CN105621769B - A kind of Zero emission method of hc effluent - Google Patents

A kind of Zero emission method of hc effluent Download PDF

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CN105621769B
CN105621769B CN201410612213.XA CN201410612213A CN105621769B CN 105621769 B CN105621769 B CN 105621769B CN 201410612213 A CN201410612213 A CN 201410612213A CN 105621769 B CN105621769 B CN 105621769B
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water
effluent
reverse osmosis
nanofiltration
unit
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CN105621769A (en
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张新妙
谢梓峰
彭海珠
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/33Wastewater or sewage treatment systems using renewable energies using wind energy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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 to utilize the Zero emission method of " nanofiltration+disc tube reverse osmosis (dt-ro)+evaporative crystallization " processing hc effluent.Multivalent ions and the partial organic substances such as the hardness in nanofiltration removal waste water are used first, disc tube reverse osmosis (dt-ro) is used to carry out depth concentration to the hc effluent after removal hardness and partial organic substances later, reverse osmosis concentrated water after the concentration of disc tube reverse osmosis (dt-ro) depth is evaporated crystallization treatment again, salt solid crystal in concentrated water is come out, desiccation disposition is concentrated.The disc tube reverse osmosis (dt-ro) production water and evaporative crystallization production water generated in the processing procedure can be back to production technology.Method processing hc effluent using the present invention has recycled water resource, has realized the zero-emission of hc effluent substantially to the maximum extent while solving this burst of discharge of wastewater problem.

Description

A kind of Zero emission method of hc effluent
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 The Zero emission method of hc effluent is handled using membrane separation technique.More specifically to it is a kind of " nanofiltration+disc tube reverse osmosis (dt-ro)+ Evaporative crystallization " handles the Zero emission method of hc effluent.
Background technology
In recent years, the hc effluent that petroleum chemical enterprise generates becomes a processing problem, this strand of waste water can neither discharge also not Energy reuse, great puzzlement is brought to each enterprise.Therefore, the processing row of such waste water is solved there is an urgent need for seeking novel isolation technics Put problem.
Nanofiltration (NF) be between ultrafiltration and it is reverse osmosis between a kind of membrane separation technique, molecular cut off 200~ In 1000 ranges, aperture is several nanometers.Nanofiltration has following technical characterstic:Can molecular cut off more than 100 organic matter and Multivalent ion allows small organic molecule and monovalention to penetrate;Can be sour in high temperature, it is run under the harsh conditions such as alkali, resistant Dye;Operating pressure is low, and membrane flux is high, and device operating cost is low;For the anion of different valence state, there are road south effects for nanofiltration.Object Charge, ion valence mumber and the concentration of material have a significant impact to the separation effect of film.With ultrafiltration or it is reverse osmosis compared with, nanofiltration process It is poor less than 200 rejection to organics to monovalention and molecular weight, and to divalent or multivalent ion and molecular weight between 200~ Organic matter between 500 has higher removal efficiency.Based on this characteristic, nanofiltration process be mainly used in water softening, purification and Relative molecular mass in the separation of hundred grades of substance, classification and concentration, decolourize and remove peculiar smell etc..It, can in actual waste water processing Nanofiltration and other sewage disposal process to be combined, to further decrease expense and improve treatment effect.
Disc tube reverse osmosis (dt-ro) film (DTRO films) is a kind of reverse osmosis form, is the film for being specifically used to processing high-concentration sewage Component, core technology are dish tubular membrane film columns.Reverse osmosis membrane and waterpower flow guiding disc are stacked together, center pull rod is used It is fixed with end plate, is then placed in pressure jacket, just form a film column.The operation principle of DTRO films is:Feed liquid passes through Entered in the flow guiding disc of bottom by flow-guiding channel behind gap between membrane stack and shell, processed liquid is fast with shortest distance Speed flows through filter membrane, and then 180 degree is reversed to another film surface, then is flowed into next filtration membrane, to be formed in film surface By flow guiding disc circumference to circle center, then circumference is arrived, then to the tangential flow filtration of circle center, concentrate is finally from feed end flange Outflow.While material flow is through filter membrane, permeate is constantly discharged by central collection tube.Concentrate passes through installation with permeate In the O-ring seal isolation on flow guiding disc.Compared with conventional reverse osmosis, disc tube reverse osmosis (dt-ro) it is a technical advantage that:(1) it avoids Physical clogging phenomenon.Dish tubular membrane component uses open runner design, and the effective runner of feed liquid is wide, avoids physical clogging;(2) Film fouling and fouling membrane are less.Using with convex point-supported flow guiding disc, feed liquid forms turbulence state, maximum journey in filter process Reduce the generation of film surface fouling, pollution and concentration polarization phenomenon on degree;(3) film service life is long.Using dish tubular membrane group Part can effectively reduce film fouling, and fouling membrane mitigates, and the cleaning frequency is long, and membrane module is readily cleaned, and flux recovery is good after cleaning, from And extend the diaphragm service life;(4) cycles of concentration is high.Dish tubular membrane component is the highest film group of current industrial applications pressure rating Part, operating pressure reach as high as 16MPa.
In view of the technical advantage of disc tube reverse osmosis (dt-ro) film, the technology is widely used in the landfill leachate of various occasions at present Processing.Chinese patent CN200510102945.5 relates to a kind of method of the landfill leachate of processing household refuse landfill sites, The patent uses disc tube reverse osmosis (dt-ro) technique to handle garbage filter on the basis of carrying out preaeration to landfill leachate Liquid;Chinese patent CN200510102946.X relate to it is a kind of processing municipal solid waste incinerator landfill leachate equipment and its Method, this method are directed to the water quality characteristics of landfill leachate, mainly use pretreatment+membrane bioreactor+disc tube reverse osmosis (dt-ro) Technological process.Wherein pretreatment is mainly separated by solid-liquid separation landfill leachate using centrifugal dehydration, removes a large amount of suspend Object;Membrane bioreactor mainly carries out aerobic biochemical to pretreated landfill leachate, passes through ultrafiltration membrance filter point later From mud mixture;Disc tube reverse osmosis (dt-ro) is detached primarily directed to the landfill leachate after Membrane Bioreactor for Wastewater Treatment Purification, obtains the preferable reverse osmosis produced water of quality and reverse osmosis concentrated liquid.
Chinese patent CN201210509879.3 is related to vulcanized sodium recovery process and device in a kind of production of barium sulfate, is used for Dilute vulcanization waste liquor of sodium is recycled, disc tube reverse osmosis (dt-ro) concentrated vitriol sodium weak solution is used in the technique which is related to, by concentration Sodium sulphate concentrate afterwards returns in barium sulfate production technology.
In addition, Chinese patent CN102557321A is related to a kind of Zero emission method of hc effluent, use crystallization technique, Film distillation technology, microwave catalysis combustion technology and solar energy and wind energy power technology realize wastewater zero discharge.In the patent, institute State hc effluent initially enter crystallizer carry out inorganic matter crystallization, after detached through membrane distillation equipment, through film steam Pure water is obtained after evaporating the vapor cooling of equipment film, other do not obtain miscellaneous water through the mixed vapour of film is condensed, wherein mixed On-condensible gas in conjunction steam enters microwave catalysis burner and is decomposed to obtain nontoxic small-molecule substance.Although the patent It is directed to a kind of Zero emission method of hc effluent, still, the patent process flow is complicated, and solar energy or wind power generation are made For the heat source of membrane distillation so that membrane distillation process is limited by weather condition, and treatment effect is unstable.
Invention content
In view of the deficiencies in the prior art, the purpose of the present invention is to provide a kind of zero-emission sides of hc effluent Method, i.e., it is a kind of to recycle water resource, the basic use " nanofiltration+disc tube reverse osmosis (dt-ro)+evaporative crystallization " for realizing zero-emission to greatest extent The method for handling hc effluent.
To achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of Zero emission method of hc effluent, including following steps:
(1) nanofiltration:Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, is detached by the nano-filtration unit dense After contracting, nanofiltration production water and nanofiltration concentrated water are obtained;
(2) disc tube reverse osmosis (dt-ro):The nanofiltration production water that step (1) obtains enters disc tube reverse osmosis (dt-ro) unit and carries out depth Concentration obtains reverse osmosis produced water and reverse osmosis concentrated water after disc tube reverse osmosis (dt-ro) unit separation concentration;
(3) evaporative crystallization:The reverse osmosis concentrated water that step (2) obtains enters evaporative crystallization unit and is evaporated at crystallization Reason, obtains the production water of salt crystalloid and evaporative crystallization.
On the basis of said program, the nanofiltration membrane component of nano-filtration unit described in step (1) uses rolled membrane module.
On the basis of said program, the membrane material of the rolled membrane module is polyamide or sulfonated polyether sulfone.
On the basis of said program, the operating condition of nano-filtration unit described in step (1) is:Feeding liquid side operating pressure For 0.5~1MPa.
On the basis of said program, the disc tube reverse osmosis (dt-ro) film of the use of disc tube reverse osmosis (dt-ro) unit described in step (2) Component is high pressure or super-pressure disc tube reverse osmosis (dt-ro) membrane module.
On the basis of said program, the operating pressure of the disc tube reverse osmosis (dt-ro) unit is 12~16MPa.
On the basis of said program, the disc tube reverse osmosis (dt-ro) film of the use of disc tube reverse osmosis (dt-ro) unit described in step (2) The form of component is that multiple disc-type diaphragms are connected on composition disc-type film column on a central tube.
On the basis of said program, evaporative crystallization unit described in step (3) uses crystallizing evaporator, and heat source is using useless Steam heats.
On the basis of said program, addition salt gets off calcium ions precipitate in the nanofiltration concentrated water that step (1) obtains, Solid concentrates desiccation disposition, and the supernatant of remaining nanofiltration concentrated water, which enters after activated carbon adsorption unit carries out activated carbon adsorption, to be returned It returns to before the nano-filtration unit and the hc effluent is mixed into nano-filtration unit circular treatment.
On the basis of said program, the salt being added in the nanofiltration concentrated water is sodium sulphate and/or sodium carbonate, salt Dosage be Ca2+:The molar ratio of salt is 1:1.
On the basis of said program, the activated carbon is Powdered Activated Carbon or granular activated carbon, and dosage is activated carbon: The mass ratio of COD is 2:1~10:1.
On the basis of said program, the water quality characteristic of hc effluent is:Wastewater pH 7~8, conductivity 10000~ 20000 μ s/cm, CODcr100~500mg/L, Na+2000~4000mg/L, Cl-2500~5000mg/L, with CaCO3Meter is total hard Spend 1500~3000mg/L, SS100~500mg/L, molten 50~100mg/L of silicon, NH450~500mg/L of-N.
On the basis of said program, the hc effluent is handled by the nano-filtration unit, and the water rate of recovery is higher than 85%.
On the basis of said program, the nanofiltration production water passes through the disc tube reverse osmosis (dt-ro) cell processing, the water rate of recovery Higher than 85%.
On the basis of said program, the reverse osmosis concentrated water passes through the evaporative crystallization cell processing, and the water rate of recovery is high In 80%.
On the basis of said program, system produces the μ S/cm of water conductivity≤300, production water CODcr<10mg/L, production water TOC< 3mg/L, the whole system water rate of recovery are higher than 90%.
The Zero emission method of hc effluent of the present invention has advantageous effect below:
1, the present invention is directed to hc effluent, and the multivalent ions such as hardness in being removed hc effluent using nanofiltration and part are had On the basis of machine object, by disc tube reverse osmosis (dt-ro) technology and evaporative crystallization technique depth concentration, recycle to greatest extent Water resource solves the advanced treating even zero-emission problem of hc effluent;
2, the present invention takes full advantage of the advantage of the multivalent ions and partial organic substances such as nanofiltration removal hardness, removes highly concentrated useless Hardness in water and partial organic substances are handled convenient for subsequent disc tube reverse osmosis (dt-ro);
3, the nanofiltration technique in the present invention effectively reduces the fouling membrane of disc tube reverse osmosis (dt-ro) process, and it is anti-to improve dish tubular type The rate of recovery of osmosis system;
4, the present invention in compared with conventional reverse osmosis using disc tube reverse osmosis (dt-ro) technique, disc tube reverse osmosis (dt-ro) by using Disc tube reverse osmosis (dt-ro) membrane module, effectively slows down fouling membrane, extends cleaning frequency and the service life of film, improves system and returns Yield;
5, method using the present invention 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 recycling water resource to greatest extent, realizes zero-emission substantially, has important Environmental Effect Benefit;
6, method of the invention has effectively integrated respective technical advantage, optimizes the work of hc effluent advanced treatment and reclamation Skill flow.For the method for the present invention for waste water directly carries out multiple-effect evaporation, operating cost is low, and effectively reduces fouling With the pollution of organic matter.
Hc effluent is after the method for the present invention is handled, the production μ S/cm of water conductivity≤300, production water CODcr<10mg/L, production Water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
Description of the drawings
The present invention has following attached drawing:
Fig. 1 is the process flow diagram of the Zero emission method of hc effluent of the present invention.
Specific implementation mode
Below in conjunction with attached drawing, invention is further described in detail.
A kind of Zero emission method of hc effluent of the present invention, including following steps:
(1) nanofiltration:Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, is detached by the nano-filtration unit dense After contracting, nanofiltration production water and nanofiltration concentrated water are obtained;
(2) disc tube reverse osmosis (dt-ro):The nanofiltration production water that step (1) obtains enters disc tube reverse osmosis (dt-ro) unit and carries out depth Concentration obtains reverse osmosis produced water and reverse osmosis concentrated water after disc tube reverse osmosis (dt-ro) unit separation concentration;
(3) evaporative crystallization:The reverse osmosis concentrated water that step (2) obtains enters evaporative crystallization unit and is evaporated at crystallization Reason, obtains the production water of salt crystalloid and evaporative crystallization.
On the basis of said program, the nanofiltration membrane component of nano-filtration unit described in step (1) uses rolled membrane module.
On the basis of said program, the membrane material of the rolled membrane module is polyamide or sulfonated polyether sulfone.
On the basis of said program, the operating condition of nano-filtration unit described in step (1) is:Feeding liquid side operating pressure For 0.5~1MPa.
On the basis of said program, the disc tube reverse osmosis (dt-ro) film of the use of disc tube reverse osmosis (dt-ro) unit described in step (2) Component is high pressure or super-pressure disc tube reverse osmosis (dt-ro) membrane module.
On the basis of said program, the operating pressure of the disc tube reverse osmosis (dt-ro) unit is 12~16MPa.
On the basis of said program, the disc tube reverse osmosis (dt-ro) film of the use of disc tube reverse osmosis (dt-ro) unit described in step (2) The form of component is that multiple disc-type diaphragms are connected on composition disc-type film column on a central tube.
On the basis of said program, evaporative crystallization unit described in step (3) uses crystallizing evaporator, and heat source is using useless Steam heats.
On the basis of said program, salt is added in the nanofiltration concentrated water that step (1) obtains by calcium ions precipitate Get off, solid concentrates desiccation disposition, the supernatant of remaining nanofiltration concentrated water to enter activated carbon adsorption unit and carry out activated carbon suction Attached return to before the nano-filtration unit is mixed into the nano-filtration unit circular treatment with the hc effluent.
On the basis of said program, the salt being added in the nanofiltration concentrated water is sodium sulphate and/or sodium carbonate, salt Dosage be Ca2+:The molar ratio of salt is 1:1.
On the basis of said program, the activated carbon is Powdered Activated Carbon or granular activated carbon, and dosage is activated carbon: The mass ratio of COD is 2:1~10:1.
On the basis of said program, the water quality characteristic of hc effluent is:Wastewater pH 7~8, conductivity 10000~ 20000 μ s/cm, CODcr100~500mg/L, Na+2000~4000mg/L, Cl-2500~5000mg/L, with CaCO3Meter is total hard Spend 1500~3000mg/L, SS100~500mg/L, molten 50~100mg/L of silicon, NH450~500mg/L of-N.
In the above process, the evaporative crystallization production water generated in the reverse osmosis produced water and step (3) that are generated in step (2) is equal Production technology can be back to.Activated carbon after adsorption saturation regenerate or directly carries out burning processing as fuel.
Heretofore described hc effluent is handled by the nano-filtration unit, and the water rate of recovery is higher than 85%.
Heretofore described nanofiltration production water passes through the disc tube reverse osmosis (dt-ro) cell processing, and the water rate of recovery is higher than 85%.
Heretofore described reverse osmosis concentrated water passes through the evaporative crystallization cell processing, and the water rate of recovery is higher than 80%.
For the hc effluent after the method for the present invention is handled, system produces the μ S/cm of water conductivity≤300, production water CODcr< 10mg/L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
The essential distinction of the present invention and the prior art is, for asking in the prior art the processing that is difficult to of hc effluent Topic handles hc effluent using " nanofiltration+disc tube reverse osmosis (dt-ro)+evaporative crystallization ".First, using the hardness in the waste water of nanofiltration place to go It waits multivalent ions and partial organic substances, the nanofiltration concentrated water generated in the processing procedure to add salt to carry out precipitation process, obtain calcium slag, sinks Supernatant behind shallow lake carries out activated carbon adsorption, and the production water and nanofiltration water inlet after activated carbon adsorption are mixed at nano-filtration unit cycle Reason.Disc tube reverse osmosis (dt-ro) technology is used to carry out at depth concentration the hc effluent after removal hardness and partial organic substances later Reason, the reverse osmosis concentrated water after the concentration of disc tube reverse osmosis (dt-ro) depth are evaporated crystallization treatment, the salt in concentrated water are consolidated again Body crystallizes out, and concentrates desiccation disposition.Reverse osmosis produced water and evaporative crystallization the production water generated in the processing procedure can reuse In production technology.By above-mentioned technological process, the present invention recycles to the maximum extent while solving this burst of discharge of wastewater problem Water resource, realizes the zero-emission of hc effluent substantially.Compared to the prior art, the application is special for the water quality of itself waste water Point takes full advantage of respective technical advantage, it is proposed that more rational technological process.Technique of zero discharge flow in the application Step is simple, and treatment effect is stablized.
Embodiment 1
Process flow diagram is shown in Fig. 1.The water quality characteristic of the hc effluent of the present embodiment is:Wastewater pH 7, conductivity 10000 μ s/cm, CODcr100mg/L, Na+2000mg/L, Cl-2500mg/L, total hardness (CaCO3) 1500mg/L, SS 100mg/L, molten silicon 50mg/L, NH4-N 50mg/L。
The step of Zero emission method processing hc effluent of hc effluent through the invention, is as follows:
(1) nanofiltration:Hc effluent enters nano-filtration unit and carries out nanofiltration processing, removes the multivalence such as the hardness in hc effluent Ion and partial organic substances.Nanofiltration production water and nanofiltration concentrated water are obtained after nano-filtration unit separation concentration, nanofiltration production water enters step Suddenly (2) are handled, and sodium carbonate are added in nanofiltration concentrated water by under calcium ions precipitate, solid concentrates desiccation disposition, sodium carbonate Dosage be Ca2+:The molar ratio of sodium carbonate is 1:1, the supernatant of remaining nanofiltration concentrated water is lived using Powdered Activated Carbon Property charcoal absorption, the dosage of Powdered Activated Carbon is Powdered Activated Carbon:The mass ratio of COD is 2:1.Nanofiltration after activated carbon adsorption The hc effluent that the supernatant of concentrated water returns to before nano-filtration unit and as nanofiltration water inlet is mixed into nano-filtration unit circular treatment;
(2) disc tube reverse osmosis (dt-ro):It is further dense that the nanofiltration production water obtained in step (1) enters disc tube reverse osmosis (dt-ro) unit Contracting.After the separation concentration of disc tube reverse osmosis (dt-ro) unit, reverse osmosis produced water and reverse osmosis concentrated water are obtained;
(3) evaporative crystallization:Reverse osmosis concentrated water in step (2) enters evaporative crystallization unit and is evaporated crystallization treatment, steams Pyrotoxin is heated using exhaust steam, after evaporative crystallization, obtains the production water of salt crystalloid and evaporative crystallization.
In above-mentioned steps, the nanofiltration membrane component of the nano-filtration unit of step (1) uses polyamide rolled membrane module;
In above-mentioned steps, the operating condition of the nano-filtration unit of step (1) is:Feeding liquid side operating pressure 0.5MPa;
Under the service condition of above-mentioned nano-filtration unit, nanofiltration goes out the water hardness substantially in 70mg/L or so;
In above-mentioned steps, the supernatant in step (1) after sodium carbonate precipitation is added goes out the water hardness and is less than 15mg/L;
In above-mentioned steps, the water outlet COD in step (1) after powder electroless platingcrIt is less than less than 10mg/L, TOC 3mg/L;
In above-mentioned steps, disc tube reverse osmosis (dt-ro) membrane module used in disc tube reverse osmosis (dt-ro) unit uses the high pressure dish of PALL companies The operating pressure of tubular type reverse osmosis membrane column, disc tube reverse osmosis (dt-ro) unit is 12MPa;
Under the operating condition of above-mentioned nano-filtration unit, nanofiltration membrane flux is maintained at 13~16L/m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned disc tube reverse osmosis (dt-ro) unit, disc tube reverse osmosis (dt-ro) membrane flux is maintained at 17~22L/ m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned evaporative crystallization unit, the evaporative crystallization unit water rate of recovery is higher than 80%;
In above-mentioned steps, the evaporative crystallization production water generated in the reverse osmosis produced water and step (3) that are generated in step (2) is equal Production technology can be back to.Powdered Activated Carbon in step (1) after adsorption saturation directly carries out burning processing as fuel.
In above-mentioned steps, evaporative crystallization processing of the reverse osmosis concentrated water Jing Guo step (3) obtains salt crystalloid, concentrates desiccation Disposition.
For hc effluent after the method for the present invention is handled, system produces the μ S/cm of water conductivity≤300, production water CODcr<10mg/ L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
Embodiment 2
Process flow diagram is shown in Fig. 1.The water quality characteristic of the hc effluent of the present embodiment is:Wastewater pH 7.5, conductivity 15000 μ s/cm, CODcr300mg/L, Na+3000mg/L, Cl-3500mg/L, total hardness (CaCO3) 2200mg/L, SS 300mg/L, molten silicon 80mg/L, NH4-N 200mg/L。
The operating procedure of embodiment 2 is same as Example 1.Wherein, as different from Example 1:It is added in nanofiltration concentrated water Be sodium sulphate for calcium ions precipitate to get off, the dosage of sodium sulphate is Ca2+:The molar ratio of sodium sulphate is 1:1;It is remaining The supernatant of nanofiltration concentrated water carries out activated carbon adsorption using granular activated carbon, and the dosage of granular activated carbon is granular activated carbon: The mass ratio of COD is 10:1;
In above-mentioned steps, the nanofiltration membrane component of the nano-filtration unit of step (1) uses sulfonated polyether sulfone rolled membrane module;
In above-mentioned steps, the operating condition of the nano-filtration unit of step (1) is:Feeding liquid side operating pressure 0.7MPa;
In above-mentioned steps, the supernatant in step (1) after sodium sulphate precipitation is added goes out the water hardness and is less than 20mg/L;
In above-mentioned steps, the water outlet COD in step (1) after granular activated carbon adsorbscrIt is less than less than 10mg/L, TOC 3mg/L;
Under the service condition of above-mentioned nano-filtration unit, nanofiltration goes out the water hardness substantially in 80mg/L or so;
In above-mentioned steps, disc tube reverse osmosis (dt-ro) membrane module used uses the high pressure disc tube reverse osmosis (dt-ro) film column of PALL companies, The operating pressure of disc tube reverse osmosis (dt-ro) unit is 12MPa;
Under the operating condition of above-mentioned nano-filtration unit, nanofiltration membrane flux is maintained at 15~18L/m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned disc tube reverse osmosis (dt-ro) unit, disc tube reverse osmosis (dt-ro) membrane flux is maintained at 16~21L/ m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned evaporative crystallization unit, the evaporative crystallization unit water rate of recovery is higher than 80%;
In above-mentioned steps, the evaporative crystallization production water generated in the reverse osmosis produced water and step (3) that are generated in step (2) is equal Production technology can be back to.Granular activated carbon in step (1) after adsorption saturation carries out regeneration treatment.
In above-mentioned steps, evaporative crystallization processing of the reverse osmosis concentrated water Jing Guo step (3) obtains salt crystalloid, concentrates desiccation Disposition.
For hc effluent after the method for the present invention is handled, system produces the μ S/cm of water conductivity≤300, production water CODcr<10mg/ L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
Embodiment 3
Process flow diagram is shown in Fig. 1.The water quality characteristic of the hc effluent of the present embodiment is:Wastewater pH 8, conductivity 20000 μ s/cm, CODcr500mg/L, Na+4000mg/L, Cl-5000mg/L, total hardness (CaCO3) 3000mg/L, SS 500mg/L, molten silicon 100mg/L, NH4-N 500mg/L。
The operating procedure of embodiment 3 is same as Example 1.Wherein, as different from Example 1:It is added in nanofiltration concentrated water Be sodium carbonate and sodium sulphate mixture for calcium ions precipitate to be got off, the mixture dosage of sodium carbonate and sodium sulphate is Ca2+:The molar ratio of (sodium carbonate+sodium sulphate) is 1:1;The supernatant of nanofiltration concentrated water carries out activated carbon suction using Powdered Activated Carbon Attached, the dosage of Powdered Activated Carbon is Powdered Activated Carbon:The mass ratio of COD is 8:1;
In above-mentioned steps, the nanofiltration membrane component of the nano-filtration unit of step (1) uses polyamide rolled membrane module;
In above-mentioned steps, the operating condition of the nano-filtration unit of step (1) is:Feeding liquid side operating pressure 0.8MPa;
In above-mentioned steps, the supernatant in step (1) after sodium carbonate and sodium sulphate precipitation is added goes out the water hardness and is less than 15mg/L;
In above-mentioned steps, the water outlet COD in step (1) after powder electroless platingcrIt is less than less than 10mg/L, TOC 3mg/L;
Under the service condition of above-mentioned nano-filtration unit, nanofiltration goes out the water hardness substantially in 90mg/L or so;
In above-mentioned steps, disc tube reverse osmosis (dt-ro) membrane module used uses the super-pressure disc tube reverse osmosis (dt-ro) film of PALL companies The operating pressure of column, disc tube reverse osmosis (dt-ro) unit is 16MPa;
Under the operating condition of above-mentioned nano-filtration unit, nanofiltration membrane flux is maintained at 14~18L/m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned disc tube reverse osmosis (dt-ro) unit, disc tube reverse osmosis (dt-ro) membrane flux is maintained at 15~19L/ m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned evaporative crystallization unit, the evaporative crystallization unit water rate of recovery is higher than 80%;
In above-mentioned steps, the evaporative crystallization production water generated in the reverse osmosis produced water and step (3) that are generated in step (2) is equal Production technology can be back to.Powdered Activated Carbon in step (1) after adsorption saturation directly carries out burning processing as fuel.
In above-mentioned steps, evaporative crystallization processing of the reverse osmosis concentrated water Jing Guo step (3) obtains salt crystalloid, concentrates desiccation Disposition.
For hc effluent after the method for the present invention is handled, system produces the μ S/cm of water conductivity≤300, production water CODcr<10mg/ L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
Embodiment 4
Process flow diagram is shown in Fig. 1.The water quality characteristic of the hc effluent of the present embodiment is:Wastewater pH 8, conductivity 20000 μ s/cm, CODcr500mg/L, Na+4000mg/L, Cl-5000mg/L, total hardness (CaCO3) 3000mg/L, SS 500mg/L, molten silicon 100mg/L, NH4-N 500mg/L。
The operating procedure of embodiment 4 is same as Example 1.Wherein, as different from Example 1, it is added in nanofiltration concentrated water Be sodium carbonate for calcium ions precipitate to get off, the dosage of sodium carbonate is Ca2+:The molar ratio of sodium carbonate is 1:1;It is remaining The supernatant of nanofiltration concentrated water carries out activated carbon adsorption using Powdered Activated Carbon, and the dosage of Powdered Activated Carbon is Powdered Activated Carbon: The mass ratio of COD is 8:1.
In above-mentioned steps, the nanofiltration membrane component of step (1) uses polyamide rolled membrane module;
In above-mentioned steps, the operating condition of the nano-filtration unit of step (1) is:Feeding liquid side operating pressure 1.0MPa;
In above-mentioned steps, the supernatant in step (1) after sodium carbonate precipitation is added goes out the water hardness and is less than 15mg/L;
In above-mentioned steps, the water outlet COD in step (1) after powder electroless platingcrIt is less than less than 10mg/L, TOC 3mg/L;
Under the service condition of above-mentioned nano-filtration unit, nanofiltration goes out the water hardness substantially in 100mg/L or so;
In above-mentioned steps, disc tube reverse osmosis (dt-ro) membrane module used uses the super-pressure disc tube reverse osmosis (dt-ro) film of PALL companies The operating pressure of column, disc tube reverse osmosis (dt-ro) unit is 16MPa;
Under the operating condition of above-mentioned nano-filtration unit, nanofiltration membrane flux is maintained at 15~18L/m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned disc tube reverse osmosis (dt-ro) unit, disc tube reverse osmosis (dt-ro) membrane flux is maintained at 15~19L/ m2H, the water rate of recovery are higher than 85%;
Under the operating condition of above-mentioned evaporative crystallization unit, the evaporative crystallization unit water rate of recovery is higher than 80%;
In above-mentioned steps, the evaporative crystallization production water generated in the reverse osmosis produced water and step (3) that are generated in step (2) is equal Production technology can be back to.Powdered Activated Carbon in step (1) after adsorption saturation directly carries out burning processing as fuel.
In above-mentioned steps, evaporative crystallization processing of the reverse osmosis concentrated water Jing Guo step (3) obtains salt crystalloid, concentrates desiccation Disposition.
For hc effluent after the method for the present invention is handled, system produces the μ S/cm of water conductivity≤300, production water CODcr<10mg/ L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
The present invention in the specific implementation, disc tube reverse osmosis (dt-ro) unit described in step (2) use disc tube reverse osmosis (dt-ro) film The form of component is that multiple disc-type diaphragms are connected on composition disc-type film column on a central tube.
In the specific implementation, evaporative crystallization unit described in step (3) optionally uses existing commercially available steaming to the present invention Crystallizer is sent out, heat source optionally uses exhaust steam to heat.
The foregoing is merely the preferable possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore all It is to be both contained in protection scope of the present invention with equivalence changes made by description of the invention and accompanying drawing content.
The content not being described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.

Claims (13)

1. a kind of Zero emission method of hc effluent, which is characterized in that including following steps:
(1) nanofiltration:Hc effluent enters nano-filtration unit and carries out nanofiltration filtration treatment, detaches and concentrates by the nano-filtration unit Afterwards, nanofiltration production water and nanofiltration concentrated water are obtained;
(2) disc tube reverse osmosis (dt-ro):It is dense that the nanofiltration production water that step (1) obtains enters disc tube reverse osmosis (dt-ro) unit progress depth Contracting obtains reverse osmosis produced water and reverse osmosis concentrated water after disc tube reverse osmosis (dt-ro) unit separation concentration;
(3) evaporative crystallization:The reverse osmosis concentrated water that step (2) obtains enters evaporative crystallization unit and is evaporated crystallization treatment, Obtain the production water of salt crystalloid and evaporative crystallization;
Salt is added in the nanofiltration concentrated water that step (1) obtains calcium ions precipitate gets off, solid concentrates desiccation disposition, remains The supernatant of remaining nanofiltration concentrated water enters activated carbon adsorption unit and carries out after activated carbon adsorption back to before the nano-filtration unit It is mixed into the nano-filtration unit circular treatment with the hc effluent;
The activated carbon is Powdered Activated Carbon or granular activated carbon, and dosage is activated carbon:The mass ratio of COD is 2:1~10:1;
The water quality characteristic of hc effluent is:Wastewater pH 7~8, conductivity 10000~20000 μ s/cm, CODcr100~500mg/ L, Na+2000~4000mg/L, Cl-2500~5000mg/L, with CaCO3Meter total hardness 1500~3000mg/L, SS 100~ 500mg/L, molten 50~100mg/L of silicon, NH450~500mg/L of-N.
2. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:Nano-filtration unit described in step (1) Nanofiltration membrane component use rolled membrane module.
3. the Zero emission method of hc effluent as claimed in claim 2, it is characterised in that:The membrane material of the rolled membrane module For polyamide or sulfonated polyether sulfone.
4. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:Nano-filtration unit described in step (1) Operating condition be:Feeding liquid side operating pressure is 0.5~1MPa.
5. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:Dish tubular type is anti-described in step (2) The disc tube reverse osmosis (dt-ro) membrane module that permeation unit uses is high pressure or super-pressure disc tube reverse osmosis (dt-ro) membrane module.
6. the Zero emission method of hc effluent as claimed in claim 5, it is characterised in that:The disc tube reverse osmosis (dt-ro) unit Operating pressure is 12~16MPa.
7. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:Dish tubular type is anti-described in step (2) The form for the disc tube reverse osmosis (dt-ro) membrane module that permeation unit uses is connected on a central tube for multiple disc-type diaphragms and constitutes Disc-type film column.
8. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:Evaporative crystallization described in step (3) Unit uses crystallizing evaporator, heat source to be heated using exhaust steam.
9. the Zero emission method of hc effluent as described in claim 1, it is characterised in that:It is added in the nanofiltration concentrated water Salt is sodium sulphate and/or sodium carbonate, and the dosage of salt is Ca2+:The molar ratio of salt is 1:1.
10. such as the Zero emission method of hc effluent described in any item of the claim 1 to 8, it is characterised in that:It is described highly concentrated useless Water is handled by the nano-filtration unit, and the water rate of recovery is higher than 85%.
11. such as the Zero emission method of hc effluent described in any item of the claim 1 to 8, it is characterised in that:The nanofiltration production Water passes through the disc tube reverse osmosis (dt-ro) cell processing, and the water rate of recovery is higher than 85%.
12. such as the Zero emission method of hc effluent described in any item of the claim 1 to 8, it is characterised in that:It is described reverse osmosis Concentrated water passes through the evaporative crystallization cell processing, and the water rate of recovery is higher than 80%.
13. such as the Zero emission method of hc effluent described in any item of the claim 1 to 8, it is characterised in that:System produces water power The μ S/cm of conductance≤300, production water CODcr<10mg/L, production water TOC<3mg/L, the whole system water rate of recovery are higher than 90%.
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