CN105198143B - A kind of Zero emission method of hc effluent - Google Patents
A kind of Zero emission method of hc effluent Download PDFInfo
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- CN105198143B CN105198143B CN201410273247.0A CN201410273247A CN105198143B CN 105198143 B CN105198143 B CN 105198143B CN 201410273247 A CN201410273247 A CN 201410273247A CN 105198143 B CN105198143 B CN 105198143B
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- 238000000034 method Methods 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 256
- 239000012528 membrane Substances 0.000 claims abstract description 208
- 238000001728 nano-filtration Methods 0.000 claims abstract description 150
- 238000004821 distillation Methods 0.000 claims abstract description 120
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 claims abstract description 87
- 238000002425 crystallisation Methods 0.000 claims abstract description 60
- 230000008025 crystallization Effects 0.000 claims abstract description 60
- 238000001764 infiltration Methods 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000005516 engineering process Methods 0.000 claims abstract description 27
- 239000006228 supernatant Substances 0.000 claims abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000012141 concentrate Substances 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 239000003610 charcoal Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 239000007788 liquid Substances 0.000 claims description 49
- 239000002351 wastewater Substances 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910001424 calcium ion Inorganic materials 0.000 claims description 16
- 239000004952 Polyamide Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- -1 Ether sulfone Chemical class 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 239000012510 hollow fiber Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000000149 penetrating effect Effects 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000006277 sulfonation reaction Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 230000004907 flux Effects 0.000 description 16
- 230000008901 benefit Effects 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 5
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 4
- 230000029219 regulation of pH Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229940045872 sodium percarbonate Drugs 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The present invention relates to field of industrial waste water treatment, specifically a kind of Zero emission method of hc effluent.The present invention is using " nanofiltration+efficient counter-infiltration+membrane distillation+evaporative crystallization " method processing hc effluent, the multivalent ions such as the hardness in hc effluent are removed using nanofiltration first and partial organic substances obtain nanofiltration production water and nanofiltration concentrated water, depth concentration is carried out to nanofiltration production water using efficient reverse osmosis technology afterwards, obtained efficient reverse osmosis concentrated water carries out membrane distillation depth concentration again, obtained membrane distillation concentrated water is evaporated crystallization treatment again, salt solid crystal in membrane distillation concentrated water is come out, concentrates desiccation disposal.Wherein, nanofiltration concentrated water adds salt to carry out precipitation process to obtain calcium slag, and the supernatant after precipitation is carried out after charcoal absorption and hc effluent is mixed into nano-filtration unit circular treatment.The method of the present invention has reclaimed water resource, has realized the zero-emission of hc effluent substantially to greatest extent while solving this burst of hc effluent discharge problem.
Description
Technical field
The present invention relates to field of industrial waste water treatment, specifically a kind of Zero emission method of hc effluent.It is espespecially a kind of
Using the Zero emission method of membrane separation technique processing hc effluent, more specifically to a kind of " nanofiltration+efficient counter-infiltration+film
Distillation+evaporative crystallization " handles the Zero emission method of hc effluent.
Background technology
In recent years, hc effluent caused by petroleum chemical enterprise turns into a processing problem, and this strand of hc effluent can neither discharge
Can not reuse, bring great puzzlement to each enterprise.Therefore, need badly and seek new isolation technics and solve such hc effluent
Processing emission problem.
Nanofiltration (NF) is a kind of membrane separation technique between ultrafiltration and counter-infiltration, and aperture is several nanometers, retains molecule
Amount is between 200~1000.Nanofiltration has the characteristics that：Energy molecular cut off is more than 100 organic matter and multivalent ion, permits
Perhaps small organic molecule and monovalention pass through；It can be run under the harsh conditions such as high temperature, acid, alkali, anti-pollution；Operating pressure
Low, membrane flux is high, and plant running expense is low；South effect, charge, the ion of material be present for the anion of different valence state
Valence mumber and concentration have a significant impact to nanofiltration membrane separation efficiency.Nanofiltration is compared with ultrafiltration or counter-infiltration, and nanofiltration process is to unit price
Ion and molecular weight are poor less than 200 rejection to organics, and to divalence or multivalent ion and molecular weight between 200~500 it
Between organic matter have higher removal efficiency.Based on this characteristic, nanofiltration process is mainly used in the softening of water, purification and relative
Molecular mass in the separation of hundred grades of material, classification and concentration, decolourize and remove peculiar smell etc..In actual waste water processing, it can incite somebody to action
Nanofiltration and other sewage disposal process are combined, further to reduce expense and improve treatment effect.
Efficient counter-infiltration (HERO) technology is the new technology in the exploitation nineties in last century, and it combines ion exchange and anti-
The advantages of both infiltrations, it is current state-of-the-art reverse osmosis technology.The technological principle of its core is：Using ion exchange by water
Hardness remove, salinity then by counter-infiltration remove；Meanwhile counter-infiltration is run under high ph conditions, silicon is mainly in the form of an ion
In the presence of will not pollute reverse osmosis membrane and can be removed by counter-infiltration；And saponification can occur under high ph conditions for the organic matter in water
Or it is weakly ionized, organic matter and the biological pollution of reverse osmosis membrane will not be caused, had both saved substantial amounts of soda acid, is improved again efficiently anti-
The rate of recovery of osmosis system.Reverse osmosis concentrated water can be further concentrated to using efficient reverse osmosis technology by higher level, so
And be to first have to remove the hardness in waste water to extremely low level using the premise of the technology, so as to reverse osmosis concentrated system
Run under high pH operating modes.
Although the high salts such as reverse osmosis concentrated water, high rigidity waste water can further be concentrated into higher dense by efficient reverse osmosis technology
Degree, but have a small amount of denseer high salt concentrated water discharge and come out.Salinity of the membrane distillation (MD) due to higher concentration can be removed
And higher salt rejection rate and gradually paid attention to by various countries expert and expand widely studied, it can desalination so far at last
Efficiency highest membrane technology, salt rejection rate are up to more than 99%.Membrane distillation is to use microporous hydrophobic membrane, using film both sides steam pressure difference as
A kind of Aspect of some new membrane processes of driving force.Film used in membrane distillation is by the dewatering microporous film of pending solution-wet, i.e.,
Only steam can enter fenestra, and liquid can not pass through fenestra.The advantage of membrane distillation is mainly：Producing water water quality is good, and salt rejection rate is high,
Water Sproading rate is high, using industrial waste heat.Compared with multiple-effect evaporation, membrane distillation can be with low-temperature operation, and producing water water quality is more preferable, distillation
More efficient, fouling and etching problem in the absence of evaporating column, equipment manufacturing cost is also lower than conventional distil-lation tower；Compared with counter-infiltration,
Membrane distillation can normal pressure operation, it is low to pre-processing requirements, the not treatable high-salt wastewater of counter-infiltration can be handled, Water Sproading rate is higher.
Chinese patent CN102557321A is related to a kind of Zero emission method of hc effluent, using crystallization technique, membrane distillation
Technology, microwave catalysis combustion technology and solar energy and wind energy power technology, realize the zero-emission of hc effluent.In the patent, institute
State hc effluent initially enter crystallizer carry out inorganic matter crystallization, after separated through membrane distillation equipment, through film steam
Evaporate film vapor cooling after obtain pure water, other do not pass through membrane distillation film mixed vapour it is condensed obtain miscellaneous water, wherein
On-condensible gas in mixed vapour is decomposed to obtain nontoxic small-molecule substance into follow-up microwave catalysis burner.Although
The patent is directed to a kind of Zero emission method of hc effluent, and still, the technique of zero discharge flow of the patent fails to each work
Skill optimizes, and the technique of zero discharge flow in the application fully incorporates the advantage of every technology, and it is special to be totally different from this
Technological process in profit.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of zero-emission side of hc effluent
Method, it is desirable to provide the method that one kind handles hc effluent using " nanofiltration+efficient counter-infiltration+membrane distillation+evaporative crystallization ".This method
Multivalent ion and the partial organic substances such as the hardness in hc effluent are removed using nanofiltration first, nanofiltration production water is obtained and nanofiltration is dense
Water, carry out depth concentration to nanofiltration production water using efficient reverse osmosis technology afterwards and obtain efficient reverse osmosis produced water and efficiently anti-
Concentrated water is permeated, efficient reverse osmosis concentrated water carries out membrane distillation depth concentration and obtains membrane distillation production water and membrane distillation concentrated water, film again
Distillation concentrated water is evaporated crystallization treatment again, and the saline crystallization in membrane distillation concentrated water is come out, and concentrates desiccation disposal.This is treated
Caused nanofiltration concentrated water adds salt to carry out precipitation process in journey, obtains calcium slag, and the supernatant after precipitation carries out charcoal absorption, absorption
Production water and hc effluent afterwards is mixed into nano-filtration unit circular treatment.In the processing procedure it is caused efficiently reverse osmosis produced water,
Membrane distillation, which produces water and evaporative crystallization production water, can be back to production technology.Hc effluent is handled using the method for the present invention,
While solving this burst of hc effluent discharge problem, water resource has been reclaimed to greatest extent, has realized the zero of hc effluent substantially
Discharge.
To achieve the above objectives, the present invention adopts the technical scheme that：
A kind of Zero emission method of hc effluent, it is characterised in that specifically include following steps：
(1) nanofiltration：Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, and the hardness etc. removed in hc effluent is more
Valency ion and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), and nanofiltration is dense
Water, which enters sedimentation basin and adds salt thereto, gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, sedimentation basin
In supernatant enter activated carbon adsorption unit carry out charcoal absorption, afterwards adsorb after production water return to nano-filtration unit, and
Hc effluent is mixed into nano-filtration unit and carries out circular treatment；
(2) efficient counter-infiltration：Nanofiltration production water carries out alkali tune processing, enters the further concentration point of efficient reverse osmosis units afterwards
From obtaining efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
(3) membrane distillation：Efficient reverse osmosis concentrated water carries out acid adjustment processing, is carried out afterwards into membrane distillation unit at depth concentration
Reason, obtain membrane distillation production water and membrane distillation concentrated water；
(4) evaporative crystallization：Membrane distillation concentrated water is evaporated crystallization treatment into evaporative crystallization unit, obtain salt crystalloid and
Evaporative crystallization produces water.
On the basis of above-mentioned technical proposal, efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water
It is back to production technology.
On the basis of above-mentioned technical proposal, the main water quality characteristic of hc effluent is：PH7~9, electrical conductivity 10000~
20000 μ s/cm, CODcr100~500mg/L, Na+2000~4000mg/L, Cl-2500~5000mg/L, total hardness (CaCO3)
1500~3000mg/L, molten 50~100mg/L of silicon.
On the basis of above-mentioned technical proposal, in the nano-filtration unit of step (1), nanofiltration membrane component uses rolled film group
Part, nanofiltration membrane material are polyamide or sulfonated polyether sulfone.
On the basis of above-mentioned technical proposal, the operating condition of step (1) nano-filtration unit is：Feeding liquid side operating pressure
0.5~1MPa.
On the basis of above-mentioned technical proposal, the salt in step (1) is the mixture of sodium sulphate or sodium carbonate or both,
Its dosage needs to meet：Ca2+：The mol ratio of salt is 1：1.
On the basis of above-mentioned technical proposal, the activated carbon described in step (1) is Powdered Activated Carbon or granular activated carbon,
Its dosage needs to meet：Activated carbon：COD mass ratio is 2：1~10：1, the activated carbon after adsorption saturation can be used as fuel direct
Carry out burning processing.
On the basis of above-mentioned technical proposal, the hc effluent is handled by nano-filtration unit, and Water Sproading rate is higher than 92%.
On the basis of above-mentioned technical proposal, the alkali tune processing in step (2) is that nanofiltration is produced to the pH of water with sodium hydroxide
Adjust to 9~11.
On the basis of above-mentioned technical proposal, the operating condition of the efficient reverse osmosis units of step (2) is：Feeding liquid side waste water
PH9~11, feeding liquid side 2~5MPa of operating pressure.
On the basis of above-mentioned technical proposal, in the efficient reverse osmosis units of step (2), the membrane module form of efficient counter-infiltration
For rolled membrane module, membrane material is polyamide；Efficient reverse osmosis module is one group, or multigroup series connection, or multigroup parallel connection.
On the basis of above-mentioned technical proposal, the nanofiltration production water handled by alkali tune is by efficient reverse osmosis units
Reason, Water Sproading rate are higher than 75%.
On the basis of above-mentioned technical proposal, the acid adjustment processing described in step (3) is will be efficiently reverse osmosis concentrated with hydrochloric acid
The pH of water is adjusted to 7~9.
On the basis of above-mentioned technical proposal, the operating condition of membrane distillation unit is in step (3)：Feeding liquid side waste water
PH7~9,65 DEG C~85 DEG C, feeding liquid side 0.6~1.2m/s of crossflow velocity of feeding liquid side wastewater temperature, penetrating fluid side vacuum-
0.075~-0.095MPa.
On the basis of above-mentioned technical proposal, in step (3) in membrane distillation unit, the membrane material of membrane component is poly- inclined
PVF, polytetrafluoroethylene (PTFE) or polypropylene；Membrane aperture scope is 0.15 μm~0.2 μm.
On the basis of above-mentioned technical proposal, the membrane component form is hollow fiber form or board-like.
On the basis of above-mentioned technical proposal, membrane distillation form is inner pressed vacuum membrane distillation；Membrane component is one group,
Or multigroup series connection, or multigroup parallel connection.
On the basis of above-mentioned technical proposal, the efficient reverse osmosis concentrated water by acid adjustment processing passes through membrane distillation unit
Processing, Water Sproading rate are higher than 75%.
On the basis of above-mentioned technical proposal, evaporative crystallization unit described in step (4) uses existing commercially available evaporative crystallization
Device, thermal source is heated using exhaust steam or electrical heating.
On the basis of above-mentioned technical proposal, the membrane distillation concentrated water passes through evaporative crystallization cell processing, and Water Sproading rate is high
In 80%.
The essential distinction of the present invention and prior art are：For asking in the prior art the difficult of hc effluent
Topic, handled using " nanofiltration+efficient counter-infiltration+membrane distillation+evaporative crystallization " method.First, removed using nanofiltration in waste water
Multivalent ion and the partial organic substances such as hardness, depth concentration is carried out to nanofiltration production water using efficient reverse osmosis technology afterwards
Efficient reverse osmosis produced water and efficient reverse osmosis concentrated water are obtained, efficient reverse osmosis concentrated water carries out membrane distillation depth concentration and obtained again
Membrane distillation produces water and membrane distillation concentrated water, membrane distillation concentrated water are evaporated crystallization treatment again, by the saline crystallization in membrane distillation concentrated water
Out, desiccation disposal is concentrated.Caused efficiently reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water in the processing procedure
Production technology can be back to.By above-mentioned technological process, while solving this burst of hc effluent discharge problem, to greatest extent
Ground has reclaimed water resource, realizes the zero-emission of hc effluent substantially.Compared with existing patent, the application takes full advantage of various
The technical advantage of handling process, handling process are more reasonable, feasible.
The Zero emission method of hc effluent of the present invention, its advantage are：
1st, the present invention is directed to hc effluent, and the multivalent ion such as hardness in hc effluent is removed using nanofiltration and part are had
On the basis of machine thing, film distillation technology and evaporative crystallization technique depth concentration are coupled by efficient reverse osmosis technology, it is maximum
Limit has reclaimed water resource, realizes the advanced treating even zero-emission problem of hc effluent；
2nd, the present invention takes full advantage of the advantage that nanofiltration removes the multivalent ions such as hardness and partial organic substances, removes highly concentrated useless
Hardness and partial organic substances in water, it is easy to follow-up efficient reverse-osmosis treated；
3rd, the nanofiltration technique in the present invention effectively reduces the fouling membrane of follow-up efficiently reverse osmosis process, improves efficiently anti-
The rate of recovery of osmosis system；
4th, efficient reverse osmosis process is used in the present invention, is compared with conventional reverse osmosis, efficient counter-infiltration is intake by adjusting
PH, fouling membrane is effectively slow down, extend cleaning frequency and the service life of reverse osmosis membrane；
5th, the membrane distillation process in the present invention does not need impressed pressure or outer pressure pressure very little, and method is simple and easy, easily
Operation；
6th, the fouling membrane of the membrane distillation process in the present invention is lighter, extends the continuous and steady operation time of the process；
7th, using the method for the present invention, it can not only obtain and largely meet the production water of reuse demand, while also solve height
Density wastewater is difficult to process problem, while water resource is reclaimed to greatest extent, realizes zero-emission substantially, has important environment
Benefit and social benefit；
8th, method of the invention has effectively integrated the technical advantage of various handling process, optimizes hc effluent advanced treating
The technological process of reuse.For the method for the present invention for waste water directly carries out multiple-effect evaporation or membrane distillation, operating cost is low,
And effectively reduce fouling and the pollution of organic matter；
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
Brief description of the drawings
The present invention has drawings described below：
The process chart of Fig. 1 present invention.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing.
As shown in figure 1, the Zero emission method of hc effluent of the present invention, specifically includes following steps：
(1) nanofiltration：Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, and the hardness etc. removed in hc effluent is more
Valency ion and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), and nanofiltration is dense
Water, which enters sedimentation basin and adds salt thereto, gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, sedimentation basin
In supernatant enter activated carbon adsorption unit carry out charcoal absorption, afterwards adsorb after production water return to nano-filtration unit, and
Hc effluent is mixed into nano-filtration unit and carries out circular treatment；
(2) efficient counter-infiltration：Nanofiltration production water carries out alkali tune processing, enters the further concentration point of efficient reverse osmosis units afterwards
From obtaining efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
(3) membrane distillation：Efficient reverse osmosis concentrated water carries out acid adjustment processing, is carried out afterwards into membrane distillation unit at depth concentration
Reason, obtain membrane distillation production water and membrane distillation concentrated water；
(4) evaporative crystallization：Membrane distillation concentrated water is evaporated crystallization treatment into evaporative crystallization unit, obtain salt crystalloid and
Evaporative crystallization produces water；
Wherein, efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water can be back to production technology.
On the basis of such scheme, the main water quality characteristic of hc effluent is：PH7~9, electrical conductivity 10000~20000
μ s/cm, CODcr100~500mg/L, Na+2000~4000mg/L, Cl-2500~5000mg/L, total hardness (CaCO3) 1500~
3000mg/L, molten 50~100mg/L of silicon.
On the basis of such scheme, in the nano-filtration unit of step (1), nanofiltration membrane component uses rolled membrane module, receives
Filter membrane material is polyamide or sulfonated polyether sulfone.
On the basis of such scheme, the operating condition of step (1) nano-filtration unit is：Feeding liquid side operating pressure 0.5~
1MPa。
On the basis of such scheme, the salt in step (1) is (any for the mixture of sodium sulphate or sodium carbonate or both
The mixture of proportioning), its dosage needs to meet：Ca2+：The mol ratio of salt is 1：1.
On the basis of such scheme, the activated carbon described in step (1) is Powdered Activated Carbon or granular activated carbon, and it is thrown
Dosage needs to meet：Activated carbon：COD mass ratio is 2：1~10：1, the activated carbon after adsorption saturation can directly be carried out as fuel
Burning is handled.
On the basis of such scheme, the hc effluent is handled by nano-filtration unit, and Water Sproading rate is higher than 92%.
On the basis of such scheme, the alkali tune processing in step (2) is that the pH that nanofiltration is produced to water with sodium hydroxide is adjusted
To 9~11.
On the basis of such scheme, the operating condition of the efficient reverse osmosis units of step (2) is：Feeding liquid side wastewater pH 9
~11, feeding liquid side 2~5MPa of operating pressure.
On the basis of such scheme, for step (2) efficiently in reverse osmosis units, the membrane module form of efficient counter-infiltration is volume
Formula membrane module, membrane material are polyamide；
Efficient reverse osmosis module is one group, or multigroup series connection, or multigroup parallel connection.
On the basis of such scheme, the nanofiltration handled by alkali tune is produced water and handled by efficient reverse osmosis units,
Water Sproading rate is higher than 75%.
On the basis of such scheme, acid adjustment described in step (3) processing is by efficient reverse osmosis concentrated water with hydrochloric acid
PH is adjusted to 7~9.
On the basis of such scheme, the operating condition of membrane distillation unit is in step (3)：Feeding liquid side wastewater pH 7~
9,65 DEG C~85 DEG C, feeding liquid side 0.6~1.2m/s of crossflow velocity of feeding liquid side wastewater temperature, penetrating fluid side vacuum -0.075
~-0.095MPa.
On the basis of such scheme, in step (3) in membrane distillation unit, the membrane material of membrane component is polyvinylidene fluoride
Alkene, polytetrafluoroethylene (PTFE) or polypropylene；Membrane aperture scope is 0.15 μm~0.2 μm.
On the basis of such scheme, the membrane component form is hollow fiber form or board-like.
On the basis of such scheme, membrane distillation form is inner pressed vacuum membrane distillation；Membrane component is one group, or more
Group series connection, or multigroup parallel connection.
On the basis of such scheme, the efficient reverse osmosis concentrated water by acid adjustment processing is by membrane distillation unit
Reason, Water Sproading rate are higher than 75%.
On the basis of such scheme, evaporative crystallization unit described in step (4) uses existing commercially available crystallizing evaporator, heat
Source is heated using exhaust steam or electrical heating.
On the basis of such scheme, the membrane distillation concentrated water passes through evaporative crystallization cell processing, and Water Sproading rate is higher than
80%.
It is some specific embodiments below.
Embodiment 1
The main water quality characteristic of hc effluent is：Wastewater pH 7, electrical conductivity 10000 μ s/cm, CODcr100mg/L, Na+
2000mg/L, Cl-2500mg/L, total hardness (CaCO3) 1500mg/L, molten silicon 50mg/L, NH4-N0mg/L。
As shown in figure 1, as follows to the processing procedure of the hc effluent：
(1) nanofiltration.Hc effluent enters nano-filtration unit and carries out nanofiltration processing, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), in nanofiltration concentrated water
Middle addition sodium carbonate gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, and supernatant is entered using Powdered Activated Carbon
Row charcoal absorption, nano-filtration unit is returned to afterwards, and hc effluent is mixed into nano-filtration unit and carries out circular treatment；
Wherein, the dosage of sodium carbonate is Ca2+：The mol ratio of sodium carbonate is 1：1, the dosage of Powdered Activated Carbon is powder
Activated carbon：COD mass ratio is 2：1；
Nanofiltration membrane component uses polyamide rolled membrane module；The operating condition of nano-filtration unit is：Feeding liquid side operating pressure
0.5MPa, nanofiltration produce the water hardness substantially in 70mg/L or so；Under the operating conditions described above, nanofiltration membrane flux is maintained at 13~16L/
m2H, nanofiltration system Water Sproading rate are higher than 92%；Supernatant after SODIUM PERCARBONATE precipitates goes out the water hardness and is less than 15mg/L；Through
The supernatant C OD crossed after powder electroless platingcrLess than 10mg/L；
(2) efficient counter-infiltration.The pH that nanofiltration is produced to water using sodium hydroxide is adjusted to 9, afterwards into efficient counter-infiltration list
The further concentrating and separating of member, obtains efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
Wherein, efficient reverse osmosis membrane assembly uses polyamide rolled membrane module；In running, efficient reverse osmosis units
Operating condition is：Feeding liquid side wastewater pH 9, feeding liquid side operating pressure 2MPa；Under the operating conditions described above, efficient reverse osmosis membrane
Flux is maintained at 17~22L/m2H, Water Sproading rate are higher than 75%；
(3) membrane distillation.The pH regulations of efficient reverse osmosis concentrated water are carried out into membrane distillation unit afterwards to 7 using hydrochloric acid
Depth concentration, obtain membrane distillation production water and membrane distillation concentrated water；
Membrane component used uses polytetrafluoroethylene (PTFE) (PTFE) hollow fiber hydrophobic membrane component, and membrane aperture is 0.2 μm, film
Distillation form is inner pressed vacuum membrane distillation.In running, the operating condition of membrane distillation unit is：Feeding liquid side wastewater pH 7,
65 DEG C of feeding liquid side wastewater temperature, feeding liquid side crossflow velocity 1.2m/s, penetrating fluid side vacuum -0.095MPa；In above-mentioned behaviour
Under the conditions of work, membrane distillation membrane flux is maintained at 3~5L/m2H, Water Sproading rate are higher than 75%；
(4) evaporative crystallization.Membrane distillation concentrated water is evaporated crystallization treatment, and evaporation thermal source is heated using exhaust steam, obtains salt
Crystalloid and evaporative crystallization production water.
Wherein, the Water Sproading rate of evaporative crystallization unit is higher than 80%.
Wherein, salt crystalloid concentrates desiccation disposal；Efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water are equal
Production technology can be back to；Activated carbon in step (1) after adsorption saturation can directly carry out burning processing as fuel.
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
Embodiment 2
The main water quality characteristic of hc effluent is：Wastewater pH 7, electrical conductivity 13000 μ s/cm, CODcr150mg/L, Na+
2000mg/L, Cl-2500mg/L, total hardness (CaCO3) 2000mg/L, molten silicon 50mg/L, NH4-N0mg/L。
As shown in figure 1, as follows to the processing procedure of the hc effluent：
(1) nanofiltration.Hc effluent enters nano-filtration unit and carries out nanofiltration processing, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), in nanofiltration concentrated water
Middle addition sodium sulphate gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, and supernatant is entered using granular activated carbon
Row charcoal absorption, nano-filtration unit is returned to afterwards, and hc effluent is mixed into nano-filtration unit and carries out circular treatment,
Wherein, the dosage of sodium sulphate is Ca2+：The mol ratio of sodium sulphate is 1：1, the dosage of granular activated carbon is particle
Activated carbon：COD mass ratio is 10：1, the supernatant after sodium peroxydisulfate precipitates goes out the water hardness and is less than 20mg/L；By particle
Supernatant C OD after charcoal absorptioncrLess than 10mg/L；
Nanofiltration membrane component uses sulfonated polyether sulfone rolled membrane module；The operating condition of nano-filtration unit is：Feeding liquid side operates
Pressure 0.7MPa, nanofiltration produce the water hardness substantially in 80mg/L or so；Under the operating conditions described above, nanofiltration membrane flux be maintained at 15~
18L/m2H, Water Sproading rate are higher than 92%；
(2) efficient counter-infiltration.The pH that nanofiltration is produced to water using sodium hydroxide is adjusted to 9.5, afterwards into efficient counter-infiltration
The further concentrating and separating of unit, obtains efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
Wherein, efficient reverse osmosis membrane assembly uses polyamide rolled membrane module；In running, efficient reverse osmosis units
Operating condition is：Feeding liquid side wastewater pH 9.5, feeding liquid side operating pressure 2MPa；Under the operating conditions described above, efficient counter-infiltration
Membrane flux is maintained at 18~22L/m2H, Water Sproading rate are higher than 75%；
(3) membrane distillation.The pH of efficient reverse osmosis concentrated water is adjusted to 7.5 using hydrochloric acid, entered afterwards into membrane distillation unit
Row depth concentration, obtain membrane distillation production water and membrane distillation concentrated water；
Membrane component used uses polytetrafluoroethylene (PTFE) (PTFE) hollow fiber hydrophobic membrane component, and membrane aperture is 0.2 μm, film
Distillation form is inner pressed vacuum membrane distillation.In running, the operating condition of membrane distillation unit is：Feeding liquid side waste water
PH7.5,75 DEG C of feeding liquid side wastewater temperature, feeding liquid side crossflow velocity 0.8m/s, penetrating fluid side vacuum -0.085MPa；
Under the conditions of aforesaid operations, membrane distillation membrane flux is maintained at 4~6L/m2H, Water Sproading rate are higher than 75%；
(4) evaporative crystallization.Membrane distillation concentrated water is evaporated crystallization treatment, and evaporation thermal source is heated using exhaust steam, obtains salt
Crystalloid and evaporative crystallization production water.
Wherein, the Water Sproading rate of evaporative crystallization unit is higher than 80%.
Wherein, salt crystalloid concentrates desiccation disposal；Efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water are equal
Production technology can be back to；Activated carbon in step (1) after adsorption saturation can directly carry out burning processing as fuel.
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
Embodiment 3
The main water quality characteristic of hc effluent is：Wastewater pH 8, electrical conductivity 15000 μ s/cm, CODcr300mg/L, Na+
3000mg/L, Cl-3500mg/L, total hardness (CaCO3) 2500mg/L, molten silicon 80mg/L, NH4-N3mg/L。
As shown in figure 1, as follows to the processing procedure of the hc effluent：
(1) nanofiltration.Hc effluent enters nano-filtration unit and carries out nanofiltration processing, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), in nanofiltration concentrated water
The mixture of middle addition sodium carbonate and sodium sulphate gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, supernatant
Charcoal absorption is carried out using Powdered Activated Carbon, returns to nano-filtration unit afterwards, and hc effluent is mixed into nano-filtration unit and entered
Row circular treatment,
Wherein, the dosage of the mixture of sodium carbonate and sodium sulphate is Ca2+：Mole of the mixture of sodium carbonate and sodium sulphate
Than for 1：1, the dosage of Powdered Activated Carbon is Powdered Activated Carbon：COD mass ratio is 8：1；Through SODIUM PERCARBONATE and sodium sulphate
Supernatant after mixture precipitation goes out the water hardness and is less than 15mg/L；Supernatant C OD after powder electroless platingcrIt is less than
10mg/L；
Nanofiltration membrane component uses polyamide rolled membrane module；The operating condition of nano-filtration unit is：Feeding liquid side operating pressure
0.8MPa, nanofiltration produce the water hardness substantially in 90mg/L or so；Under the operating conditions described above, nanofiltration membrane flux is maintained at 14~18L/
m2H, Water Sproading rate are higher than 92%；
(2) efficient counter-infiltration.The pH that nanofiltration is produced to water using sodium hydroxide is adjusted to 10, afterwards into efficient counter-infiltration list
The further concentrating and separating of member, obtains efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
Wherein, efficient reverse osmosis membrane assembly uses polyamide rolled membrane module；In running, efficient reverse osmosis units
Operating condition is：Feeding liquid side wastewater pH 10, feeding liquid side operating pressure 3MPa；Under the operating conditions described above, efficient counter-infiltration
Membrane flux is maintained at 15~19L/m2H, Water Sproading rate are higher than 75%；
(3) membrane distillation.The pH regulations of efficient reverse osmosis concentrated water are carried out into membrane distillation unit afterwards to 8 using hydrochloric acid
Depth concentration, obtain membrane distillation production water and membrane distillation concentrated water；
Membrane component used uses polypropylene (PP) hollow fiber hydrophobic membrane component, and membrane aperture is 0.2 μm, membrane distillation shape
Formula is inner pressed vacuum membrane distillation.In running, the operating condition of membrane distillation unit is：Feeding liquid side wastewater pH 8, feeding liquid
85 DEG C of side wastewater temperature, feeding liquid side crossflow velocity 1.0m/s, penetrating fluid side vacuum -0.075MPa；In aforesaid operations condition
Under, membrane distillation membrane flux is maintained at 4~6L/m2H, Water Sproading rate are higher than 75%；
(4) evaporative crystallization.Membrane distillation concentrated water is evaporated crystallization treatment, and evaporation thermal source uses electrical heating, obtains salt crystalline substance
Body and evaporative crystallization production water.
Wherein, the Water Sproading rate of evaporative crystallization unit is higher than 80%.
Wherein, salt crystalloid concentrates desiccation disposal；Efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water are equal
Production technology can be back to；Activated carbon in step (1) after adsorption saturation can directly carry out burning processing as fuel.
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
Embodiment 4
The water quality characteristic of hc effluent is：Wastewater pH 9, electrical conductivity 20000 μ s/cm, CODcr500mg/L, Na+4000mg/
L, Cl-5000mg/L, total hardness (CaCO3) 3000mg/L, molten silicon 100mg/L, NH4-N5mg/L；
As shown in figure 1, as follows to the processing procedure of the hc effluent：
(1) nanofiltration.Hc effluent enters nano-filtration unit and carries out nanofiltration processing, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), in nanofiltration concentrated water
Middle addition sodium carbonate gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, and supernatant is entered using Powdered Activated Carbon
Row charcoal absorption, nano-filtration unit is returned to afterwards, and hc effluent is mixed into nano-filtration unit and carries out circular treatment,
Wherein, the dosage of sodium carbonate is Ca2+：The mol ratio of sodium carbonate is 1：1, the dosage of Powdered Activated Carbon is powder
Activated carbon：COD mass ratio is 8：1；Supernatant after SODIUM PERCARBONATE precipitates goes out the water hardness and is less than 15mg/L；Lived by powder
Property charcoal absorption after supernatant C ODcrLess than 10mg/L；
Nanofiltration membrane component uses polyamide rolled membrane module；The operating condition of nano-filtration unit is：Feeding liquid side operating pressure
1.0MPa, nanofiltration produce the water hardness substantially in 100mg/L or so；Under the operating conditions described above, nanofiltration membrane flux be maintained at 15~
18L/m2H, Water Sproading rate are higher than 92%；
(2) efficient counter-infiltration.The pH that nanofiltration is produced to water using sodium hydroxide is adjusted to 11, afterwards into efficient counter-infiltration list
The further concentrating and separating of member, obtains efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
Wherein, efficient reverse osmosis membrane assembly uses polyamide rolled membrane module；In running, efficient reverse osmosis units
Operating condition is：Feeding liquid side wastewater pH 11, feeding liquid side operating pressure 5MPa；Under the operating conditions described above, efficient counter-infiltration
Membrane flux is maintained at 16~22L/m2H, Water Sproading rate are higher than 75%；
(3) membrane distillation.The pH regulations of efficient reverse osmosis concentrated water are carried out into membrane distillation unit afterwards to 9 using hydrochloric acid
Depth concentration, obtain membrane distillation production water and membrane distillation concentrated water；
Membrane component used uses polypropylene (PP) hollow fiber hydrophobic membrane component, and membrane aperture is 0.15 μm, membrane distillation
Form is inner pressed vacuum membrane distillation.In running, the operating condition of membrane distillation unit is：Feeding liquid side wastewater pH 9, charging
85 DEG C of liquid side wastewater temperature, feeding liquid side crossflow velocity 0.6m/s, penetrating fluid side vacuum -0.09MPa；In aforesaid operations condition
Under, membrane distillation membrane flux is maintained at 5~7L/m2H, Water Sproading rate are higher than 75%；
(4) evaporative crystallization.Membrane distillation concentrated water is evaporated crystallization treatment, and evaporation thermal source is heated using exhaust steam, obtains salt
Crystalloid and evaporative crystallization production water.
Wherein, the Water Sproading rate of evaporative crystallization unit is higher than 80%.
Wherein, salt crystalloid concentrates desiccation disposal；Efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water are equal
Production technology can be back to；Activated carbon in step (1) after adsorption saturation can directly carry out burning processing as fuel.
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
Embodiment 5
The water quality characteristic of hc effluent is：Wastewater pH 7, electrical conductivity 10000 μ s/cm, CODcr100mg/L, Na+2000mg/
L, Cl-2500mg/L, total hardness (CaCO3) 1500mg/L, molten silicon 50mg/L, NH4-N0mg/L。
As shown in figure 1, as follows to the processing procedure of the hc effluent：
(1) nanofiltration.Hc effluent enters nano-filtration unit and carries out nanofiltration processing, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), in nanofiltration concentrated water
Middle addition sodium carbonate gets off calcium ions precipitate to obtain calcium slag, and calcium slag concentrates desiccation disposal, and supernatant is entered using Powdered Activated Carbon
Row charcoal absorption, nano-filtration unit is returned to afterwards, and hc effluent is mixed into nano-filtration unit and carries out circular treatment,
Wherein, the dosage of sodium carbonate is Ca2+：The mol ratio of sodium carbonate is 1：1, the dosage of Powdered Activated Carbon is powder
Activated carbon：COD mass ratio is 5：1；Supernatant after SODIUM PERCARBONATE precipitates goes out the water hardness and is less than 15mg/L；Lived by powder
Property charcoal absorption after supernatant C ODcrLess than 10mg/L；
Nanofiltration membrane component uses polyamide rolled membrane module；The operating condition of nano-filtration unit is：Feeding liquid side operating pressure
0.5MPa, nanofiltration produce the water hardness substantially in 70mg/L or so；Under the operating conditions described above, nanofiltration membrane flux is maintained at 13~16L/
m2H, Water Sproading rate are higher than 92%；
(2) efficient counter-infiltration.The pH that nanofiltration is produced to water using sodium hydroxide is adjusted to 10, afterwards into efficient counter-infiltration list
The further concentrating and separating of member, obtains efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
Wherein, efficient reverse osmosis membrane assembly uses polyamide rolled membrane module；In running, efficient reverse osmosis units
Operating condition is：Feeding liquid side wastewater pH 10, feeding liquid side operating pressure 2MPa；Under the operating conditions described above, efficient counter-infiltration
Membrane flux is maintained at 17~22L/m2H, Water Sproading rate are higher than 75%；
(3) membrane distillation.The pH regulations of efficient reverse osmosis concentrated water are carried out into membrane distillation unit afterwards to 9 using hydrochloric acid
Depth concentration, obtain membrane distillation production water and membrane distillation concentrated water；
Membrane component used uses polytetrafluoroethylene (PTFE) (PTFE) hollow fiber hydrophobic membrane component, and membrane aperture is 0.18 μm,
Membrane distillation form is inner pressed vacuum membrane distillation.In running, the operating condition of membrane distillation unit is：Feeding liquid side waste water
PH9,80 DEG C of feeding liquid side wastewater temperature, feeding liquid side crossflow velocity 0.9m/s, penetrating fluid side vacuum -0.09MPa；Above-mentioned
Under operating condition, membrane distillation membrane flux is maintained at 7~10L/m2H, Water Sproading rate are higher than 75%；
(4) evaporative crystallization.Membrane distillation concentrated water is evaporated crystallization treatment, and evaporation thermal source is heated using exhaust steam, obtains salt
Crystalloid and evaporative crystallization production water.
Wherein, the Water Sproading rate of evaporative crystallization unit is higher than 80%.
Wherein, salt crystalloid concentrates desiccation disposal；Efficient reverse osmosis produced water, membrane distillation production water and evaporative crystallization production water are equal
Production technology can be back to；Activated carbon in step (1) after adsorption saturation can directly carry out burning processing as fuel.
Hc effluent after the inventive method is handled, whole system the production μ S/cm of water conductivity≤300, production water CODcr<
10mg/L, whole system Water Sproading rate are higher than 93%.
The preferable possible embodiments of the present invention are the foregoing is only, not thereby limit to the scope of the claims of the present invention, thus it is all
It is the equivalence changes made with description of the invention and accompanying drawing content, is both contained in protection scope of the present invention.
The content not being described in detail in this specification belongs to prior art known to professional and technical personnel in the field.
Claims (15)
1. a kind of Zero emission method of hc effluent, it is characterised in that specifically include following steps：
(1) nanofiltration：Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, remove the multivalence such as hardness in hc effluent from
Son and partial organic substances, nanofiltration production water and nanofiltration concentrated water are obtained, nanofiltration production water is handled into step (2), and nanofiltration concentrated water is entered
Enter sedimentation basin and add salt thereto and calcium ions precipitate is got off to obtain calcium slag, calcium slag concentrates desiccation to dispose, in sedimentation basin
Supernatant enters activated carbon adsorption unit and carries out charcoal absorption, and the production water after adsorbing afterwards returns to nano-filtration unit, and highly concentrated
Waste water is mixed into nano-filtration unit and carries out circular treatment；
(2) efficient counter-infiltration：Nanofiltration production water carries out alkali tune processing, afterwards into the further concentrating and separating of efficient reverse osmosis units,
Obtain efficient reverse osmosis produced water and efficient reverse osmosis concentrated water；
(3) membrane distillation：Efficient reverse osmosis concentrated water carries out acid adjustment processing, carries out depth concentration into membrane distillation unit afterwards,
Obtain membrane distillation production water and membrane distillation concentrated water；
(4) evaporative crystallization：Membrane distillation concentrated water is evaporated crystallization treatment into evaporative crystallization unit, obtains salt crystalloid and evaporation
Crystallization production water；
The main water quality characteristic of hc effluent is：PH7~9, electrical conductivity 10000~20000 μ s/cm, CODcr100~500mg/L,
Na+2000~4000mg/L, Cl-2500~5000mg/L, total hardness (CaCO3) 1500~3000mg/L, molten 50~100mg/ of silicon
L；
Activated carbon described in step (1) is Powdered Activated Carbon or granular activated carbon, and its dosage needs to meet：Activated carbon：COD's
Mass ratio is 2：1~10：1, the activated carbon after adsorption saturation can directly carry out burning processing as fuel；
In the nano-filtration unit of step (1), nanofiltration membrane component uses rolled membrane module, and nanofiltration membrane material is that polyamide or sulfonation gather
Ether sulfone；
Efficiently the operating conditions of reverse osmosis units is step (2)：Feeding liquid side wastewater pH 9~11, feeding liquid side operating pressure 2~
5MPa；
Step (2) is efficiently in reverse osmosis units, and the membrane module form of efficient counter-infiltration is rolled membrane module, and membrane material is polyamides
Amine；Efficient reverse osmosis module is one group, or multigroup series connection, or multigroup parallel connection.
2. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Efficient reverse osmosis produced water, membrane distillation
Production water and evaporative crystallization production water can be back to production technology.
3. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The operation of step (1) nano-filtration unit
Condition is：Feeding liquid side 0.5~1MPa of operating pressure.
4. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Salt in step (1) is sulfuric acid
The mixture of sodium or sodium carbonate or both, its dosage need to meet：Ca2+：The mol ratio of salt is 1：1.
5. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The hc effluent passes through nanofiltration list
Member processing, Water Sproading rate are higher than 92%.
6. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Alkali tune in step (2) is handled
The pH that nanofiltration is produced to water with sodium hydroxide is adjusted to 9~11.
7. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The nanofiltration handled by alkali tune
Produce water to handle by efficient reverse osmosis units, Water Sproading rate is higher than 75%.
8. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：At acid adjustment described in step (3)
Reason is to be adjusted the pH of efficient reverse osmosis concentrated water to 7~9 with hydrochloric acid.
9. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Membrane distillation unit in step (3)
Operating condition is：Feeding liquid side wastewater pH 7~9,65 DEG C~85 DEG C of feeding liquid side wastewater temperature, feeding liquid side crossflow velocity 0.6
~1.2m/s, penetrating fluid side -0.075~-0.095MPa of vacuum.
10. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Membrane distillation unit in step (3)
In, the membrane material of membrane component is Kynoar, polytetrafluoroethylene (PTFE) or polypropylene；Membrane aperture scope is 0.15 μm~0.2 μ
m。
11. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The membrane component form is
Hollow fiber form is board-like.
12. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Membrane distillation form is that inner pressed is true
Empty membrane distillation；Membrane component is one group, or multigroup series connection, or multigroup parallel connection.
13. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The height handled by acid adjustment
Effect reverse osmosis concentrated water passes through membrane distillation cell processing, and Water Sproading rate is higher than 75%.
14. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：Evaporative crystallization described in step (4)
Unit uses existing commercially available crystallizing evaporator, and thermal source is heated using exhaust steam or electrical heating.
15. the Zero emission method of hc effluent as claimed in claim 1, it is characterised in that：The membrane distillation concentrated water is by steaming
Crystalline element processing is sent out, Water Sproading rate is higher than 80%.
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| CN107010643B (en) * | 2016-01-27 | 2019-02-15 | 神华集团有限责任公司 | A kind of continuous salt production method and continuous salt production system |
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| TW404847B (en) * | 1996-08-12 | 2000-09-11 | Debasish Mukhopadhyay | Method and apparatus for high efficiency reverse osmosis operation |
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