CN110330165A - Strong brine zero-emission and sub-prime crystallizing treatment process and processing system - Google Patents
Strong brine zero-emission and sub-prime crystallizing treatment process and processing system Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
The present invention relates to a kind of strong brine zero-emission and sub-prime crystallizing treatment process and processing systems.The method includes being used for HCO3 2‑It is converted into CO3 2‑And the pre-reaction of heavy-metal ion removal, for carrying out flocculated magnetic flocculation to the waste water after pre-reaction, precipitating for being precipitated to the waste water after flocculation, for the supernatant after precipitating successively to be carried out just permeating with reverse osmosis separation and exporting the concentration of the purified water after separation, the crystallization that high strong brine for obtaining to concentration is crystallized, slurry for generating to crystallization is separated by solid-liquid separation and is exported the crystal separation of the crystal crystallization after separation and for carrying out magnetic kind, the magnetic kind of separation and the magnetic kind reuse of sludge and water separates.The system comprises reaction tank, flocculation basin, sedimentation basin, enrichment facility, crystallization reactor and equipment for separating liquid from solid etc..The present invention is suitable for handling the desulfurization strong brine and other similar high slat-containing wastewater of catalytic cracking flue gas, can be realized the zero-emission and crystal salt commercialization of strong brine.
Description
Technical field
The present invention relates to environmental technology fields, more particularly, to strong brine zero-emission and sub-prime crystallizing treatment process, also
It is related to strong brine zero-emission and sub-prime crystallization treatment system in this way, this method and system is suitable for processing catalysis and splits
Change the desulfurization strong brine and other similar high slat-containing wastewater of flue gas.
Background technique
SO in atmospherexMainly SO2, SO2Aerial mass concentration reaches (0.3~1.0) × 10-6mg/m3When,
People can smell smell, and the mankind and other animals are to SO2Reaction be bronchoconstriction.It is reported that the SO in atmosphere2To state, China
Direct economic loss caused by people's economy accounts for about the 2% of GDP, seriously hinders the development of Chinese national economy.Therefore, to SO2
The control of discharge is imperative.
According to statistics, the SO of oil plant dischargexAccount for SO in atmospherexThe 6%~7% of total release, wherein only catalytic cracking unit
Regenerated flue gas just accounts for SOx5% or so of total release.Moreover, a large amount of NO is also contained in regeneration fume from catalytic crackingx、
Particulate matter, it is just of increasing concern that regeneration fume from catalytic cracking discharges bring pollution problem.
In May, 2014, " it is anti-that energy industry reinforces atmosphere pollution for the Committee of Development and Reform, Bureau of Energy and the joint publication of three department, Chinese Ministry of Environmental Protection
Control programme of work ", it is desirable that all petroleum chemical enterprise's catalytic cracking units will install desulfurizer, catalytic cracking flue gas desulfurization construction
It comes into operation and has been very urgent.
EDV wet scrubbing technology of the country for the mainly non-resource eliminating dampness method sulfur removal technology of catalytic cracking flue gas desulfurization
With WGS wet scrubbing technology, but the high concentration saliferous that the major defect of the two technologies is that fresh water consumption amount is big, is discharged
Sewage is difficult to handle, and saline sewage has a characteristic that 1) concentration of suspension is high, hundred of catalyst dust partial size less than 1.44 μm
It is point relatively high, and hardness is big；2) containing the Na of 3%~8wt%2SO4, catalyst dust, heavy metal compound, if directly steam
Crystallization treatment is sent out, the crystal salt of generation can only be handled by dangerous waste, greatly increase operating cost, therefore there has been no split to catalysis for the country
Change the device and technology that the strong brine that flue gas desulfurization generates is handled.
With the publication and implementation of new revision " Law on Environmental Protection ", and increasingly stringent environmental regulation, high saliferous is limited
Sewage has mentioned agenda, and the discharge for the strong brine that catalytic cracking flue gas sodium method desulfurization generates is one and urgently to be resolved asks
Topic.
So domestic be badly in need of a kind of zero-emission suitable for catalytic cracking flue gas desulfurization strong brine and sub-prime crystallization technique,
It is short to make up the big defect of existing sulfur removal technology fresh water consumption amount, solution some areas water resource for the zero-emission for realizing strong brine
Scarce problem, and can be reduced to pollution caused by local environment and ecology and destroy, the sulfate crystal salt of generation is as product
Sell, there is certain economic benefit, to build with proposed project, play important realistic meaning and far-reaching history meaning
Justice.
Summary of the invention
For problem present in the relevant technologies, the purpose of the present invention is to provide a kind of strong brine zero-emission and sub-prime knots
Brilliant processing method and processing system, to realize the zero-emission (near-zero release) and crystal salt commercialization of strong brine.
To achieve the above object, the technical scheme is that
A kind of strong brine zero-emission and sub-prime crystallizing treatment process, are adapted to the place of catalytic cracking flue gas desulfurization strong brine
Reason, including the following steps:
Waste water is introduced reaction tank, sodium hydroxide is added, makes the HCO in waste water by pre-reaction3 2-It is converted into CO3 2-, and remove
Ca2+、Mg2+Organic sulfur, the heavy metal ion such as removal nickel, antimony, vanadium are added in ion；
Magnetic flocculation is added flocculant and magnetic kind, flocculates to the waste water after pre-reaction；
Precipitating, precipitates the waste water after flocculation；
Concentration: the supernatant after precipitating is successively just being permeated and reverse osmosis separation, and the purified water after output separation (produces
Product water)；
Crystallization: the high strong brine (concentrate) obtained to concentration crystallizes；
Crystal separation (separation of solid and liquid): the slurry generated to crystallization is separated by solid-liquid separation, the knot after output separation
Brilliant object generates crystalline mother solution.
It can also include the following steps:
The separation of magnetic kind: the sediment that precipitating is generated introduces high shearing machine, destroys the combination of magnetic kind and sludge material, carries out magnetic
The separation of kind, sludge and water, the magnetic kind for separating acquisition return to magnetic flocculation step cycle and utilize, and sludge passes through or without desiccation
It is exported after processing, water returns to magnetic flocculation step and handled together with the waste water after pre-reaction.
The concentration step may include the following steps:
Positive permeability and separation: the supernatant water after precipitating is introduced into positive permeability apparatus and carries out positive infiltration processing, by positive permeability apparatus
The concentration salt water isolated introduces highly concentrated brine tank, by draw liquid recyclable device to positive permeability apparatus generate it is dense draw liquid into
Row separation, the liquid that draws isolated are back to positive permeability apparatus；
Reverse osmosis separation: the upper light liquid that liquid recyclable device is isolated will be drawn and be sent into the reverse osmosis place of reverse osmosis unit progress
Reason, the positive permeability apparatus of high-pressure side liquid phase output return of reverse osmosis unit, which is used as, draws liquid, the low-pressure side liquid phase of reverse osmosis unit
Output is exported as purified water (product water).
It is preferred that the low-pressure steam that Crystallization Separation device generates is converted to high steam through vapour compression machine, with high pressure steaming
Vapour heats it before high strong brine is sent into Crystallization Separation device as exothermic medium, and heating is using one or more levels heat
Exchanger carries out, and the condensed water formed after heating by the high steam for being used as exothermic medium is in progress ion-exchange treatment or not
In the case where carrying out ion-exchange treatment, exported as purified water (product water).
Crystallization Separation device is preferably provided with the circulatory system, by crystallisation cycle pump by crystallisation cycle liquid from Crystallization Separation device
Middle extraction, by or without return to Crystallization Separation device after heating, when crystallisation cycle liquid returns to Crystallization Separation by heating
When device, the mode heated to the high strong brine for being sent into Crystallization Separation device is Multi-stage heating, from the Multi-stage heating
Centre introduce crystallisation cycle liquid, crystallisation cycle liquid is entered with high strong brine together with subsequent heat device heat, then together into
Enter Crystallization Separation device.
It is preferred that being no more than according to the concentration of the impurity salinity (salinity for constituting the impurity in crystal) in crystalline mother solution
When given thresholds, crystalline mother solution and high strong brine and crystallisation cycle liquid are fed together Crystallization Separation device and carry out crystallization treatment,
When being more than given threshold, crystalline mother solution introducing drying device is dried, output drying solid (as solid waste or
Resource can be recycled in person).
A kind of strong brine zero-emission and sub-prime crystallization treatment system, using any one strong brine zero-emission disclosed by the invention
It puts and sub-prime crystallizing treatment process, is adapted to the processing of catalytic cracking flue gas desulfurization strong brine, comprising:
Reaction tank makes the HCO in waste water by the way that sodium hydroxide is added for the pre-reaction of waste water3 2-It is converted into CO3 2-, and
Remove Ca2+、Mg2+Organic sulfur, the heavy metal ion such as removal nickel, antimony, vanadium are added in ion；
Flocculation basin, for flocculant and magnetic kind to be added, to the carry out magnetic flocculation after pre-reaction, entrance connects the reaction
The outlet (water outlet) in pond；
Sedimentation basin, for precipitating to the waste water after flocculation, entrance connects the outlet (water outlet) of the flocculation basin,
The entrance of its supernatant outlet connection strong brine tank；
Enrichment facility, for the concentration and separation of supernatants after precipitation, including the positive permeability apparatus that sets gradually and reverse osmosis
Device, the positive permeability apparatus are equipped with and draw liquid recyclable device, and the entrance of the positive permeability apparatus connects the strong brine tank
Outlet, the concentration brine outlet of the positive permeability apparatus connects the entrance of highly concentrated brine tank, described to draw the upper of liquid recyclable device
Light liquid outlet connects the entrance of the reverse osmosis unit；
Crystallization reactor is equipped with crystallisation cycle system for the crystallization of high strong brine, and the crystallisation cycle system includes knot
Brilliant circulating pump, the entrance of the crystallisation cycle pump connect the circulation fluid outlet and the highly concentrated brine tank of the crystallization reactor
The outlet of outlet, the crystallisation cycle pump connects the material inlet of the crystallization reactor；
Equipment for separating liquid from solid, for the separation of solid and liquid of slurry, import connects the crystallization slurry of the crystallization reactor
Material outlet is equipped with crystal outlet and crystalline mother solution outlet.
It is preferably provided with magnetic kind separator.
The magnetic kind separator may include high shearing machine and magnetic separator.The entrance and the sedimentation basin of the high shearing machine
Sludge outlet connection, the high shearing machine outlet the entrance of the magnetic separator between be provided with cyclone separator, it is described
The upper outlet of the connection of entrance described in the sludge outlet and flocculation basin of cyclone separator, the cyclone separator connects the magnetic
The entrance of separator, the magnetic kind outlet of the magnetic separator connect the magnetic kind entrance of the flocculation basin, the dirt of the magnetic separator
Mud is exported for exporting sludge.
It is preferably provided with preheater and crystallization heater.
The outlet of the highly concentrated brine tank is connect with the heat-absorbing medium entrance of the preheater, and the heat absorption of the preheater is situated between
Matter exports the heat-absorbing medium entrance that crystallized circulating pump connects the crystallization heater, and the heat-absorbing medium of the crystallization heater goes out
Mouth connects the feed(raw material)inlet of the crystallization reactor, and the top exit of the crystallization reactor connects the entrance of vapour compression machine,
The outlet of the vapour compression machine connects the exothermic medium entrance of the crystallization heater, the exothermic medium of the crystallization heater
Outlet connects the exothermic medium entrance of the preheater, the entrance of the exothermic medium outlet connection condensate water pot of the preheater.
The outlet of the condensate water pot can connect resin ion exchanger (using resin as the ion exchange of ion-exchanger
Device) inlet port.
The bottom of the crystallization reactor can be equipped with elutriating cylinder, crystallization reactor described in the export mixes of the elutriating cylinder
Slurry outlet, connect with the import of salt pump out, the outlet of salt pump out is divided into two-way, be separately connected thickener into
The circulation fluid import of mouth and the elutriating cylinder, the equipment for separating liquid from solid use centrifuge, and the outlet of the thickener connects institute
State the entrance of centrifuge, the import connection of the mother liquor outlet connection mother liquor tank of the centrifuge.
The import that the outlet of the mother liquor tank can be pumped with mother liquor is connect, and the outlet of the mother liquor pump is divided into two-way, respectively
Connect the import of drying machine and the entrance of crystallisation cycle pump.
The beneficial technical effect of the present invention lies in: the synergistic effect of different disposal technique is made full use of, is reacted by setting
Sodium hydroxide is added in reaction tank, by HCO in pond, flocculation basin, sedimentation basin, high shearing machine, cyclone separator, magnetic separator3 2-Conversion
For CO3 2-, remove Ca2+、Mg2+Ion, is added the heavy metal ion such as organic removal of sulphur nickel, antimony, vanadium, be added in flocculation basin magnetic kind,
PAM forms highdensity wadding body in flocculation basin and increases the specific gravity of wadding body, enhances flocculated effect, reaches efficiently removal effect
Fruit, and magnetic kind is recycled and reused by high shearing machine, cyclone separator, magnetic separator, i.e. removal impurity guarantees sulfuric acid
Sodium purity and the purpose of rapid subsidence keep minimum preprocessing part land occupation, investment and operating cost all low；The positive infiltration dress of setting
It sets, draws liquid recyclable device, the pretreated strong brine of magnetic flocculation is carried out high magnification numbe concentration, TDS=by reverse osmosis unit
30000~80000mg/L is concentrated to TDS=200000mg/L, substantially reduces the scale and operating cost of evaporative crystallization, and draws
The liquid rate of recovery is high, low energy consumption, reduces the operating cost of whole system；Preheater, crystallization heater, crystallization reactor, steaming are set
Vapour compressor, the secondary steam increasing temperature and pressure that vapour compression machine generates crystallization reactor improve heat content, then are transported to crystallization and add
Hot device, for the heating of strong brine, the steam condensate of generation does not have in addition to driving substantially for preheating high strong brine raw material
Live steam substantially reduces the energy consumption of whole system；Resin ion switch is set, removes the ammonia nitrogen in product water, makes to produce
Product water water quality meets circulating cooling make-up water water quality requirement, is achieved in catalytic cracking flue gas desulfurization strong brine zero-emission and sub-prime knot
Low investment, the low operating cost of crystallographic system system, and the crystal salt generated can be used as that product is sold, product water is as circulating cooling make-up water,
Fresh water consumption is saved, so that whole system has certain economic benefit.
Detailed description of the invention
Fig. 1 is structural schematic diagram of the invention.
Specific embodiment
As shown in Figure 1, processing system of the invention includes reaction tank 1, flocculation basin 2, sedimentation basin 3, high shearing machine 5, eddy flow point
From device 6, magnetic separator 7, strong brine tank 8, positive permeability apparatus 10, draw liquid recyclable device 11, reverse osmosis unit 14, high strong brine
Tank 15, crystallisation cycle pump 18, crystallization heater 19, crystallization reactor 20, elutriating cylinder 21, vapour compression machine 22, goes out preheater 17
Salt pump 23, thickener 24, centrifuge 25, drying machine 26, condensate water pot 29 and resin ion switch 31.
Three lattice that reaction tank 1 divides to be sequentially communicated are respectively equipped with sodium hydroxide, organic sulfur and PAC (aluminium polychloride) and add
Material mouth, and it is equipped with blender, two lattice that flocculation basin 2 is divided to be sequentially communicated are respectively equipped with magnetic kind and PAM (polyacrylamide) charging
Mouthful, and it is equipped with blender, the input channel of entrance (the first lattice entrance) connection waste water (strong brine to be processed) of reaction tank 1,
The entrance (the first lattice entrance) of flocculation basin 2 is connect, the entrance and wadding of sedimentation basin 3 with the outlet (outlet of last lattice) of reaction tank 1
Outlet (outlet of last lattice) connection in solidifying pond 2, the entrance of high shearing machine 5 are connect with the sludge outlet of sedimentation basin 3, the connection of the two
Pipeline is equipped with sludge pump 4, and cyclone separator 6, eddy flow point are provided between the entrance of outlet and the magnetic separator 7 of high shearing machine 5
Sludge outlet (outlet at bottom) from device 6 is connect with the entrance of flocculation basin 2, the upper outlet (water after separation of cyclone separator 6
Outlet) connection magnetic separator 7 entrance, magnetic separator 7 magnetic kind outlet connection flocculation basin 2 magnetic kind entrance, magnetic separator 7
Sludge outlet is for exporting sludge.
Specifically contain calcium and magnesium, heavy metal ion, catalyst dust and bicarbonate hardness, reaction tank in desulfurization strong brine
In sequentially add the medicaments such as NaOH (sodium hydroxide), heavy metal chelating agent (organic sulfur), PAC (aluminium polychloride), with strong brine
In calcium and magnesium, heavy metal ion sufficiently react, generate chemical precipitation, and coagulant PAC effect under start with catalyst dust,
The suspended matters such as chemical precipitation form reaction wadding body, and before reaction wadding body is not formed also completely, gravity flow enters flocculation basin 2, flocculation
Magnetic kind is added in pond 2 and continues flocculation reaction, magnetic kind is entrenched in wadding body during this, and gravity flow enters flocculation basin later
In 2 the second lattice, under flocculation aid PAM effect, the wadding body embedded with magnetic kind increases rapidly and completes to react, and enters sedimentation basin later
3, supernatant flows automatically to strong brine tank 8 after the magnetic kind of magnetic kind filter recycling entrainment in sedimentation basin 3, and sediment is through sludge pump 4
Be transported to high shearing machine 5, in sludge wadding body magnetic powder and sludge it is fully dispersed, so that magnetic kind is decomposed into free form, enter later
Cyclone separator 6 carries out initial gross separation, and separation magnetic kind enters flocculation basin 2, and the sludge for carrying magnetic kind secretly enter magnetic separator 7 into
After one step recycles magnetic kind, magnetic kind enters flocculation basin 2, and the sludge isolated is by outlet.
With continued reference to Fig. 1, the entrance of strong brine tank 8 is connect with the supernatant outlet of sedimentation basin 3, and positive permeability apparatus 10 enters
Mouth (pending water entrance or material liquid entrance) is connect with the outlet of strong brine tank 8, and the concentration salt water of positive permeability apparatus 10 goes out
Mouth is connect with the entrance of highly concentrated brine tank 15, is equipped with the first pump between the outlet of strong brine tank 8 and the entrance of positive permeability apparatus 10
9, it draws liquid (or the driving liquid) entrance of recycling separator 11 and the dilute of positive permeability apparatus 10 draws liquid outlet and connect, draw
The dense liquid outlet of drawing of liquid recyclable device 11 is connect with the dense liquid entrance (or drawing liquid entrance) that draws of positive permeability apparatus 10, is drawn
It takes the dense of liquid recyclable device 11 to draw liquid outlet and dense draw of positive permeability apparatus 10 is equipped with the second pump 12 between liquid entrance, draws
The upper light liquid outlet of liquid recyclable device 11 and the entrance (pending water entrance or material liquid entrance) of reverse osmosis unit 14 connect
It connects, draws and be equipped with third pump 13, reverse osmosis dress between the upper light liquid outlet of liquid recyclable device 11 and the entrance of reverse osmosis unit 14
Set 14 concentrated water outlet with second pump 12 entrance connect, draw liquid entrance, reverse osmosis dress to access the dense of positive permeability apparatus 10
Set the purified water that 14 water outlet is used to be formed after output processing.
The dense salt of removing calcium and magnesium, heavy carbonate, heavy metal ion and catalyst dust is further removed through magnetic flocculation pretreatment
Water is sent into positive permeability apparatus 10 through the first pump 9, is to draw liquid with alkali organic solution, will be dense by the osmotic pressure of film two sides
Brine side water naturally osmotic draws liquid side to dense, makes strong brine by original TDS=30000~80000mg/L, is concentrated to TDS
=200000mg/L, and the liquid that draws being diluted returns to and draws liquid recyclable device 11 when being heated to 65 DEG C, water phase and draws liquid phase
AUTOMATIC ZONING, the recyclable 98wt%'s or more of this process draws liquid, and the regenerated dense liquid that draws after layering is sent through the second pump 12
To positive permeability apparatus 10, continue that strong brine is concentrated, and upper light liquid is sent into reverse osmosis unit 14, recycling remaining 1 through third pump 13
~2wt% draw liquid after, produce water reach circulating cooling make-up water water quality requirement, can be used for circulating cooling make-up water or substitution flue gas desulfurization
Fresh water in system, and concentrated water returns to 12 entrance of the second pump and is sent to positive permeability apparatus 10 together with liquid with regenerated dense draw.It draws
Take in liquid recyclable device 11, entrance it is dilute draw liquid and it is regenerated it is dense draw liquid, upper light liquid carry out heat exchange carry out heat recovery,
Therefore, as long as supplementing a small amount of heat loss can be achieved with drawing liquid regeneration, therefore entire forward osmosis membrane concentration process energy consumption is lower than
15kw.h/t strong brine.
With continued reference to Fig. 1, the 4th is connected between the outlet of highly concentrated brine tank 15 and the heat-absorbing medium entrance of preheater 17
Pump 16, the heat-absorbing medium of preheater 17 export the heat-absorbing medium entrance that crystallized circulating pump 18 connects crystallization heater 19, crystallization
The feed(raw material)inlet of the heat-absorbing medium outlet connection crystalline substance reactor 20 of heater 19, the top exit (steam of crystallization reactor 20
Outlet) connection vapour compression machine 22 entrance, the exothermic medium entrance of the outlet connection crystalline substance heater 19 of vapour compression machine 22,
The exothermic medium entrance of the exothermic medium outlet connection preheater 17 of crystallization heater 19, the exothermic medium of preheater 17, which exports, to be connected
Connect the entrance of condensate water pot 29.
The entrance and exit of vapour compression machine 22 respectively with the top exit of crystallization reactor 20 and crystallization heater 19
The connection of exothermic medium entrance, the material inlet of the outlet connection crystalline substance reactor 20 of crystallisation cycle pump 18, crystallisation cycle pump 18
Entrance is also connected with the circulation fluid outlet of crystallization reactor 20, and the exothermic medium of crystallization heater 19 exports (condensation-water drain) and pre-
The exothermic medium import of hot device 17 connects, and the bottom of crystallization reactor 20 is equipped with elutriating cylinder 21, the outlet of elutriating cylinder 21 and salt out
The import connection of pump 23, the outlet of salt pump 23 is divided into two-way out, respectively with the circulation fluid import of elutriating cylinder 21 and thickener 24
Import connection, the entrance of the outlet connection centrifuge 25 of thickener 24, the import of the mother liquor outlet and mother liquor tank 27 of centrifuge 25
Connection, the outlet of mother liquor tank 27 are connect with the import of mother liquor pump 28, and the outlet that mother liquor pumps 28 is divided into two-way, respectively with drying machine 26
The entrance of import and crystallisation cycle pump 18 connect, crystallisation cycle pump 18 has three tunnels to input as a result, respectively from crystallization reactor
20 circulation fluid outlet, the heat-absorbing medium of preheater 17 exports and the outlet of mother liquor tank 27.
More specifically, the high strong brine for being concentrated to TDS=200000mg/L enters highly concentrated brine tank through positive permeability apparatus 10
15, enter preheater 17 through the 4th pump 16, after improving temperature by the steam condensate of shell side, enters into crystallisation cycle pump 18
Mouthful, it is mixed with the high strong brine in circulation, into crystallization heater 19, in crystallization heater 19, high strong brine is by shell side
Secondary-steam heating after increasing temperature and pressure, into vapour solid-liquor separation is carried out in crystallization reactor 20, is isolated to after 93 DEG C or more
Secondary steam enter vapour compression machine 22 under differential pressure action, and after increasing temperature and pressure, into the shell side of crystallization heater 19, add
The high strong brine recycled in heat pipe journey, the steam condensate condensed out enter 17 shell side of preheater heating raw material；It isolates
Crystal deposits to elutriating cylinder 12 under the effect of gravity；Temperature of the high strong brine in crystallization reactor is controlled at 90~100 DEG C,
It is evaporated crystallization under -10~-20kPaG negative pressure, the high continuous circulating-heating evaporation of strong brine, high strong brine is from TDS=
200000mg/L to the TDS=427000mg/L of saturation state, then arrives hypersaturated state, and the sodium sulphate in high strong brine is formed
Nucleus, the increase with degree of supersaturation, nucleus are constantly grown up, and deposit to the elutriation of crystallization reactor bottom under gravity later
Column 12 deposits to the sodium sulphate magma of elutriating cylinder 12 under the action of salt pump 23 out, and constantly circulation plays magma in elutriating cylinder 12
Stirring action also makes sodium sulfate crystal grow up to 0.09-0.12m m, when magma concentration reaches 35-45% in elutriating cylinder 12,
Gone out salt pump 23 to be transported to after thickener 24 continues enrichment, isolate sodium sulphate product salt to centrifuge 25, the mother liquor of generation into
Enter mother liquor tank 27, sends crystallisation cycle 18 entrances of pump back to through mother liquor pump 28 and continue cycling through evaporative crystallization, when chlorine ion concentration in mother liquor
When reaching certain value, mother liquor is sent to the progress carnallite mother liquor crystallization of drying machine 26 through mother liquor pump 28 and is dried to carnallite.
With continued reference to Fig. 1, the import of condensate water pot 29 is connect with the exothermic medium of preheater 17 outlet (condensed water), resin
The material inlet of ion interchange unit 31 is connect with the outlet of condensate water pot 29, is provided with the 5th pump 30 between the two.
Again specifically, the high strong brine of raw material is heated, the steam condensate (SC) after reducing temperature enters condensate water pot, because desulfurization is dense
NH of the salt water in evaporation and crystal process, in desulfurization strong brine4 +It can also be evaporate into secondary steam with the evaporation of strong brine,
It is entered in condensed water as secondary steam condensation can also condense, according to the NH in desulfurization strong brine4 +Ion concentration size, selection
The setting resin ion switch 31 of property, if NH4 +When ion concentration is low, the condensed water in condensate water pot 29 is sent through the 5th pump 30
Fresh water is substituted as moisturizing or desulfurizer to circulation water station, if NH4 +Condensed water when ion concentration is high, in condensate water pot 29
It is sent to resin ion switch 31 through the 5th pump 30, removes the NH in condensed water4 +Ion makes water quality meet industrial circulating water benefit
After water water quality requirement, circulation water station is sent to as moisturizing or desulfurizer substitution fresh water.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, omit, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
" strong brine " so-called in the present invention be primarily referred to as TDS (dissolvable solid sum) concentration be 30000~
80000mg/L, and can containing a kind of in catalyst dust, heavy metal, calcium salt, magnesium salts, carbonate, nitrate and sodium chloride etc. or
Mixing strong brine based on the sodium sulphate of several impurity is also adapted to the high waste water of other similar salt concentration.
It is disclosed by the invention it is each preferably with optional technological means, unless otherwise indicated and one preferably or can selecting technology hand
Section is that further limiting for another technological means is outer, can form several different technical solutions in any combination.
Claims (10)
1. a kind of strong brine zero-emission and sub-prime crystallizing treatment process, are adapted to the processing of catalytic cracking flue gas desulfurization strong brine,
Include the following steps:
Waste water is introduced reaction tank, sodium hydroxide is added, makes the HCO in waste water by pre-reaction3 2-It is converted into CO3 2-, and remove Ca2+、
Mg2+Ion is added organic sulfur, goes heavy metal ion；
Magnetic flocculation is added flocculant and magnetic kind, flocculates to the waste water after pre-reaction；
Precipitating, precipitates the waste water after flocculation；
Concentration: the supernatant after precipitating is successively just being permeated and reverse osmosis separation, the purified water after output separation；
Crystallization: the high strong brine obtained to concentration crystallizes；
Crystal separation: the slurry generated to crystallization is separated by solid-liquid separation, the crystal after output separation.
2. the method as described in claim 1, it is characterised in that further include the following steps:
Magnetic kind separates: the high shearing machine of sediment introducing that precipitating is generated, the combination of destruction magnetic kind and sludge material, progress magnetic kind,
The separation of sludge and water, separate acquisition magnetic kind return magnetic flocculation step cycle utilize, sludge by or without desiccation at
It is exported after reason, water returns to magnetic flocculation step and handled together with the waste water after pre-reaction.
3. the method as described in claim 1, it is characterised in that the concentration step includes the following steps:
Positive permeability and separation: the supernatant water after precipitating is introduced into positive permeability apparatus and carries out positive infiltration processing, positive permeability apparatus is separated
Concentration salt water out introduces highly concentrated brine tank, is divided by drawing liquid recyclable device the dense liquid that draws that positive permeability apparatus generates
From the liquid that draws isolated is back to positive permeability apparatus；
Reverse osmosis separation: the upper light liquid that liquid recyclable device is isolated will be drawn and be sent into reverse osmosis unit progress reverse osmosis treatment, instead
The high-pressure side liquid phase output of permeability apparatus returns to positive permeability apparatus as liquid is drawn, and the low-pressure side liquid phase of reverse osmosis unit, which exports, to be made
For purified water output.
4. the method as described in claim 1, it is characterised in that according to the concentration of the impurity salinity in crystalline mother solution, be no more than
When given thresholds, crystalline mother solution and high strong brine and crystallisation cycle liquid are fed together Crystallization Separation device and carry out crystallization treatment,
When being more than given threshold, crystalline mother solution introducing drying device is dried, drying solid is exported.
5. the method as described in claim 1-4 is any, it is characterised in that the low-pressure steam for generating Crystallization Separation device is through steaming
Vapour compressor is converted to high steam, using the high steam as exothermic medium, before high strong brine is sent into Crystallization Separation device
It is heated, heating is carried out using one or more levels heat exchanger, by the high steam shape as exothermic medium after heating
At condensed water carrying out ion-exchange treatment or in the case where without ion-exchange treatment, exported as purified water.
6. method as claimed in claim 5, it is characterised in that Crystallization Separation device is equipped with the circulatory system, is pumped by crystallisation cycle
Crystallisation cycle liquid is drawn from Crystallization Separation device, by or without return Crystallization Separation device after heating, works as crystallization
When circulation fluid returns to Crystallization Separation device by heating, the mode heated to the high strong brine for being sent into Crystallization Separation device is
Multi-stage heating, intermediate from the Multi-stage heating introduce crystallisation cycle liquid, after crystallisation cycle liquid is entered together with high strong brine
Continuous heating devices heat, then enters Crystallization Separation device together.
7. a kind of strong brine zero-emission and sub-prime crystallization treatment system are adapted to using any method of claim 1-6
The processing of catalytic cracking flue gas desulfurization strong brine, characterized by comprising:
Reaction tank makes the HCO in waste water by the way that sodium hydroxide is added for the pre-reaction of waste water3 2-It is converted into CO3 2-, and remove
Ca2+、Mg2+Ion is added organic sulfur, goes heavy metal ion；
Flocculation basin, for flocculant and magnetic kind to be added, to the carry out magnetic flocculation after pre-reaction, entrance connects the reaction tank
Outlet；
Sedimentation basin, for precipitating to the waste water after flocculation, entrance connects the outlet of the flocculation basin, supernatant outlet
Connect the entrance of strong brine tank；
Enrichment facility, for the concentration and separation of supernatants after precipitation, including the positive permeability apparatus set gradually and reverse osmosis unit,
The positive permeability apparatus is equipped with and draws liquid recyclable device, and the entrance of the positive permeability apparatus connects the outlet of the strong brine tank,
The concentration brine outlet of the positive permeability apparatus connects the entrance of highly concentrated brine tank, and the upper light liquid for drawing liquid recyclable device goes out
Mouth connects the entrance of the reverse osmosis unit；
Crystallization reactor is equipped with crystallisation cycle system for the crystallization of high strong brine, and the crystallisation cycle system includes that crystallization follows
Ring pump, the entrance of the crystallisation cycle pump connect the circulation fluid outlet of the crystallization reactor and going out for the highly concentrated brine tank
Mouthful, the outlet of the crystallisation cycle pump connects the material inlet of the crystallization reactor；
Equipment for separating liquid from solid, for the separation of solid and liquid of slurry, the slurry that import connects the crystallization reactor goes out
Mouthful, it is equipped with crystal outlet and crystalline mother solution outlet.
8. system as claimed in claim 7, it is characterised in that be equipped with magnetic kind separator, the magnetic kind separator includes height
The entrance of shearing machine and magnetic separator, the high shearing machine is connect with the sludge outlet of the sedimentation basin, the outlet of the high shearing machine with
Cyclone separator is provided between the entrance of the magnetic separator, described in the sludge outlet and flocculation basin of the cyclone separator
Entrance connection, the upper outlet of the cyclone separator connect the entrance of the magnetic separator, and the magnetic kind of the magnetic separator goes out
Mouth connects the magnetic kind entrance of the flocculation basin, and the sludge outlet of the magnetic separator is for exporting sludge.
9. system as claimed in claim 7, it is characterised in that the bottom of the crystallization reactor is equipped with elutriating cylinder, the elutriation
The slurry of crystallization reactor described in the export mixes of column exports, and connect with the import of salt pump out, the outlet of the salt pump out
Be divided into two-way, be separately connected the import of thickener and the circulation fluid import of the elutriating cylinder, the equipment for separating liquid from solid use from
Scheming, the outlet of the thickener connect the entrance of the centrifuge, the mother liquor outlet connection mother liquor tank of the centrifuge into
Mouth connection, the outlet of the mother liquor tank are connect with the import that mother liquor pumps, and the outlet of the mother liquor pump is divided into two-way, are separately connected dry
The entrance of the import of dry machine and crystallisation cycle pump.
10. the system as described in claim 7-9 is any, it is characterised in that it is equipped with preheater and crystallization heater, it is described highly concentrated
The outlet of brine tank is connect with the heat-absorbing medium entrance of the preheater, and the heat-absorbing medium of the preheater exports crystallized circulation
Pump connects the heat-absorbing medium entrance of the crystallization heater, and the heat-absorbing medium outlet connection crystallization of the crystallization heater is anti-
The feed(raw material)inlet of device is answered, the top exit of the crystallization reactor connects the entrance of vapour compression machine, the vapour compression machine
Outlet connects the exothermic medium entrance of the crystallization heater, and the exothermic medium outlet of the crystallization heater connects the preheating
The exothermic medium entrance of device, the entrance of the exothermic medium outlet connection condensate water pot of the preheater, the condensate water pot go out
The inlet port of mouth connection resin ion-exchanger.
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