CN109879507A - A kind of technique and device of coking high-salt wastewater resource utilization - Google Patents
A kind of technique and device of coking high-salt wastewater resource utilization Download PDFInfo
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- CN109879507A CN109879507A CN201910261858.6A CN201910261858A CN109879507A CN 109879507 A CN109879507 A CN 109879507A CN 201910261858 A CN201910261858 A CN 201910261858A CN 109879507 A CN109879507 A CN 109879507A
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Abstract
The present invention provides the techniques and device of a kind of coking high-salt wastewater resource utilization.The technique has successively carried out evaporation for coking high-salt wastewater, burnings, the dissolution of fume treatment, mixed salt clean, freeze and divide salt, double flash evaporation.Cooperate coking high-salt wastewater resource utilization device of the invention using the technique, it can be realized recycling, purification and the recycling of the salt (sodium chloride, sodium sulphate) of the industrial coking high-salt wastewater in process of coking, it can be realized the fully recovering of recirculated water and the resource utilization of solid salt, the discharge of solid waste is reduced, really realizes the zero-emission of coking high-salt wastewater；And coking workshop section remained ammonia waste heat is made full use of in production process, perfect technology, device operating cost are low, stable, and energy-saving effect is good, invest relative moderate.
Description
Technical field
The invention belongs to coking high-salt wastewater application technology as the second resource fields, and in particular to a kind of coking high-salt wastewater resource
Change the technique utilized and device.
Background technique
The coking wastewater ingredient generated in coal chemical industry production process is complex, especially by filtering, concentration, evaporation etc.
Remaining coking high-salt wastewater after processing, main component is as shown in table 1 below, because containing toxic, harmful, hard-degraded substance, place
Reason difficulty is larger, is always the bottleneck for perplexing industry development, especially with the increasingly stringent of environmental protection management, coking high-salt wastewater
Qualified discharge and resource utilization contradiction it is outstanding day by day.Currently, the resource utilization process used is various, it is main to collect
In the coking high-salt wastewater that is generated after the techniques such as membrane separation process, evaporation concentration method, processing be mainly used for quenching and coal blending.
Table 1:
Membrane separation process is separated using porous membrane, principle be using two-phase in liquid-liquid dispersion system with
Solid film surface affinity is different, once achievees the purpose that separation.Fluorine removal first is carried out to coking wastewater, sodium carbonate softening precipitating is removed
Calcium and magnesium processing, then TOC degradation is carried out using advanced oxidation, organic carbon is removed by multimedium, active carbon filter and ultrafiltration membrane
And suspended matter, it is then separated through nanofiltration membrane, obtained nanofiltration is evaporated processing by liquid and nanofiltration strong brine respectively, most
Sodium chloride product, sodium sulphate product are obtained eventually.However such technique is taken to have the following disadvantages: (1) because containing in coking wastewater
Great amount of soluble organic pollutant handles by advanced oxidation and is difficult to thoroughly eliminate, and some organic pollutants enter sodium chloride, sulphur
Sour sodium finished product pollutes object transfer, influences product quality and application；(2) sodium sulphate, sodium chloride content become in coking wastewater
To change larger, nanofiltration can not adapt to the variation of water salt content in normal productive process, and cause the fluctuation of sodium chloride product quality larger,
It is unable to satisfy quality requirement；(3) membrane technology is still immature, and equipment manufacturing cost is costly；Because containing benzene in coking wastewater
Equal organic substances, long-play are larger to filtering membrane damage, and treatment effect decaying is fast, and life of equipment is short, maintenance cost
It is expensive.
Evaporating and concentrating process is separated by the way of evaporation, and principle is to be steamed using steam to coking wastewater
Hair.Coking wastewater first passes through pretreatment unit removal organic matter and solid insoluble, is then sent to multi-effect evaporator and is evaporated,
The steam condensate (SC) reuse steamed to production system moisturizing, remaining high-salt wastewater is used for coal-blending coking.However take such work
Skill has the following disadvantages: in (1) high-salt wastewater containing inorganic mixed salt and hardly degraded organic substances such as a large amount of sodium sulphate, sodium chloride, matches
Enter the indexs such as the heat reactivity, cold strength, sodium content of raw coal coking STRENGTH ON COKE to have a significant effect, reduces the quality product of coke
Matter；(2) a large amount of high-salt wastewater enters coke oven coal blending, energy consumption is significantly increased, and inorganic salts at high temperature cause coke oven
Certain corrosion reduces core equipment service life, be easy to cause coke oven corrosion string leakage, adversely affects to environment protection control；
(3) the purification purification that cannot achieve point salt and inorganic salts, cannot achieve the resource utilization of abraum salt, results in waste of resources.
It would therefore be highly desirable to provide, a kind of perfect technology, stable, energy-saving effect is good, and can be realized coking high-salt wastewater
Fully recovering and solid salt resource utilization process and its processing system, to reduce the discharge of solid waste.
Summary of the invention
Based on defect of the existing technology, the purpose of the present invention is to provide a kind of coking high-salt wastewater resource utilizations
Technique；The object of the invention is also to provide a kind of systems of coking high-salt wastewater resource utilization.Cooperated using the system
Process of the invention can be realized returning for the salt (sodium chloride, sodium sulphate) of the industrial coking high-salt wastewater in process of coking
It receives, refine and recycles, can be realized the fully recovering of recirculated water and the resource utilization of solid salt, reduce solid waste
The zero-emission of coking high-salt wastewater is really realized in discharge.
The purpose of the present invention is achieved by the following technical programs:
On the one hand, the present invention provides a kind of technique of coking high-salt wastewater resource utilization, which includes the following steps:
Step 1 is evaporated coking high-salt wastewater, is centrifuged that obtain the first distilled water, saturated salt solution and solid mixed
Salt；
Saturated salt solution and solid mixed salt are heated and are burned by step 2, burn off wherein poisonous and hazardous organic matter,
Solid mixed salt and hot fume after being burned；
Step 3, the solid mixed salt after burning are dissolved by water, then sequentially add active powdered carbon, sodium hydroxide, carbonic acid
Sodium, for removing coloring matter, adjusting pH value to alkalinity and removing calcium and magnesium from then progress sedimentation filtration obtains the first salt
Solution and sludge；
Step 4, first salting liquid carry out low-temperature centrifugation separation after heat exchange cooling, obtain the sulphur with the crystallization water
Sour sodium and the second salting liquid；
Step 5, second salting liquid are evaporated after pre-heating temperature elevation, obtain the first salt slurry and after-fractionating water；
First salt slurry carries out centrifugation and obtains solid sodium chloride and third salting liquid；
Step 6, the third salting liquid are evaporated after pre-heating temperature elevation, obtain the second salt slurry and third distilled water；
Second salt slurry carries out centrifugation and obtains a small amount of solid salt-mixture and a small amount of mixed salt solution；Obtained a small amount of solid mixture foldback
It re-dissolves and recycles to step 3.
In the prior art, in coal chemical industry production process, in coking high-salt wastewater resource utilization process, film point is taken
Costly from technical equipment cost, because containing the organic substances such as benzene in coking wastewater, long-play to filtering membrane damage compared with
Greatly, treatment effect decaying is fast, and life of equipment is short, and maintenance cost is expensive.And existing evaporation concentration technique is mainly at present
Recovered steam condensed water is evaporated for production system moisturizing to coking wastewater, remaining high-salt wastewater is used for coal-blending coking,
Due to containing inorganic mixed salt and the hardly degraded organic substances such as a large amount of sodium sulphate, sodium chloride in high-salt wastewater, coal-blending coking is directly carried out
The quality of coke can be reduced, and certain corrosion will cause to coke oven, while cannot achieve the recycling of sodium sulphate and sodium chloride
It utilizes, causes the wasting of resources.
Process of the invention is taken, can be realized the salt (chlorination of the industrial coking high-salt wastewater in process of coking
Sodium, sodium sulphate) recycling, purification and recycling, can be realized the fully recovering of recirculated water and the resource utilization of solid salt, subtract
The discharge of few solid waste.Such as: a small amount of solid salt-mixture in step 6 can further be returned to step 3 and re-dissolve
It recycles, sufficiently recycles sodium chloride and sodium sulphate therein, realize waste zero-emission.The sodium sulphate of technique recycling purification
Quality meet " industrial anhydrous sodium sulfate " GB/T6009-2014 standard requirement；The quality for recycling the sodium chloride of purification meets
The requirement of " Nacl " GB/T5462-2015 standard.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 1, the coking high-salt wastewater
Salt content be 70000mg/L-90000mg/L, COD 2000-10000mg/L；After pervaporation is centrifuged, first distillation
Salt content≤300mg/L of water, the first distilled water preferably can be used as recirculated water use；The salt content of the saturated salt solution is
250000mg/L。
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 2, the temperature of burning is 650
℃-800℃.The organic substances such as phenol, cyanide in solid mixed salt can be effectively removed under this incineration temperature.
The technique of above-mentioned coking high-salt wastewater resource utilization, the hot fume are emitted into atmosphere afterwards after post treatment
In；Preferably, the step of hot fume is post-processed are as follows:
The hot fume is subjected to secondary afterburning, temperature rises to the organic matter in >=1100 DEG C of burn off flue gases (in 650-800
The substances such as phenol cyanogen can be partially converted into complicated gaseous organic substance at DEG C, and needing further could be thorough at a high temperature of 1100 DEG C or more
Bottom removal), it then carries out hot fume heat exchange and recycles heat simultaneously；After hot fume after heat exchange is cooled to 200 DEG C or less, then pass through
After crossing the de- dioxin of depickling, dedusting and desulphurization denitration, make content of sulfur dioxide≤50mg/m in hot fume3, nitrogen oxides contains
Amount≤100mg/m3, dust≤10mg/m3Heel row is amplified in gas.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 3, the pH value regulated value is
8.3-11.3.It can guarantee effectively removing for calcium ions and magnesium ions under the pH value condition.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that suspended matter in first salting liquid≤
100mg/L.The content of suspended matter is about 100-300mg/L in coking high-salt wastewater, can be substantially reduced using present invention process
The content of suspended matter.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the sludge that sedimentation filtration obtains passes through filters pressing
It is handled afterwards for coal blending；Reduce the discharge of pollutant.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 4, the low-temperature centrifugation separation
Temperature be -5 DEG C~-4 DEG C.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the sodium sulphate with the crystallization water is after post treatment
Sodium sulphate product is obtained, is included the following steps:
Solid sodium sulfate with the crystallization water is heated to 103 DEG C -106 DEG C to be evaporated, is then cooled to 20 DEG C -30
DEG C, and be centrifuged and obtain solid sodium sulfate and liquid aqueous solution, the solid sodium sulfate is used to pack after drying to be sold outside, the liquid
The cryogenic separation again of body aqueous solution return step four.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 5, the after-fractionating water is made
The cycling use of water dissolved for the solid mixed salt of step 3.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 6, the third distilled water is made
The cycling use of water dissolved for the solid mixed salt of step 3.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 6, obtained a small amount of mixed salt is molten
Liquid is handled for coal blending.Remaining a small amount of mixed salt solution is used for coal blending due to containing organic matter and other impurities, outlet, to avoid
Impurities accumulation reduces environmental pollution simultaneously.
The technique of above-mentioned coking high-salt wastewater resource utilization, it is preferable that in step 5 and step 6, described second
The waste heat of the heat source that salting liquid and the third salting liquid are preheated remained ammonia in the production of coking workshop section, temperature are
71-72 DEG C, the heat source of coking workshop section is made full use of, reduces evaporated vapor consumption.
On the other hand, the present invention also provides a kind of device of coking high-salt wastewater resource utilization, which includes triple effect
Vaporising device, incinerator, flue gas processing device, dissolution exclusion device, freezing divide salt device, sodium sulphate process units and two-stage
Vaporising device；
The triple-effect evaporation plant is for being evaporated and being centrifuged to coking high-salt wastewater；
The incinerator is used to heat the saturated salt solution for burning the triple-effect evaporation plant centrifugation acquisition and solid is mixed
Salt；
The flue gas processing device is used to carry out aftertreatment technology to the hot fume for burning acquisition in the incinerator；
Solid mixed salt after the dissolution exclusion device is used to burn the incinerator carries out calcium ions and magnesium ions and coloured
The removal of substance；
The freezing divides salt device for changing the first salting liquid obtained after cleaning in the dissolution exclusion device
Heat, low-temperature centrifugation separation are to obtain band crystallization aqueous sodium persulfate and the second salting liquid；
The sodium sulphate process units is used to carry out aftertreatment technology to the sodium sulphate with the crystallization water to obtain sulphur up to standard
Sour sodium product；
The double flash evaporation device, which is used to further evaporate the second salting liquid centrifugation, obtains sodium chloride product, cycling use of water
And mixed salt.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the triple-effect evaporation plant includes structure
Identical 1st effective evaporator, 2nd effect evaporator and triple effect evaporator；Each evaporator includes heater, separation chamber, circulating pump
And connecting line.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the incinerator includes incinerator.This
Invention can thoroughly eliminate the harmful organic substance in coking wastewater by the method burned, and prevent pollutant with the transfer of product
And diffusion, it ensure that the quality of sodium chloride, sodium sulphate product.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the flue gas processing device includes successively
Secondary combustion chamber, waste heat boiler, chilling tower, extracting tower, bag filter and the desulphurization denitration dioxin removal apparatus being connected.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the dissolution exclusion device includes dissolved salt
Pond, a settling tank, dosing pond, secondary settling tank, filter and filter press；It is the dissolved salt pond, a settling tank, described
Dosing pond, the secondary settling tank and the filter are sequentially connected logical；Settling tank, the secondary settling tank and institute
Filter is stated to be connected with the filter press respectively；Settling tank is for loading active powdered carbon；The dosing Chi Zhongyong
In loading sodium hydroxide and sodium carbonate.It is solid by the settling tank part of sulfuric acid calcium carried secretly in mixed salt solution that can tentatively go out
Body reduces the consumption of sodium carbonate in subsequent dosing pond；And active carbon decoloring is carried out in a settling tank simultaneously, remove colored substance
Matter.It is mounted with sodium hydroxide and sodium carbonate in the dosing pond, by sodium hydroxide condition pH to alkalinity, in favor of calcium ions and magnesium ions
It is reacted with sodium carbonate, removes calcium ions and magnesium ions.The solids obtained by once settling, after the separation of secondary settlement and filter passes through
Filter press filters pressing produces sludge, to be used for coal blending, reduces the discharge of pollutant.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the freezing divides salt device to include successively
First Heat Exchanger, multistage refrigerator and the first centrifuge being connected.Take multistage refrigerator that can prevent single-stage freezing from causing
Equipment blocking.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the sodium sulphate process units include according to
The secondary pyrolysis evaporator being connected, the second heat exchanger, the second centrifuge and the first dry packing machine.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the double flash evaporation device includes level-one
Preheater, level-one evaporator, third centrifuge, the second dry packing machine, second level preheater, secondary evaporimeter and the 4th centrifugation
Machine.The level-one preheater, the level-one evaporator, the third centrifuge and the second dry packing machine are sequentially connected
It connects；The third centrifuge, the second level preheater, the secondary evaporimeter and the 4th centrifuge are sequentially connected and connect.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the 1st effective evaporator includes 2 heating
Device, and the 1st effective evaporator is provided with crystal seed scale prevention device.2 heaters are set in the 1st effective evaporator, can be increased
Heat exchange area reduces fouling probability；The setting of crystal seed scale prevention device further decreases the fouling probability in 1st effective evaporator simultaneously,
Conducive to subsequent two effect, triple effect evaporation.In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that described secondary
Combustion chamber, the waste heat boiler, the chilling tower, the extracting tower, the bag filter and the desulphurization denitration de- two is disliked
English device successively carries out afterburning, heat exchange, cooling, dedusting and desulphurization denitration de- two to the hot fume for burning acquisition in the incinerator
English is disliked to obtain flue gas up to standard for discharging.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the level-one evaporator and the second level
The distilled water that evaporator evaporation obtains is for carrying out the complex salt in the dissolved salt pond in the dissolution exclusion device.Not only recycle
Distilled water, has saved water resource, while can reduce bringing into for calcium ions and magnesium ions.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the level-one preheater and the second level
Preheater heat source is heated using remained ammonia, makes full use of waste heat, reduces evaporator steam consumption.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the liquid that second centrifuge is isolated
Body aqueous solution is back to freezing and salt device is divided to recycle.The a small amount of sodium sulphate contained in liquid aqueous solution is sufficiently returned
It receives.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the residue after the filter press filters pressing is dirty
Mud is used for coal blending.
In the device of above-mentioned coking high-salt wastewater resource utilization, it is preferable that the 4th centrifuge is isolated
A small amount of mixing salt solution is used for coal blending, and isolated a small amount of solid salt-mixture is returned to the dissolution exclusion device and is recycled
It utilizes.
Beneficial effects of the present invention:
(1) present invention can convert industrial products for sodium sulphate, the sodium chloride in coking high-salt wastewater, realize discarded
The resource utilization of object, avoids the wasting of resources；The distilled water generated in technique can greatly reduce as the recirculated water of reuse
The utilization of water resource in salt recovery process；Meanwhile the sludge generated in technique and a small amount of solid mixed salt can be into one
Step is used for coal blending, takes present invention process that can really realize the zero-emission of coking high-salt wastewater.
(2) present invention has perfect technology, device operating cost low, stable, and energy-saving effect is good, invests relatively low
It is honest and clean.
Detailed description of the invention
Fig. 1 is the technique overall flow figure of coking high-salt wastewater resource utilization in the embodiment of the present invention；
Fig. 2 is the work of the triple-effect evaporation plant workshop section in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Skill flow chart；
Fig. 3 is the incinerator and fume treatment dress in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Set the process flow chart of workshop section；
Fig. 4 is the work of the dissolution exclusion device workshop section in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Skill flow chart；
Fig. 5 is the work of the freezing Fen Yan device workshop section in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Skill flow chart；
Fig. 6 is the sodium sulphate process units workshop section in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Process flow chart；
Fig. 7 is the work of the double flash evaporation device workshop section in the embodiment of the present invention in coking high-salt wastewater resource utilization device
Skill flow chart.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment
The device for present embodiments providing a kind of coking high-salt wastewater resource utilization, with reference to description of the invention attached drawing 1
To 7, the device of the coking high-salt wastewater resource utilization includes triple-effect evaporation plant, incinerator, flue gas processing device, dissolution
Exclusion device, freezing divide salt device, sodium sulphate process units and double flash evaporation device.
The triple-effect evaporation plant is for being evaporated and being centrifuged to coking high-salt wastewater.
The incinerator is used to heat the saturated salt solution for burning the triple-effect evaporation plant centrifugation acquisition and solid is mixed
Salt.
The flue gas processing device is used to carry out aftertreatment technology to the hot fume for burning acquisition in the incinerator.
Solid mixed salt after the dissolution exclusion device is used to burn the incinerator carries out calcium ions and magnesium ions and coloured
The removal of substance.
The freezing divides salt device for changing the first salting liquid obtained after cleaning in the dissolution exclusion device
Heat, low-temperature centrifugation separation obtain band crystallization aqueous sodium persulfate and the second salting liquid.
The sodium sulphate process units is used to carry out aftertreatment technology to the sodium sulphate with the crystallization water to have obtained sulphur up to standard
Sour sodium product.
The double flash evaporation device, which is used to further evaporate the second salting liquid centrifugation, obtains sodium chloride product, cycling use of water
And mixed salt.
In one preferred embodiment of the present embodiment, the triple-effect evaporation plant includes the identical effect evaporation of structure
Device, 2nd effect evaporator and triple effect evaporator；Each evaporator includes heater, separation chamber, circulating pump and connecting line.
The incinerator includes incinerator；It can thoroughly be eliminated by the method for burning harmful organic in coking wastewater
Substance (such as: phenol, cyanide etc.), prevent pollutant with the transfer and diffusion of product, ensure that sodium chloride, sodium sulphate product
Quality.
The flue gas processing device includes being sequentially connected the secondary combustion chamber connect, waste heat boiler, chilling tower, extracting tower, cloth
Bag dust collector and desulphurization denitration dioxin removal apparatus.
The dissolution exclusion device includes dissolved salt pond, a settling tank, dosing pond, secondary settling tank, filter and filters pressing
Machine；The dissolved salt pond, a settling tank, the dosing pond, the secondary settling tank and the filter are sequentially connected logical；
Settling tank, the secondary settling tank and the filter are connected with the filter press respectively；The primary sedimentation
Active powdered carbon is mounted in pond；Sodium hydroxide and sodium carbonate are mounted in the dosing pond.
The freezing divides salt device to include being sequentially connected the First Heat Exchanger connect, multistage refrigerator and the first centrifuge.It adopts
Take multistage refrigerator that can prevent single-stage freezing from equipment being caused to block.
The sodium sulphate process units include be sequentially connected the pyrolysis evaporator connect, the second heat exchanger, the second centrifuge and
First dry packing machine.
The double flash evaporation device include level-one preheater, level-one evaporator, third centrifuge, the second dry packing machine,
Second level preheater, secondary evaporimeter and the 4th centrifuge.The level-one preheater, the level-one evaporator, third centrifugation
Machine and the second dry packing machine are sequentially connected and connect；The third centrifuge, the second level preheater, the secondary evaporimeter
It is sequentially connected and connects with the 4th centrifuge.
In one preferred embodiment of the present embodiment, the 1st effective evaporator includes 2 heaters, and an effect is steamed
Hair device is provided with crystal seed scale prevention device.2 heaters are set in the 1st effective evaporator, heat exchange area can be increased, reduce knot
Dirty probability；The setting of crystal seed scale prevention device further decreases the fouling probability in 1st effective evaporator simultaneously, imitated conducive to subsequent two,
Triple effect evaporation.
The hot ammonium hydroxide that is generated from coking workshop section of heat source of the level-one preheater, the second level preheater.Coking workshop section
The waste heat of remained ammonia in production, temperature are 71-72 DEG C, make full use of the heat source of coking workshop section, reduce evaporated vapor consumption.
The secondary combustion chamber, the waste heat boiler, the chilling tower, the extracting tower, the bag filter and institute
Desulphurization denitration dioxin removal apparatus is stated successively to carry out afterburning to the hot fume for burning acquisition in the incinerator, heat exchange, cooling, take off
Acid, dedusting and desulphurization denitration take off dioxin to obtain flue gas up to standard for discharging.
The distilled water that the level-one evaporator and secondary evaporimeter evaporation obtain is in the dissolution exclusion device
Carry out the complex salt in the dissolved salt pond.Distilled water has not only been recycled, has saved water resource, while calcium ions and magnesium ions can be reduced
It brings into.
Excess sludge after the filter press filters pressing is used for coal blending.
The isolated a small amount of mixing salt solution of 4th centrifuge is used for coal blending, isolated a small amount of solid mixing
Salt is returned in second salting liquid and is recycled.
The present embodiment, which also provides, utilizes technique of the above-mentioned apparatus to coking high-salt wastewater resource utilization, technique overall flow
Figure as shown in Figure 1, the coking high-salt wastewater salt content 70000mg/L-90000mg/L in the present embodiment (total salt content is about chlorine
Change sodium+sodium sulphate not indicate in component list because sodium ion can not be detected), COD content about 2000-10000mg/L is specific main
Ingredient is wanted to see the table below 2:
Table 2:
Following process is taken, resource utilization is carried out to the coking high-salt wastewater of the present embodiment, to realize coking height
The zero-emission of salt waste water, the technique specifically comprise the following steps:
Step 1 carries out triple effect evaporation as shown in Fig. 2, sending to coking high-salt wastewater into triple effect evaporator, then passes through
Centrifugation obtains the first distilled water, saturated salt solution and solid mixed salt, salt content≤300mg/L of first distilled water, described
The salt content of saturated salt solution is about 250000mg/L；Wherein, first distilled water is used as recirculated water, realizes water resource
Recycle, save water resource.
Step 2 is carried out as shown in figure 3, sending saturated salt solution and solid mixed salt into incinerator using coke-stove gas
It heating and burns, incineration temperature is 650 DEG C -800 DEG C, after burn off poisonous and hazardous organic matter therein, consolidating after being burned
Body mixed salt and about 700 DEG C of hot fume；
Wherein, the hot fume is emitted into atmosphere after taking following aftertreatment technology processing up to standard:
Obtain in this step about 700 DEG C of hot fume is subjected to secondary afterburning by secondary combustion chamber, makes its temperature liter
Temperature is to >=1100 DEG C, with the organic matter in burn off flue gas；Subsequently into exchanging heat in waste heat boiler, recovery section heat；It changes
Hot fume after heat is sent again to chilling tower and is cooled to 200 DEG C hereinafter, using extracting tower, bag filter, desulphurization denitration de- two
Dislike English device, in treated flue gas, content of sulfur dioxide≤50mg/m3, amount of nitrogen oxides≤100mg/m3, dust≤
10mg/m3, then it is emitted into atmosphere, which can reach the standard that flue gas is discharged in atmosphere.
Step 3 is dissolved, then successively as shown in figure 4, the solid mixed salt after burning is sent into dissolved salt pond by recirculated water
The dosing pond for being passed through and being mounted with the first settling tank of active powdered carbon, be mounted with sodium hydroxide and sodium carbonate removes coloring matter, and
PH value is adjusted to 8.3-11.3, removes calcium ions and magnesium ions；Then it is settled by the second settling tank, and was carried out by filter
Filter obtains the first salting liquid and solids；Suspended matter≤100mg/L in first salting liquid (greatly reduces suspended matter
Content)；The solids that the solids that filter generates is generated together with the first settling tank, the second settling tank enters filter press and is pressed
Filter, the sludge that filters pressing generates are handled for coal blending, realize the resource utilization of sludge.
Step 4, as shown in figure 5, first salting liquid carries out low-temperature centrifugation separation after heat exchange cooling, consolidate
Body Na2SO4·10H2O and the second salting liquid；
Wherein, as shown in fig. 6, solid Na2SO4·10H2O post-processes the rear sodium sulphate that obtains up to standard by the following method and produces
Product:
By solid Na2SO4·10H2O, which is sent, carries out heating evaporation into pyrolysis evaporator, leads to after being heated to 103 DEG C -106 DEG C
Heat exchanger cooling down is crossed to 20 DEG C -30 DEG C, it is water-soluble to be then sent to centrifugation acquisition solid anhydrous sodium sulfate and liquid in centrifuge
Liquid；Also contain a small amount of sodium sulphate in liquid aqueous solution, cryogenic separation again is returned it in step 4, sufficiently to recycle sulfuric acid
Sodium；Solid anhydrous sodium sulfate is outer after drying, packaging to be sold, the quality testing data such as the following table 3 institute for the sodium sulphate that this implementation obtains
Show, as can be seen from Table 3, which meets the requirement of " industrial anhydrous sodium sulfate " GB/T6009-2014 standard.
Table 3:
| Project | Sodium sulphate % | Calcium and magnesium % | Chloride % | Moisture % |
| Standard value | >=95% | ≤0.6 | ≤2.0 | ≤1.5 |
| Detected value | 98.33 | 0.25 | 1.1 | 0.32 |
Step 5, as shown in fig. 7, second salting liquid is evaporated after pre-heating temperature elevation, obtain the first salt slurry and
After-fractionating water；Wherein, the after-fractionating water is used for the recirculated water of step 3, and first salt slurry carries out centrifugation and obtains chlorination
Sodium solid and third salting liquid；
The solid sodium chloride that centrifugation obtains is outer after drying, packaging to sell, the quality testing number for the sodium chloride that this implementation obtains
According to as shown in table 4 below, as can be seen from Table 4, the quality of the sodium chloride can reach " Nacl " GB/T5462-2015 standard
It is required that.
Table 4:
Step 6, the third salting liquid are evaporated after pre-heating temperature elevation, obtain the second salt slurry and third distilled water；
Wherein, the third distilled water is used for the recirculated water of step 3, and second salt slurry carries out centrifugation and obtains a small amount of solid salt-mixture
And a small amount of mixed salt solution；Wherein, a small amount of mixed salt solution obtained is handled for coal blending, and obtained a small amount of solid salt-mixture is returned to
It is recycled in the dissolved salt pond of step 3, realizes the zero-emission of pollutant.
Sodium sulphate, the sodium chloride in coking high-salt wastewater can be turned using the present embodiment process unit cooperation technological operation
Industrial products are turned to, the resource utilization of waste is realized, avoids the wasting of resources；The distilled water generated in technique can be made
For the recirculated water of reuse, the utilization of the water resource in salt recovery process is greatly reduced；Coking production is made full use of in technique
In remained ammonia waste heat for raw water heat, reduce evaporation heat consumption；Meanwhile the sludge that is generated in technique and a small amount of consolidating
Body mixed salt can be further used for coal blending, take the present embodiment technique that can really realize the zero-emission of coking high-salt wastewater.
Claims (10)
1. a kind of technique of coking high-salt wastewater resource utilization, which is characterized in that the technique includes the following steps:
Step 1 is evaporated coking high-salt wastewater, is centrifuged the first distilled water of acquisition, saturated salt solution and solid mixed salt；
Saturated salt solution and solid mixed salt are heated and are burned by step 2, and burn off wherein poisonous and hazardous organic matter obtains
Solid mixed salt and hot fume after burning；
Step 3, the solid mixed salt after burning are dissolved by water, are then sequentially added active powdered carbon, sodium hydroxide, sodium carbonate, are used
In removal coloring matter, adjust pH value to alkalinity and remove calcium and magnesium from, then carry out sedimentation filtration obtain the first salting liquid and
Sludge；
Step 4, first salting liquid carry out low-temperature centrifugation separation after heat exchange cooling, obtain the sodium sulphate with the crystallization water
And second salting liquid；
Step 5, second salting liquid are evaporated after pre-heating temperature elevation, obtain the first salt slurry and after-fractionating water；It is described
First salt slurry carries out centrifugation and obtains solid sodium chloride and third salting liquid；
Step 6, the third salting liquid are evaporated after pre-heating temperature elevation, obtain the second salt slurry and third distilled water；It is described
Second salt slurry carries out centrifugation and obtains a small amount of solid salt-mixture and a small amount of mixed salt solution；Obtained a small amount of solid salt-mixture is returned to step
Rapid three dissolving circulation utilizations again.
2. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 1,
The salt content of the coking high-salt wastewater is 70000mg/L-90000mg/L, COD 2000-10000mg/L；Through pervaporation from
After the heart, salt content≤300mg/L of first distilled water, the first distilled water preferably can be used as recirculated water use；The saturation
The salt content of salting liquid is 250000mg/L.
3. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 2,
The temperature of burning is 650 DEG C -800 DEG C；
The hot fume is emitted into atmosphere afterwards after post treatment；Preferably, the step of hot fume is post-processed are as follows:
The hot fume is subjected to secondary afterburning, temperature rises to the organic matter in >=1100 DEG C of burn off flue gases, then carries out hot cigarette
Gas heat exchange simultaneously recycles heat simultaneously；It is de- using depickling, dedusting and desulfurization after hot fume after heat exchange is cooled to 200 DEG C or less
After nitre takes off dioxin, make content of sulfur dioxide≤50mg/m in hot fume3, amount of nitrogen oxides≤100mg/m3, dust≤
10mg/m3Heel row is amplified in gas.
4. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 3,
The pH value regulated value is 8.3-11.3；
Preferably, suspended matter≤100mg/L in first salting liquid；
Preferably, the sludge that sedimentation filtration obtains is handled after filters pressing for coal blending.
5. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 4,
The temperature of the low-temperature centrifugation separation is -5 DEG C~-4 DEG C；
Preferably, the sodium sulphate with the crystallization water obtains sodium sulphate product after post treatment, includes the following steps:
Solid sodium sulfate with the crystallization water is heated to 103 DEG C -106 DEG C to be evaporated, is then cooled to 20 DEG C -30 DEG C,
And be centrifuged and obtain solid sodium sulfate and liquid aqueous solution, the solid sodium sulfate is used to pack after drying to be sold outside, the liquid
The cryogenic separation again of aqueous solution return step four.
6. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 5,
The cycling use of water that the after-fractionating water is dissolved as the solid mixed salt of step 3；
Preferably, in step 6, cycling use of water of the third distilled water as the solid mixed salt dissolution of step 3；
Preferably, in step 6, obtained a small amount of mixed salt solution is handled for coal blending.
7. the technique of coking high-salt wastewater resource utilization according to claim 1, it is characterised in that: in step 5 and step
In rapid six, the heat source that second salting liquid and the third salting liquid are preheated remained ammonia in the production of coking workshop section
Waste heat, temperature be 71 DEG C -72 DEG C.
8. a kind of device of coking high-salt wastewater resource utilization, it is characterised in that: the device includes triple-effect evaporation plant, burns
Device, flue gas processing device, dissolution exclusion device, freezing divide salt device, sodium sulphate process units and double flash evaporation device；
The triple-effect evaporation plant is for being evaporated and being centrifuged to coking high-salt wastewater；
The incinerator, which is used to heat, burns saturated salt solution and solid mixed salt that the triple-effect evaporation plant centrifugation obtains；
The flue gas processing device is used to carry out aftertreatment technology to the hot fume for burning acquisition in the incinerator；
Solid mixed salt after the dissolution exclusion device is used to burn the incinerator carries out calcium ions and magnesium ions and coloring matter
Removal；
The freezing divides salt device for being exchanged heat to the first salting liquid obtained after cleaning in the dissolution exclusion device, is low
Temperature centrifuge separation is to obtain band crystallization aqueous sodium persulfate and the second salting liquid；
The sodium sulphate process units is used to carry out aftertreatment technology to the sodium sulphate with the crystallization water to obtain sodium sulphate up to standard
Product；
The double flash evaporation device is used to further evaporate the second salting liquid centrifugation and obtains sodium chloride product, cycling use of water and mix
Salt.
9. the device of coking high-salt wastewater resource utilization according to claim 8, it is characterised in that: the triple effect evaporation
Device includes the identical 1st effective evaporator of structure, 2nd effect evaporator and triple effect evaporator；Each evaporator includes heater, divides
From room, circulating pump and connecting line；
Preferably, the incinerator includes incinerator；
Preferably, the flue gas processing device include be sequentially connected the secondary combustion chamber connect, waste heat boiler, chilling tower, extracting tower,
Bag filter and desulphurization denitration dioxin removal apparatus；
Preferably, the dissolution exclusion device includes dissolved salt pond, a settling tank, dosing pond, secondary settling tank, filter and pressure
Filter；The dissolved salt pond, a settling tank, the dosing pond, the secondary settling tank and the filter are sequentially connected
It is logical；Settling tank, the secondary settling tank and the filter are connected with the filter press respectively；It is described primary heavy
For loading active powdered carbon in drop pond；For loading sodium hydroxide and sodium carbonate in the dosing pond；
Preferably, the freezing divides salt device to include being sequentially connected the First Heat Exchanger connect, multistage refrigerator and the first centrifuge；
Preferably, the sodium sulphate process units includes being sequentially connected the pyrolysis evaporator, the second heat exchanger, the second centrifuge connect
With the first dry packing machine；
Preferably, the double flash evaporation device includes level-one preheater, level-one evaporator, third centrifuge, the second dry packing
Machine, second level preheater, secondary evaporimeter and the 4th centrifuge；The level-one preheater, the level-one evaporator, the third from
Scheming and the second dry packing machine are sequentially connected and connect；The third centrifuge, the second level preheater, the dual evaporation
Device and the 4th centrifuge are sequentially connected and connect.
10. the device of coking high-salt wastewater resource utilization according to claim 9, it is characterised in that: an effect is steamed
Sending out device includes 2 heaters, and the 1st effective evaporator is provided with crystal seed scale prevention device；Preferably, the secondary combustion chamber, institute
State waste heat boiler, the chilling tower, the extracting tower, the bag filter and the desulphurization denitration dioxin removal apparatus successively
Afterburning, heat exchange, cooling, depickling, dedusting and desulphurization denitration are carried out to the hot fume for burning acquisition in the incinerator and take off dioxin
To obtain flue gas up to standard for discharging；
Preferably, the distilled water that the level-one evaporator and secondary evaporimeter evaporation obtain is used for the dissolution exclusion device
The middle complex salt for carrying out the dissolved salt pond；
Preferably, the liquid aqueous solution that second centrifuge is isolated is back to freezing and salt device is divided to recycle；
Preferably, the excess sludge after the filter press filters pressing is used for coal blending；
Preferably, the isolated a small amount of mixing salt solution of the 4th centrifuge is used for coal blending, isolated a small amount of solid
Salt-mixture is returned in the dissolution exclusion device and is recycled.
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