CN108726609A - A kind of processing method of catalyst production waste water - Google Patents

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

Info

Publication number
CN108726609A
CN108726609A CN201710265653.6A CN201710265653A CN108726609A CN 108726609 A CN108726609 A CN 108726609A CN 201710265653 A CN201710265653 A CN 201710265653A CN 108726609 A CN108726609 A CN 108726609A
Authority
CN
China
Prior art keywords
waste water
evaporation
crystal
sodium chloride
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710265653.6A
Other languages
Chinese (zh)
Other versions
CN108726609B (en
Inventor
殷喜平
李叶
顾松园
杨凌
周岩
伊红亮
王涛
张志民
苑志伟
胡学武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Catalyst Co
Original Assignee
China Petroleum and Chemical Corp
Sinopec Catalyst Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Catalyst Co filed Critical China Petroleum and Chemical Corp
Priority to CN201710265653.6A priority Critical patent/CN108726609B/en
Publication of CN108726609A publication Critical patent/CN108726609A/en
Application granted granted Critical
Publication of CN108726609B publication Critical patent/CN108726609B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The present invention relates to sewage treatment fields, disclose the processing method of catalyst production waste water, which contains NH4 +、SO4 2‑、Cl‑And Na+, this method includes 1) and pending waste water is passed through the first evaporation of progress in MVR vaporising devices, the first concentrate of the first steam containing ammonia and sulfur acid sodium crystal and sodium chloride crystal is obtained, the pending waste water contains catalyst production waste water；2) first concentrate is subjected to low-temperature treatment, so that sodium sulfate crystal is dissolved, obtains the treatment fluid of sodium chloride-containing crystal；3) treatment fluid of the sodium chloride-containing crystal is carried out first to be separated by solid-liquid separation, and the second evaporation of each effect evaporator progress that obtained liquid phase is passed through multi-effect evaporating device successively is separated by solid-liquid separation by first, obtain the second concentrate of sulfur acid sodium crystal；4) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation.Ammonium and sodium sulphate, sodium chloride in waste water can be separately recovered in this method, farthest recycle the resource in waste water.

Description

A kind of processing method of catalyst production waste water
Technical field
The present invention relates to sewage treatment fields, and in particular, to a kind of processing method of catalyst production waste water, especially It is related to a kind of containing NH4 +、SO4 2-、Cl-And Na+Catalyst production waste water processing method.
Background technology
In the production process of oil refining catalyst, a large amount of sodium hydroxide, hydrochloric acid, sulfuric acid, ammonium salt, sulfate, salt are needed The inorganic acids alkali salt such as hydrochlorate generates and largely contains ammonium, sodium chloride and sodium sulphate and alumino-silicate combined sewage.For such Sewage, common practice is first in the range of adjusting pH value to 6~9, after removing most suspended substances, then to adopt in the prior art The removing of ammonium ion is carried out with biochemical process, blow-off method or vaporizing extract process, then, by saline sewage through overregulating pH value, the big portion of removing Divide suspended matter, remove hardness, except silicon and partial organic substances and then by ozone biological activated carbon adsorption and oxidation or other advanced oxygen Change method oxidation removal major part organic matter, then, after further removing hardness into ion interchange unit, into thickening device After (such as reverse osmosis and/or electrodialysis) concentration, then using MVR evaporative crystallizations or multiple-effect evaporation crystallization, obtain the chlorine containing a small amount of ammonium salt Change sodium and sodium sulphate mixing carnallite；Either；First adjust pH value in the range of 6.5~7.5, removing most suspended substances, so Afterwards, it removes hardness, remove silicon and partial organic substances, gone using ozone biological activated carbon adsorption and oxidation or the oxidation of other advanced oxidation processes It is (such as reverse osmosis and/or electric into thickening device after further removing hardness into ion interchange unit after most of organic matter Dialysis) after concentration, then crystallized using MVR evaporative crystallizations or multiple-effect evaporation, sodium chloride and the sodium sulphate mixing for obtaining ammonium salt-containing are miscellaneous Salt.But these carnallites containing ammonium are difficult to handle at present, or the processing cost is high, also, the process of removing early period ammonium ion, Add additional the processing cost of waste water.
In addition, biochemical process deamination can only handle the waste water of low ammonium content, and due to COD contents deficiency in Catalyst sewage Biochemical treatment cannot be directly carried out, machine object, such as glucose or starch are also additionally supplemented with during biochemical treatment, just may be used To handle ammoniacal nitrogen using biochemical process.Sixty-four dollar question is biochemical process deamination treated waste water often total nitrogen (nitre not up to standard Acid ion, nitrite ion content are exceeded), it is also necessary to advanced treating, in addition the content of salt does not reduce (20g/ in waste water L~30g/L), it is unable to direct emission, needs further to carry out desalting processing.
Air- extraction deamination needs to add a large amount of adjusting PH with base value, alkaline consumption is very high, due to de- to deviate from the ammoniacal nitrogen in waste water The alkali in waste water after ammonia cannot recycle, and treated, and pH value of waste water is very high, and the processing cost is high, and air lift rear catalyst is dirty The not big variation of COD contents in water, the salt content in waste water do not reduce (20g/L~30g/L), are unable to direct emission, It needs further to carry out desalting processing, wastewater treatment operating cost is high, remains a large amount of alkali in treated waste water, pH value is very Height, waste is big, and processing cost is up to 50 yuan/ton.
Invention content
The purpose of the present invention is overcome to contain NH in the prior art4 +、SO4 2-、Cl-And Na+Catalyst production waste water be processed into This height, and the problem of can only obtain mixing salt crystal provides and a kind of at low cost and environmentally friendly contains NH4 +、SO4 2-、Cl-And Na+ Wastewater treatment method, ammonium and sodium chloride, sodium sulphate in waste water can be separately recovered in this method, farthest recycle useless Resource in water.
To achieve the goals above, the present invention provides a kind of processing method of catalyst production waste water, catalyst production Waste water contains NH4 +、SO4 2-、Cl-And Na+, this approach includes the following steps,
1) pending waste water is passed through in MVR vaporising devices and carries out the first evaporation, obtain the first steam containing ammonia and sulfur acid First concentrate of sodium crystal and sodium chloride crystal, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal and sodium chloride crystal is subjected to low-temperature treatment, makes sodium sulfate crystal Dissolving, obtains the treatment fluid of sodium chloride-containing crystal；
3) treatment fluid of the sodium chloride-containing crystal is carried out first to be separated by solid-liquid separation, and obtained liquid is separated by solid-liquid separation by first Each effect evaporator for being mutually passed through multi-effect evaporating device successively carries out the second evaporation, obtains the second concentrate of sulfur acid sodium crystal；
4) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is big In 9；The second steam containing ammonia that the preceding 1st effective evaporator of the multi-effect evaporating device evaporates is passed through in rear 1st effective evaporator, Described first is separated by solid-liquid separation obtained liquid phase and the second steam containing ammonia cocurrent heat exchange；Second evaporation makes sodium chloride not Crystallization is precipitated；Relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 7.15 mole or more.
Through the above technical solutions, for NH is contained4 +、SO4 2-、Cl-And Na+Catalyst production waste water, by that will wait in advance After the pH value of processing waste water is adjusted to specific range, MVR vaporising devices are recycled to be evaporated isolated sulfur acid sodium brilliant The concentrate of body and sodium chloride crystal and compared with concentrated ammonia liquor, then recycles low-temperature treatment to make the dissolving of sodium sulphate in concentrate, chlorine Change sodium and further crystallize precipitation, obtains sodium chloride crystallization.Then multi-effect evaporating device is recycled to be evaporated to obtain sulfur-bearing again The concentrate of sour sodium crystal and compared with weak aqua ammonia, obtains sulfate crystal.This method can respectively obtain high-purity sodium chloride and Sodium sulphate, the difficulty during avoiding mixed salt processing and recycling, is completed at the same time separation of ammonia and the process of salt, and using heat Exchanged form makes waste water heating and steam cooling containing ammonia simultaneously, energy saving rationally using the heat in evaporation process, reduces useless Cost of water treatment, the ammonium in waste water are recycled in the form of ammonium hydroxide, and sodium sulphate and sodium chloride are recycled with crystal form respectively, entire mistake Journey does not have waste residue and liquid generation, realizes the purpose to turn waste into wealth.
Further, this method is matched by the first evaporation and low-temperature treatment so that the first evaporation can be in higher temperatures Degree is lower to carry out, and improves the solid content and evaporation efficiency in the first evaporation concentrated solution, can be simultaneously reached energy-saving effect.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of the catalyst production waste water processing method of embodiment provided by the invention.
Reference sign
1, multi-effect evaporating device 22, low-temperature treatment tank
2, MVR vaporising devices 31, the first heat-exchanger rig
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 76, the 6th circulating pump
36, the 6th heat-exchanger rig 78, the 8th circulating pump
51, the first tank used for storing ammonia 79, the 9th circulating pump
52, the second tank used for storing ammonia 80, the tenth circulating pump
53, the first mother liquor tank 81, vacuum pump
54, the second mother liquor tank 82, circulating water pool
55, brilliant liquid collecting tank 83, tail gas absorber
61, the first pH value measuring device 91, the first equipment for separating liquid from solid
62, the second pH value measuring device 92, the second equipment for separating liquid from solid
71, first circulation pump 10, compressor
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Below in conjunction with Fig. 1, the present invention will be described, and the present invention is not limited by Fig. 1.
The processing method of catalyst production waste water provided by the invention, the catalyst production waste water contain NH4 +、SO4 2-、Cl- And Na+, this approach includes the following steps,
1) pending waste water is passed through in MVR vaporising devices 2 and carries out the first evaporation, obtain the first steam containing ammonia and sulfur acid First concentrate of sodium crystal and sodium chloride crystal, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal and sodium chloride crystal is subjected to low-temperature treatment, makes sodium sulfate crystal Dissolving, obtains the treatment fluid of sodium chloride-containing crystal；
3) treatment fluid of the sodium chloride-containing crystal is carried out first to be separated by solid-liquid separation, and obtained liquid is separated by solid-liquid separation by first Each effect evaporator for being mutually passed through multi-effect evaporating device 1 successively carries out the second evaporation, obtains the second concentrate of sulfur acid sodium crystal；
4) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices 2, the pH value of the pending waste water is adjusted More than 9；
The second steam containing ammonia that the preceding 1st effective evaporator of the multi-effect evaporating device 1 evaporates is passed through latter effect evaporation In device, described first is separated by solid-liquid separation obtained liquid phase and the second steam containing ammonia cocurrent heat exchange；Second evaporation makes chlorine Change sodium and does not crystallize precipitation；Relative to the SO contained in 1 mole of pending waste water4 2-, contain in the pending waste water Cl-It is 7.15 moles or more.
Preferably, the pending waste water is the catalyst production waste water；Alternatively, the pending waste water contain it is described Catalyst production waste water and described second is separated by solid-liquid separation obtained liquid phase.
It is highly preferred that the pending waste water is the catalyst production waste water is separated by solid-liquid separation obtained liquid with described second At least part of mixed liquor of phase.
It is obtained with second separation of solid and liquid it is further preferred that the pending waste water is the catalyst production waste water Liquid phase mixed liquor.
Preferably, before the pending waste water is passed through MVR vaporising devices 2, the pH of the pending waste water is adjusted Value is more than 10.8.In addition, for the pending waste water pH value the upper limit there is no limit, such as can be 14 hereinafter, it is preferred that For 13.5 hereinafter, more preferable 13 or less.
Method provided by the invention, which can be directed to, contains NH4 +、SO4 2-、Cl-And Na+Catalyst production waste water at Reason, in addition to containing NH4 +、SO4 2-、Cl-And Na+Outside, to the catalyst production waste water, there is no particular limitation.From raising waste water Treatment effeciency from the point of view of, relative to the SO contained in 1 mole of pending waste water4 2-, contain in the pending waste water Some Cl-It is 7.15 moles or more, preferably 9.5 moles or more, preferably 10 moles or more, preferably 50 moles hereinafter, more Preferably 40 moles hereinafter, further preferably 30 moles hereinafter, for example can be 9-20 moles, preferably 9-12 moles, more Preferably 10-12 moles.By by SO4 2-And Cl-Molar ratio control in above range, sodium chloride in low-temperature treatment can be made Be precipitated and sodium sulphate is completely dissolved, to achieve the purpose that efficiently separate sodium chloride.In addition, it is as above described below, in the present invention In and can also thus come in pending waste water by the second Recycling Mother Solution obtained in the second evaporation process to the first evaporation SO4 2-And Cl-Molar ratio be adjusted, and the balance of sodium hydroxide can be maintained.
In the present invention, first evaporation needs that sodium sulfate crystal is made to dissolve in low-temperature treatment, specifically, the The first concentrate of sulfur acid sodium crystal and sodium chloride crystal is obtained in one evaporation, need to ensure that sodium sulfate crystal therein can be It is completely dissolved in low-temperature treatment.By controlling the evaporation capacity of first evaporation, makes sodium sulphate, sodium chloride while crystallizing precipitation (the i.e. first evaporation obtains the first concentrate of sulfur acid sodium crystal and sodium chloride crystal), then sulfur-bearing is made by the low-temperature treatment Sodium sulfate crystal dissolving in first concentrate of sour sodium crystal and sodium chloride crystal, sodium chloride further crystallize precipitation, obtain Contain only the treatment fluid of sodium chloride crystal.Treatment fluid about the sodium chloride-containing crystal, it is not excluded that sodium chloride crystallization entrainment or The sodium sulphate of adsorption.Since the water content of crystal after separation of solid and liquid is different, sodium sulphate in the sodium chloride crystal generally yielded Content below 8 mass % (preferably 4 mass %), in the present invention, the content of sodium sulphate in obtained sodium chloride crystal It can think that sodium sulphate has dissolved when below 8 mass %.
In the present invention, second evaporation makes sodium chloride not crystallize precipitation, refers to that the sodium chloride of control mixed system is dense Degree is no more than the solubility under the second evaporation conditions (including but not limited to temperature, pH value etc.), it is not excluded that sulfate crystal presss from both sides The sodium chloride of band or adsorption.Since the water content of crystal after separation of solid and liquid is different, chlorine in the sodium sulfate crystal generally yielded Change the content of sodium below 8 mass % (preferably 4 mass %), in the present invention, sodium chloride in obtained sodium sulfate crystal It can think that sodium chloride does not crystallize precipitation when content is below 8 mass %.
In the present invention, it is to be understood that first steam containing ammonia and second steam containing ammonia are this field So-called indirect steam.The liquid phase and the first steam containing ammonia cocurrent heat exchange that first separation of solid and liquid obtains refer to adopting With the forward flow process in multiple-effect evaporation.The pressure is the pressure in terms of gauge pressure.
In the present invention, there is no particular limitation for the MVR vaporising devices 2, can be commonly used in the art various MVR vaporising devices.Such as can be selected from MVR falling film evaporators, MVR forced-circulation evaporators, the evaporation of MVR-FC continuous crystallisations It is one or more in device, MVR-OSLO continuous crystallisation evaporators.Wherein, preferably MVR forced-circulation evaporators, MVR-FC connect Continuous crystallizing evaporator, more preferably falling liquid film+forced circulation two-stage MVR crystallizing evaporators.
In the present invention, the condition of first evaporation can be selected suitably as needed, and described the can be controlled by reaching One evaporation evaporation capacity, make sodium sulphate, sodium chloride simultaneously crystallize precipitation (i.e. first evaporate obtain sulfur acid sodium crystal and sodium chloride First concentrate of crystal), then made in the first concentrate of sulfur acid sodium crystal and sodium chloride crystal by the low-temperature treatment Sodium sulfate crystal dissolving, sodium chloride further crystallizes precipitation, obtains the purpose for the treatment fluid for containing only sodium chloride crystal.Institute The condition for stating the first evaporation may include：Temperature is 35 DEG C or more, and pressure is -95kPa or more.It is excellent in order to improve evaporation efficiency Selection of land, it is described first evaporation condition include：Temperature is 45 DEG C~175 DEG C, and pressure is -95kPa~18110kPa；Preferably, It is described first evaporation condition include：Temperature is 60 DEG C~175 DEG C, and pressure is -87kPa~18110kPa；Preferably, described One evaporation condition include：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；Preferably, it is described first evaporation Condition includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；Preferably, the condition packet of first evaporation It includes：Temperature is 95 DEG C~110 DEG C, and pressure is -37kPa~12kPa；Preferably, the condition of first evaporation includes：Temperature is 105 DEG C~107 DEG C, pressure is -8kPa~0kPa.
In the present invention, the operating pressure of the first evaporation is preferably the saturated vapor pressure of evaporated feed liquid.
In the present invention, the flow of the first evaporation can suitably be selected according to the ability that equipment is handled, such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
By making the first evaporation carry out under these conditions, the efficiency of evaporation can be improved, energy consumption is reduced.Ensureing maximum While evaporation capacity (cycles of concentration), ensure the first concentrate sulfate crystal fully dissolved after low-temperature treatment, to The purity for the sodium chloride crystal that can ensure.
It can be evaporated in the pending waste water according to the present invention by controlling the evaporation conditions of MVR vaporising devices 2 The 90 mass % or more (preferably 95 mass % or more) of contained ammonia, to obtain higher first ammonium hydroxide of concentration, the first ammonium hydroxide Can with direct reuse in the production process of catalyst, either with acid neutralization obtain carrying out after ammonium salt reuse or to water and corresponding Ammonium salt or ammonium hydroxide allotment use.
According to the present invention, first evaporation makes sodium sulfate crystal be dissolved in low-temperature treatment, it is preferable that described first steams Hair makes a concentration of Y or less (preferably 0.9Y-0.99Y, preferably 0.95Y-0.98Y) of sodium sulphate in the treatment fluid, wherein Y is the concentration of sodium sulphate when sodium chloride and sodium sulphate reach saturation in treatment fluid under conditions of low-temperature treatment.Pass through Within the above range by the extent control of the first evaporation, can make under conditions of ensureing that low-temperature treatment can be such that sodium sulphate dissolves Sodium chloride crystallization as much as possible is precipitated.By making sodium chloride crystallize in the first evaporation as possible, wastewater treatment effect can be improved Rate reduces energy waste.
In the present invention, the carry out degree of first evaporation obtains liquid by the evaporation capacity of the first evaporation of monitoring The mode of amount carries out, and specifically, cycles of concentration is controlled by the evaporation capacity i.e. amount of the first ammonium hydroxide of the first evaporation of control, makes the The sulfate crystal being precipitated in one evaporation concentrated solution can be dissolved in low-temperature treatment.Here the first degree being concentrated by evaporation is led to The mode for crossing measurement evaporation capacity is monitored, and specifically can carry out flow measurement with use quality flowmeter.
A preferred embodiment according to the present invention, before the pending waste water is passed through MVR vaporising devices 2, The first steam containing ammonia that the MVR vaporising devices 2 obtain is subjected to the first heat exchange with the pending waste water and obtains first Ammonium hydroxide.There is no particular limitation for the mode of first heat exchange, and the heat exchange mode that this field routine may be used carries out.It is described The number of heat exchange can be preferably 2-4 times, more preferably 2-3 times more than primary.Pass through the heat exchange, the ammonia of output Water is further cooled, and heat utmostly recycles inside processing unit, and the energy is rationally utilized, and reduces waste.
A preferred embodiment according to the present invention, first heat exchange pass through the first heat-exchanger rig the 31, the 5th Heat-exchanger rig 35 and the second heat-exchanger rig 32 carry out, and specifically, a part for the pending waste water is filled by the first heat exchange Set 31 and first the condensation water of the steam containing ammonia carry out the first heat exchange, another part concentrated by the 5th heat-exchanger rig 35 and first After liquid carries out the first heat exchange, then pending waste water is converged, then by the second heat-exchanger rig 32 and the first steam containing ammonia into The first heat exchange of row.By first heat exchange, the pending waste water heating is made to be convenient for evaporating, while making described the One steam containing ammonia condenses to obtain the first ammonium hydroxide, and first ammonium hydroxide can be stored in the first tank used for storing ammonia 51.
In the present invention, do not have for first heat-exchanger rig 31, the 5th heat-exchanger rig 35 and the second heat-exchanger rig 32 It is special to limit, various heat exchangers commonly used in the art can be used, reaches first steam containing ammonia and waits locating with described Reason waste water carries out the purpose of first heat exchange.Specifically, it can be jacketed type exchanger, plate heat exchanger, shell Formula heat exchanger etc., wherein preferably plate heat exchanger.The material of the heat exchanger can be specifically chosen as needed, such as in order to Resist chloride ion corrosion, material can be selected for two phase stainless steel, the heat exchanger of titanium or titanium alloy, Hastelloy, temperature compared with The heat exchanger containing plastic material can be selected when low.
According to the present invention, in order to make full use of the first steam containing ammonia condensation water thermal energy, preferably changed by described first After thermal 31 carries out the first heat exchange, the temperature of the pending waste water is 44 DEG C~174 DEG C, more preferably 69 DEG C~174 DEG C, further preferably 79 DEG C~129 DEG C, be still more preferably 94 DEG C~109 DEG C.
According to the present invention, in order to make full use of the thermal energy of the first concentrate, preferably the is carried out by the 5th heat-exchanger rig 35 After one heat exchange, the temperature of the pending waste water is 44 DEG C~174 DEG C, more preferably 69 DEG C~174 DEG C, further preferably 79 DEG C~129 DEG C, be still more preferably 94 DEG C~109 DEG C.
Preferably pass through second heat-exchanger rig 32 according to the present invention in order to make full use of the thermal energy of the first steam containing ammonia After carrying out the first heat exchange, the temperature of the pending waste water is 52 DEG C~182 DEG C, more preferably 67 DEG C~182 DEG C, further Preferably 87 DEG C~137 DEG C, be still more preferably 102 DEG C~117 DEG C.
In the present invention, for the method for pH value adjusting, there is no particular limitation, such as can use additional basic species The mode of matter adjusts the pH value of the pending waste water.There is no particular limitation for the alkaline matter, reaches above-mentioned adjusting pH value Purpose.In order not to introduce new impurity in pending waste water, the purity of gained crystal is improved, the basic species are of fine quality It is selected as NaOH.
Feed postition as the alkaline matter is the feed postition of this field routine, but preferably makes alkaline matter It is mixed in form of an aqueous solutions with the pending waste water, such as the aqueous solution containing alkaline matter can be passed into and import institute It states and is mixed in the pipeline of pending waste water.For the content of alkaline matter in aqueous solution, there is no particular limitation, as long as It can achieve the purpose that above-mentioned adjusting pH value.But it in order to reduce the dosage of water, further reduces the cost, it is preferable to use alkalinity The saturated aqueous solution of substance.In order to monitor the pH value of the pending waste water, can be waited for described in measurement after above-mentioned adjusting pH value Handle the pH value of waste water.
A preferred embodiment according to the present invention, first evaporation process carry out in MVR vaporising devices 2, Before the pending waste water to be sent into the first heat-exchanger rig 31 or the 5th heat-exchanger rig 35 carries out the first heat exchange, by The pending waste water is sent into the main pipeline of the first heat-exchanger rig 31 or the 5th heat-exchanger rig 35 described in importing containing alkalinity The aqueous solution of substance and mixing, to carry out first time pH value adjusting；Then the pending waste water is being sent into the second heat exchange dress After setting 32 the first heat exchanges of carry out, by containing described in it will be imported in the pipeline of the pending waste water feeding MVR vaporising devices 2 There are the aqueous solution of alkaline matter and mixing, to carry out second of pH value adjusting.It is adjusted, is made described pending useless by pH value twice PH value of the water before being passed through MVR vaporising devices 2 is more than 9, preferably greater than 10.8.Preferably, first time pH value is adjusted So that the pH value of pending waste water is more than 7 (preferably 7-9), second of pH value is adjusted so that the pH value of pending waste water is more than 9 (being preferably greater than 10.8).In accordance with the present invention it is preferred that before carrying out first heat exchange, adjust described pending useless The pH value of water is more than 7.
In order to detect above-mentioned first time pH value adjust and second of pH value adjust after pH value, preferably will be described pending Waste water, which is sent on the main pipeline of the first heat-exchanger rig 31 and the 5th heat-exchanger rig 35, is arranged the first pH value measuring device 61 to measure The second pH value is being arranged the pending waste water to be sent on the pipeline of MVR vaporising devices 2 in pH value after the adjusting of first time pH value Measuring device 62 measures the pH value after second pH value is adjusted.
In the present invention, the first heat exchange, adjust the pH value of the pending waste water and the tune of the pending waste water With process, (the pending waste water contains the case where catalyst production waste water is separated by solid-liquid separation obtained liquid phase with described second Under, need the allocation process for carrying out the pending waste water) carry out priority there is no particular limitation, can be fitted as needed When selection, before the pending waste water is passed through MVR vaporising devices 2 complete.
In the present invention, in order to improve the crystalline content of concentrate in the MVR vaporising devices 2, the ammonia in liquid is reduced Content, preferably by partially liq (namely the liquid inside MVR vaporising devices after the MVR vaporising devices 2 evaporation Body, hereinafter also referred to as circulation fluid) it again returns in the MVR vaporising devices 2 after heating and evaporates.It is above-mentioned to return to the circulation fluid Process to the MVR vaporising devices 2 is preferably, by the circulation fluid and after the adjusting of first time pH value and to second It is again returned in MVR vaporising devices 2 after pending waste water mixing before pH value adjusting, for example, can be pumped by second circulation 72 by the circulation fluid back in waste water conveyance conduit between the first heat-exchanger rig 31 and the second heat-exchanger rig 32 with wait locating Waste water mixing is managed, heat exchange is carried out in the second heat-exchanger rig 32, after then being adjusted using second of pH value, is finally sent into institute It states in MVR vaporising devices 2.It is evaporated as the partially liq after the MVR vaporising devices 2 evaporation is flowed back into the MVR The ratio of device 2 is not particularly limited, for example, the reflux ratio of first evaporation can be appropriately configured as needed, Can be 10-200, preferably 40-150.Here, the reflux ratio refers to：Regurgitant volume and the liquid being sent into MVR vaporising devices 2 Body total amount subtracts the ratio of regurgitant volume.
In the case of, according to the invention it is preferred to, the method further include after first steam containing ammonia is compressed again Carry out first heat exchange.The compression of first steam containing ammonia can be carried out by the first compressor 10.By to described First steam containing ammonia is compressed, and to input energy in MVR vapo(u)rization systems, ensures that the process of waste water heating-evaporation-cooling is continuous It carries out, needs to input startup steam when MVR evaporation processes start, only be supplied by the first compressor 10 after reaching continuously running state It can, it is no longer necessary to input other energy.Various compressors commonly used in the art, example may be used in first compressor 10 Such as centrifugal blower, turbocompressor or lobed rotor compressor.After first compressor 10 compression, described first steams containing ammonia The temperature of vapour increases 5 DEG C~20 DEG C.
In the present invention, the first concentrate of the sulfur acid sodium crystal and sodium chloride crystal is subjected to low-temperature treatment, made Sodium sulfate crystal dissolves, and obtains the treatment fluid of sodium chloride-containing crystal.By controlling the evaporation capacity of first evaporation, make the place A concentration of Y of sodium sulphate in liquid is managed hereinafter, can make in low-temperature process, sodium sulfate crystal can be completely dissolved.
According to the present invention, there is no particular limitation for the mode that the low-temperature treatment carries out, as long as reaching control temperature appropriate Spend the sodium sulfate crystal dissolving in the first concentrate of the sulfur acid sodium crystal and sodium chloride crystal that make the first evaporation obtain. According to the present invention, the temperature of the low-temperature treatment is less than the temperature of the first evaporation, and specifically, the condition of the low-temperature treatment can be with Including：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 ℃；Such as can be 18 DEG C, 19 DEG C, 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 ℃、31℃、32℃、33℃、34℃、35℃、36℃、37℃、38℃、39℃、40℃、41℃、42℃、43℃、44℃、45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 55 DEG C and 60 DEG C.In order to ensure the effect of low-temperature treatment, the stop of low-temperature treatment Time can be 10min~600min, preferably 20min~300min, preferably 50min~70min.
In the present invention, pass through the condition of first evaporation and low-temperature treatment of control so that the first evaporation can be higher Evaporating temperature, closer to normal pressure evaporating pressure under carry out, avoid at a lower temperature evaporation when the low problem of efficiency, not only Evaporation efficiency is improved, and the energy consumption of evaporation process can be reduced, improves wastewater treatment speed.On this basis, low temperature The temperature control of processing is easier, and low-temperature treatment temperature can be under conditions of less than evaporating temperature (such as 45 DEG C or less) It is operated, is more conducive to the dissolving of sodium sulphate and the precipitation of sodium chloride.
In the present invention, the low-temperature treatment may be used various cooling systems commonly used in the art and carry out, such as It can select low-temperature treatment tank 22.Preferably, it can be provided with cooling-part in the low-temperature treatment tank 22, can is specifically Import the component of cooling water.By the cooling-part, the first concentrate in low-temperature treatment tank can be cooled down rapidly.It is preferred that Ground can be provided with mixing component in the low-temperature treatment tank 22, by the mixing component, can make in the first concentrate Solid-liquid distributed mutually, Temperature Distribution are uniform, and reaching makes sodium sulfate crystal fully dissolve, and the mesh that sodium chloride crystal is precipitated to greatest extent 's.
In the present invention, the treatment fluid of the sodium chloride-containing crystal by first be separated by solid-liquid separation after obtain sodium chloride 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 It can be selected from one or more in centrifugation, filtering, sedimentation.
According to the present invention, the separation of solid and liquid of first concentrate may be used the first equipment for separating liquid from solid (be, for example, from Scheming, band filter, flame filter press etc.) 91 progress.After the separation of solid and liquid, the first equipment for separating liquid from solid 91 obtain One mother liquor is temporarily stored into the first mother liquor tank 53, and can be sent into multi-effect evaporating device 1 by the 6th circulating pump 76 and be carried out the second steaming Hair.In addition, the impurity such as certain chlorion, free ammonia, hydroxide ion can be adsorbed by being difficult to avoid that on obtained sodium chloride crystal, In order to remove the impurity of absorption, the peculiar smell of solid salt is reduced, corrosivity is reduced, improves the purity of the crystal, it is preferable that described Sodium chloride crystal water, the catalyst production waste water or sodium chloride solution carry out the first washing and drying.In order to avoid washing The dissolving of sodium chloride crystal in the process, it is preferable that the sodium chloride crystal is washed with sodium-chloride water solution.It is highly preferred that Sodium chloride and sodium sulphate reach simultaneously at the concentration of the sodium-chloride water solution preferably temperature corresponding to sodium chloride crystal to be washed To the concentration of sodium chloride in the aqueous solution of saturation.
It is separated by solid-liquid separation the mode washed with first as above-mentioned first, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.Preferably, first washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, It can be carried out by the method for this field routine.It is described elutriation and elution number there is no particular limitation, can be 1 time with On, the sodium chloride crystal of higher purity, preferably 2-4 times in order to obtain.During elutriation, made with the catalyst production waste water It does not recycle generally when liquid to eluriate, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the first washing recycling. Before carrying out the elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (liquid of sodium chloride-containing crystal Content is 35 mass % or less).During elutriation, relative to the slurries of 1 parts by weight sodium chloride-containing crystal, eluriates and use Liquid is 1~20 parts by weight.It is preferable to use sodium-chloride water solution progress for elution.In order to further increase the effect of elutriation, obtain The higher sodium chloride crystal of purity, in the case of preferred, the liquid that elution can be used to obtain be washed, it is preferable to use water or Sodium chloride solution.For the liquid that washing generates, second of the pH value preferably returned it to before the evaporation of MVR vaporising devices is adjusted Before, such as by the 8th circulating pump 78 it returns after being mixed with pending waste water before second of pH is adjusted, by second of pH tune After the heat exchange of section and the second heat-exchanger rig 32, the evaporation of the first MVR vaporising devices is returned.
A preferred embodiment according to the present invention, the treatment fluid containing sodium chloride obtained by low-temperature treatment, After settling progress tentatively separation of solid and liquid, first time elutriation is carried out in eluriating tank with the catalyst production waste water, then It reuses the liquid obtained when subsequent wash sodium chloride crystal and carries out second of elutriation in another elutriation tank, will finally pass through Slurries after eluriating twice are sent into equipment for separating liquid from solid and are separated by solid-liquid separation, and the crystal being separated by solid-liquid separation uses aqueous sodium chloride again During liquid is eluted, and the liquid that elution is obtained is eluriated back to second.By above-mentioned washing process, not only make The purity of sodium chloride crystal improves, and will not be excessive introducing cleaning solution, improve the efficiency of wastewater treatment.
In the present invention, there is no particular limitation for each effect evaporator of the multi-effect evaporating device 1, can be normal by this field Advise the various evaporators composition used.Such as can selected from downward film evaporator, film-rising evaporator, scraper-type evaporator, in It entreats in circulating tube type multi-effect evaporator, basket evaporator, external heating type evaporator, forced-circulation evaporator and Liewen evaporator It is one or more.Wherein, preferably forced-circulation evaporator, external heating type evaporator.Each effect of the multi-effect evaporating device 1 is steamed Hair device is formed by heating room and vaporization chamber respectively, can also include other evaporation accessories as needed, for example, make liquid foam into The demister of one step separation, the vacuum plant the etc. when condenser and decompression operation that make indirect steam all condense.It is described more There is no particular limitation for the evaporator quantity that effect vaporising device 1 contains, and can be 2 effects or more, preferably 2-5 is imitated, more preferably 3-4 is imitated.
In the present invention, it in order to which the first mother liquor to be passed through to each effect evaporator of multi-effect evaporating device 1 successively, can be steamed in each effect Circulating pump is set between hair device, the waste water after the evaporation of preceding 1st effective evaporator is passed through next effect by the circulating pump to be evaporated Device.
In the present invention, the circulating pump between selected each effect evaporator can be various forms commonly used in the art Pump, generate a large amount of fine grain cores to make material be uniformly evaporated, avoid, prevent crystal grain and impeller high velocity impact in cycle magma Generate a large amount of secondary nucleus, the circulating pump is preferably the centrifugal pump of the slow-speed of revolution, more preferably big flow, the slow-speed of revolution guide pump Wheel or big flow, low lift, the slow-speed of revolution axial-flow pump.
A preferred embodiment according to the present invention, first evaporation carries out in multi-effect evaporating device 1, described Multi-effect evaporating device 1 is by 1st effective evaporator 1a, 2nd effect evaporator 1b, third effect evaporator 1c and fourth evaporator 1d groups At.First mother liquor is passed through to the 1st effective evaporator 1a, 2nd effect evaporator 1b, triple effect evaporation of multi-effect evaporating device 1 successively It is evaporated in device 1c and fourth evaporator 1d, obtains the second concentrate of sulfur acid sodium crystal.By multi-effect evaporating device 1 The second steam containing ammonia evaporated in preceding 1st effective evaporator, which is passed through in rear 1st effective evaporator, to carry out heat exchange and obtains the second ammonia Water.It is highly preferred that the condensation water of second steam containing ammonia carries out heat exchange in the 4th heat-exchanger rig 34 with the first mother liquor, fill Divide and utilizes energy.It is passed through heating steam (life steam i.e. commonly used in the art) in 1st effective evaporator 1a, heats steam The condensate liquid obtained after being condensed in 1st effective evaporator 1a, further preheating first is female by the 6th heat-exchanger rig 36 for condensate liquid After liquid, it is used further to prepare sodium sulphate washing solution.The second steam containing ammonia that fourth evaporator 1d evaporates exchanges heat in third It is carried out with cooling water (it is preferable to use the pending waste water before being passed through MVR vaporising devices 2 as cooling water) in device 33 Heat exchange simultaneously obtains ammonium hydroxide, and is stored in the second tank used for storing ammonia 52.
In the present invention, the evaporation conditions of second evaporation can be selected suitably as needed, and reaching makes sodium sulphate knot Brilliant and purpose that sodium chloride is not precipitated.It is described second evaporation condition may include：Temperature be 35 DEG C or more, pressure be- 95kPa or more.In order to improve evaporation efficiency, the condition of preferably described second evaporation includes：Temperature is 45 DEG C~365 DEG C, pressure For -95kPa~18110kPa；Preferably, the condition of second evaporation includes：Temperature be 60 DEG C~365 DEG C, pressure be- 87kPa~18110kPa；Preferably, the condition of second evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa ~653kPa；Preferably, the condition of second evaporation includes：Temperature be 80 DEG C~130 DEG C, pressure be -66kPa~ 117kPa；Preferably, the condition of second evaporation includes：Temperature is 95 DEG C~110 DEG C, and pressure is -37kPa~12kPa；It is excellent Selection of land, it is described second evaporation condition include：Temperature is 95 DEG C~105 DEG C, and pressure is -37kPa~-7kPa.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 order to make full use of the heat in evaporation process, it is preferable that 5 DEG C of the evaporating temperature difference of adjacent two-effect evaporation device~ 30℃；It is highly preferred that the evaporating temperature of adjacent two-effect evaporation device differs 10 DEG C~20 DEG C.
In the present invention, the operating pressure of the second evaporation is preferably the saturated vapor pressure of evaporated feed liquid.
In addition, ability and pending wastewater flow rate that the evaporation capacity of the second evaporation can be handled according to equipment suitably select, Such as can be 0.1m3/ h or more (such as 0.1m3/ h~500m3/h)。
, can be while ensureing sulfate crystal by making the second evaporation carry out under these conditions, sodium chloride is not tied Crystalline substance, the purity for the sodium sulfate crystal that thereby may be ensured that.
According to the present invention, second evaporation is not so that (i.e. chlorination is precipitated in the sodium chloride crystallization in the pending waste water Sodium is not up to supersaturation), it is preferable that second evaporation makes a concentration of X or less of sodium chloride in the second concentrate (preferably 0.999X is hereinafter, more preferably 0.95X-0.999X, further preferred 0.99X-0.9967X).Wherein, X is in the second evaporation Under the conditions of, the concentration of sodium chloride when sodium sulphate and sodium chloride reach saturation in the second concentrate.Pass through the journey evaporated second Degree control within the above range, can be such that sulfate crystal as much as possible is precipitated under conditions of ensureing that sodium chloride is not precipitated. By making sulfate crystal in the second evaporation as possible, waste water treatment efficiency can be improved, energy waste is reduced.
In the present invention, the carry out degree of second evaporation is in such a way that the second evaporation of monitoring obtains the concentration of liquid It carries out, specifically, the concentration for obtaining liquid by the second evaporation of control makes the second evaporation not make sodium chloride knot in above range Partial crystallization goes out.Here the second evaporation obtains the concentration of liquid, is monitored by way of measuring density, can specifically use density Meter carries out density measure.
According to the present invention, this method can also include the second concentrate by the sulfur acid sodium crystal in crystallization apparatus Crystallization obtains the magma of sulfur acid sodium crystal.Make in crystallization apparatus at this point, the evaporation conditions of second evaporation need to meet Sulfate crystal is precipitated and purpose that sodium chloride is not precipitated can (second evaporation makes the concentration of sodium chloride in the second concentrate For X or less).There is no particular limitation for the crystallization apparatus, such as can be brilliant flow container, brilliant liquid collecting tank, band stirring thickener Or without stirring thickener etc..A preferred embodiment according to the present invention, it is described crystallization in brilliant liquid collecting tank 55 into Row.There is no particular limitation for the condition of the crystallization, such as may include：Temperature be 45 DEG C or more, preferably 95 DEG C~107 DEG C, more preferably 85 DEG C~105 DEG C；Crystallization time can be 5min~for 24 hours, preferably 5min~30min.According to the present invention, The crystallization process of second concentrate of the sulfur acid sodium crystal can also be in the second vaporising device with crystallizer (as forced Circulation evaporation crystallizer) in carry out, the temperature crystallized at this time be it is corresponding second evaporation temperature.In the present invention, it crystallizes Temperature preferably with second evaporation temperature it is identical.
According to the present invention, in order to make full use of the second steam containing ammonia condensation water thermal energy, preferably lead to by the first mother liquor Before entering multi-effect evaporating device, the condensation water for the second steam containing ammonia that the first mother liquor and the multi-effect evaporating device are obtained carries out Second heat exchange, and obtain the second ammonium hydroxide.It is highly preferred that before the first mother liquor is passed through multi-effect evaporating device, by the first mother The condensate liquid that liquid is obtained with heating steam in the first effect evaporator heat exchange of the multi-effect evaporating device carries out the second heat exchange.
A preferred embodiment according to the present invention, what the first mother liquor was obtained with the multi-effect evaporating device second contains Second heat exchange of the condensation water of ammonia steam is carried out by the 4th heat-exchanger rig 34, specifically, by the first mother liquor and multiple-effect evaporation The condensation water for the second steam containing ammonia that device obtains by the 4th heat-exchanger rig 34, makes the first mother liquor heat up, and make multiple-effect respectively The condensation water for the second steam containing ammonia that vaporising device obtains cools down to obtain the second ammonium hydroxide.According to the present invention, in the 4th heat-exchanger rig After 34 carry out the second heat exchange, the temperature of first mother liquor is 39 DEG C or more, more preferably 84 DEG C~134 DEG C, further excellent It is selected as 99 DEG C~114 DEG C.
A preferred embodiment according to the present invention, first mother liquor and the second of the condensate liquid of heating steam Heat exchange is further carried out by the 6th heat-exchanger rig 36, and specifically, the condensate liquid of the first mother liquor and heating steam is led to respectively The 6th heat-exchanger rig 36 is crossed, the first mother liquor is made to further heat up.According to the present invention, carries out the second heat in the 6th heat-exchanger rig 36 and hand over After changing, the temperature of first mother liquor is 41 DEG C or more, more preferably 77 DEG C~182 DEG C, further preferably 86 DEG C~136 DEG C, it is still more preferably 101 DEG C~116 DEG C.
A preferred embodiment according to the present invention obtains in the last 1st effective evaporator of multi-effect evaporating device Second steam containing ammonia carries out heat exchange with cold medium in third heat-exchanger rig 33, obtains the second ammonium hydroxide.By the second ammonia of two parts It is hydrated and is stored in the second tank used for storing ammonia 52.
There is no particular limitation for the third heat-exchanger rig 33, the 4th heat-exchanger rig 34 and the 6th heat-exchanger rig 36, can be with Using various heat exchangers commonly used in the art, achieve the purpose that the second heat exchange.Specifically, it can be changed for jacket type Hot device, plate heat exchanger, shell-and-tube heat exchanger, screw heat exchange of heat pipe etc..The material of the heat exchanger can be as needed Specific choice, such as since indirect steam does not have corrosivity, preferably stainless steel spiral screwed tube heat exchanger to stainless steel.Third is changed Cold medium in thermal 33 can be cooling water, glycol water etc..When using conventional cooling water, the cooling water follows Ring uses, and when using the catalyst production waste water as cooling water, the waste water after heat exchange preferably directly returns to processing procedure (such as It is back to first time pH value adjustment process).
A preferred embodiment according to the present invention, second evaporation process carry out in multi-effect evaporating device 1, First mother liquor is passed through in each effect evaporator of the multi-effect evaporating device 1 by the 6th circulating pump 76 and carries out the second evaporation Obtain the second concentrate of the second steam containing ammonia and sulfur acid sodium crystal.
In the present invention, sodium chloride is made not crystallize precipitation in order to reach second evaporation, described first is precipitated when evaporating The purpose that can be dissolved in low-temperature process of sodium sulfate crystal, preferably make the condition of the second evaporation and low-temperature treatment full Foot：The temperature of second evaporation is at least 5 DEG C higher than the temperature of low-temperature treatment, preferably 20 DEG C high, more preferably 35 DEG C high~90 DEG C, It is further preferably 35 DEG C high~70 DEG C, it is particularly preferably 50 DEG C high~60 DEG C.The temperature with low-temperature treatment is evaporated by control second, So that the sodium sulphate in the sodium sulfate crystal and sodium chloride crystal that the first evaporation is precipitated in low-temperature treatment is dissolved, makes the second evaporation Middle sodium sulphate individually crystallizes precipitation, to improve the purity of obtained sodium sulphate and sodium chloride crystal.
In the present invention, the second concentrate of the sulfur acid sodium crystal that second evaporation obtains is separated by solid-liquid separation by second Obtain sodium sulfate crystal and the second mother liquor afterwards (i.e. second is separated by solid-liquid separation obtained liquid phase).Described second method being separated by solid-liquid separation does not have There is special restriction, such as can be selected from one or more in centrifugation, filtering and sedimentation.
According to the present invention, second separation of solid and liquid can (be, for example, centrifuge, belt by the second equipment for separating liquid from solid Filter, flame filter press etc.) 92 progress.After described second is separated by solid-liquid separation, the second equipment for separating liquid from solid 92 obtains second female Liquid returns to MVR vaporising devices 2 and carries out the first evaporation again, specifically can by the 9th circulating pump 79 by the second mother liquor back to the Before secondary pH value is adjusted.In addition, certain sulfate ion can be adsorbed, dissociate by being difficult to avoid that on obtained sodium sulfate crystal The impurity such as ammonia, hydroxide ion reduce the peculiar smell of solid salt to remove the impurity of absorption, reduce corrosivity, improve the crystalline substance The purity of body, it is preferable that sodium sulfate crystal water, the catalyst production waste water or metabisulfite solution carry out the second washing And it is dry.In order to avoid the dissolving of sodium sulfate crystal in washing process, it is preferable that the sodium sulfate crystal aqueous sodium persulfate solution It is washed.It is highly preferred that the concentration of the aqueous sodium persulfate solution is preferably sulphur at the temperature corresponding to sodium sulfate crystal to be washed Sour sodium and sodium chloride reach the concentration of sodium sulphate in the aqueous solution of saturation simultaneously.
It is separated by solid-liquid separation the mode washed with second as above-mentioned second, there is no particular limitation, and ability can be used for example The elutriation apparatus and solid-liquid separating equipment of domain routine, which combine, to carry out, can also be in the equipment for separating liquid from solid such as band filter of segmentation Upper progress.Preferably, second washing includes eluriating and/or eluting.For above-mentioned elutriation and elution, there is no particular limitation, It can be carried out by the method for this field routine.It is described elutriation and elution number there is no particular limitation, can be 1 time with On, the sodium sulfate crystal of higher purity, preferably 2-4 times in order to obtain.During elutriation, made with the catalyst production waste water It does not recycle generally when liquid to eluriate, can be used with circulated in countercurrent when doing elutriation liquid using the cleaning solution of the second washing recycling. Before carrying out the elutriation, tentatively separation of solid and liquid is carried out preferably by way of sedimentation and obtains the slurries (liquid of sulfur acid sodium crystal Content is 35 mass % or less).During elutriation, relative to the slurries of 1 parts by weight sulfur acid sodium crystal, eluriates and use Liquid is 1~20 parts by weight.It is preferable to use aqueous sodium persulfate solution progress for elution.In order to further increase the effect of elutriation, obtain The higher sodium sulfate crystal of purity, in the case of preferred, the liquid that elution can be used to obtain is washed.Washing is generated Liquid, it is preferable that the catalyst production waste water eluriates liquid and is back to second of pH value tune before MVR vaporising devices 2 evaporate Before section, other cleaning solutions are back to multi-effect evaporating device 1, such as return to multi-effect evaporating device 1 again by the tenth circulating pump 80 It is secondary to carry out the second evaporation.
A preferred embodiment according to the present invention obtains the second of sulfur acid sodium crystal dense by the second evaporation Contracting liquid carries out first time elutriation with the catalyst production waste water after settling progress tentatively separation of solid and liquid in eluriating tank, Then it reuses the liquid obtained when subsequent wash sodium sulfate crystal and carries out second of elutriation in another elutriation tank, finally will Slurries after eluriating twice are sent into the second equipment for separating liquid from solid and are separated by solid-liquid separation, and the crystal being separated by solid-liquid separation uses sulphur again Acid sodium aqueous solution is eluted, and the liquid that elution is obtained is used as back in eluriating for the second time and eluriates liquid.It is washed in a pan by above-mentioned Wash and elute the washing process combined, the purity of the sodium sulfate crystal not only made improves, and will not excessive introducing wash Liquid is washed, the efficiency of wastewater treatment is improved.
A preferred embodiment according to the present invention, first steam containing ammonia is cold by first heat exchange Remaining tail gas is coagulated to discharge after removing ammonia；Second steam containing ammonia is condensed into remaining tail gas by second heat exchange It is discharged after removing ammonia.First steam containing ammonia condenses remaining tail gas, that is, second heat exchange by first heat exchange The tail gas that device 32 is discharged, second steam containing ammonia condense remaining tail gas, that is, third heat exchange dress by second heat exchange Set the tail gas of 33 discharges.By the way that above-mentioned tail gas is removed ammonia, the pollutant load in emission can be further decreased, makes it can With direct emission.
As the mode except ammonia, can be absorbed with tail gas absorber 83.The tail gas absorber 83 is without spy Other restriction can be various absorption towers commonly used in the art, such as tray absorption columns, packed absorber, falling film absorption Tower or void tower etc..There is recirculated water in the tail gas absorber 83, the recirculated water is under the action of the 4th circulating pump 74 in tail gas It is recycled in absorption tower 83, water can also be added to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73, recycled Pond 82 can add fresh water, while can reduce by the temperature and ammonia content of 81 work water of vacuum pump.The tail gas absorber The type of flow of 83 inner exhaust gas and recirculated water can adverse current also can cocurrent, preferably adverse current.The recirculated water can be by additional Fresh water is supplemented.In order to ensure that tail gas fully absorbs, dilute sulfuric acid can also be further added in the tail gas absorber 83, To absorb a small amount of ammonia in tail gas etc..The recirculated water can be used as ammonium hydroxide or ammonium sulfate to be back to after absorbing tail gas It produces or sells.As the mode that above-mentioned tail gas is passed through to tail gas absorber 83, can be carried out by vacuum pump 81.
In the present invention, there is no particular limitation for the catalyst production waste water, as long as containing NH4 +、SO4 2-、Cl-And Na+ Waste water.In addition, the method for the present invention is particularly suitable for the processing of high-salt wastewater.Catalyst production as the present invention is useless Water is specifically as follows the waste water from molecular sieve, aluminium oxide or oil refining catalyst production process, and can also be will be from molecule The waste water of sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.It will preferably come from and divide The waste water of son sieve, aluminium oxide or oil refining catalyst production process carries out the waste water after following removal of impurities and concentration.
As the NH in the catalyst production waste water4 +Can be 8mg/L or more, preferably 300mg/L or more.
As the Na in the catalyst production waste water+Can be 510mg/L or more, preferably 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-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 30g/L or less.
It is useless relative to catalyst production from the point of view of the energy consumption for reducing processing procedure from the efficiency for improving the first evaporation The SO contained in water4 2-, the Cl in catalyst production waste water-The higher the better for content, for example, useless relative to 1 mole of ammonium salt-containing The SO contained in water4 2-, the Cl that contains in the catalyst production waste water-It is 1 mole or more, preferably 2 moles or more, preferably It is 5 moles or more, more preferably 9.5 moles or more, further preferably 10 moles or more.And from the point of view of practicability, Relative to the SO contained in 1 mole of catalyst production waste water4 2-, the Cl that contains in the catalyst production waste water-Preferably 200 moles hereinafter, more preferably 150 moles hereinafter, further preferably 100 moles hereinafter, still more preferably be 50 moles Hereinafter, being still more preferably 30 moles or less.Pass through the Cl that will contain in catalyst production waste water-And SO4 2-Molar ratio limit It is scheduled on above range, most of water can be steamed in the first evaporation, be reduced the circulation fluid scale of construction in system for handling, save energy Source keeps processing procedure more economical.
In the present invention, the inorganic ion contained in the catalyst production waste water is in addition to NH4 +、SO4 2-、Cl-And Na+ In addition, Mg can also be contained2+、Ca2+、K+、Fe3+, the inorganic ions such as rare earth element ion, Mg2+、Ca2+、K+、Fe3+, rare earth member The respective content of the inorganic ions such as plain ion is preferably 100mg/L hereinafter, more preferably 50mg/L is hereinafter, further preferably Following 10mg/L is not hereinafter, contain other inorganic ions particularly preferably.By controlling other inorganic ions in above-mentioned model It encloses, the purity of finally obtained sodium chloride crystal and sodium sulfate crystal can be further increased.In order to reduce the catalyst life 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, more preferably 7-7.2.
In addition, due to the COD of waste water may block up film in concentration, in evaporative crystallization when influence the purity and color and luster etc. of salt, The COD more fewer better (preferably 20mg/L is hereinafter, more preferably 10mg/L or less) of the catalyst production waste water, preferably pre- By oxidation removal when processing, such as bioanalysis, advanced oxidation processes progress specifically can be used, it is preferred when COD contents are very high Using oxidizing, the oxidant for example can be Fenton reagent.
In the present invention, in order to reduce the concentration impurity ion in waste water, ensure that the continuous-stable of processing procedure carries out, drop Low equipment operation maintenance cost, the catalyst production waste water using the present invention processing method handle before preferably through except It is miscellaneous.Preferably, the removal of impurities is one or more in separation of solid and liquid, chemical precipitation, absorption, ion exchange and oxidation.
Can be filtering, centrifugation, sedimentation etc. as the separation of solid and liquid；Can be to adjust as the chemical precipitation PH, carbonate deposition, magnesium salts precipitation etc.；Can be physical absorption and/or chemisorption, specific absorption as the absorption Agent can select activated carbon, silica gel, aluminium oxide, molecular sieve, natural clay etc.；As the ion exchange, strong acid may be used Any one in property resin cation, acidulous cation resin；As the oxidation, may be used commonly used in the art Various oxidants, such as ozone, hydrogen peroxide, potassium permanganate, in order to avoid introducing new impurity, it is preferred to use ozone, dioxygen Water etc..
Specific removal of impurities mode can be specifically chosen according to the dopant species contained in the catalyst production waste water.For Suspended matter can select solid-liquid isolation method to clean；For inorganic matter and organic matter, chemical precipitation method, ion exchange can be selected Method, absorption method removal of impurities, such as Subacidity cation exchange process, active carbon adsorption etc.；For organic matter, absorption may be used And/or the mode of oxidation cleans, wherein preferably ozone biological activated carbon adsorption and oxidation method.One according to the present invention preferred Embodiment, catalyst production waste water is successively by filtering, Subacidity cation exchange process, ozone biological activated carbon adsorption and oxidation Method cleans.By above-mentioned dedoping step, most suspended substances, hardness, silicon and organic matter can be removed, reduces device fouling Risk ensures wastewater treatment process continuous and steady operation.
It in the present invention, can be in the processing method using the present invention for the lower catalyst production waste water of salt content Before processing (preferably after above-mentioned removal of impurities), made required by the catalyst production waste water that salt content reaches the present invention by concentrating Range.Preferably, it is described concentration selected from ED films concentration and/or it is reverse osmosis；It is highly preferred that it is described be concentrated by ED films concentration and There is no particular limitation for the sequencing of reverse osmosis progress, the ED films concentration and reverse osmosis progress.ED films concentration and anti- The mode that this field routine may be used in infiltration processing unit and condition carries out, and can specifically be selected according to the case where pending waste water It selects.Specifically, it is concentrated as the ED films, unidirectional electrodialysis system or pole-reversing electroosmosis system can be selected to carry out；As institute State it is reverse osmosis, can select rolled film, plate membrane, dish tubular membrane, vibrating membrane or combinations thereof carry out.It can be carried by the concentration The efficiency of high wastewater treatment avoids energy waste caused by largely evaporating.
In the preferred embodiment of the present invention, catalyst production waste water is the waste water in process of producing molecular sieve It cleans, and passes through by chemical precipitation, filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method ED films concentrate and the waste water after reverse osmosis concentration.
Condition as above-mentioned chemical precipitation is preferably：Using sodium carbonate as inorganic agent, relative to 1 mole of calcium in waste water 1.2-1.4 mole of either sodium carbonate is added in ion, and the pH for adjusting waste water is more than 7, and reaction temperature is 20-35 DEG C, reaction time 0.5- 4h。
Condition as above-mentioned filtering is preferably：Filter element is situated between more using the double-layer filter material of anthracite and quartz sand composition Mass filter, anthracite granule size used are 0.7-1.7mm, 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 preferably：PH value range is 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 velocitys are 4.5-5.5m/h, and regeneration time of contact is 35-45min；It is 18-22m/h just to wash flow velocity, It is 2-30min just to wash the time；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 resins.
Condition as above-mentioned ozone biological activated carbon adsorption and oxidation method is preferably：The ozone residence time is 50-70min, Empty bed filtering velocity is 0.5-0.7m/h.
As above-mentioned ED films concentration condition be preferably：Electric current 145-155A, voltage 45-65V.It for example can be with as ED films For the ED films of Japanese A Sitong companies production.
It is preferably as above-mentioned reverse osmosis condition：Operating pressure 5.4-5.6MPa, 25-35 DEG C of inflow temperature, pH value are 6.5-7.5.It is for example carried out using the sea water desalination membrane TM810C that blue star Toray produces as reverse osmosis membrane.
It according to the present invention, when proceeding by wastewater treatment, can directly be gone into operation using catalyst production waste water, if catalysis The ion concentration of agent production waste water meets the condition of the present invention, the first evaporation can be first carried out with condition according to the invention and carried out again Second evaporation；If the ion concentration of catalyst production waste water is unsatisfactory for the condition of the present invention, can control the first evaporation makes the In one concentrate then the first concentrate is carried out the second evaporation, obtains the second concentration by the concentration of sodium sulphate close to concentration is precipitated Liquid is simultaneously separated by solid-liquid separation and obtains sodium sulfate crystal and the second mother liquor, then the second mother liquor is mixed with the catalyst production waste water to adjust It saves the ion concentration of pending waste water and obtains sodium chloride crystal to carry out the first evaporation again after range of the presently claimed invention.Certainly Na can also be used in the starting stage2SO4Or the ion concentration in pending waste water is adjusted in NaCl, as long as making described wait for Waste water is handled to meet in the present invention to SO in pending waste water4 2-、Cl-Requirement.
The present invention will be described in detail by way of examples below.
In following embodiment, catalyst production waste water be process of producing molecular sieve in waste water successively pass through chemical precipitation, Filtering, Subacidity cation exchange process and ozone biological activated carbon adsorption and oxidation method clean, and pass through ED films successively and concentrate Waste water after being concentrated with reverse osmosis.
Embodiment 1
As shown in Figure 1, by catalyst production waste water (149g/L containing NaCl, Na2SO4 49g/L、NH4Cl 45g/L、 (NH4)2SO415g/L, pH 7.0) with inlet amount it is 5m3The speed of/h is sent in the pipeline of processing system, is being sent to A concentration of 45.16 are imported in pipeline before one heat-exchanger rig 31 or the 5th heat-exchanger rig 35 (being titanium alloy plate heat exchanger) The sodium hydrate aqueous solution of quality % carries out first time pH value adjusting, and by the first pH value measuring device 61 (pH meter) to mixing PH value afterwards is monitored (measured value 8), and 71 are pumped by a part (4.5m of catalyst production waste water by first circulation3/h) It is sent into the first heat-exchanger rig 31, carrying out the first heat exchange with the first liquid of steam condensation containing ammonia of recycling makes catalyst production waste water liter For temperature to 103 DEG C, rest part is sent into the 5th heat-exchanger rig 35, and carrying out the first heat exchange with the first concentrate keeps catalyst production useless Water is warming up to 103 DEG C, and being mixed to get pending waste water with the second mother liquor after catalyst production waste water is converged (wherein contains SO4 2-And Cl-Molar ratio be 1：11.227) it, then by pending waste water is sent into the second heat-exchanger rig 32 and the first steam containing ammonia The first heat exchange is carried out, pending waste water is made to be warming up to 112 DEG C；Then pending waste water is being sent to MVR vaporising devices 2 The sodium hydrate aqueous solution that a concentration of 45.16 mass % is imported in pipeline carries out second of pH value adjusting, and passes through the second pH value Measuring device 62 (pH meter) is monitored (measured value 10.8) to the pH value after adjusting, will be after second of pH value is adjusted Pending waste water is sent into MVR vaporising devices 2 (falling liquid film+forced circulation two-stage MVR crystallizing evaporators) and is evaporated, and obtains first and contains First concentrate of ammonia steam and sulfur acid sodium crystal and sodium chloride crystal.The first obtained steam containing ammonia is evaporated by the first pressure Contracting machine 10 compress after (17 DEG C of temperature rise) pass sequentially through the second heat-exchanger rig 32 and the first heat-exchanger rig 31, respectively with it is pending Waste water and catalyst production waste water carry out heat exchange, and cooling obtains the first ammonium hydroxide, and is stored in the first tank used for storing ammonia 51.Separately Outside, in order to improve the crystalline content of concentrate in MVR vaporising devices 2, the partially liq after being evaporated in MVR vaporising devices 2 is made The second heat-exchanger rig 32 is recycled to by second circulation pump 72 for circulation fluid, MVR vaporising devices 2 is then again introduced into and carries out first It evaporates (reflux ratio 92.6).The degree evaporated by the mass flowmenter pair first being arranged on MVR vaporising devices 2 is supervised It surveys, the evaporation capacity of the first evaporation of control is 4.69m3/ h (is equivalent to a concentration of 0.976Y (83g/ of sodium sulphate in control process liquid L)).Wherein, the evaporation conditions of MVR vaporising devices 2 such as the following table 1：
Table 1
First concentrate of obtained sulfur acid sodium crystal and sodium chloride crystal is subjected to low temperature in low-temperature treatment tank 22 Processing, temperature are 25 DEG C, and residence time 55min obtains the treatment fluid of sodium chloride-containing crystal.
The treatment fluid of above-mentioned sodium chloride-containing crystal is sent into the first equipment for separating liquid from solid 91 (centrifuge) and carries out the first solid-liquid Separation, obtains 9.38m per hour3Contain NaCl 281g/L, Na2SO4 83g/L、NaOH 1.66g/L、NH3The of 0.18g/L One mother liquor is temporarily stored into the first mother liquor tank 53, is separated by solid-liquid separation gained solid sodium chloride and (is obtained the chlorine of aqueous 14 mass % per hour Change sodium crystalli-zation cake 1157.43kg, wherein the content of sodium sulphate be 3.6 mass % or less), with sodium chloride crystalli-zation cake butt The sodium chloride solution of the equal 281g/L of quality elutes, dry in drying machine, obtains sodium chloride 995.39kg (purity per hour For 99.4 weight %), after cleaning solution is sent into the second heat-exchanger rig 32 by the 8th circulating pump 78, it is again introduced into MVR vaporising devices 2 Carry out the first evaporation.
Second evaporation process carries out in multi-effect evaporating device 1, multi-effect evaporating device 1 by 1st effective evaporator 1a, 2nd effect evaporator 1b, third effect evaporator 1c and fourth evaporator 1d (being forced-circulation evaporator) compositions.Pass through The first mother liquor in above-mentioned first mother liquor tank 53 is sequentially sent to the 4th heat-exchanger rig 34 and the 6th heat-exchanger rig by six circulating pumps 76 After 36 heat exchange, the second evaporation of each effect evaporator progress for being sequentially sent to multi-effect evaporating device 1 obtains the second of sulfur acid sodium crystal Concentrate, evaporation conditions such as upper table 1.By the second steam containing ammonia that preceding 1st effective evaporator evaporates be passed through rear 1st effective evaporator into Row heat exchange simultaneously obtains condensation water, and further exchanges heat to obtain the second ammonium hydroxide in the 4th heat-exchanger rig 34 and the first mother liquor, and the 4th The second steam containing ammonia evaporated in effect evaporator 1d carries out in third heat-exchanger rig 33 with the catalyst production waste water Heat exchange simultaneously obtains the second ammonium hydroxide, and the second ammonium hydroxide is merged and is stored in the second tank used for storing ammonia 52.In 1st effective evaporator 1a It is passed through heating steam (life steam i.e. commonly used in the art), what heating steam obtained after being condensed in 1st effective evaporator 1a Condensate liquid is passed through the 6th heat-exchanger rig 36, is used to prepare washing solution after further preheating the first mother liquor.It is filled by multiple-effect evaporation It sets the degree that the densitometer pair first being arranged on 1 evaporates to be monitored, controls a concentration of of the second evaporation concentrated solution sodium chloride 0.9935X(308.1g/L).Above-mentioned multi-effect evaporating device 1 is evaporated the second obtained concentrate to carry out in brilliant liquid collecting tank 55 Crystallization, crystallization temperature are 100 DEG C, and crystallization time 5min obtains the magma of sulfur acid sodium crystal.
The magma of above-mentioned sulfur acid sodium crystal is sent into the second equipment for separating liquid from solid 92 (centrifuge) to be separated by solid-liquid separation, often Hour obtains 8.70m3Contain NaCl 308.1g/L, Na2SO4 53.9g/L、NaOH 1.82g/L、NH3The second of 0.01g/L Mother liquor is temporarily stored into the second mother liquor tank 54.Second mother liquor is recycled to waste water import pipe and is urged by the 9th circulating pump 79 Change agent production waste water and is mixed to get pending waste water.Being separated by solid-liquid separation gained solid sodium sulfate, (it is 15 matter to obtain water content per hour Measure % sulfate crystal filter cake 378.37kg, wherein the content of sodium chloride be 4.3 mass % or less) with sodium sulphate butt matter It is dry in drying machine after measuring equal 53.9g/L metabisulfite solutions elution, sodium sulphate 321.62kg (purity is obtained per hour For 99.5 weight %), cleaning solution is recycled to multi-effect evaporating device 1 by the tenth circulating pump 80.
In addition, the tail gas that the second heat-exchanger rig 32 and third heat-exchanger rig 33 are discharged introduces tail gas absorption by vacuum pump 81 Tower 83 is absorbed, and recirculated water is connected in tail gas absorber 83, the recirculated water is under the action of the 4th circulating pump 74 in tail gas It is recycled in absorption tower 83, while water is added to tail gas absorber 83 from circulating water pool 82 by third circulating pump 73, and Fresh water is added in circulating water pool 82, reduces by the temperature and ammonia content of 81 work water of vacuum pump.In the tail gas absorber 83 It is further passed through dilute sulfuric acid, to absorb ammonia in tail gas etc..In addition, the initial period of MVR evaporations, is 143.3 by temperature DEG C steam started.
In the present embodiment, the ammonium hydroxide 4.69m of a concentration of 1.8 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 0.99m of a concentration of 0.17 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
Embodiment 2
The processing of catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl 69g/L, Na2SO4 138g/L、NH4Cl 12g/L、(NH4)2SO4The catalyst production waste water that 24.4g/L, pH are 7.1 is handled, and is obtained To pending waste water in the SO that contains4 2-And Cl-Molar ratio be 1：9.085.It is exchanged heat by the first heat-exchanger rig 31 and the 5th The temperature that device 35 carries out heat exchange rear catalyst production waste water is 104 DEG C, after carrying out heat exchange by the second heat-exchanger rig 32 The temperature of pending waste water is 114 DEG C.The evaporation conditions of MVR vaporising devices 2 and multi-effect evaporating device 1 such as the following table 2.Low-temperature treatment Temperature be 30 DEG C, residence time 50min.
Table 2
First equipment for separating liquid from solid 91 obtains 475.12kg tons of the sodium chloride crystalli-zation cake of aqueous 14 mass % per hour, most Obtain sodium chloride 408.95kg per hour eventually (purity is 99.4 weight %)；26.11m is obtained per hour3A concentration of NaCl 283.4g/L、Na2SO4 79.9g/L、NaOH 2.66g/L、NH3The first mother liquor of 0.077g/L.
Second equipment for separating liquid from solid 92 obtains the sulfate crystal filter cake 968.12kg that water content is 15 mass % per hour, It is final to obtain sodium sulphate 822.91kg per hour (purity is 99.5 weight %)；24.04m is obtained per hour3, a concentration of NaCl 306.3g/L、Na2SO4 52.5g/L、NaOH 2.97g/L、NH3The second mother liquor of 0.003g/L.
In the present embodiment, the ammonium hydroxide 3.31m of a concentration of 1.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 2.32m of a concentration of 0.08 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
Embodiment 3
The processing of catalyst production waste water is carried out according to the method for embodiment 1, unlike：To contain NaCl 106g/L, Na2SO4 103g/L、NH4Cl 21g/L、(NH4)2SO4The catalyst production waste water that 20.7g/L, pH are 7.2 is handled, and is obtained To pending waste water in the SO that contains4 2-And Cl-Molar ratio be 1：9.189.It is exchanged heat by the first heat-exchanger rig 31 and the 5th The temperature that device 35 carries out heat exchange rear catalyst production waste water is 103 DEG C, after carrying out heat exchange by the second heat-exchanger rig 32 The temperature of pending waste water is 112 DEG C.The evaporation conditions of MVR vaporising devices 2 and multi-effect evaporating device 1 such as the following table 3.Low-temperature treatment Temperature be 25 DEG C, residence time 55min.
Table 3
First equipment for separating liquid from solid 91 obtains 757.97kg tons of the sodium chloride crystalli-zation cake of aqueous 15 mass % per hour, most Obtain sodium chloride 644.27kg per hour eventually (purity is 99.4 weight %)；19.57m is obtained per hour3A concentration of NaCl 280.4g/L、Na2SO4 82.7g/L、NaOH 2.64g/L、NH3The first mother liquor of 0.15g/L.
Second equipment for separating liquid from solid 92 obtains the sulfate crystal filter cake 737.81kg that water content is 15 mass % per hour, It is final to obtain sodium sulphate 627.14kg per hour (purity is 99.5 weight %)；18.09m is obtained per hour3, a concentration of NaCl 303.2g/L、Na2SO4 55.1g/L、NaOH 2.85g/L、NH3The second mother liquor of 0.0049g/L.
In the present embodiment, the ammonium hydroxide 3.86m of a concentration of 1.4 mass % is obtained in the first tank used for storing ammonia 51 per hour3, the The ammonium hydroxide 1.76m of a concentration of 0.16 mass % is obtained in two tank used for storing ammonia 52 per hour3, ammonium hydroxide can be back to the production of molecular sieve Process.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (12)

1. a kind of processing method of catalyst production waste water, the catalyst production waste water contain NH4 +、SO4 2-、Cl-And Na+, special Sign is that this approach includes the following steps,
1) pending waste water is passed through in MVR vaporising devices and carries out the first evaporation, obtained the first steam containing ammonia and sulfur acid sodium is brilliant First concentrate of body and sodium chloride crystal, the pending waste water contain the catalyst production waste water；
2) the first concentrate of the sulfur acid sodium crystal and sodium chloride crystal is subjected to low-temperature treatment, keeps sodium sulfate crystal molten Solution, obtains the treatment fluid of sodium chloride-containing crystal；
3) treatment fluid of the sodium chloride-containing crystal first is carried out to be separated by solid-liquid separation, and by first be separated by solid-liquid separation obtained liquid phase according to The secondary each effect evaporator for being passed through multi-effect evaporating device carries out the second evaporation, obtains the second concentrate of sulfur acid sodium crystal；
4) the second concentrate of the sulfur acid sodium crystal second is carried out to be separated by solid-liquid separation；
Wherein, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is more than 9；
The second steam containing ammonia that the preceding 1st effective evaporator of the multi-effect evaporating device evaporates is passed through in rear 1st effective evaporator, Described first is separated by solid-liquid separation obtained liquid phase and the second steam containing ammonia cocurrent heat exchange；
Second evaporation makes sodium chloride not crystallize precipitation；
Relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It is 7.15 moles More than.
2. according to the method described in claim 1, wherein, the pending waste water is the catalyst production waste water；Alternatively, institute State the liquid phase that pending waste water contains the catalyst production waste water and second separation of solid and liquid obtains；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 9.5 moles or more；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-It is 10 Mole or more；
Preferably, relative to the SO contained in 1 mole of pending waste water4 2-, the Cl that contains in the pending waste water-For 10-20 moles；
Preferably, before the pending waste water is passed through MVR vaporising devices, the pH value for adjusting the pending waste water is more than 10.8；
Preferably, the pH value for adjusting the pending waste water is carried out using NaOH.
3. method according to claim 1 or 2, wherein first evaporation makes the concentration of sodium sulphate in the treatment fluid For Y or less, wherein Y is sulfuric acid when sodium sulphate and sodium chloride reach saturation in treatment fluid under conditions of low-temperature treatment The concentration of sodium；
Second evaporation makes a concentration of X or less of sodium chloride in the second concentrate, wherein X be under conditions of second evaporates, The concentration of sodium chloride when sodium sulphate and sodium chloride reach saturation in second concentrate；
Preferably, first evaporation makes a concentration of 0.9Y-0.99Y of sodium sulphate in the treatment fluid；
Preferably, second evaporation makes a concentration of 0.95X-0.999X of sodium chloride in second concentrate.
4. according to the method described in any one of claim 1-3, wherein it is described first evaporation condition include：Temperature is 35 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of first evaporation includes：Temperature is 45 DEG C~175 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 60 DEG C~175 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of first evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；
Preferably, the condition of first evaporation includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；
Preferably, the condition of first evaporation includes：Temperature is 95 DEG C~110 DEG C, and pressure is -37kPa~12kPa.
5. according to the method described in any one of claim 1-3, wherein it is described second evaporation condition include：Temperature is 35 DEG C or more, pressure is -95kPa or more；
Preferably, the condition of second evaporation includes：Temperature is 45 DEG C~365 DEG C, and pressure is -95kPa~18110kPa；
Preferably, the condition of second evaporation includes：Temperature is 60 DEG C~365 DEG C, and pressure is -87kPa~18110kPa；
Preferably, the condition of second evaporation includes：Temperature is 75 DEG C~175 DEG C, and pressure is -73kPa~653kPa；
Preferably, the condition of second evaporation includes：Temperature is 80 DEG C~130 DEG C, and pressure is -66kPa~117kPa；
Preferably, the condition of second evaporation includes：Temperature is 95 DEG C~110 DEG C, and pressure is -37kPa~12kPa.
6. according to the method described in any one of claim 1-3, wherein the condition of the low-temperature treatment includes：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.
7. the method according to claim 4 or 6, wherein the temperature of second evaporation is 5 DEG C higher than the temperature of low-temperature treatment More than, it is preferably high 20 DEG C or more, more preferably 35 DEG C high~90 DEG C.
8. according to the method described in claim 1, wherein, before the pending waste water is passed through MVR vaporising devices, by institute The first steam containing ammonia that MVR vaporising devices obtain is stated to carry out the first heat exchange with the pending waste water and obtain the first ammonium hydroxide；
Preferably, before carrying out first heat exchange, the pH value for adjusting pending waste water is more than 7；
Preferably, first steam containing ammonia remaining tail gas is condensed by first heat exchange to discharge after removing ammonia.
9. according to the method described in claim 1, wherein, multi-effect evaporating device is passed through being separated by solid-liquid separation obtained liquid phase by first Before, described first is separated by solid-liquid separation the condensation water for the second steam containing ammonia that obtained liquid phase is obtained with the multi-effect evaporating device Carry out the second heat exchange；
The second steam containing ammonia obtained in the last 1st effective evaporator of the multi-effect evaporating device and cold medium are carried out the second heat to hand over It changes；
Preferably, second steam containing ammonia remaining tail gas is condensed by second heat exchange to discharge after removing ammonia.
10. according to the method described in any one of claim 1-9, this method further includes by the place of the sodium chloride-containing crystal Reason liquid obtains sodium chloride crystal after first is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtained sodium chloride crystal.
11. according to the method described in any one of claim 1-9, this method further includes by the of the sulfur acid sodium crystal Two concentrates obtain sodium sulfate crystal after second is separated by solid-liquid separation；
Preferably, this method further includes being washed to obtained sodium sulfate crystal.
12. according to the method described in any one of claim 1-9, wherein NH in the catalyst production waste water4 +For 8mg/ L or more, SO4 2-For 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 concentrated.
CN201710265653.6A 2017-04-21 2017-04-21 Treatment method of catalyst production wastewater Active CN108726609B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710265653.6A CN108726609B (en) 2017-04-21 2017-04-21 Treatment method of catalyst production wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710265653.6A CN108726609B (en) 2017-04-21 2017-04-21 Treatment method of catalyst production wastewater

Publications (2)

Publication Number Publication Date
CN108726609A true CN108726609A (en) 2018-11-02
CN108726609B CN108726609B (en) 2021-09-17

Family

ID=63933941

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710265653.6A Active CN108726609B (en) 2017-04-21 2017-04-21 Treatment method of catalyst production wastewater

Country Status (1)

Country Link
CN (1) CN108726609B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1944256A (en) * 2006-10-25 2007-04-11 中国中轻国际工程有限公司 Process for producing sodium sulfate and sodium chloride in Na2SO4-NaCl-H2O system
CN101935128A (en) * 2010-07-22 2011-01-05 上海西恩化工设备有限公司 Process for treating wastewater comprising high-concentration ammonium salt and sodium salt
CN104609633A (en) * 2015-02-16 2015-05-13 阮氏化工（常熟）有限公司 Method and device for utilizing sewage containing ammonia and sodium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1944256A (en) * 2006-10-25 2007-04-11 中国中轻国际工程有限公司 Process for producing sodium sulfate and sodium chloride in Na2SO4-NaCl-H2O system
CN101935128A (en) * 2010-07-22 2011-01-05 上海西恩化工设备有限公司 Process for treating wastewater comprising high-concentration ammonium salt and sodium salt
CN104609633A (en) * 2015-02-16 2015-05-13 阮氏化工（常熟）有限公司 Method and device for utilizing sewage containing ammonia and sodium

Also Published As

Publication number Publication date
CN108726609B (en) 2021-09-17

Similar Documents

Publication Publication Date Title
CN109422409A (en) The processing method of ammonium salt-containing waste water
CN109422399A (en) The processing method of ammonium salt-containing waste water
CN108314114A (en) A kind of method of ammonium salt-containing wastewater treatment
CN109422402A (en) The processing method of catalyst production waste water
CN109422407A (en) The processing method of catalyst production waste water
CN109422400A (en) The processing method of catalyst production waste water
CN108726756A (en) The processing method of ammonium salt-containing waste water
CN108726612A (en) The processing method of ammonium salt-containing waste water
CN108726610A (en) The processing method of ammonium salt-containing waste water
CN108726611A (en) A kind of processing method of catalyst production waste water
CN109422396A (en) The processing method of catalyst production waste water
CN108726603A (en) A kind of processing method of catalyst production waste water
CN108726609A (en) A kind of processing method of catalyst production waste water
CN109422398A (en) The processing method of catalyst production waste water
CN108726606A (en) A kind of processing method of catalyst production waste water
CN108726604A (en) A kind of processing method of catalyst production waste water
CN108726765A (en) A kind of processing method of catalyst production waste water
CN108726759A (en) The processing method of ammonium salt-containing waste water
CN108314115A (en) A kind of method of ammonium salt-containing wastewater treatment
CN108726766A (en) A kind of processing method of catalyst production waste water
CN108726768A (en) A kind of processing method of catalyst production waste water
CN108726767A (en) A kind of processing method of catalyst production waste water
CN108726763A (en) A kind of processing method of catalyst production waste water
CN108726613A (en) A kind of processing method of catalyst production waste water
CN108726762A (en) A kind of processing method of catalyst production waste water

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant