CN109422401A - The processing method of catalyst production waste water - Google Patents

The processing method of catalyst production waste water Download PDF

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Publication number
CN109422401A
CN109422401A CN201710752082.9A CN201710752082A CN109422401A CN 109422401 A CN109422401 A CN 109422401A CN 201710752082 A CN201710752082 A CN 201710752082A CN 109422401 A CN109422401 A CN 109422401A
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CN
China
Prior art keywords
waste water
evaporation
concentrate
cooling
crystal
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Granted
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CN201710752082.9A
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Chinese (zh)
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CN109422401B (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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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 method includes 1) and waste water to be processed is subjected to the first evaporation, the first steam containing ammonia and the first concentrate are obtained, the waste water to be processed contains the catalyst production waste water；2) first concentrate is subjected to crystallisation by cooling, obtains the crystal solution of sulfur acid sodium crystal；3) crystal solution is carried out first to be separated by solid-liquid separation, and is separated by solid-liquid separation the second evaporation of each effect evaporator progress that obtained liquid phase is passed through multi-effect evaporating device for first, obtain the second steam containing ammonia and crystalliferous second concentrate；4) second concentrate is subjected to cooling processing, obtains the treatment fluid of sodium chloride-containing crystal；5) treatment fluid second is carried out to be separated by solid-liquid separation.Ammonium and sodium sulphate, sodium chloride in waste water can be separately recovered in this method, farthest recycle the resource in waste water.

Description

The processing method of 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 technique
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 method, blow-off method or vaporizing extract process, then, saline sewage is overregulated into 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 crystallization 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 to 6.5-7.5 in the range of, removing most suspended substances, so Afterwards, it except hardness, except silicon and partial organic substances, is 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 crystallization 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 method deamination can only handle the waste water of low ammonium content, and due to COD content 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 method.Sixty-four dollar question is biochemical method 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 does not reduce (20- in waste water 30g/L), it is unable to direct emission, needs further progress 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 content in water, the salt content in waste water do not reduce (20-30g/L), are unable to direct emission, need Further progress desalting processing, wastewater treatment operating cost is high, remains a large amount of alkali in treated waste water, pH value is very high, wave Fei great, processing cost are up to 50 yuan/ton.
Summary of the invention
The purpose of the invention is to overcome in the prior art containing NH4 +、SO4 2-、Cl-And Na+Cost for wastewater treatment it is high, And the problem of can only obtain mixing salt crystal, it provides a kind of at low cost and environmentally friendly containing NH4 +、SO4 2-、Cl-And Na+Catalysis Ammonium and sodium sulphate, sodium chloride in catalyst production waste water can be separately recovered in agent production waste water processing method, this method, maximum Recycle to degree the resource in waste water.
To achieve the goals above, one aspect of the present invention provides a kind of processing method of catalyst production waste water, the catalysis Agent production waste water contains NH4 +、SO4 2-、Cl-And Na+, this approach includes the following steps,
1) waste water to be processed is subjected to the first evaporation, obtains the first steam containing ammonia and the first concentrate, it is described to be processed useless Water contains the catalyst production waste water；
2) first concentrate is subjected to crystallisation by cooling, obtains the crystal solution of sulfur acid sodium crystal；
3) crystal solution of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and is separated by solid-liquid separation obtained liquid for first Each effect evaporator for being mutually passed through multi-effect evaporating device carries out the second evaporation, obtains the second steam containing ammonia and crystalliferous second concentration Liquid；
4) crystalliferous second concentrate is subjected to cooling processing, obtains the treatment fluid of sodium chloride-containing crystal；
5) treatment fluid second is carried out to be separated by solid-liquid separation；
Wherein, before waste water to be processed is carried out the first evaporation, the pH value for adjusting the waste water to be processed is greater than 9；Institute State SO in the first concentrate4 2-Concentration be 0.01mol/L or more, Cl-Concentration be 5.2mol/L or less.
Through the above technical solutions, for NH is contained4 +、SO4 2-、Cl-And Na+Waste water, by advance by waste water to be processed After pH value is adjusted to specific range, carries out the first evaporation and obtain denseer ammonium hydroxide, recycle the isolated sulfuric acid of crystallisation by cooling Then sodium crystal obtains the second concentrate and diluter ammonium hydroxide of sodium chloride-containing crystal and sodium sulfate crystal by the second evaporation, Then cooling processing is recycled to dissolve the sodium sulfate crystal in the second concentrate, sodium chloride further crystallizes precipitation, obtains chlorine Change sodium crystallization.This method can respectively obtain the sodium sulphate and sodium chloride of high-purity, avoid mixed salt processing and recycle process In difficulty, be completed at the same time the process of separation of ammonia and salt, and waste water is made using heat exchange method to heat up and steam containing ammonia simultaneously Cooling is not necessarily to condenser, energy saving rationally using the heat in evaporation process, reduces cost for wastewater treatment, the ammonium in waste water It is recycled in the form of ammonium hydroxide, sodium chloride and sodium sulphate are recycled respectively with crystal form, and whole process does not have waste residue and liquid generation, real The purpose to turn waste into wealth is showed.
Further, this method has been obtained denseer ammonium hydroxide, convenient for the utilization of ammonium hydroxide, has been improved molten by the first evaporation The ion concentration of liquid improves the eduction rate of crystallisation by cooling, improves efficiency；It is matched by the second evaporation and cooling processing, Second evaporation process is carried out at relatively high temperatures, improves the solid content and the second evaporation efficiency of the second evaporation, subtracts The circulation fluid scale of construction in few processing system, can be simultaneously reached energy-saving effect.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the catalyst production waste water processing method of embodiment provided by the invention.
Description of symbols
1, multi-effect evaporating device 62, the second pH value measuring device
2, equipment of crystallisation by cooling 60, third pH value measuring device
3, MVR vaporising device 70, the 11st circulating pump
31, the first heat-exchanger rig 71, first circulation pump
32, the second heat-exchanger rig 72, second circulation pump
33, third heat-exchanger rig 73, third circulating pump
34, the 4th heat-exchanger rig 74, the 4th circulating pump
35, the 5th heat-exchanger rig 75, the 5th circulating pump
36, the 6th heat-exchanger rig 76, the 6th circulating pump
37, the 7th heat-exchanger rig 78, the 8th circulating pump
38, the 8th heat-exchanger rig 79, the 9th circulating pump
30, the tenth heat-exchanger rig 80, the tenth circulating pump
51, the first tank used for storing ammonia 81, vacuum pump
52, the second tank used for storing ammonia 82, circulating water pool
53, the first mother liquor tank 83, tail gas absorber
54, the second mother liquor tank 91, the first equipment for separating liquid from solid
55, low-temperature treatment tank 92, the second equipment for separating liquid from solid
61, the first pH value measuring device 101, the first compressor
Specific embodiment
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) waste water to be processed is subjected to the first evaporation, obtains the first steam containing ammonia and the first concentrate, it is described to be processed useless Water contains the catalyst production waste water；
2) first concentrate is subjected to crystallisation by cooling, obtains the crystal solution of sulfur acid sodium crystal；
3) crystal solution of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and is separated by solid-liquid separation obtained liquid for first Each effect evaporator for being mutually passed through multi-effect evaporating device carries out the second evaporation, obtains the second steam containing ammonia and crystalliferous second concentration Liquid；
4) crystalliferous second concentrate is subjected to cooling processing, obtains the treatment fluid of sodium chloride-containing crystal；
5) treatment fluid second is carried out to be separated by solid-liquid separation；
Wherein, before waste water to be processed is carried out the first evaporation, the pH value for adjusting the waste water to be processed is greater than 9；Institute State SO in the first concentrate4 2-Concentration be 0.01mol/L or more, Cl-Concentration be 5.2mol/L or less；Relative to 1mol institute State the SO contained in the liquid phase that the first separation of solid and liquid obtains4 2-。
Preferably, the waste water to be processed is the catalyst production waste water；Alternatively, the waste water to be processed 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 waste water to be processed is that the catalyst production waste water and described second are separated by solid-liquid separation obtained liquid At least part of mixed liquor of phase.
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 catalyst production waste water, there is no particular limitation.From the treatment effeciency for improving waste water Angle considers, as long as the first concentrate is in following ranges after meeting concentration.The SO contained in first concentrate4 2-For 0.01mol/L or more, more preferably 0.07mol/L or more, further preferably 0.1mol/L or more, still more preferably for 0.2mol/L or more, particularly preferably 0.3mol/L or more, for example, can for 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.1mol/L、0.3mol/L、0.5mol/L、0.7mol/L、0.9mol/L、1mol/L、1.2mol/L、1.4mol/L、1.5mol/ L、1.8mol/L、2mol/L、2.2mol/L、2.5mol/L、2.8mol/L、3mol/L、3.2mol/L、3.5mol/L、3.8mol/ L or 4mol/L etc..Also, Cl in first concentrate-Concentration be 5mol/L hereinafter, preferably 4.5mol/L hereinafter, example It such as can be 0.5mol/L, 0.8mol/L, 1mol/L, 1.3mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/ L、2mol/L、2.2mol/L、2.4mol/L、2.5mol/L、2.8mol/L、3mol/L、3.2mol/L、3.5mol/L、3.8mol/ L, 4mol/L, 4.2mol/L, 4.5mol/L, 4.8mol/L or 5mol/L etc..By by the SO in the first concentrate4 2-、Cl-'s Concentration is controlled in above range, can make in crystallisation by cooling that sodium sulphate is precipitated and sodium chloride is not precipitated, and is efficiently separated to reach The purpose of sodium sulphate.
In the present invention, it is to be understood that first steam containing ammonia and the second steam containing ammonia are so-called for this field Secondary steam.The pressure is the pressure in terms of gauge pressure.
In the present invention, the tune of the first heat exchange, the pH value of the adjusting waste water to be processed and the waste water to be processed With process, (waste water to be processed contains the case where catalyst production waste water is separated by solid-liquid separation obtained liquid phase with described second Under, need to carry out the allocation process of the waste water to be processed) carry out successively there is no particular limitation, can according to need and fitted When selection, completed before the waste water to be processed is carried out the first evaporation.
In the present invention, the purpose of first evaporation is to make Waste water concentrating to be processed, while obtaining denseer ammonium hydroxide, The concentration for improving ion, improves the eduction rate of crystallisation by cooling, and there is no particular limitation for the degree that first evaporation carries out, can be with It is selected as needed with the ingredient of waste water to be processed, meets requirement of the crystallisation by cooling to the first concentrate.Such as it can A small amount of steam containing ammonia is only obtained with control evaporation, to obtain the higher ammonium hydroxide of concentration；It can also be abundant by control evaporation It carries out, waste water to be processed is concentrated sufficiently, convenient for the progress of subsequent crystallisation by cooling.Preferably, in first evaporation not Sodium chloride crystallization is precipitated.
In the present invention, the vaporising device that this field routine can be used in first evaporation carries out, such as MVR evaporation dress It sets, single-effect evaporating equipment or multi-effect evaporating device.As MVR vaporising device, such as can be for selected from MVR falling film evaporator, MVR One of forced-circulation evaporator, MVR-FC continuous crystallisation evaporator, MVR-OSLO continuous crystallisation evaporator are a variety of.Its In, preferably MVR forced-circulation evaporator, MVR-FC continuous crystallisation evaporator, more preferably falling liquid film+forced circulation two-stage MVR Crystallizing evaporator.As single-effect evaporating equipment or the evaporator of multi-effect evaporating device, such as can be selected from downward film evaporator, liter Kestner long-tube evaporator, scraper-type evaporator, standard vertical-tubes multiple-effect steaming device, basket evaporator, external heating type evaporator, pressure follow One of ring evaporator and Liewen evaporator are a variety of.Wherein, preferably forced-circulation evaporator, external heating type evaporator. Each effect evaporator of the multi-effect evaporating device is made of heating room and vaporization chamber respectively, can also be as needed comprising other steamings Send out accessory, such as the demister for separating liquid foam further, the condenser for condensing secondary steam all, and decompression behaviour Vacuum plant etc. when making.There is no particular limitation for the evaporator quantity that the multi-effect evaporating device contains, can for 2 effect with On, more preferably 3-5 effect.A preferred embodiment according to the present invention, first evaporation pass through MVR vaporising device 3 It carries out.
According to the present invention, there is no particular limitation for the condition of first evaporation, reaches the mesh for making Waste water concentrating to be processed ?.For example, it is 35 DEG C or more that the condition of first evaporation, which may include: temperature, pressure is -98kPa or more.In order to mention The efficiency of height evaporation, it is preferable that it is 75 DEG C~130 DEG C that the condition of first evaporation, which may include: temperature, and pressure is -73kPa ~117kPa；Preferably, it is described first evaporation condition include: temperature be 85 DEG C~130 DEG C, pressure be -58kPa~ 117kPa；Preferably, it is 95 DEG C~110 DEG C that the condition of first evaporation, which includes: temperature, and pressure is -37kPa~12kPa；It is excellent Selection of land, it is 105 DEG C~107 DEG C that the condition of first evaporation, which includes: temperature, and pressure is -8kPa~0kPa.
In the present invention, the operating pressure of evaporation is preferably the saturated vapor pressure of evaporated feed liquid.In addition, the first evaporation The ability and wastewater flow rate to be processed that evaporation capacity can be handled according to equipment suitably select, such as can be 0.1m3/ h or more is (such as 0.1m3/ h~500m3/h)。
The condition evaporated by suitable control first, can evaporate to obtain 80 mass % of contained ammonia in waste water to be processed with On, preferably 90 mass % or more, such as can for 80 mass %, 83 mass %, 85 mass %, 86 mass %, 87 mass %, 88 mass %, 89 mass %, 90 mass %, 91 mass %, 93 mass %, 95 mass % or 98 mass % etc., the first ammonium hydroxide can With direct reuse in the production process of catalyst, perhaps with acid neutralization obtain carrying out after ammonium salt reuse or with water and corresponding Ammonium salt or ammonium hydroxide allotment use.
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 does not make the first evaporation wait locate in above-mentioned range The sodium chloride managed in waste water crystallizes precipitation.Here the first evaporation obtains the concentration of liquid, is supervised by way of measuring density It surveys, densitometer specifically can be used and carry out density measure.
According to the present invention, before waste water to be processed is carried out the first evaporation, the pH value for adjusting the waste water to be processed is big In 9, preferably greater than 10.8, for pH value the adjusting upper limit there is no limit, such as can be 14 hereinafter, preferably 13.5 with Under, more preferable 13 hereinafter, further preferably 12 hereinafter, still more preferably be 11.5 or less.By making the first evaporation upper It states and is carried out under pH value, the evaporation of ammonia can be promoted, obtain the higher ammonium hydroxide of concentration, and convenient for obtaining height in subsequent crystallization The sodium sulphate and sodium chloride crystal of purity.
Before waste water to be processed is carried out the first evaporation, the specific example for adjusting the pH value of the waste water to be processed can be with Enumerate: 9,9.5,9.6,9.7,9.8,9.9,10,10.1,10.2,10.3,10.4,10.5,10.6,10.7,10.8,10.9, 11、11.1、11.2、11.3、11.4、11.5、11.6、11.7、11.8、11.9、12、12.2、12.4、12.6、12.8、13、 13.5 or 14 etc..
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 waste water to be processed.There is no particular limitation for the alkaline matter, reaches the mesh of above-mentioned adjusting pH value ?.In order not to introduce new impurity in waste water to be processed, the purity of gained crystal is improved, the alkaline matter is preferably NaOH.In addition, the NaOH containing higher concentration is, it is preferable to use second in the second mother liquor (i.e. second is separated by solid-liquid separation obtained liquid phase) In addition mother liquor can add NaOH as the alkaline matter.
Adding manner as the alkaline matter is the adding manner of this field routine, but preferably makes alkaline matter Mixed in form of an aqueous solutions with waste water to be processed, for example, the aqueous solution containing alkaline matter can be passed into import it is to be processed It is mixed in the pipeline of waste water.For the content of alkaline matter in aqueous solution, there is no particular limitation, as long as can reach The purpose of above-mentioned adjusting pH value.But it in order to reduce the dosage of water, further reduces the cost, it is preferable to use alkaline matter is satisfied And aqueous solution or the second mother liquor.In order to monitor the pH value of the waste water to be processed, can be measured after above-mentioned adjusting pH value The pH value of the waste water to be processed.
A preferred embodiment according to the present invention, first evaporation are carried out in MVR vaporising device 3, are being incited somebody to action Waste water to be processed is sent into before MVR vaporising device 3, by will import in the pipeline of waste water to be processed feeding MVR vaporising device 3 The aqueous solution containing alkaline matter and mixing, Lai Jinhang pH value are adjusted, and pass through the first pH value measuring device after adjustment 61 and 60 pairs of third pH value measuring device adjust after pH value measure.
According to the present invention, it in order to make full use of the heat of the first steam containing ammonia, is preferably carried out by the waste water to be processed Before first evaporation, so that waste water to be processed and the first steam containing ammonia is carried out the first heat exchange, obtain the first ammonium hydroxide, while making wait locate Waste water heating is managed convenient for evaporation.
First heat exchange of a preferred embodiment according to the present invention, waste water to be processed and the first steam containing ammonia is logical It crosses the first heat-exchanger rig 31 and the 8th heat-exchanger rig 38 carries out, specifically, ammonia steam will be contained and pass sequentially through the 8th heat-exchanger rig 38 With the first heat-exchanger rig 31, while by waste water to be processed by the first heat-exchanger rig 31 and the first steam condensation containing ammonia liquid heat exchange, Then waste water to be processed is passed through the 8th heat-exchanger rig 38 and the first steam heat-exchanging containing ammonia.By the first heat exchange, first is obtained Ammonium hydroxide is stored in the first tank used for storing ammonia 51, while waste water to be processed being made to be warming up to 74 DEG C~129 DEG C, preferably 94 DEG C~109 DEG C, convenient for the progress of evaporation.
According to the present invention, in order to make full use of the heat of the first concentrate, the waste water to be processed is preferably being carried out the Before one evaporation, waste water to be processed and the first concentrate is made to carry out the first heat exchange, makes the cooling of the first concentrate convenient for cooling knot Crystalline substance, while making waste water heating to be processed convenient for evaporation.
A preferred embodiment according to the present invention, the first heat exchange of waste water to be processed and the first concentrate pass through Tenth heat-exchanger rig 30 carries out, and waste water to be processed is exchanged heat by the tenth heat-exchanger rig 30 and the first concentrate.
There is no particular limitation for first heat-exchanger rig 31, the tenth heat-exchanger rig 30 and the 8th heat-exchanger rig 38, can be with Using various heat exchangers commonly used in the art, achieve the purpose that carry out heat exchange.Specifically, it can be changed for jacket type Hot device, plate heat exchanger, shell-and-tube heat exchanger etc., wherein preferably plate heat exchanger.The material of the heat exchanger can basis It needs to be specifically chosen, such as in order to resist chloride ion corrosion, can choose material is two phase stainless steel, titanium or titanium alloy, Kazakhstan The heat exchanger of alloy can select the heat exchanger containing plastic material when temperature is lower.
In the present invention, in order to improve the solid content in the MVR vaporising device 3, the ammonia content in liquid is reduced, it is excellent Choosing by after the MVR vaporising device 3 evaporation partially liq (namely the liquid inside MVR vaporising device, hereinafter Referred to as first circulation liquid) it again returns in the MVR vaporising device 3 and evaporates after heating.It is above-mentioned to return to the first circulation liquid Process to the MVR vaporising device 3 is preferably, by the first circulation liquid with after the adjusting of first time pH value and to the It is again returned in MVR vaporising device 3 after waste water to be processed mixing before secondary pH value adjusting, for example, can be followed by the 5th The first circulation liquid is returned to the waste water conveyance conduit between the first heat-exchanger rig 31 and the 8th heat-exchanger rig 38 by ring pump 75 In mixed with waste water to be processed, then by second of pH value adjust and then by the 8th heat-exchanger rig 38 carry out Heat exchange is finally sent into the MVR vaporising device 3.Here, first reflux ratio refers to: the first MVR of regurgitant volume and feeding Total amount of liquid in vaporising device 3 subtracts the ratio of regurgitant volume.As will by the first MVR vaporising device 2 evaporation after The ratio that partially liq flows back into the MVR vaporising device 2 is not particularly limited, for example, first time of first evaporation Flowing ratio can be 10-200, preferably 50-100.
In the case where, according to the invention it is preferred to, the method also includes 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 system, guarantees that waste water heating-evaporation-cooling process is continuous Progress needs to input starting steam when MVR evaporation process starts, only passes through the first compressor 101 after reaching continuously running state Energy supply, it is no longer necessary to input other energy.First compressor 101 can use various compressions commonly used in the art 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 purpose of the crystallisation by cooling is that sodium sulphate is precipitated, and sodium chloride is not precipitated, so as to Sodium sulphate is separated from waste water well.Sodium sulphate only is precipitated in the crystallisation by cooling, it is not excluded that sulfate crystal entrainment Or the sodium chloride of adsorption.In the present invention, it is preferred in obtained sodium sulfate crystal sodium sulphate content be 92 mass % with On, more preferably 96 mass % or more, further preferably 98 mass % or more), it is to be understood that the obtained sulfuric acid The amount of sodium crystal is with butt meter.It can consider only sulfuric acid when the content of sodium sulphate is above range in obtained sodium sulfate crystal Sodium is precipitated.
It is adjusted by the pH value before evaporation, the pH value of first concentrate is made to be greater than 9, and NH therein4 +It is most of It is evaporated out in the first evaporation in the form of amino molecule, to guarantee that ammonium sulfate is not precipitated during crystallisation by cooling And/or ammonium chloride, simultaneously because the raising of sodium chloride concentration, can be improved the eduction rate of sodium sulphate.
In the present invention, there is no particular limitation can according to need appropriate selection for the condition of the crystallisation by cooling, reaches The effect that the sulfate crystal is precipitated.The condition of the crystallisation by cooling may include: that temperature is -21.7 DEG C~17.5 DEG C, preferably -20 DEG C~5 DEG C, more preferably -10 DEG C~5 DEG C, further -10 DEG C~0 DEG C, particularly preferably -4 DEG C~0 DEG C； Time (in terms of the residence time in equipment of crystallisation by cooling 2) be 5min or more, preferably 60min~180min, more preferably 90min~150min, further preferably 120min~150min.By controlling the condition of crystallisation by cooling in above range, Sodium sulphate can be made sufficiently to be precipitated.
The specific example of temperature as above-mentioned crystallisation by cooling can be enumerated: -21 DEG C, -20 DEG C, -19 DEG C, -18 DEG C, -17 ℃、-16℃、-15℃、-14℃、-13℃、-12℃、-11℃、-10℃、-9℃、-8℃、-7℃、-6℃、-5℃、-4℃、-3 DEG C, -2 DEG C, -1 DEG C or 0 DEG C etc..
The specific example of time as above-mentioned crystallisation by cooling for example: 5min, 6min, 7min, 8min, 10min、15min、20min、25min、30min、35min、40min、45min、50min、52min、54min、56min、 58min、60min、65min、70min、75min、80min、85min、90min、95min、100min、105min、110min、 115min, 120min, 130min, 140min, 150min or 160min.
According to the present invention, there is no particular limitation for the mode that the crystallisation by cooling carries out, and can use continuously or in batches Mode carries out, as long as reaching reduces the temperature of the first concentrate, makes the purpose of sulfate crystal precipitation, it is preferred to use even Continuous crystallisation by cooling mode carries out.The crystallisation by cooling sodium sulphate can use various cooling crystallizing equipments commonly used in the art It carries out, such as can be using the continuous cooling crystallizer with external cooling heat exchanger, or uses the knot with cooling-part Brilliant tank carries out, such as equipment of crystallisation by cooling 2.The cooling-part can make equipment of crystallisation by cooling by way of importing cooling medium Condition needed for the first interior concentrate is cooled to crystallisation by cooling.Mixing component is preferably provided in the cooling crystallizing equipment, Such as blender etc., it is uniformly cooling by achieving the effect that the mixing of the first concentrate, sodium sulphate therein can be made sufficiently to analyse Out, increase crystallite dimension.It is preferably provided with circulating pump on the equipment of crystallisation by cooling, in order to avoid generating a large amount of fine grain cores, is prevented The crystal grain and impeller high velocity impact only recycled in magma generates a large amount of secondary nucleus, and the circulating pump is preferably the centrifugation of the slow-speed of revolution Pump, more preferably big flow, the water conservancy diversion pump impeller of the slow-speed of revolution or big flow, low lift, the slow-speed of revolution axial-flow pump.
By carrying out the crystallisation by cooling under the above conditions, can make in crystallisation by cooling sodium sulphate be sufficiently precipitated and Sodium chloride is not precipitated, to achieve the purpose that separating-purifying sodium sulphate.
According to the present invention, before the first concentrate is carried out crystallisation by cooling, as needed, adjustable first concentrate The concentration of middle sodium chloride, the concentration X or less of sodium chloride in the crystal solution for obtaining crystallisation by cooling, wherein X is in crystallisation by cooling Under conditions of, the concentration of sodium chloride when sodium sulphate and sodium chloride reach saturation in crystal solution.By by chlorine in the first concentrate The concentration for changing sodium is adjusted to above range, it is ensured that sodium chloride is not precipitated in crystallisation by cooling.Preferably, make in the crystal solution The concentration of sodium chloride is 0.95X-0.999X.The method that the sodium chloride concentration is adjusted can be using the second of mixing debita spissitudo The mode of the other waste liquids generated in mother liquor, water, the catalyst production waste water and/or treatment process etc. carries out, as long as making The concentration of sodium chloride is adjusted in above range in one concentrate.In order to avoid introducing more liquid, it is preferable that adjust the The concentration of sodium chloride passes through the second mother liquor of mixing, the catalyst production waste water and/or elution sodium sulfate crystal in one concentrate Cleaning solution afterwards carries out.By the way that the concentration of sodium chloride in the first concentrate is adjusted to above range, crystallisation by cooling mistake is avoided The precipitation of journey sodium chloride improves the purity that sodium sulphate is precipitated in crystallisation by cooling process, improves the efficiency of crystallisation by cooling.
In the present invention, in order to control the Lens capsule in the equipment of crystallisation by cooling 2, containing for fine grain is reduced Amount, the partially liq for preferably crystallizing the process equipment of crystallisation by cooling 2 (namely the liquid inside equipment of crystallisation by cooling 2, Hereinafter be also referred to as cooling circulation liquid) mixed with the catalyst production waste water after return to equipment of crystallisation by cooling 2 in carry out again Crystallisation by cooling.It is above-mentioned for example to follow cooling circulation liquid by second back to the process that the equipment of crystallisation by cooling 2 crystallizes Before cooling circulation liquid is returned to the 6th heat-exchanger rig 36 by ring pump 72, the cooling is again introduced into after mixing with the first concentrate Crystallization apparatus 2 carries out crystallisation by cooling.The back amount of the cooling circulation liquid can be defined by the recycle ratio of crystallisation by cooling, institute The recycle ratio for stating crystallisation by cooling refers to: the total amount of liquid in internal circulating load and feeding equipment of crystallisation by cooling 2 subtracts the ratio of regurgitant volume. The recycle ratio can be appropriately configured according to the degree of supersaturation of sodium sulphate in the equipment of crystallisation by cooling 2, to guarantee sulfuric acid The granularity of sodium crystallization.In order to control the size distribution of crystal obtained by crystallisation by cooling, the content of fine grain is reduced, preferably control satiety It is less than 1.5g/L, more preferably less than 1g/L with degree.
In the present invention, the crystal solution of the sulfur acid sodium crystal by first be separated by solid-liquid separation after obtain sodium sulfate crystal and 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 One of centrifugation, filtering and sedimentation or a variety of can be selected from.
According to the present invention, first separation of solid and liquid can use the first equipment for separating liquid from solid (for example, centrifuge, belt Filter, flame filter press etc.) 91 progress.After described first is separated by solid-liquid separation, the first equipment for separating liquid from solid 91 is obtained first female Liquid is temporarily stored into the first mother liquor tank 53, and can be sent into multi-effect evaporating device 1 by the 6th circulating pump 76 and be carried out the second evaporation.Separately Outside, the impurity such as certain chloride ion, free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on the sodium sulfate crystal obtained, in order to The impurity for removing absorption reduces the peculiar smell of solid salt, reduces corrosivity, improves the purity of the crystal, it is preferable that the sulfuric acid Sodium crystal water or metabisulfite solution carry out the first washing, can be dried when needing to obtain anhydrous sodium sulfate.Described first Mode of washing preferably elutes, and is preferably eluted after separation of solid and liquid.
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 solid-liquid separating equipment of domain routine carries out, and can also carry out in the equipment for separating liquid from solid of segmentation.For above-mentioned washing without spy Other restriction can be carried out by the method for this field routine.There is no particular limitation for the number of the washing, can be 1 time More than, the sodium sulfate crystal of higher purity, preferably 2-4 times in order to obtain.It is preferable to use aqueous sodium persulfate solution (institutes for first washing It states sodium chloride and sodium sulphate at the concentration preferably temperature corresponding to sodium sulfate crystal to be washed of aqueous sodium persulfate solution while reaching The concentration of sodium sulphate in the aqueous solution of saturation) it carries out.The liquid generated for washing, it is preferable that water or aqueous sodium persulfate solution are washed It washs liquid and is back to equipment of crystallisation by cooling 2, such as equipment of crystallisation by cooling 2 can be back to by the 8th circulating pump 78.
A preferred embodiment according to the present invention, the crystal solution containing sodium sulphate obtained by crystallisation by cooling Afterwards, it is separated by solid-liquid separation by equipment for separating liquid from solid, also, use aqueous sodium persulfate solution (institute again for obtained crystal is separated by solid-liquid separation The concentration of aqueous sodium persulfate solution is stated as sodium chloride and sodium sulphate at the temperature corresponding to sodium sulfate crystal to be washed while reaching saturation Aqueous solution in sodium sulphate concentration) eluted, and by the obtained liquid of elution back to equipment of crystallisation by cooling 2.By upper Washing process is stated, the purity for the sodium sulfate crystal that can be improved.
According to the present invention, in order to make full use of the cooling capacity of the first mother liquor, the first concentrate is preferably being subjected to crystallisation by cooling Before, the first mother liquor and the first concentrate are subjected to the second heat exchange.
A preferred embodiment according to the present invention, second heat exchange are carried out by the second heat-exchanger rig 32, Specifically, the first mother liquor and the first concentrate are passed through into the second heat-exchanger rig 32 respectively, both make to carry out heat exchange, to make the The temperature of one concentrate reduces the progress for being convenient for crystallisation by cooling, while increases the temperature of the first mother liquor convenient for the second evaporation.It is logical It crosses after the second heat-exchanger rig 32 carries out the second heat exchange, the temperature of the first concentrate is -20.7 DEG C~16.5 DEG C, preferably -5 DEG C ~10 DEG C, close to the temperature of crystallisation by cooling.
According to the present invention, for the ease of the progress of crystallisation by cooling, first concentrate and freezing liquid are subjected to the second heat Exchange.A preferred embodiment according to the present invention, the second heat exchange of first concentrate and freezing liquid pass through the Six heat-exchanger rigs 36 carry out, and specifically, freezing liquid and the first concentrate are passed through the 6th heat-exchanger rig 36 respectively, carry out the two Heat exchange, so that making the temperature of the first concentrate reduces the progress for being convenient for crystallisation by cooling.Institute's freezing liquid can be normal using this field Freezing liquid of the rule for cooling, as long as the temperature of the first concentrate can be made to meet the needs of crystallisation by cooling.
There is no particular limitation for second heat-exchanger rig 32 and the 6th heat-exchanger rig 36, and this field, which can be used, routinely to be made Various heat exchangers achieve the purpose that carry out heat exchange.Specifically, can for jacketed type exchanger, plate heat exchanger, Shell-and-tube heat exchanger etc., wherein preferably plate heat exchanger.The material of the heat exchanger can according to need specific choice, such as In order to resist chloride ion corrosion, the heat exchanger that material is two phase stainless steel, titanium or titanium alloy, Hastelloy can choose, in temperature The heat exchanger containing plastic material can be selected when spending lower.Preferred heat exchanger of the selection containing plastic material of second heat-exchanger rig 32.
In the present invention, the purpose of second evaporation is that sodium chloride and/or sodium sulphate is precipitated, and evaporates ammonia, To achieve the purpose that separate the ammonia and salt in waste water.According to the present invention, by the condition of the second evaporation of control, with solvent It constantly reduces, sodium chloride is precipitated first, and then sodium sulphate may be made to be precipitated, obtains crystalliferous second concentrate.In order to subtract Quantity of circulating water in few processing system improves the efficiency of the second evaporation and then improves the efficiency of wastewater treatment, second evaporation The degree of progress preferably makes sodium chloride and sodium sulphate while being precipitated, that is to say, that the second evaporation preferably obtains sodium chloride-containing crystal With the second concentrate of sodium sulfate crystal.
In the present invention, there is no particular limitation for each effect evaporator of the multi-effect evaporating device 1, can be normal by this field Advise the various evaporators composition used.Such as can selected from downward film evaporator, film-rising evaporator, scraper-type evaporator, in It entreats in circulating tube type multi-effect evaporator, basket evaporator, external heating type evaporator, forced-circulation evaporator and Liewen evaporator It is one or more.Wherein, preferably forced-circulation evaporator, external heating type evaporator.Each effect of the multi-effect evaporating device 1 is steamed Hair device respectively by heating room and vaporization chamber form, can also as needed comprising other evaporation accessories, such as make liquid foam into The demister of one step separation, the vacuum plant the etc. when condenser and decompression operation that condense secondary steam all.It is described more There is no particular limitation for the evaporator quantity that effect vaporising device 1 contains, and can be 2 effects or more, preferably 2-5 is imitated, more preferably 2-4 effect.
In the present invention, there is no particular limitation for the evaporation conditions of second evaporation, can according to need appropriate selection, Achieve the purpose that crystal is precipitated.It is described second evaporation condition may include: temperature be 17.5 DEG C or more, pressure be- 101kPa or more；Preferably, it is described second evaporation condition include: temperature be 35 DEG C~110 DEG C, pressure be -98kPa~ 12kPa；Preferably, it is 45 DEG C~110 DEG C that the condition of second evaporation, which includes: temperature, and pressure is -95kPa~12kPa；It is excellent Selection of land, it is 105 DEG C~110 DEG C that the condition of second evaporation, which includes: temperature, and pressure is -8kPa~12kPa.In the present invention, The condition of second evaporation refers to the evaporation conditions of the last 1st effective evaporator of multi-effect evaporating device.
In the present invention, in the second evaporation, the evaporating temperature of preceding 1st effective evaporator is preferably high than latter high 5 DEG C of effect or more 10 DEG C or more.
In the present invention, the operating pressure of the second evaporation is preferably the saturated vapor pressure of evaporated feed liquid.
In addition, ability and wastewater flow rate to be processed that the evaporation capacity of the second evaporation can be handled according to equipment suitably select, It such as can be 100L/h or more (such as 0.1m3/ h~500m3/h).By carrying out the second evaporation under the above conditions, Ke Yi While guaranteeing sodium chloride crystallization, sodium sulphate is not crystallized, the purity for the sodium chloride crystal that thereby may be ensured that.
It in the present invention, can be each in order to which first mother liquor to be successively passed through to each effect evaporator of multi-effect evaporating device 1 Circulating pump is set between effect evaporator, the waste water after the evaporation of preceding 1st effective evaporator is passed through next effect by the circulating pump and is steamed Send out device.
In the present invention, the circulating pump between selected each effect evaporator can be various forms commonly used in the art Pump, generate a large amount of fine grain cores to be uniformly evaporated material, avoid, prevent circulation magma in crystal grain and impeller high velocity impact Generate a large amount of secondary nucleus, the circulating pump is preferably the centrifugal pump of the slow-speed of revolution, more preferably big flow, the slow-speed of revolution guide pump Wheel or big flow, low lift, the slow-speed of revolution axial-flow pump.
A preferred embodiment according to the present invention, second evaporation process carry out in multi-effect evaporating device 1, The multi-effect evaporating device 1 is by 1st effective evaporator 1a, 2nd effect evaporator 1b, third effect evaporator 1c and fourth evaporator 1d composition.First mother liquor is successively passed through in each effect evaporator of the multi-effect evaporating device 1 and is evaporated to obtain containing crystalline substance Second concentrate of body.The second steam containing ammonia that preceding 1st effective evaporator is obtained is passed through in rear 1st effective evaporator, and obtains second Ammonium hydroxide.It is passed through heating steam (life steam i.e. commonly used in the art) in 1st effective evaporator 1a, heats steam first The condensation water obtained after being condensed in effect evaporator 1a.
Make that sodium chloride crystal is precipitated in order to guarantee evaporation process as far as possible and sodium sulphate is not precipitated or is precipitated on a small quantity and can It is dissolved when cooling down processing, is separated by solid-liquid separation the SO contained in obtained liquid phase preferably with respect to described in 1mol first4 2-, described One is separated by solid-liquid separation the Cl contained in obtained liquid phase-For 7.15mol or more, preferably 20mol or more, more preferably 44mol with On, more preferably 50mol or more, more preferably 74mol or more, preferably 460mol are hereinafter, more preferably 230mol or less.Example Such as can for 7.5mol, 7.8mol, 8mol, 8.2mol, 8.4mol, 8.6mol, 8.8mol, 9mol, 9.2mol, 9.4mol, 9.5mol、10.5mol、11mol、11.5mol、12mol、12.5mol、13mol、13.5mol、14mol、14.5mol、15mol、 15.5mol、16mol、16.5mol、17mol、17.5mol、18mol、18.5mol、19mol、19.5mol、20mol、21mol、 22mol, 23mol, 25mol, 27mol, 29mol, 31mol, 35mol, 40mol, 45mol, 50mol, 60mol, 65mol etc..It is logical It crosses SO4 2-And Cl-Molar ratio control in above range, can be by evaporating and cooling handles to obtain more pure chlorination Sodium crystal, realizes the separation of sodium sulphate and sodium chloride, while reducing the energy consumption of crystallisation by cooling process.
According to the present invention, from the aspect of improving waste water treatment efficiency, the higher the better for the second evaporation carry out degree； But if the second evaporation is more than to a certain degree, it will so that cooling processing is unable to get the treatment fluid for containing only sodium chloride crystal, this Although when can make dissolution of crystals by adding the modes such as water in treatment fluid, will affect the efficiency of wastewater treatment.Therefore institute The carry out degree for stating the second evaporation preferably makes sodium chloride crystal and sodium sulfate crystal while being precipitated, that is, preferred steps 3) it obtains Crystalliferous second concentrate be sodium chloride-containing crystal and sodium sulfate crystal concentrate, and cooling processing makes described contain Sodium sulfate crystal dissolution in the concentrate of sodium chloride crystal and sodium sulfate crystal.In order to enable the cooling processing can make to contain Sodium sulfate crystal dissolution in the concentrate of sodium chloride crystal and sodium sulfate crystal, such as can control the steaming of second evaporation Hair degree, making the concentration Y or less of sodium sulphate in treatment fluid, (wherein, Y is under conditions of cooling processing, in the treatment fluid The concentration of sodium sulphate when sodium sulphate and sodium chloride reach saturation).From in subsequent cooling treatment process, make sodium chloride as far as possible It is precipitated and viewpoint that sodium sulphate is completely dissolved considers, it is preferable that second evaporation makes the concentration of sodium sulphate in treatment fluid 0.9Y-0.99Y, more preferably 0.95Y-0.98Y.By the way that the extent control of the second evaporation within the above range, can protected Sodium chloride precipitation as much as possible in the second evaporation process is demonstrate,proved, and in cooling processing, sodium sulfate crystal is completely dissolved, finally It is separated to pure sodium chloride crystal.By crystallizing sodium chloride in the second evaporation as far as possible, waste water treatment efficiency can be improved, save The about energy.
In the present invention, the carry out degree of second evaporation obtains liquid by the evaporation capacity of the second evaporation of monitoring The mode of amount carries out, and specifically, controls cycles of concentration by evaporation capacity, that is, ammonium hydroxide amount of the second evaporation of control, makes the second steaming Sending out the sulfate crystal being precipitated in the second obtained concentrate being capable of the dissolution when cooling down processing.Here the second journey being concentrated by evaporation Degree, is monitored by way of measuring the second evaporation capacity, and mass flowmenter specifically can be used and carry out flow measurement, can survey The amount for measuring secondary steam, can also measure the amount of condensate liquid.
According to the present invention, in order to make full use of the second evaporation to obtain the second liquid of steam condensation containing ammonia in heat, preferably Before the second cleaning solution for obtaining the second washing returns to multi-effect evaporating device 1, the second cleaning solution is contained into ammonia with described second Steam condensation liquid carries out third heat exchange.
The third heat of a preferred embodiment according to the present invention, the first mother liquor and the second steam condensation containing ammonia liquid is handed over It changes and is carried out by the 4th heat-exchanger rig 34, the first mother liquor and the second steam condensation containing ammonia liquid are passed through into the 4th heat-exchanger rig respectively 34, make the heating of the first mother liquor convenient for evaporation, while the second liquid of steam condensation containing ammonia being made to cool down to obtain the second ammonium hydroxide, is stored in second In tank used for storing ammonia 52.After 34 heat exchange of the 4th heat-exchanger rig, first mother liquor is warming up to 34 DEG C~190 DEG C, It is preferred that 44 DEG C~130 DEG C.
According to the present invention, in order to make full use of the second evaporation to obtain the second concentrate in heat, preferably will be described First mother liquor is sent into before multi-effect evaporating device 1, and the first mother liquor and the second concentrate are carried out third heat exchange.
A preferred embodiment according to the present invention, the third heat exchange of the first mother liquor and the second concentrate pass through the Five heat-exchanger rigs 35 carry out, and the first mother liquor and the second concentrate are passed through the 5th heat-exchanger rig 35 respectively, and the first mother liquor is made to heat up Convenient for evaporation, while making the second concentrate convenient for cooling processing.After 35 heat exchange of the 5th heat-exchanger rig, described first The temperature of mother liquor is increased to 34 DEG C~174 DEG C, preferably 94 DEG C~109 DEG C.
, according to the invention it is preferred to the second steam containing ammonia that the last 1st effective evaporator of multi-effect evaporating device 1 is obtained and cooling Water carries out third heat exchange, obtains the second ammonium hydroxide.The second steam containing ammonia that the last 1st effective evaporator of multi-effect evaporating device obtains with The third heat exchange of cooling water is carried out by third heat-exchanger rig 33, and obtained the second ammonium hydroxide merging is stored in the second tank used for storing ammonia In 52.
, according to the invention it is preferred to will heat condensate liquid that steam is obtained in the 1st effective evaporator of multi-effect evaporating device 1 with Second cleaning solution carries out heat exchange, and above-mentioned heat exchange is carried out by the 7th heat-exchanger rig 37.
The third heat-exchanger rig 33, the 4th heat-exchanger rig 34, the 5th heat-exchanger rig 35 and the 7th heat-exchanger rig 37 do not have It is special to limit, various heat exchangers commonly used in the art can be used, reach the second steam containing ammonia and the first mother liquor carries out The purpose of heat exchange.Specifically, can for jacketed type exchanger, plate heat exchanger, shell-and-tube heat exchanger etc., wherein it is preferred that For plate heat exchanger.The material of the heat exchanger can according to need specific choice, such as in order to resist chloride ion corrosion, can be with Select material for two phase stainless steel, titanium or titanium alloy, Hastelloy heat exchanger, material containing plastics can be selected when temperature is lower The heat exchanger of matter.Preferably, two phase stainless steel plate heat exchanger is selected.
, according to the invention it is preferred to the pH value of the first mother liquor is monitored before the first mother liquor is passed through multi-effect evaporating device 1, Such as the pH value of the first mother liquor is monitored by the second pH value measuring device 62.
In the present invention, the purpose of the cooling processing is to make to contain in crystalliferous second concentrate Sodium sulfate crystal dissolution, is precipitated sodium chloride further.The cooling processing makes the sodium sulphate in crystalliferous second concentrate Dissolution of crystals refers to that sodium chloride crystal pure in order to obtain, the degree needs that second evaporation carries out are appropriately controlled, also It is to say, controls the solubility that the sodium sulphate in mixed system is no more than under conditions of corresponding cooling processing.In addition, being handled in cooling In, sodium chloride crystallization can carry secretly or adsorption sodium sulfate crystal.In the present invention, it is preferred to sulfuric acid in obtained sodium chloride crystal The content of sodium is in 8 mass % hereinafter, preferably 4 mass % are hereinafter, in the present invention, sodium sulphate is brilliant in obtained sodium chloride crystal It can think that sodium sulphate dissolves when the content of body is below 8 mass %.
There is no particular limitation for the condition that the cooling processing carries out, so that the sodium sulphate in crystalliferous second concentrate Crystal can cooling treatment process in be completely dissolved, such as the processing that cools down condition may include: temperature be 13 DEG C~ 100 DEG C, preferably 15 DEG C~45 DEG C, more preferably 15 DEG C~35 DEG C, further preferably 17.9 DEG C~35 DEG C.In order to guarantee to drop Temperature processing effect, it is preferable that it is described cooling processing condition include: the time be 5min or more, preferably 5min~120min, More preferably 30min~90min；Further preferably 50min~60min.
As cooling processing temperature specific example for example: 13 DEG C, 14 DEG C, 15 DEG C, 15.5 DEG C, 16 DEG C, 16.5℃、17℃、17.5℃、17.9℃、18℃、18.5℃、19℃、19.5℃、20℃、21℃、23℃、25℃、27℃、30 DEG C, 31 DEG C, 31.5 DEG C, 32 DEG C, 33 DEG C, 34 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C etc..
As cooling processing time specific example for example: 5min, 6min, 7min, 8min, 10min, 15min、20min、25min、30min、35min、40min、45min、50min、52min、54min、56min、58min、 60min、70min、100min、120min。
According to the present invention, the cooling processing carries out in low-temperature treatment tank 55, and crystalliferous second concentrate is in low temperature After process tank 55 carries out cooling processing, the treatment fluid of the sodium chloride-containing crystal is obtained.The low-temperature treatment tank 55 is without special Restriction, such as can be thickener, crystallizing tank and crystallizing tank with outer circulation etc. of band stirring, wherein preferably with stirring Crystallizing tank.Low-temperature treatment tank 55 is preferably provided with mixing component, so that the cooling treatment process is in the second concentrate and mixes State, such as can preferably make the using the conventional mechanical stirring used, electromagnetic agitation and/or the external circulating device having Solid-liquid distribution in two concentrates reaches uniform state.Second concentrate each section is set to keep temperature, concentration uniform by mixing, To avoid sodium sulfate crystal dissolution that from cannot sufficiently carrying out, the efficiency of cooling processing is improved.Low-temperature treatment tank 55 is preferably provided with Cooling-part, such as so that low-temperature treatment tank 55 is cooled to the required condition of cooling processing by way of importing cooling medium.
According to the present invention, second separation of solid and liquid can pass through the second equipment for separating liquid from solid (for example, centrifuge, belt 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 is obtained second female Liquid (i.e. second is separated by solid-liquid separation obtained liquid phase) returns to MVR device 3 and is evaporated again, can specifically pass through the 9th circulating pump 79 Before second mother liquor is adjusted completion back to the pH value before the first evaporation.In addition, the meeting of being difficult to avoid that on obtained sodium chloride crystal The impurity such as certain sulfate ion, free ammonia, hydroxide ion are adsorbed, in order to remove the impurity of absorption, reduce solid salt Peculiar smell reduces corrosivity, improves the purity of the crystal, it is preferable that the sodium chloride crystal water, catalyst production are useless Water or sodium chloride solution carry out the second washing and drying.In order to avoid the dissolution of sodium chloride crystal in washing process, it is preferable that institute Sodium chloride crystal is stated to be washed with sodium-chloride water solution.It is highly preferred that the concentration of the sodium-chloride water solution preferably to It washes sodium chloride and sodium sulphate at temperature corresponding to sodium chloride crystal while reaching the concentration of sodium chloride in the aqueous solution of saturation.It is described Second mode of washing is preferably first eluriated to be eluted again.The second cleaning solution that above-mentioned washing process obtains preferably passes through Ten circulating pumps 80 return to multi-effect evaporating device 1 and carry out the second evaporation again.
It is separated by solid-liquid separation the mode washed with second as above-mentioned second, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.For above-mentioned elutriation and elution, there is no particular limitation, can be carried out by the method for this field routine.The elutriation There is no particular limitation with the number of elution, can be 1 time or more, in order to obtain the sodium chloride crystal of higher purity, preferably 2-4 times.During elutriation, it can be used when doing elutriation liquid using the cleaning solution of the second washing recycling with circulated in countercurrent.Progress described in Before elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (content liquid 35 of sodium chloride-containing crystal Quality % or less).During elutriation, relative to the slurries of 1 parts by weight sodium chloride-containing crystal, eluriating the liquid used is 1- 20 parts by weight.It is preferable to use sodium-chloride water solution, (concentration of the sodium-chloride water solution is preferably in sodium chloride crystalline substance to be washed for elution Sodium chloride and sodium sulphate reach the concentration of sodium chloride in the aqueous solution of saturation simultaneously at temperature corresponding to body) it carries out.In order into one Step improves the effect eluriated, and obtains the higher sodium chloride crystal of purity, and in preferred situation, the elution that elution obtains can be used Liquid is eluriated.The liquid generated for washing, it is preferable that water or sodium-chloride water solution cleaning solution and elutriation liquid are back to multiple-effect Vaporising device 1.
A preferred embodiment according to the present invention, by the processing for the sodium chloride-containing crystal that cooling is handled Liquid is carried out after being tentatively separated by solid-liquid separation by sedimentation, and the liquid obtained when with subsequent wash sodium chloride crystal eluriates tank at another In eluriated, then by through elutriation sodium chloride-containing crystal treatment fluid be sent into equipment for separating liquid from solid be separated by solid-liquid separation, Gu The isolated crystal of liquid uses sodium-chloride water solution again, and (concentration of the sodium-chloride water solution is right in sodium chloride crystal to be washed At a temperature of answering sodium chloride and sodium sulphate and meanwhile reach the concentration of sodium chloride in the aqueous solution of saturation) eluted, and will elute To liquid back to eluriate in as eluriate liquid.The washing process combined by above-mentioned elutriation and elution, not only makes The purity of sodium chloride crystal improves, and introducing cleaning solution that will not be excessive, improves the efficiency of wastewater treatment.
A preferred embodiment according to the present invention discharges the tail gas that crystallisation by cooling generates after except ammonia；It will The third heat exchange condenses remaining tail gas and discharges after except ammonia；First heat exchange is condensed remaining tail gas to pass through Except being discharged after ammonia.The tail gas that the tail gas that the crystallisation by cooling generates, that is, equipment of crystallisation by cooling 2 is discharged, the third heat exchange Condense the on-condensible gas that remaining tail gas i.e. third heat-exchanger rig 33 is discharged；First heat exchange condenses remaining tail gas i.e. the The tail gas of eight heat-exchanger rigs 38 discharge.By the way that above-mentioned tail gas is removed ammonia, the pollutant that can be further decreased in emission contains Amount, allows to 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 Recycled in absorption tower 83, can also by third circulating pump 73 from circulating water pool 82 to 83 water supplement of tail gas absorber, circulation 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 can also cocurrent, preferably adverse current.The recirculated water can be by additional Fresh water is supplemented.In order to guarantee 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 after absorbing tail gas or ammonium sulfate is back to 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, method of the invention is particularly suitable for the processing of ammoniated wastewater with high salt.It is produced as catalyst of the invention Waste water is specifically as follows the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process, is also possible to that molecule will be come from The waste water of sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.It will preferably come from and divide The waste water of son sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.
As the NH in the catalyst production waste water4 +It 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 1g/L or more, more preferably For 2g/L or more, further preferably 4g/L or more, further preferably 8g/L or more, further preferably 16g/L or more, into One step is preferably 32g/L or more, further preferably 40g/L or more, further preferably 50g/L or more, further preferably 60g/L or more.
As the SO in the catalyst production waste water4 2-Can be 1g/L or more, preferably 2g/L or more, more preferably 4g/L or more, further preferably 8g/L or more, further preferably 16g/L or more, further preferably 32g/L or more, into One step is preferably 40g/L or more, further preferably 50g/L or more, further preferably 60g/L or more, further preferably 70g/L or more.
As the Cl in the catalyst production waste water-It can be 970mg/L or more, more preferably 2g/L or more, into one Step is preferably 4g/L or more, further preferably 8g/L or more, further preferably 16g/L or more, further preferably 32g/L More than, further preferably 40g/L or more, further preferably 50g/L or more, further preferably 60g/L or more.
The NH contained in the catalyst production waste water4 +、SO4 2-、Cl-And Na+The upper limit there is no particular limitation.From useless Water is easy from the point of view of starting with, SO in catalyst production waste water4 2-、Cl-And Na+The upper limit be respectively 200g/L hereinafter, it is preferred that For 150g/L or less；NH in catalyst production waste water4 +For 50g/L hereinafter, preferably 40g/L or less.
From the point of view of the energy consumption for reducing treatment process, the SO that contains in the catalyst production waste water4 2-Concentration it is excellent Choosing is higher than Cl-, SO relative to 1mol4 2-, Cl-Preferably 10mol hereinafter, more preferably 8mol hereinafter, such as 1.3-6.5mol； From the point of view of improving sodium sulphate product purity, the Cl that contains in the catalyst production waste water-It is for 5.5mol/L hereinafter, excellent 5mol/L is selected as hereinafter, more preferably 4.5mol/L is hereinafter, such as 1.8-3.9mol/L.By will contain in catalyst production waste water Some SO4 2-And Cl-Concentration be limited to above range, can obtain pure sodium sulphate during crystallisation by cooling, save energy Source keeps treatment process 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 Following 10mg/L is not hereinafter, contain other inorganic ions particularly preferably.By controlling other inorganic ions in above-mentioned model It encloses, can be further improved the purity of finally obtained sodium sulfate crystal and sodium chloride crystal.It is raw in order to reduce the catalyst The content for producing other inorganic ions in waste water, preferably carries out following removal of impurities.
The TDS of the catalyst production waste water can be 1.6g/L or more, preferably 4g/L or more, more preferably 8g/L with On, further preferably 16g/L or more, further preferably 32g/L or more, further preferably 40g/L or more are further excellent It is selected as 50g/L or more, further preferably 60g/L or more, further preferably 100g/L or more, further preferably 150g/L More than, further preferably 200g/L or more.
In the present invention, the pH value of the catalyst production waste water is preferably 4-8, such as 6-7.
In addition, due to the COD of waste water may block up film in concentration, in evaporative crystallization when influence the purity and color etc. of salt, The COD of the catalyst production waste water more fewer better (preferably 20mg/L is hereinafter, more preferably 10mg/L or less), preferably pre- By oxidation removal when processing, such as bioanalysis, advanced oxidation processes progress specifically can be used, in the very high Shi Youxuan of COD content 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, guarantee that the continuous-stable for the treatment of process carries out, drop Low equipment operation maintenance cost, the catalyst production waste water using processing method of the invention before being handled preferably through removing It is miscellaneous.Preferably, the removal of impurities is selected from one of separation of solid and liquid, chemical precipitation, absorption, ion exchange and oxidation or a variety of.
It can be filtering, centrifugation, sedimentation etc. as the separation of solid and liquid；It can be adjusting as the chemical precipitation PH, carbonate deposition, magnesium salts precipitating etc.；It can be physical absorption and/or chemisorption, specific absorption as the absorption Agent can select active carbon, silica gel, aluminium oxide, molecular sieve, natural clay etc.；As the ion exchange, strong acid can be used Any one in property resin cation, acidulous cation resin；As the oxidation, can use 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 choose solid-liquid isolation method removal of impurities；For inorganic matter and organic matter, chemical precipitation method, ion exchange can choose Method, absorption method removal of impurities, such as Subacidity cation exchange process, active carbon adsorption etc.；It, can be using absorption for organic matter And/or the mode of oxidation cleans, wherein preferably ozone biological activated carbon adsorption and oxidation method.One according to the present invention preferred Embodiment, catalyst production waste water successively pass through filtering, Subacidity cation exchange process, ozone biological activated carbon adsorption and oxidation Method cleans.By above-mentioned dedoping step, most suspended substances, hardness, silicon and organic matter can be removed, reduces device fouling Risk guarantees wastewater treatment process continuous and steady operation.
It in the present invention, can be before using processing method processing of the invention (preferably for the lower waste water of salt content After above-mentioned removal of impurities), so that salt content is reached range required by catalyst production waste water of the invention by being concentrated.It is preferred that Ground, it is described concentration selected from ED film concentration and/or it is reverse osmosis；It is highly preferred that described be concentrated by the concentration of ED film and reverse osmosis progress, There is no particular limitation for the sequencing of the ED film concentration and reverse osmosis progress.The ED film concentration and reverse osmosis treatment device It can carry out, can be specifically chosen according to the case where waste water to be processed in such a way that this field is conventional with condition.Specifically, make For ED film concentration, unidirectional electrodialysis system or pole-reversing electroosmosis system can be selected to carry out；It, can be with as described reverse osmosis Rolled film, plate membrane, dish tubular membrane, vibrating membrane or combinations thereof is selected to carry out.Wastewater treatment can be improved by the concentration Efficiency avoids energy waste caused by largely evaporating.
In a preferred embodiment of the invention, catalyst production waste water is the waste water in process of producing molecular sieve It cleans, and passes through by chemical precipitation, filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method Waste water after the concentration of ED film and reverse osmosis concentration.
Condition as above-mentioned chemical precipitation is preferred are as follows: uses sodium carbonate as inorganic agent, relative to 1mol calcium in waste water 1.2-1.4mol sodium carbonate is added in ion, and the pH for adjusting waste water is greater than 7, and reaction temperature is 20-35 DEG C, reaction time 0.5- 4h。
Condition as above-mentioned filtering is preferred are as follows: 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 0.7-1.7mm, quartz sand particle size 0.5-1.3mm, filtering velocity 10-30m/h.Filter The regeneration method of " gas backwash-gas and water backwash-water backwashing " is used to carry out media regeneration, regeneration period 10- after expecting use 15h。
Condition as above-mentioned Subacidity cation exchange process is preferred are as follows: pH value range 6.5-7.5；Temperature≤40 DEG C, Resin layer height is 1.5-3.0m, regenerated liquid HCl concentration: 4.5-5 mass %；Regenerant consumption (based on 100%), 50-60kg/ m3Wet resin；Regenerated liquid HCl flow velocity is 4.5-5.5m/h, and regeneration time of contact is 35-45min；Just washing flow velocity is 18-22m/h, Just washing the time is 2-30min；Operation flow velocity is 15-30m/h；Langfang sanat can be used for example in acid cation exchange resin Chemical Co., Ltd., SNT board D113 acid cation exchange resin.
Condition as above-mentioned ozone biological activated carbon adsorption and oxidation method is preferred are as follows: and the ozone residence time is 50-70min, Empty bed filtering velocity is 0.5-0.7m/h.
Condition as the concentration of above-mentioned ED film is preferred are as follows: electric current 145-155A, voltage 45-65V.It for example can be with as ED film For the ED film of Japanese A Sitong company production.
It is preferred as above-mentioned reverse osmosis condition are as follows: operating pressure 5.4-5.6MPa, 25-35 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.
According to the present invention, when starting to carry out wastewater treatment, catalyst production waste water can be used and directly go into operation, if catalysis The ion concentration of agent production waste water meets condition of the invention, can first carry out the first evaporation, cooling with condition according to the invention Crystallization carries out the second evaporation, cooling processing again；If the ion concentration of catalyst production waste water is unsatisfactory for condition of the invention, can It first to carry out the second evaporation, cooling processing, obtains treatment fluid and is separated by solid-liquid separation to obtain sodium chloride crystal and the second mother liquor, then by the Two mother liquors mix to adjust the ion concentration of waste water to be processed as range of the presently claimed invention with the catalyst production waste water Carry out the first evaporation again afterwards, crystallisation by cooling obtains sodium sulfate crystal.Certainly sodium sulphate or chlorination also can be used in the initial stage The ion concentration in waste water to be processed is adjusted in sodium, as long as meeting the waste water to be processed in the present invention to be processed useless SO in 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 are successively concentrated by ED film With the waste water after reverse osmosis concentration.
Embodiment 1
As shown in Figure 1, by catalyst production waste water (46g/L containing NaCl, Na2SO4 89g/L、NH4Cl 23g/L、(NH4)2SO445.2g/L, pH 6.6) it with inlet amount is 10m3The speed of/h is sent in the pipeline of processing system, is imported into pipeline The sodium hydrate aqueous solution of 45.16 mass % carries out the adjusting of first time pH value, right by the first pH value measuring device 61 (pH meter) PH value after adjusting is monitored (measured value 8), then pumps 71 for a part of catalyst production waste water by first circulation It is sent into the first heat-exchanger rig 31 (two phase stainless steel plate heat exchanger) and the heat exchange of the first liquid of steam condensation containing ammonia, another part and the Nine circulating pumps 79 return the second mother liquor mixing, be then fed into the tenth heat-exchanger rig 30 (two phase stainless steel plate heat exchanger) with The heat exchange of first concentrate, two parts are merged to obtain waste water to be processed, (double waste water to be processed is sent into the 8th heat-exchanger rig 38 Phase stainless steel plate type heat exchanger) pipeline in import again 45.16 mass % sodium hydrate aqueous solution carry out pH value adjusting, so After the 8th heat-exchanger rig 38 of feeding and the first steam heat-exchanging containing ammonia make waste water to be processed be warming up to 112 DEG C afterwards, and pass through the 3rd pH Value measurement mechanism 60 (pH meter) is monitored (measured value 11.0) to the pH value after adjusting.
First evaporation carries out in MVR vaporising device 3 (falling liquid film+the second crystallizing evaporator of forced circulation two-stage MVR), condition Such as the following table 1, the first steam containing ammonia and the first concentrate are obtained.First steam containing ammonia is compressed into (temperature by the first compressor 101 Rise 18 DEG C) after, successively in the 8th heat-exchanger rig 38 and the first heat-exchanger rig 31 with the first steam containing ammonia and waste water to be processed Heat exchange, obtains the first ammonium hydroxide and stores in the first tank used for storing ammonia 51.In addition, containing to improve the solid in MVR vaporising device 3 Partially liq after evaporating in MVR vaporising device 3 is recycled to the 8th by the 5th circulating pump 75 as first circulation liquid and changed by amount Then thermal 38 is again introduced into MVR vaporising device 3 and carries out the first evaporation (the first reflux ratio is 25.7).Pass through control first The degree that the flow control first of circulating pump 70 is evaporated controls the concentration of the concentrate of the first evaporation, the first obtained concentration 119.8g/L containing NaCl, Na in liquid2SO4 181.5g/L(Cl-Concentration be 2.048mol/L, SO4 2-Concentration be 1.278mol/L)。
First concentrate is sent into the tenth heat-exchanger rig 30 with after catalyst production waste water heat exchange, is re-fed into the second heat exchange dress Setting 32 (heat exchangers of plastic material) and the first mother liquor and carrying out the second heat exchange makes waste water to be processed be cooled to 20 DEG C, then with the The circulation fluid mixing of the equipment of crystallisation by cooling 2 of two circulating pumps 72 conveying exchanges heat further through the 6th heat-exchanger rig 36 with freezing liquid After cooling, it is sent into equipment of crystallisation by cooling 2 (freezing and crystallizing tank) and carries out crystallisation by cooling, obtain the crystal solution of sulfur acid sodium crystal.Its In, the temperature of crystallisation by cooling is -2 DEG C, time 120min, and the internal circulating load for controlling crystallisation by cooling is 1165m3/ h, control cooling The degree of supersaturation of sodium sulphate is not more than 1.1g/L in crystallization process.
The crystal solution of sulfur acid sodium crystal obtained above is sent into the first equipment for separating liquid from solid 91 (centrifuge) to be consolidated Liquid separation, obtains 3.71m per hour3Contain NaCl 258.6g/L, Na2SO4 20.3g/L、NaOH 5.6g/L、NH3 0.3g/L The first mother liquor, be temporarily stored into the first mother liquor tank 53, obtain per hour purity be 98.6 mass %, aqueous 75 mass % ten water Sulfate crystal filter cake 5570.57kg.
Second evaporation process carries out in multi-effect evaporating device 1 (each effect is forced-circulation evaporation crystallizer).It will For first mother liquor after the second heat-exchanger rig 32 and the heat exchange of the first concentrate, a part is sent into 34 (two-phase stainless of the 4th heat-exchanger rig Steel plate type heat exchanger) it exchanges heat with the second liquid of steam condensation containing ammonia, another part is sent into 35 (two-phase stainless steel plate of the 5th heat-exchanger rig Formula heat exchanger) it exchanges heat with the second concentrate of sodium chloride-containing crystal and sodium sulfate crystal, then the first mother liquor of two parts is merged, It is sent into multi-effect evaporating device 1 after being mixed again with the second cleaning solution, passes through second in the pipeline for being sent to multi-effect evaporating device 1 PH value measuring device 62 (pH meter) is monitored (measured value 11.4) to pH value.The multi-effect evaporating device 1 is steamed by the first effect Send out device 1a, 2nd effect evaporator 1b, third effect evaporator 1c and fourth evaporator 1d composition.First mother liquor is successively led to Enter and be evaporated in each effect evaporator of the multi-effect evaporating device 1, finally obtains sodium chloride-containing crystal and sodium sulfate crystal Second concentrate.The second steam containing ammonia that preceding 1st effective evaporator is obtained is passed through in rear 1st effective evaporator, and obtains the second ammonium hydroxide. It is passed through heating steam in 1st effective evaporator 1a, heats the condensation water obtained after steam condenses in 1st effective evaporator 1a, It exchanges heat in the 7th heat-exchanger rig 37 and the second cleaning solution.The second steam containing ammonia that last 1st effective evaporator 1d is obtained exchanges heat in third It exchanges heat in device 33 with the first mother liquor, obtains the second ammonium hydroxide.The merging of above-mentioned second ammonium hydroxide is stored in the second tank used for storing ammonia In 52.Second evaporation evaporation conditions such as the following table 1.
The degree of second evaporation is monitored by the mass flowmenter being arranged on multi-effect evaporating device 1, control second Evaporation capacity is 2.91m3/ h (concentration for being equivalent to sodium sulphate in control treatment fluid is 0.9761Y (81.8g/L)).
Table 1
The second concentrate of sodium chloride-containing crystal and sodium sulfate crystal that second evaporation obtains in low-temperature treatment tank 55 into Row cooling processing, temperature are 20 DEG C, and time 55min obtains the treatment fluid of sodium chloride-containing crystal.Setting in low-temperature treatment tank 55 There are agitating paddle, revolving speed 60r/min.
The treatment fluid of sodium chloride-containing crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) and carries out the second separation of solid and liquid, 0.92m is obtained per hour3Contain NaCl 268.7g/L, Na2SO4 81.8g/L、NaOH 22.6g/L、NH30.0003g/L's Second mother liquor is temporarily stored into the second mother liquor tank 54.Gained solid sodium chloride (is obtained into the chlorine that water content is 14 mass % per hour Change sodium crystalli-zation cake 808.69kg, wherein the content of sodium sulphate is 1.5 mass % or less) with equal with sodium chloride butt quality Dry in drying machine after the sodium chloride solution elution of 268g/L, obtaining sodium chloride 695.47kg per hour, (purity is 99.5 matter Measure %), the second cleaning solution washed is recycled to multi-effect evaporating device 1 by the tenth circulating pump 80.
In the present embodiment, the ammonium hydroxide 2.92m that concentration is 5.5 mass % is obtained in the first tank used for storing ammonia 51 per hour3；The The ammonium hydroxide 2.91m that concentration is 0.03 mass % is obtained in two tank used for storing ammonia 52 per hour3。
In addition, the tail gas of the 8th heat-exchanger rig 38, equipment of crystallisation by cooling 2 and the discharge of the 4th heat-exchanger rig 34 passes through vacuum pump 81 introducing tail gas absorbers 83 are absorbed, and recirculated water are connected in tail gas absorber 83, the recirculated water is in the 4th circulating pump 74 Under the action of recycled in tail gas absorber 83, while by third circulating pump 73 from circulating water pool 82 to tail gas absorber 83 Water supplement, and fresh water is added in circulating water pool 82, reduce temperature and ammonia content that water is used in the work of vacuum pump 81.The tail It is further passed through dilute sulfuric acid in aspiration tower 83, to absorb ammonia in tail gas etc..The initial phase of MVR evaporation, pass through temperature Steam for 143.3 DEG C is started.
Embodiment 2
According to the method for embodiment 1 carry out catalyst production waste water processing, unlike: to 66g/L containing NaCl, Na2SO4 56g/L、NH4Cl 40g/L、(NH4)2SO4The waste water that 34.5g/L, pH are 6.3 is handled, and is filled by the 8th heat exchange The temperature for setting waste water to be processed after 38 carry out heat exchanges is 114 DEG C.
Condition such as the following table 2 of first evaporation and the second evaporation；The temperature of crystallisation by cooling is -4 DEG C, time 120min；Drop 25 DEG C of temperature of temperature processing, time 50min.172.6g/L containing NaCl, Na in the first obtained concentrate2SO4126.4g/L (Cl-Concentration be 2.95mol/L, SO4 2-Concentration be 0.89mol/L).
Table 2
First equipment for separating liquid from solid 91 obtains the sal glauberi crystalli-zation cake of aqueous 75.5 mass % per hour 3828.19kg, purity are 98.7 mass %)；5.02m is obtained per hour3Concentration is NaCl 275.1g/L, Na2SO4 16g/L、 NaOH 4.2g/L、NH3The first mother liquor of 0.25g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake that water content is 14.5 mass % per hour 1275.60kg finally obtains sodium chloride 1090.64kg per hour (purity is 99.5 mass %)；Second equipment for separating liquid from solid 92 1.05m is obtained per hour3Concentration is NaCl 269.6g/L, Na2SO4 76.3g/L、NaOH 20.1g/L、NH30.0002g/L's Second mother liquor.
The ammonium hydroxide 3.05m that concentration is 5.9 mass % is obtained in first tank used for storing ammonia 51 per hour3；Second tank used for storing ammonia 52 In obtain per hour concentration be 0.03 mass % ammonium hydroxide 4.16m3。
Embodiment 3
According to the method for embodiment 1 carry out catalyst production waste water processing, unlike: to 103g/L containing NaCl, Na2SO4 46g/L、NH4Cl 30g/L、(NH4)2SO4The waste water that 13.6g/L, pH are 6.5 is handled, and is filled by the 8th heat exchange The temperature for setting waste water to be processed after 38 carry out heat exchanges is 112 DEG C.
Condition such as the following table 3 of first evaporation and the second evaporation；The temperature of crystallisation by cooling is 0 DEG C, time 120min；Cooling 30 DEG C of the temperature of processing, time 55min.220g/L containing NaCl, Na in the first obtained concentrate2SO4 89.6g/L(Cl- Concentration be 3.761mol/L, SO4 2-Concentration be 0.631mol/L).
Table 3
First equipment for separating liquid from solid 91 obtains the sal glauberi crystalli-zation cake of aqueous 76 mass % per hour 2525.91kg, purity are 98.5 mass %)；6.00m is obtained per hour3Concentration is NaCl 293g/L, Na2SO4 18.4g/L、 NaOH3.46g/L、NH3The first mother liquor of 0.12g/L.
Second equipment for separating liquid from solid 92 obtains the sodium chloride crystalli-zation cake that water content is 15 mass % per hour 1598.18kg finally obtains sodium chloride 1358.45kg per hour (purity is 99.3 mass %)；Second equipment for separating liquid from solid 92 1.45m is obtained per hour3Concentration is NaCl 276.5g/L, Na2SO4 76g/L、NaOH 14.3g/L、NH3The of 0.008g/L Two mother liquors.
The ammonium hydroxide 3.45m that concentration is 9.5 mass % is obtained in first tank used for storing ammonia 51 per hour3；Second tank used for storing ammonia 52 In obtain per hour concentration be 0.01 mass % ammonium hydroxide 4.79m3。
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (12)

1. a kind of processing method of catalyst production waste water, the catalyst production waste water contain NH4 +、SO4 2-、Cl-And Na+, special Sign is that this approach includes the following steps,
1) waste water to be processed is subjected to the first evaporation, obtains the first steam containing ammonia and the first concentrate, the waste water to be processed contains There is the catalyst production waste water；
2) first concentrate is subjected to crystallisation by cooling, obtains the crystal solution of sulfur acid sodium crystal；
3) crystal solution of the sulfur acid sodium crystal is carried out first to be separated by solid-liquid separation, and is separated by solid-liquid separation obtained liquid phase for first and leads to Each effect evaporator for entering multi-effect evaporating device carries out the second evaporation, obtains the second steam containing ammonia and crystalliferous second concentrate；
4) crystalliferous second concentrate is subjected to cooling processing, obtains the treatment fluid of sodium chloride-containing crystal；
5) treatment fluid second is carried out to be separated by solid-liquid separation；
Wherein, before waste water to be processed is carried out the first evaporation, the pH value for adjusting the waste water to be processed is greater than 9；
SO in first concentrate4 2-Concentration be 0.01mol/L or more.
2. according to the method described in claim 1, wherein, the waste water to be processed is the catalyst production waste water；Alternatively, institute Stating waste water to be processed is that the catalyst production waste water is mixed at least part of of liquid phase that second separation of solid and liquid obtains Liquid；
Preferably, the SO contained in first concentrate4 2-Concentration be 0.1mol/L or more, more preferably 0.2mol/L with On；
Preferably, the Cl contained in first concentrate-Concentration be 5mol/L or less；
Preferably, the SO contained in obtained liquid phase is separated by solid-liquid separation relative to described in 1mol first4 2-, described first is separated by solid-liquid separation The Cl contained in obtained liquid phase-For 7.15mol or more；
Preferably, before waste water to be processed is carried out the first evaporation, the pH value for adjusting the waste water to be processed is greater than 10.8；
Preferably, pH value is adjusted to carry out using NaOH.
3. method according to claim 1 or 2, wherein before the crystallisation by cooling, SO in first concentrate4 2- Concentration be 0.01mol/L or more, Cl-Concentration be 5.2mol/L or less；
Preferably, the crystallisation by cooling is precipitated sodium chloride crystallization；
Preferably, before the crystallisation by cooling, the concentration of sodium chloride in first concentrate is adjusted；
Preferably, the concentration for adjusting sodium chloride in first concentrate is separated by solid-liquid separation obtained liquid phase, institute by mixing second It states catalyst production waste water and/or elutes the cleaning solution progress of sodium sulfate crystal.
4. method described in any one of -3 according to claim 1, wherein crystalliferous second concentrate that step 3) obtains For the concentrate of sodium chloride-containing crystal and sodium sulfate crystal, and cooling processing keeps the sodium chloride-containing crystal and sodium sulphate brilliant Sodium sulfate crystal dissolution in the concentrate of body.
5. method described in any one of -4 according to claim 1, wherein the condition of first evaporation includes: that temperature is 35 DEG C or more, pressure is -98kPa or more；
Preferably, it is 75 DEG C~130 DEG C that the condition of first evaporation, which includes: temperature, and pressure is -73kPa~117kPa；
Preferably, it is 85 DEG C~130 DEG C that the condition of first evaporation, which includes: temperature, and pressure is -58kPa~117kPa；
Preferably, it is 95 DEG C~110 DEG C that the condition of first evaporation, which includes: temperature, and pressure is -37kPa~12kPa；
Preferably, first evaporation is carried out using MVR vaporising device.
6. method described in any one of -4 according to claim 1, wherein the condition of the crystallisation by cooling include: temperature be - 21.7 DEG C~17.5 DEG C, preferably -20 DEG C~5 DEG C, more preferably -10 DEG C~5 DEG C, further preferably -10 DEG C~0 DEG C；
Preferably, the condition of the crystallisation by cooling include: the time be 5min or more, preferably 60min~180min, more preferably 90min~150min.
7. method described in any one of -4 according to claim 1, wherein the condition of second evaporation includes: that temperature is 17.5 DEG C or more, pressure is -101kPa or more；
Preferably, it is 35 DEG C~110 DEG C that the condition of second evaporation, which includes: temperature, and pressure is -98kPa~12kPa；
Preferably, it is 45 DEG C~110 DEG C that the condition of second evaporation, which includes: temperature, and pressure is -95kPa~12kPa；
Preferably, 5 DEG C higher than rear 1st effective evaporator of the evaporating temperature of preceding 1st effective evaporator or more, preferably high by 10 in the second evaporation DEG C or more.
8. method described in any one of -4 according to claim 1, wherein the condition of the cooling processing includes: that temperature is 13 DEG C~100 DEG C, preferably 15 DEG C~45 DEG C, more preferably 15 DEG C~35 DEG C, further preferably 17.9 DEG C~35 DEG C；
Preferably, it is described cooling processing condition include: the time be 5min or more, preferably 5min~120min, more preferably 45min~90min.
9. method described in any one of -9 according to claim 1, wherein the waste water to be processed is being carried out the first evaporation Before, the waste water to be processed and first steam containing ammonia are subjected to the first heat exchange, and obtain the first ammonium hydroxide；
Preferably, before first concentrate is carried out crystallisation by cooling, by first concentrate and first solid-liquid Isolated liquid phase carries out the second heat exchange；
Preferably, before the liquid phase for obtaining first separation of solid and liquid is passed through multi-effect evaporating device, contain ammonia for described second Steam and described first is separated by solid-liquid separation obtained liquid phase progress third heat exchange and obtains ammonium hydroxide.
10. method described in any one of -9 according to claim 1, this method further includes by the knot of the sulfur acid sodium crystal Brilliant liquid obtains sodium sulfate crystal after first is separated by solid-liquid separation；
Preferably, this method further includes washing to obtained sodium sulfate crystal.
11. method described in any one of -9 according to claim 1, this method further includes by the place of the sodium chloride-containing crystal Reason liquid obtains sodium chloride crystal after second is separated by solid-liquid separation；
Preferably, this method further includes washing to obtained sodium chloride crystal.
12. method described in any one of -9 according to claim 1, wherein NH in the catalyst production waste water4 +For 8mg/ L or more, SO4 2-For 1g/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 is concentrated.
CN201710752082.9A 2017-08-28 2017-08-28 Method for treating catalyst production wastewater Active CN109422401B (en)

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