 Application of MVR (mechanical vapor recompression) crystallizing evaporator in sodium sulfate and sodium chloride separation technology
CN105036222A (en) * 2015-08-19 2015-11-11 石家庄工大化工设备有限公司 High-salinity wastewater recovery treatment method
CN105110536A (en) * 2015-08-19 2015-12-02 石家庄工大化工设备有限公司 Recycling method for high-salinity wastewater containing sodium chloride and sodium sulfate

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Publication number Priority date Publication date Assignee Title
CN1944256A (en) * 2006-10-25 2007-04-11 中国中轻国际工程有限公司 Process for producing sodium sulfate and sodium chloride in Na2SO4-NaCl-H2O system
CN103172088A (en) * 2013-04-11 2013-06-26 南风化工集团股份有限公司 Application of MVR (mechanical vapor recompression) crystallizing evaporator in sodium sulfate and sodium chloride separation technology
CN105036222A (en) * 2015-08-19 2015-11-11 石家庄工大化工设备有限公司 High-salinity wastewater recovery treatment method
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