CN208667351U - A kind of pulp and paper making wastewater zero discharge softening plant - Google Patents
A kind of pulp and paper making wastewater zero discharge softening plant Download PDFInfo
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- CN208667351U CN208667351U CN201821135475.1U CN201821135475U CN208667351U CN 208667351 U CN208667351 U CN 208667351U CN 201821135475 U CN201821135475 U CN 201821135475U CN 208667351 U CN208667351 U CN 208667351U
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Abstract
The utility model relates to a kind of pulp and paper making wastewater zero discharge softening plants.It include: waste water softening plant, for carrying out removing calcium and magnesium ion processing to paper-making effluent；Reverse osmosis membrane is connected to waste water softening plant, for carrying out concentration to the waste water after waste water softening plant deliming magnesium ion；Ion exchange resin column is connected to the dope side of reverse osmosis membrane, carries out ion-exchange except hardness processing for the dope to reverse osmosis membrane；Enrichment facility is connected to the production mouth of a river of ion exchange resin column, carries out concentration for the production water after removing firmly to ion exchange resin column；Membrane reactor is connected to enrichment facility, and the dope for obtaining to enrichment facility carries out precipitation method removal calcium ions and magnesium ions and removes the precipitating generated in reaction in real time with seperation film.
Description
Technical field
The utility model relates to a kind of pulp and paper making wastewater zero discharge softening plant, in particular by dosing softening-precipitating/
The a variety of softening process combination such as filtering, resin softening, dosing-membrane reactor, improves the removal effect of hardness, reduce softening at
This.Belong to environmentally friendly water treatment field.
Background technique
Paper-making effluent salt content is high, hardness is big, basicity is big, sulphates content is high.Hardness, basicity in waste water, sulphur
Hydrochlorate etc. has a significant impact the stable operation of waste water recycling and zero-emission process membranous system.Softening process is to restrict waste water zero
One of the critical process of exhaust system stable operation.
The high saliferous high rigidity process without drainage of waste water of Chinese patent CN104370405A report is heavy to water use is reflected
Water inlet of the multi-medium filtering as two workshop section's ultrafiltration systems behind shallow lake.The process route is long, complicated for operation, the control requirement to SS
Height does not do differential processing to hardness removal.Chinese patent CN103342432A is using integration technique of membrane to paper-making effluent
Zero discharge treatment is carried out, the process combined using dosing softening with ultrafiltration after reverse osmosis first, what which referred to
Membrane treatment process does not couple with medicine system but handles the supernatant after dosing precipitating.
Utility model content
The utility model is directed to the softening demand during pulp and paper making wastewater zero discharge, provides a kind of the soft of integration
Change method, this method, by coupling softening-water decrement technology, make dosing-membrane reactor using dosing-membrane reactor as core
Operation have the characteristics that reactor is stable, water is few, fully reacting, water outlet except hard effect it is good.This method is as a whole
Technique packet, have the advantages that it is stable, except the operating cost of good, the entire wastewater zero discharge system of hard effect is low.
Technical solution is:
A kind of pulp and paper making wastewater zero discharge softening process, includes the following steps:
Step 1, dosing-precipitation method are except hard: medicament is added in paper-making effluent makes Ca2+And Mg2+Precipitating, and pass through
The method of precipitating removes sediment；
Step 2, reverse osmosis concentration: the waste water that step 1 is obtained is concentrated using reverse osmosis membrane；
Step 3, ion exchange resin is except hard: the counter-infiltration dope that step 2 is obtained is using ion exchange resin except hard；
Wastewater minimisation processing: step 4 the waste water that step 3 obtains is concentrated using electrodialysis or evaporation mode；
Step 5, membrane reactor is except hard: precipitating reagent is added to the dope that step 4 obtains in membrane reactor and is reacted simultaneously
The precipitating generated with seperation film removal.
In one embodiment, the addition medicament in the step 1, which refers to, is added NaOH and Na2CO3, or refer to
Lime, flue gas are sequentially added, or refers to and Ca (OH) is added2And Na2CO3, or refer to and calcium and magnesium complexing agent is added.
In one embodiment, treated that pH value of waste water is maintained between 10.3~11.5 for the step 1, waste water
50~200mg/L of hardness.
In one embodiment, step 2 reverse osmosis membrane concentration makes salt quality concentration in concentrated water reach 3~6%.
In one embodiment, the step 3 ion exchange resin makes waste water hardness be less than 5mg/L except hard；Make
Ion exchange resin refers to cation exchange resin or weak-acid ion exchange resin.
In one embodiment, the step 4 electrodialytic membranes, which carries out concentration, makes salt quality concentration in waste water reach 12
~20%；Evaporation mode refers to multiple-effect evaporation or MVR evaporation.
In one embodiment, the waste water hardness that the step 5 obtains is less than 1mg/L；Point that membrane reactor uses
It is ceramic membrane or organic film from film；The organic film configuration is tubular ultra-filtration membrane or hollow fiber ultrafiltration membrane；Described is heavy
Shallow lake agent is sodium hydroxide and sodium carbonate.
In one embodiment, the waste water that step 5 obtains is handled using nanofiltration membrane, adjusts the NaCl in waste water
And Na2SO4Concentration ratio；The concentrated water of nanofiltration membrane is sent into Na2SO4Crystal system obtains Na by Crystallization Separation2SO4Nacl with
And first mother liquor；The fresh water of nanofiltration membrane is concentrated and then is sent into NaCl crystal system, obtains NaCl by Crystallization Separation
Nacl and the second mother liquor；First mother liquor, which is sent into NaCl crystal system, carries out crystallization treatment, and the second mother liquor is sent into Na2SO4Knot
Crystallographic system system carries out crystallization treatment.
In one embodiment, nanofiltration membrane concentrated water sodium sulfate quality concentration is higher than 8%, between preferred concentration 12%~20%.
In one embodiment, the first mother liquor is re-fed into NaCl crystal system after concentration and carries out at crystallization
Reason, the second mother liquor are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.
A kind of pulp and paper making wastewater zero discharge softening plant, comprising:
Waste water softening plant, for carrying out removing calcium and magnesium ion processing to paper-making effluent；
Reverse osmosis membrane is connected to waste water softening plant, for carrying out to the waste water after waste water softening plant deliming magnesium ion
Concentration；
Ion exchange resin column is connected to the dope side of reverse osmosis membrane, carries out ion friendship for the dope to reverse osmosis membrane
Method is changed except hardness processing；
Enrichment facility is connected to the production mouth of a river of ion exchange resin column, for the production after removing firmly to ion exchange resin column
Water carries out concentration；
Membrane reactor is connected to enrichment facility, dope for being obtained to enrichment facility carry out the precipitation method go removing calcium and magnesium from
Son simultaneously removes the precipitating generated in reaction with seperation film in real time.
In one embodiment, include: in the waste water softening plant
Sedimentation basin, the sediment for generating to reaction are removed by way of precipitating；
Sodium carbonate adding apparatus, is connected to sedimentation basin, for sodium carbonate to be added into sedimentation basin；
Sodium hydroxide adding apparatus, is connected to sedimentation basin, for sodium hydroxide to be added into sedimentation basin.
In one embodiment, include: in the waste water softening plant
Sedimentation basin, the sediment for generating to reaction are removed by way of precipitating；
Lime adding apparatus, is connected to sedimentation basin, for lime to be added into sedimentation basin；
Mouth is added in flue gas, sedimentation basin is connected to, for flue gas to be added into sedimentation basin.
In one embodiment, include: in membrane reactor
Precipitation reaction tank, the calcium ions and magnesium ions in the dope for obtaining to enrichment facility carry out precipitation reaction；
Seperation film is connected to precipitation reaction tank, for being filtered the heavy of removal generation to the feed liquid in precipitation reaction tank
It forms sediment；The trapped fluid outlet of seperation film is connected to precipitation reaction tank；
Mouth is added in precipitating reagent, precipitation reaction tank is connected to, for precipitating reagent to be added into precipitation reaction tank.
In one embodiment, ion exchange resin column is cation exchange resin column or weak acid ion exchange tree
Rouge column.
In one embodiment, enrichment facility is electric dialyzator or vaporising device.
In one embodiment, the seperation film is ceramic membrane or organic film；The organic film configuration is pipe
Formula ultrafiltration membrane or hollow fiber ultrafiltration membrane.
In one embodiment, it includes that mouth and sodium hydroxide addition mouth is added in sodium carbonate that mouth, which is added, in the precipitating reagent.
In one embodiment, further includes:
Nanofiltration membrane is connected to the per-meate side of seperation film, carries out a divalent salts for crossing the production water after filtering out firmly to seperation film
Separation；
Sulfate crystal system is connected to the dope side of nanofiltration membrane, for obtaining Na to nanofiltration dope crystallization treatment2SO4；
Sodium chloride crystal system is connected to the light liquid side of nanofiltration membrane, for obtaining NaCl to the light liquid crystallization treatment of nanofiltration.
Beneficial effect
Advanced treating is carried out to minimizing waste water using the technique that dosing is coupled with membrane reactor, hardness removal effect is good,
Guarantee evaporation and crystallization system stable operation.
The targeted paper-making effluent of the utility model is high with salt content, hardness is big, basicity is big, sulphates content
The features such as high.For its feature by the way of the combination of a variety of softening process, hardness removing is carried out to waste water, guarantees zero-emission system
System stable operation.
Due to being removed to the hardness in waste water using dosing membrane reactor, membrane reactor have operation continuity it is good,
The high advantage of removal rate.But the operation characteristic of membrane reactor requires influent quality high stability, is otherwise easy to cause film anti-
It answers the dosage of device to need frequently adjustment, otherwise will lead to reaction condition and control the problem that difficulty keeps removal effect bad greatly；
It therefore if wastewater flow rate is higher, is easy to cause simultaneously as membrane reactor uses seperation film progress on-line filtration processing
Energy consumption is larger.Therefore, it in the utility model, uses and preformed precipitate processing is carried out to waste water, in this step, directly adopt dosing
Precipitation reaction can remove most hardness, on the one hand, so that the fluctuating range of the hardness in waste water reduces, another party
Face eliminates a part since during precipitation reaction, the flocky precipitate of generation can adsorb a part of organic pollutant
COD pollution, can mitigate in subsequent membrane separating process for the irreversible membrane fouling on the surface of film, allow for membrane separating process only
Only operating flux can be made to restore by simply backwash；Meanwhile after being handled by preformed precipitate, can effectively it mitigate subsequent
Reverse osmosis membrane concentration, in evaporating concentration process the case where fouling.Meanwhile resin is also used in the utility model except hard place
Reason has the function of that removal effect is relatively stable, can further reduce waste water when removing hardness due to ion exchange resin
The concentration of middle hardness changes, and improves the reaction process operation stability of membrane reactor；After resin removes firmly, it can be realized into one
Waste water is concentrated in step ground, and waste water water is further reduced, makes membrane reactor in the process of running, Jin Jintong
Spending the shorter residence time can be realized reaction-separation process.In summary it can be seen, in the utility model by dosing-precipitating,
Concentration, resin remove the over all Integration of hard, concentration, film reaction, between each other by acting synergistically, so that whole wastewater hardness removing
Process operation is more stable, it is more preferable to remove hard effect.
Simultaneously as containing sodium chloride and sodium sulphate inorganic salts in raw water, concentration ratio generally can not be distinguished
Crystallization obtains sodium chloride and sodium sulphate, and nanofiltration membrane is used for the monovalent salt and divalent salts ratio in high-salt wastewater in the utility model
Example is adjusted, and meets NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces female
Liquid measure improves the efficiency that sal prunella joint process salt utilizes.High-purity is finally obtained while realizing brine waste zero emission
Monovalent salt and divalent salts realize the resource utilization of water and inorganic salts.In addition, due in NaCl and Na2SO4The mistake crystallized respectively
Cheng Zhong crystallizes NaCl and Na in feed liquid2SO4Concentration than differ it is bigger, more be conducive to crystallization process formed high-purity crystallization
Salt.And due to the fluctuation of the salinity meeting generating period in high-salt wastewater, it is easy to cause in nanofiltration process and obtains light liquid
With the fluctuation of the concentration generating period in dope, crystallization process is influenced.Therefore, by using reverse osmosis to the mother liquor after crystallization
It returns again to after the further concentrate of permeable membrane to the crystal system of upper level, can effectively make NaCl and Na2SO4Concentration ratio
It fluctuates numerical value to reduce, it is suppressed that the instable generation in crystallization process.
Detailed description of the invention
Fig. 1 is the process flow chart of the utility model；
Fig. 2 is the device figure of the utility model.
Fig. 3 is the softening plant figure of another embodiment.
Fig. 4 is the device figure with salt crystal system.
Wherein, 1, waste water softening plant；2, sedimentation basin；3, sodium carbonate adding apparatus；4, sodium hydroxide adding apparatus；5, anti-
Permeable membrane；6, ion exchange resin column；7, enrichment facility；8, precipitation reaction tank；9, seperation film；10, mouth is added in precipitating reagent；11,
Lime adding apparatus；12, mouth is added in flue gas；13, nanofiltration membrane；14, sulfate crystal system；15, sodium chloride crystal system；
16, membrane reactor.
Specific embodiment
The utility model is described in further detail below by specific embodiment.But those skilled in the art will
Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not
Indicate particular technique or condition person, according to the literature in the art described technology or conditions or according to product description into
Row.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as not only including clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
It should be understood that it can be direct with other elements when an element is mentioned with another element " connection "
It is connected or is indirectly connected with other elements, and inserted with element between them.Unless there are clearly opposite explanation, otherwise term
It includes listed element that " comprising " and " having ", which is interpreted as statement, and non-excluded any other elements.
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include
Other are not explicitly listed or belong to this technique, method, article or the intrinsic element of equipment.
The utility model relates to a kind of embrane method pulp and paper making wastewater zero discharge process softening process.Paper-making effluent zero-emission
Putting in technique includes pretreatment except hardness, hard, the film decrement softening of film concentrate control etc., and key step is as follows:
1, pretreatment remove hardness: according to waste water hardness regulate and control online machine add in pond remove hard medicament additive amount, protect pH value
It holds between 10.3~11.5, controls 50~200mg/L of hardness of waste water, to meet the water inlet requirement of low-pressure reverse osmosis membrane.
2, film concentrate softens: waste water is after reverse osmosis deaslination, and salt quality concentration reaches 3~6% in concentrated water, and hardness enrichment rises
It is high.
3,5mg/L is less than using resin tenderizer control hardness, to meet the water inlet requirement of electrodialytic membranes.
4, film minimizing softens: 90% or more wastewater flow rate reduction or salt quality concentration reach 12~20% after film minimizing, adopt
Sofening treatment is carried out to minimizing waste water with membrane reactor technique, control hardness is less than 1mg/L, to ensure evaporation and crystal process not
Fouling.
For step 1, the mode for removing the calcium ions and magnesium ions in waste water is mainly that the side of precipitating is reacted and passed through by dosing
Formula removal, dosing here can choose sodium carbonate+sodium hydroxide, lime+sodium carbonate, lime+flue gas, calcium and magnesium complexing agent
It is combined etc. different dosings；Additional amount can determine sodium carbonate, sodium hydroxide, stone according to the content of the calcium ions and magnesium ions in waste water
The dosage of ash, calcium and magnesium complexing agent, can usually determine additional amount by the way of slightly above stoichiometric ratio.For lime+
Flue gas, reaction principle are:
Milk of lime and sodium sulphate reaction generate sodium hydroxide, and the carbon dioxide reaction in sodium hydroxide and flue gas generates carbon
Sour sodium, sodium carbonate act on calcium ion generate indissoluble substance calcium carbonate again.Reaction is carried out in two steps:
The first step
MgSO4+Ca(OH)2→Mg(OH)2↓+CaSO4(slightly soluble)
Na2SO4+Ca(OH)2→CaSO4(slightly soluble)+2NaOH
Second step
2NaOH+CO2→Na2CO3+H2O
Na2CO3+ CaSO4→CaCO3↓+ Na2SO4
Precipitating is magnesium hydroxide and calcium carbonate and a part of calcium sulfate obtained in reaction, and the main component in solution
It is sodium chloride and sodium sulphate.
After precipitation reaction using above-mentioned intermittent reaction formula, can get rid of in waste water the overwhelming majority calcium and magnesiums from
Son, and the fluctuation of concentration of the calcium ions and magnesium ions in the waste water of source can be effectively reduced, and can be effectively avoided calcium and magnesium from
Son during reverse osmosis concentration in the scale problems on reverse osmosis membrane surface so that the concentration process of reverse osmosis membrane is achieved,
Can simultaneously be effectively reduce operating load when ion exchange resin removes hard；In addition, due to during precipitation reaction, it is raw
At flocculent deposit during can coat organic pollutant in a part of waste water, this can be to avoid falling in membrane reactor
The irreversible membrane fouling of organic pollutant that occurs in the process of running of seperation film, make seperation film only by recoil mode just
Long-term running stability can be improved.There are many include but is not limited to use mechanical stirring sedimentation basin or highly dense for the mode of precipitating
Sedimentation basin is spent, in addition it can assist other modes being separated by solid-liquid separation to remove precipitating, there are many include the mode of separation of solid and liquid
But it is not limited to using filter types such as sand filtration, multimedium, filtering cloth filtering pool or film filterings.
In step 2, mainly the waste water after preliminary remove firmly is concentrated using reverse osmosis membrane, salt quality is dense in concentrated water
Degree reaches 3~6%, and hardness enrichment increases, and is less than 5mg/L using resin tenderizer control hardness, to meet the water inlet of electrodialytic membranes
It is required that can also be to avoid the scale problems in evaporating concentration process.Acetic acid fibre can be used in reverse osmosis membrane in the utility model
Tie up the high molecular materials such as plain quasi polymer, polyamide, polyester, polyimides, polyvinyl, the operating pressure of reverse osmosis membrane
It can control the range in 1.0MPa~10MPa,
For step 1 and step 2, softening depends on the hardness of water with the sequencing of reverse osmosis process.When next
The water hardness is higher than 1200mg/L(with calcium carbonate) using first softening the technique being concentrated afterwards, when carrying out the water hardness 600~1200
Mg/L(is with calcium carbonate) it can be combined according to the actual situation using softening with concentration technology, it is lower than 600 when carrying out the water hardness
Mg/L(is with calcium carbonate) after-tack is preferably first concentrated.
For step 3, the calcium ions and magnesium ions in waste water can further be got rid of using the purpose of ion exchange resin, when making
5mg/L is less than using resin tenderizer control hardness, to meet the water inlet requirement of electrodialytic membranes, while can also be to avoid subsequent
Evaporating concentration process in fouling occur.Resin softening can be using techniques such as cation bed, weak acid beds.
For step 4, wastewater reduction processing is can be handled with electric dialyzator or evaporation concentration device, electrodialysis
Current density be 40A/m2~500A/m2；Evaporation process can be multiple-effect evaporation or MVR evaporation.
For step 4, the precipitation method are carried out using membrane reactor in the utility model and remove calcium ions and magnesium ions, membrane reactor is film
The new technology that process and reaction process combine.The step of being provided simultaneously with reaction and separation.With series of advantages: reaction
It is combined into single unit process with separation, reduces the expense of the processes such as separation；In this step, it is carried out on one side using reactor
Precipitation reaction, while being removed the precipitating of generation in real time using seperation film, then reaction solution is back in reactor.Used here as
Seperation film, can be using inoranic membrane or organic membrane filter；Tubular ultra-filtration membrane can be used in organic membrane filter or doughnut is super
Filter membrane.Membrane reactor goes out the water hardness and is generally below 1mg/L, can basis need to adjust membrane reactor water outlet hardness.
By the match selection to softening method in technique of zero discharge, reagent consumption amount, targeted hardness can be reduced
Removing control, can be improved the reliability of engineering operation.
In addition, containing after biochemical treatment, above-mentioned removing are handled firmly for waste water obtained in pulping and papermaking processes
NaCl and Na2SO4Equal inorganic salts, and NaCl and Na in water2SO4Concentration proportion be not able to satisfy respectively crystallization obtain NaCl
And Na2SO4Requirement when, the utility model by nanofiltration membrane be used for in high-salt wastewater monovalent salt and divalent salts ratio adjust
Section, meets NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces mother liquor amount, improves
The efficiency that sodium chloride and sulfate crystal process salt utilize.High-purity is finally obtained while realizing brine waste zero emission
Monovalent salt and divalent salts realize the resource utilization of water and inorganic salts.The utility model involved in nanofiltration membrane, be defined as
The film of " preventing the pressure drive membrane less than the particle of 2nm and the macromolecular of dissolution ", can be used cellulose acetate based polymer,
The high molecular materials such as polyamide, sulfonated polysulfone, polyacrylonitrile, polyester, polyimides and polyvinyl.In the utility model
Reverse osmosis membrane, the high scores such as cellulose acetate quasi polymer, polyamide, polyester, polyimides, polyvinyl can be used
Sub- material.The operating pressure of nanofiltration membrane can control in 0.5~4.0MPa, and the operating pressure of reverse osmosis membrane can control
The range of 1.0MPa~10MPa.Film deploys workshop section: including multistage nanofiltration system or ion exchange membranous system, to from film concentrate
Workshop section or film minimizing workshop section's waste water carry out the concentration allotment of sodium chloride and sodium sulphate, are divided into rich sodium chloride waste water and rich sodium sulphate
Waste water.Workshop section is deployed, concentrated water sodium sulfate concentration is higher than 8%, between preferred concentration 12%~20%.Mainly chlorination processed in salt manufacturing workshop section
Sodium crystal system, Sulphuric acid sodium crystal system, the rich sodium chloride waste water from film allotment workshop section enter chlorination processed after concentrate again
Sodium system obtains industrial product salt, returns to Sulphuric acid sodium crystal system after mother liquor drop COD；Sulfur-rich acid from film allotment workshop section
Sodium waste water enters Sulphuric acid sodium system and obtains sodium sulphate product, returns to sodium chloride crystal system processed after mother liquor drop COD；Na2SO4
Crystal system mother liquor is re-fed into NaCl crystal system after concentration and carries out crystallization treatment, NaCl crystal system mother liquor overrich
Na is re-fed into after contracting2SO4Crystal system carries out crystallization treatment.Since the concentration of monovalence and divalent salts in waste water can occur not
Disconnected fluctuation, and then influence whether the process of subsequent nanofiltration, crystallization, so that technological parameter needs are constantly adapted to
The variation of salinity in water, therefore will lead to that operating process is unstable, purity of crystal salt cannot reach requirement.Meanwhile
NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4Concentration than differ it is bigger, more be conducive to knot
Brilliant process forms the crystal salt of high-purity.Such as: NaCl and Na during being crystallized to NaCl, in crystal solution2SO4
Concentration proportion be C1(NaCl)/C1(Na2SO4), when by Na2SO4Mother liquor (the densimeter for mainly containing NaCl obtained after crystallization
For C2And C (NaCl),2(NaCl)> C1(NaCl)) it further adds after concentration to NaCl during being crystallized, i.e.,
The concentration on the molecule of ratio can be made to increase, improve concentration proportion；It could be aware that according to numerical value calculating, as 10 < C1
(NaCl)/C1(Na2SO4) < 100 when fluctuation, makes molecular concentration increase that the fluctuating range of whole ratio can be made obvious in ranges
Reduce, plays the effect for stabilizing fluctuation.Similarly Na2SO4Crystallization process in, the concentration proportion of a divalent salts is C1
(Na2SO4)/C1(NaCl), what is obtained after crystallizing NaCl mainly contains Na2SO4Mother liquor concentrations after, the C that will obtain2
(Na2SO4) concentrate is back to Na2SO4Crystallization process in after, due to C2(Na2SO4)> C1(Na2SO4), similarly play
Stabilize the effect of crystallization process fluctuation of concentration.Therefore, by the mother liquor after crystallization using the further concentrate of reverse osmosis membrane it
It is returned again to afterwards to the crystal system of upper level, can effectively make NaCl and Na2SO4Concentration ratio fluctuation numerical value reduce, inhibit
Instable generation during crystallization.
Based on above method, device used by the utility model is as shown in Figures 2 and 3, comprising:
Waste water softening plant 1, for carrying out removing calcium and magnesium ion processing to paper-making effluent；
Reverse osmosis membrane 5 is connected to waste water softening plant 1, for the waste water after 1 deliming magnesium ion of waste water softening plant into
Row concentration；
Ion exchange resin column 6 is connected to the dope side of reverse osmosis membrane 5, carries out ion for the dope to reverse osmosis membrane 5
Exchange process is except hardness processing；
Enrichment facility 7 is connected to the production mouth of a river of ion exchange resin column 6, after removing firmly to ion exchange resin column 6
It produces water and carries out concentration；
Membrane reactor 16 is connected to enrichment facility 7, and the dope for obtaining to enrichment facility 7 carries out the precipitation method and goes deliming
Magnesium ion simultaneously removes the precipitating generated in reaction with seperation film in real time.
As shown in Figure 2, the precipitation method are carried out by the way of pharmacy response to be removed firmly, it is in this embodiment, described
Waste water softening plant in include:
Sedimentation basin 2, the sediment for generating to reaction are removed by way of precipitating；
Sodium carbonate adding apparatus 3 is connected to sedimentation basin 2, for sodium carbonate to be added into sedimentation basin 2；
Sodium hydroxide adding apparatus 4 is connected to sedimentation basin 2, for sodium hydroxide to be added into sedimentation basin 2.
As shown in Figure 3, the precipitation method are carried out by the way of lime+flue gas to be removed firmly, in this embodiment, institute
Include: in the waste water softening plant stated
Sedimentation basin 2, the sediment for generating to reaction are removed by way of precipitating；
Lime adding apparatus 11 is connected to sedimentation basin 2, for lime to be added into sedimentation basin 2；
Mouth 12 is added in flue gas, sedimentation basin 2 is connected to, for flue gas to be added into sedimentation basin 2.
In one embodiment, include: in membrane reactor 16
Precipitation reaction tank 8, the calcium ions and magnesium ions in the dope for obtaining to enrichment facility 7 carry out precipitation reaction；
Seperation film 9 is connected to precipitation reaction tank 8, for being filtered what removal generated to the feed liquid in precipitation reaction tank 8
Precipitating；The trapped fluid outlet of seperation film 9 is connected to precipitation reaction tank 8；
Mouth 10 is added in precipitating reagent, precipitation reaction tank 8 is connected to, for precipitating reagent to be added into precipitation reaction tank 8.
In one embodiment, ion exchange resin column 6 is cation exchange resin column or weak acid ion exchange
Resin column.
In one embodiment, enrichment facility 7 is electric dialyzator or vaporising device.
In one embodiment, the seperation film 9 is ceramic membrane or organic film；The organic film configuration is pipe
Formula ultrafiltration membrane or hollow fiber ultrafiltration membrane.
In one embodiment, it includes that mouth and sodium hydroxide addition is added in sodium carbonate that mouth 10, which is added, in the precipitating reagent
Mouthful.
As shown in Figure 4, in one embodiment, further includes:
Nanofiltration membrane 13 is connected to the per-meate side of seperation film 9, carries out one or two for crossing the production water after filtering out firmly to seperation film 9
The separation of valence salt；
Sulfate crystal system 14 is connected to the dope side of nanofiltration membrane 13, for obtaining to nanofiltration dope crystallization treatment
Na2SO4；
Sodium chloride crystal system 13 is connected to the light liquid side of nanofiltration membrane 13, for obtaining to the light liquid crystallization treatment of nanofiltration
NaCl。
Concentration described in the utility model refers to mass concentration in the absence of special instructions；The percentage exists
Refer to mass percent in the case where no special instruction." salinity " described in the utility model is without specializing
Refer to the total concentration of sodium chloride and sodium sulphate.
Embodiment 1
For the pulp-making waste-water zero-emission process of certain slurrying enterprise, by the way of the combination of a variety of softening process
Reason.
Into 20000 ton/days of waste water water of Zero discharging system, the water quality indicator range of waste water water is as follows:
To technique water by handling after pretreatment using reverse osmosis process, the reverse osmosis rate of recovery 60% is designed.Through anti-
After infiltration processing, about 8000 ton/days of concentrated water amount, hardness is in 1020~1600mg/L(with CaCO3Meter) between.Using dosing and sink
The technique combined of forming sediment carries out softening operation.
Sodium hydroxide is added in pre-reaction pond to waste water first and sodium carbonate carries out intermittent precipitation reaction, the hydrogen-oxygen added
Change the amount of sodium and sodium carbonate respectively according to stoichiometric ratio excess 0.2g/L, pH value control 10.5, reaction obtain suspension into
Entering machine adds pond to precipitate, and configuration machine adds Chi Yizuo.Supernatant further removes oil removal by sand filtration.Through workshop section's processed waste water
Hardness be down to 155~180mg/L(with CaCO3Meter).
Waste water after softened enters two sections of reverse osmosis process, designs the rate of recovery 50%, reverse osmosis operating pressure 3.0MPa,
Two sections 3800~4000 ton/days of reverse osmosis concentrated water, 410~450mg/L(of hardness is with CaCO3Meter), which is handed over using ion
It changes technique to be softened, be handled using cation exchange resin, 3.1~3.3mg/L of hardness of waste water after softening.
Waste water after the softening of cation bed resin enters three sections of counter-infiltration systems, and reverse osmosis operating pressure 3.5MPa, three sections anti-
The infiltration design rate of recovery 50%, 1850~1950 ton/days of concentrated water amount, 135~141mg/L(is with CaCO for concentrated water hardness3Meter), to this
Concentrated water carries out hardness removal, the NaOH and Na of the online dosing of membrane reactor using dosing-ceramic membrane flow reactor technique2CO3Point
Mg not than needing to precipitate2+And Ca2+Stoichiometrically excess 10mg/L, the average pore size scope of the ceramic membrane of use are
The trapped fluid of 50nm, operating pressure 0.2MPa, crossflow velocity 3m/s, ceramic membrane are back in reaction system, filtered through film
Delivery turbidity is lower than 0.2NTU, and SDI value is lower than 2.5, and 0.4~0.5mg/L(of hardness is with CaCO3Meter).Softened water is further
Enter evaporation and crystallization system after being concentrated by electrodialysis process.The hardness of waste water has been carried out effective removing by membrane reactor technique,
Significantly reduce the risk of evaporation and crystallization system fouling.
4210~4510mg/L of NaCl, Na are mainly contained in the filtrate of ceramic membrane reactor2SO436700~41800
Mg/L, by nanofiltration membrane carry out the allotment of inorganic salts ratio, operating pressure 54bar, after nanofiltration is handled, fresh water sodium chloride concentration
4170~4340mg/L, 470~495mg/L of fresh water sodium sulfate concentration.After nanofiltration fresh water uses the reverse osmosis further concentration of high pressure,
18700~19200mg/L of sodium chloride concentration, 1400~1420mg/L of sodium sulfate concentration.Nanofiltration concentrated water sodium chloride concentration 4010~
4120mg/L, 122600~127900mg/L of sodium sulfate concentration.
Nanofiltration fresh water NaCl and Na2SO4Mass concentration ratio be about 13:1, meet enter NaCl crystallization processes section production
It is required that.Sodium chloride crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control using advection charging-is every
Crystallization temperature processed is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 8210mg/L, send to sulfate crystal system
Reuse, day obtain 7.4 tons of 98.2% sodium chloride.Nanofiltration concentrated water enters sulfate crystal system, and sulfate crystal system uses MVR
Technique carries out Na2SO4Crystallization controls crystallization temperature between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is 31:1,
Meet and enters Na2SO4The technique of crystallization requires, and the mass concentration 31700mg/L of NaCl in crystalline mother solution send to sodium chloride and crystallizes
System reuse, the technique produce 51.3 tons of 99.1% anhydrous sodium sulfate daily.
Embodiment 2
Implement zero-emission process for the waste water of certain papermaking enterprise, sofening treatment is carried out using the softening process.Waste water zero
12000 ton/days of exhaust system inflow.
The main water quality parameter of waste water is as follows:
It is higher into Zero discharging system waste water hardness, after removing SS using multi-medium filtering to waste water, using ozone-activity
After charcoal technique further removes COD, it is concentrated using one section of counter-infiltration system is entered after dosing softening-precipitation process.
PH value 11.2 is controlled, waste water hardness is down to 54~73mg/L(with CaCO after dosing softening-precipitation process3Meter),
Depositing technology uses potassium permanganate composites, and dosing technique uses lime-flue gas technique.One section of reverse osmosis design rate of recovery 70%,
Operating pressure 3.0MPa, 3600 ton/days of concentrated water amount.470~520mg/L(is with CaCO for concentrated water hardness3Meter), for this burst of concentrated water,
Using resin softening process, hardness is removed, weak acid bed resin softening workshop section goes out 4.3 ~ 4.7mg/L(of the water hardness with CaCO3Meter).
After softening waste water enter two sections of counter-infiltration systems, two sections of reverse osmosis design rate of recovery 70%, operating pressure 3.5MPa,
Two sections of reverse osmosis concentrated waters further enter three sections it is reverse osmosis be concentrated, three sections of reverse osmosis design rate of recovery 60%, operating pressure
4.5MPa.Three sections of 430 ton/days of reverse osmosis concentrated waters.
To three sections of reverse osmosis concentrated waters, softened using dosing-tubular membrane flow reactor integrated apparatus, membrane reactor
The NaOH and Na of online dosing2CO3Mg than needing to precipitate respectively2+And Ca2+Stoichiometrically excess 10mg/L, the pottery of use
The average pore size scope of porcelain film is 50nm, operating pressure 0.2MPa, crossflow velocity 3m/s, and the trapped fluid of ceramic membrane is back to reaction
In system, it is lower than 0.2NTU through the filtered delivery turbidity of film, SDI value is lower than 2.5, and 0.4~0.5mg/L(is with CaCO3Meter).
5830~6180mg/L of NaCl, Na are mainly contained in the filtrate of ceramic membrane reactor2SO424700~27500
Mg/L, by nanofiltration membrane carry out the allotment of inorganic salts ratio, operating pressure 54bar, after nanofiltration is handled, fresh water sodium chloride concentration
5510~5790mg/L, 490~530mg/L of fresh water sodium sulfate concentration.After nanofiltration fresh water uses the reverse osmosis further concentration of high pressure,
21500~22700mg/L of sodium chloride concentration, 1870~1930mg/L of sodium sulfate concentration.Nanofiltration concentrated water sodium chloride concentration 5620~
5970mg/L, 87300~90300mg/L of sodium sulfate concentration.
Nanofiltration fresh water NaCl and Na2SO4Mass concentration ratio be about 12:1, meet enter NaCl crystallization processes section production
It is required that.Sodium chloride crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control using advection charging-is every
Crystallization temperature processed is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 9470mg/L, send to sulfate crystal system
Reuse, day obtain 2.1 tons of 98.0% sodium chloride.Nanofiltration concentrated water enters sulfate crystal system, and sulfate crystal system uses MVR
Technique carries out Na2SO4Crystallization controls crystallization temperature between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is 16:1,
Meet and enters Na2SO4The technique of crystallization requires, and the mass concentration 27410mg/L of NaCl in crystalline mother solution send to sodium chloride and crystallizes
System reuse, the technique produce 6.4 tons of 99.2% anhydrous sodium sulfate daily.
Embodiment 3
Implement zero-emission process for the waste water of certain papermaking enterprise, sofening treatment is carried out using the softening process.Waste water zero
12000 ton/days of exhaust system inflow.
The main water quality parameter of waste water is as follows:
It is higher into Zero discharging system waste water hardness, after removing SS using multi-medium filtering to waste water, using ozone-activity
After charcoal technique further removes COD, it is concentrated using one section of counter-infiltration system is entered after dosing softening-precipitation process.
PH value 11.2 is controlled, waste water hardness is down to 54~73mg/L(with CaCO after dosing softening-precipitation process3Meter),
Depositing technology uses potassium permanganate composites, and dosing technique uses lime-flue gas technique.One section of reverse osmosis design rate of recovery 70%,
Operating pressure 3.0MPa, 3600 ton/days of concentrated water amount.470~520mg/L(is with CaCO for concentrated water hardness3Meter), for this burst of concentrated water,
Using resin softening process, hardness is removed, weak acid bed resin softening workshop section goes out 4.3 ~ 4.7mg/L(of the water hardness with CaCO3Meter).
After softening waste water enter two sections of counter-infiltration systems, two sections of reverse osmosis design rate of recovery 70%, operating pressure 3.5MPa,
Two sections of reverse osmosis concentrated waters further enter three sections it is reverse osmosis be concentrated, three sections of reverse osmosis design rate of recovery 60%, operating pressure
4.5MPa.Three sections of 430 ton/days of reverse osmosis concentrated waters.
To three sections of reverse osmosis concentrated waters, softened using dosing-tubular membrane flow reactor integrated apparatus, membrane reactor
The NaOH and Na of online dosing2CO3Mg than needing to precipitate respectively2+And Ca2+Stoichiometrically excess 10mg/L, the pottery of use
The average pore size scope of porcelain film is 50nm, operating pressure 0.2MPa, crossflow velocity 3m/s, and the trapped fluid of ceramic membrane is back to reaction
In system, it is lower than 0.2NTU through the filtered delivery turbidity of film, SDI value is lower than 2.5, and 0.4~0.5mg/L(is with CaCO3Meter).
5830~6180mg/L of NaCl, Na are mainly contained in the filtrate of ceramic membrane reactor2SO424700~27500
Mg/L, by nanofiltration membrane carry out the allotment of inorganic salts ratio, operating pressure 54bar, after nanofiltration is handled, fresh water sodium chloride concentration
5510~5790mg/L, 490~530mg/L of fresh water sodium sulfate concentration.After nanofiltration fresh water uses the reverse osmosis further concentration of high pressure,
21500~22700mg/L of sodium chloride concentration, 1870~1930mg/L of sodium sulfate concentration.Nanofiltration concentrated water sodium chloride concentration 5620~
5970mg/L, 87300~90300mg/L of sodium sulfate concentration.
Nanofiltration fresh water NaCl and Na2SO4Mass concentration ratio be about 12:1, meet enter NaCl crystallization processes section production
It is required that.Sodium chloride crystal system uses triple effect evaporation, imitates out salt-mother liquor reflux mode of operation, control using advection charging-is every
Crystallization temperature processed is between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 9470mg/L, after high pressure reverse osmosis concentration
Make Na2SO4Mass concentration 12830mg/L send to sulfate crystal system reuse, day obtains 2.3 tons of 98.5% sodium chloride.Nanofiltration
Concentrated water enters sulfate crystal system, and sulfate crystal system carries out Na using MVR technique2SO4Crystallization, control crystallization temperature exist
Between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is 16:1, meets and enters Na2SO4The technique requirement of crystallization, crystallization
The mass concentration 27410mg/L of NaCl in mother liquor, make after high pressure reverse osmosis concentration the mass concentration 35510mg/L of NaCl send to
Sodium chloride crystal system reuse, the technique produce 6.7 tons of 99.5% anhydrous sodium sulfate daily.
Claims (9)
1. a kind of pulp and paper making wastewater zero discharge softening plant characterized by comprising
Waste water softening plant (1), for carrying out removing calcium and magnesium ion processing to paper-making effluent；
Reverse osmosis membrane (5) is connected to waste water softening plant (1), for the waste water after waste water softening plant (1) deliming magnesium ion
Carry out concentration；
Ion exchange resin column (6) is connected to the dope side of reverse osmosis membrane (5), for the dope of reverse osmosis membrane (5) carry out from
Sub- exchange process is except hardness processing；
Enrichment facility (7) is connected to the production mouth of a river of ion exchange resin column (6), after removing firmly to ion exchange resin column (6)
Production water carry out concentration；
Membrane reactor (16) is connected to enrichment facility (7), and the dope for obtaining to enrichment facility (7) carries out the precipitation method and goes deliming
Magnesium ion simultaneously removes the precipitating generated in reaction with seperation film in real time.
2. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that the waste water softening
Include: in device
Sedimentation basin (2), the sediment for generating to reaction are removed by way of precipitating；
Sodium carbonate adding apparatus (3) is connected to sedimentation basin (2), for sodium carbonate to be added into sedimentation basin (2)；
Sodium hydroxide adding apparatus (4) is connected to sedimentation basin (2), for sodium hydroxide to be added into sedimentation basin (2).
3. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that the waste water softening
Include: in device
Sedimentation basin (2), the sediment for generating to reaction are removed by way of precipitating；
Lime adding apparatus (11) is connected to sedimentation basin (2), for lime to be added into sedimentation basin (2)；
Flue gas is added mouth (12) and is connected to sedimentation basin (2), for flue gas to be added into sedimentation basin (2).
4. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that in membrane reactor (16)
Include:
Precipitation reaction tank (8), the calcium ions and magnesium ions in dope for obtaining to enrichment facility (7) carry out precipitation reaction；
Seperation film (9) is connected to precipitation reaction tank (8), generates for being filtered removal to the feed liquid in precipitation reaction tank (8)
Precipitating；The trapped fluid outlet of seperation film (9) is connected to precipitation reaction tank (8)；
Precipitating reagent is added mouth (10) and is connected to precipitation reaction tank (8), for precipitating reagent to be added into precipitation reaction tank (8).
5. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that ion exchange resin column
It (6) is cation exchange resin column or weak-acid ion exchange resin column.
6. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that enrichment facility (7) is
Electric dialyzator or vaporising device.
7. pulp and paper making wastewater zero discharge softening plant according to claim 4, which is characterized in that the seperation film
It (9) is ceramic membrane or organic film；The organic film configuration is tubular ultra-filtration membrane or hollow fiber ultrafiltration membrane.
8. pulp and paper making wastewater zero discharge softening plant according to claim 4, which is characterized in that the precipitating reagent adds
Entrance (10) includes that mouth and sodium hydroxide addition mouth is added in sodium carbonate.
9. pulp and paper making wastewater zero discharge softening plant according to claim 1, which is characterized in that further include:
Nanofiltration membrane (13) is connected to the per-meate side of seperation film (9), carries out one or two for seperation film (9) to be crossed with the production water after filtering out firmly
The separation of valence salt；
Sulfate crystal system (14) is connected to the dope side of nanofiltration membrane (13), for obtaining to nanofiltration dope crystallization treatment
Na2SO4；
Sodium chloride crystal system (13) is connected to the light liquid side of nanofiltration membrane (13), for obtaining to the light liquid crystallization treatment of nanofiltration
NaCl。
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| CN110104839A (en) * | 2019-06-04 | 2019-08-09 | 北京赛科康仑环保科技有限公司 | One kind being used for the reverse osmosis concentrated water pretreatment system of industrial wastewater and its method |
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2018
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110104839A (en) * | 2019-06-04 | 2019-08-09 | 北京赛科康仑环保科技有限公司 | One kind being used for the reverse osmosis concentrated water pretreatment system of industrial wastewater and its method |
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