CN110407361A - A kind of zero-emission of silica gel waste water and recycling treatment process and silica gel waste water treatment system - Google Patents
A kind of zero-emission of silica gel waste water and recycling treatment process and silica gel waste water treatment system Download PDFInfo
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- CN110407361A CN110407361A CN201910739629.0A CN201910739629A CN110407361A CN 110407361 A CN110407361 A CN 110407361A CN 201910739629 A CN201910739629 A CN 201910739629A CN 110407361 A CN110407361 A CN 110407361A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000000741 silica gel Substances 0.000 title claims abstract description 58
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- 238000004064 recycling Methods 0.000 title claims abstract description 33
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000012528 membrane Substances 0.000 claims abstract description 185
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 80
- 238000001728 nano-filtration Methods 0.000 claims abstract description 67
- 238000004062 sedimentation Methods 0.000 claims abstract description 49
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 45
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 claims abstract description 40
- 238000001816 cooling Methods 0.000 claims abstract description 39
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 18
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000005189 flocculation Methods 0.000 claims abstract description 7
- 230000016615 flocculation Effects 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 35
- 238000001223 reverse osmosis Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 17
- 239000012141 concentrate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- -1 sulfate radical Chemical class 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- POJAQDYLPYBBPG-UHFFFAOYSA-N 2-(2,4,7-trinitrofluoren-9-ylidene)propanedinitrile Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=C(C#N)C#N)C2=C1 POJAQDYLPYBBPG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011549 crystallization solution Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of zero-emissions of silica gel waste water and recycling treatment process and silica gel waste water treatment system, the following steps are included: impurity is concentrated, produce water recycling, flocculation sedimentation, circulating filtration, sodium sulphate concentration, crystallisation by cooling and recycling solid sodium sulfate, production water can be eliminated to 99% or more sulfate radical using the filtering of level-one dish tubular nanofiltration membrane group, calcium ions and magnesium ions and part of silica are had also been removed simultaneously, production water is set to meet silica gel acid cleaning process water requirement, the concentrated water of level-one dish tubular nanofiltration membrane group enters reaction settling basin, silica crystalline in concentrated water is precipitated by the way that flocculant is added, concentrated water is concentrated after entering back into second level dish tubular nanofiltration membrane group, and pass through heating, further concentration makes sodium sulphate crystallize precipitation in crystallizing pond for cooling, remove sodium sulphate in processing system.The present invention solves the problems, such as that existing silica gel waste water treatment process low efficiency, at high cost and effect are poor, realizes silica gel wastewater zero discharge and resource recycling.
Description
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of zero-emission and recycling treatment work of silica gel waste water
Skill and silica gel waste water treatment system.
Background technique
Chinese 240,000 tons of (2018 annual data) silica gel of production every year, are wanted by the consumption of current silica gel industry resource and blowdown condition
It asks, 15 tons of product water consumption per ton, while generating 12 tons of waste water, to generate nearly 3,000,000 tons of waste water every year.
The primary raw material for producing silica gel is sodium metasilicate (being commonly called as waterglass, sodium silicate), it is to be processed by silica chemistry and obtained.
I.e. quartzy miberal powder and soda ash roast the fusant of generation at a high temperature of 1100~1350 DEG C, are obtained with water extraction colorless and transparent
Thick liquid.The production method of silica gel is mainly sulfuric acid process, i.e., obtains sodium metasilicate and sulfuric acid reaction.
Silica gel production main technique includes: glue, aging, acid is soaked the processes such as washes, dries.
Silica gel waste water is mainly derived from that silica gel acid is soaked to wash link, and waste water acidity is high, and pH value is in 2-3 or so, wherein containing
A large amount of sulfate and silicate, sodium sulphate content can reach 4%, in addition also contain a small amount of chloride ion, calcium ion and magnesium
Ion.Silica gel waste water has acidity high, and salt content is high, siliceous height, intractable feature.
Existing silica gel pickling waste waters treatment process is usually first to adjust pH with quick lime, and flocculant is then added, such as polymerize
Aluminium chloride, poly-ferric chloride, polyacrylamide etc. make silicon-containing wastewater flocculation sedimentation, then carry out filters pressing, will be separated by solid-liquid separation.This
Kind treatment process can generate a large amount of solid waste, and a large amount of calcium, magnesium addition are introduced in waste water, increase for subsequent processing
The problems such as more burden, there are low efficiencys, at high cost, poor processing effect.
Also there is silica gel waste water treatment process using the reaction of pH+ multi stage precipitation is adjusted, be then concentrated with membrane technology, then use MVR
Evaporative crystallization.This technology, and a large amount of medicaments of addition, generate a large amount of solid waste, and the investment of evaporative crystallization method is huge,
Operating cost is high, it is difficult to promotion and implementation.
Existing processing mode is summarized, only silica gel waste water as Normal wastewater processing, does not combine water quality special very well
Point.Secondly, also being required, being existed with water without conscientious binding silica gel production technology when pressing reuse standard design treatment technique
The phenomenon that degree processing.In addition, having ignored the recycling value of sodium sulphate in terms of utilization of resources angle.
Water standard after handling in fact, washes adhesive process if being back to, and the index that cannot follow conventional lines is measured.Washing glue is silica gel
Indispensable technical process in production is in order to which granulated gel is formed by Na2SO4It washes off, by each zwitterion (predominantly H+, Na+, SO4 2-With SiO3 2-Deng) control into technique claimed range.Therefore, reach recycle-water (washing adhesive process) to producing water water quality
It is required that being then mainly considered as removal sodium sulphate, and reach recycling.
The characteristics of being changed according to sodium sulphate solubility with temperature, the method crystallized with saturated solution temperature is reduced, than steaming
Hair crystallization processes are more feasible, and equipment investment is few, and operating cost is low.Sodium sulphate is water-soluble, but its solubility with temperature variation and
It is different: at 0~10 DEG C, solubility 5~9%, at 30~40 DEG C, solubility 41~49%.Therefore, can try 30
DEG C or more when, sodium sulphate in solution is concentrated to high concentration, such as 30% or more, then reduce the temperature to 10 DEG C hereinafter, making sulfuric acid
Sodium saturated crystallization, is separated.
It is both economical effective method using the concentration of nanofiltration (NF) membrane technology.Nanofiltration (NF) technology is referred to as " loose anti-
Permeable membrane " is apparently higher than monovalention to the rejection of divalent and high valence ion, to sulfate radical removal efficiency reach 99% with
On, operating pressure is low, and water flux is big.The transmembrane pressure that usual nanofiltration (NF) separation needs is generally 0.5-2.0MPa, than with anti-
Infiltration reaches the low 0.5-3.0MPa of pressure difference that same permeation flux must apply.
Highly concentrated sodium sulfate wastewater is concentrated, needs using multistage nanofiltration (NF) film concentration technology.Sodium sulphate contains in waste water raw water
Amount reaches as high as 4%, and at 30 DEG C or more, sodium sulphate solubility is up to 30 grams or more, the saturated crystallization concentration at 10 DEG C or less
9 grams or less, it is therefore desirable to which high concentration multiple could improve concentrate sodium sulfate concentration, meet high crystalline rate.It is high to reach
Cycles of concentration needs multistage concentration technology.Wherein in first order nanofiltration concentration, although having part calcium ions and magnesium ions and dioxy in water
SiClx, but pH is very low, and about 2-3, fouling tendency is not serious, in conjunction with addition antisludging agent, it may not be necessary to dosing tune pH precipitation process.
Using the nanofiltration of dish tubular type (dish tubular membrane component) technology, the stifled harm of fouling dirt to film is advantageously reduced.Dish tubular type
Nanofiltration membrane, with its special runner design, special water conservancy diversion dish structure, the water flow of high speed scrubs film surface, is resistant to certain
The aggregation of colloidal solid object, therefore improve anti-pollution and block up ability.Even if water inlet SDI (pollution index) reaches 15, can also operate normally.
And common wound membrane element, SDI < 5 are generally required, thus common Spiral-wound membrane technology cannot be used.
After level-one dish tubular type nanofiltration processing, concentrated water is reduced more than half, and ion concentration is concentrated one times or more, in water
Hardness components and silica be all concentrated, then carry out concentration, drop hardness must be just carried out, except silicon is handled, to prevent
The stifled nanofiltration diaphragm of dirt, is then just suitable for carrying out film concentration.
Summary of the invention
The present invention is directed to existing silica gel waste water treatment process low efficiency, problem at high cost and poor effect, provides a kind of silicon
The zero-emission of glue waste water and recycling treatment process and silica gel waste water treatment system can will produce water and be used for silica gel acid cleaning process, and
Sodium sulphate is recycled by crystallisation by cooling, reduces cost, energy conservation and environmental protection.
The present invention is achieved through the following technical solutions:
Zero-emission and the recycling treatment process of a kind of silica gel waste water are provided, comprising the following steps:
The first step, impurity concentration, produce water recycling: waste water is preprocessed filter out suspended matter after, be passed through level-one dish tubular membrane
Component simultaneously sulfate radical, calcium ions and magnesium ions and part of silica is concentrated in concentrated water side by level-one dish tubular membrane component, level-one dish
Tubular membrane component permeate side produces water recycling and is used for silica gel acid cleaning process water；
Flocculation sedimentation, circulating filtration: second step the concentrated water of level-one dish tubular membrane component is passed through in sedimentation basin, is first adjusted
Flocculant is added to neutrality in pH afterwards, so that calcium ions and magnesium ions and silica in water is formed precipitating, is separated by solid-liquid separation in sedimentation basin,
Sedimentation basin liquid solution is passed through tubular membrane group, forms circulating filtration in the concentrate recirculation to sedimentation basin of tubular membrane group；
Third step, sodium sulphate concentration, crystallisation by cooling: the production water of tubular membrane group is passed through second level dish tubular membrane component to sodium sulphate
It is concentrated, carrying out cooling down to the concentrated water of second level dish tubular membrane component is precipitated sulfate crystal therein, after crystallization
Solution be back to second level dish tubular membrane component water inlet in and in reflux course to the solution heat temperature raising after crystallization, make its for
Sodium sulphate is in undersaturated condition, after being further concentrated using second level dish tubular membrane component, to concentrated water crystallisation by cooling, realizes concentrated water
Multistage concentration, crystallisation by cooling；
4th step recycles solid sodium sulfate.
Further, the level-one dish tubular membrane component is dish tubular nanofiltration membrane group；The second level dish tubular membrane group
Part is dish tubular nanofiltration membrane group or disc tube reverse osmosis (dt-ro) film group.
Further, in second step, when calcium ions and magnesium ions concentration is lower than 1mmol/L in solution in sedimentation basin, silica is dense
When degree is lower than 20mg/L, the production water of tubular membrane group is passed through the processing of second level dish tubular membrane component.
Further, in the third step, the concentrated water cooling down of second level dish tubular membrane component is to 10 DEG C or less；After crystallization
Solution is back to during second level dish tubular membrane component, and temperature is heated to 30~35 DEG C.
Sodium sulphate is water-soluble, but its solubility with temperature variation and it is different: at 0~10 DEG C, solubility 5~9%,
At 30~40 DEG C, solubility 41~49%.Therefore, can try that sodium sulphate in solution is concentrated to height at 30 DEG C or more
Concentration, such as 30% or more, then reduce the temperature to 10 DEG C hereinafter, make sodium sulphate saturated crystallization, separate.
Further, in the third step, the production water recycling of the second level dish tubular membrane component is used for silica gel pickling work
Skill water.
Further, the tubular membrane group is tubular ultra-filtration membrane group or tube microfiltration membrane group.
Further, in second step, the flocculant is calcium chloride, magnesium chloride, aluminium polychloride, one in PAM
Kind or several combinations.
A kind of silica gel waste water treatment system using the treatment process, including wastewater equalization pond, further include level-one dish
Tubular membrane component, second level dish tubular membrane component, sedimentation basin and tubular membrane group；
The water inlet end of level-one dish tubular membrane component is connect with wastewater equalization pond, and the concentrated water end of level-one dish tubular membrane component passes through
Sedimentation basin is connect with the water inlet end of tubular membrane group, and the concentrated water end of tubular ultra-filtration membrane group is connect by the first return pipe with sedimentation basin；
The water inlet end of second level dish tubular membrane component is connect by intermediate water tank with the production water end (W.E.) of tubular membrane group, second level dish tubular type
The concentrated water end of membrane module is connected with crystallizing pond, is equipped with the cooling device that can cool down to concentrated water in crystallizing pond, and crystallizing pond also pass through the
Two return pipes are connect with the water inlet end of second level dish tubular membrane component, and the heating that phegma heats up can be filled by being equipped in the second return pipe
It sets.
Production water can be eliminated 99% or more sulfate radical using the filtering of level-one dish tubular membrane component by this programme, while
Calcium ions and magnesium ions and part of silica are eliminated, production water is made to meet silica gel acid cleaning process water requirement, level-one dish tubular membrane component
Concentrated water enter reaction settling basin, silica crystalline in concentrated water precipitate by the way that chemicals is added, in entrance second level dish pipe
Concentrated water is concentrated after formula membrane module, and being further concentrated by heating, cooling is precipitated sodium sulphate in crystallizing pond crystallization, at removal
Sodium sulphate and solid sodium sulfate is recycled in reason system.
Further, the level-one dish tubular membrane component is dish tubular nanofiltration membrane group；The second level dish tubular membrane group
Part is dish tubular nanofiltration membrane group or disc tube reverse osmosis (dt-ro) film group.
Further, the production water end (W.E.) for producing water end (W.E.) and second level dish tubular membrane component of the level-one dish tubular membrane component with
Produce the connection of water reuse tank.
The production water of firsts and seconds dish tubular nanofiltration membrane group can be recycled for silica gel acid cleaning process, realize following for resource
Ring utilizes, and reduces waste.
Beneficial effects of the present invention:
One, in front end, pretreatment is not required to adjust pH, be may be adapted to run between 2-11 in pH value based on DT nanofiltration, and
When running between pH value 2-4, nanofiltration membrane fouling tendency can be reduced, is conducive to the operation steady in a long-term of membranous system.
Two, in the pretreatment of front end, without dosing tune pH and precipitation process, production water pH is low, is more suitable for being back to silica gel
Acid cleaning process water only adds adjusting PH with base in level-one DTNF concentrated water flocculation sedimentation processing stage, this stage water is reduced than raw water
More than half, and pH is higher than raw water, produces the acid medium retained in water, exactly required for reuse technology, reduces recycle-water
Acid adding amount, adjusting pH more direct than raw water in this way adds base amount to reduce by 50% or more, while reducing the yield 50% of solid waste
More than, precipitation reaction effect is more preferable, also saves medicament, saves equipment investment and space occupied.
Three, precipitation reaction pond and tubular type ultrafiltration composition circulation solid-liquid separation system, ultra-filtration water water quality is good, so that second level dish
Tubular membrane component can have very high concentration ratio, improve the efficiency of subsequent sulphuric acid sodium Crystallization Separation.It is clear without building large-scale precipitating
Clear pond, occupied area are small；System integration degree is high, and operability is good, is convenient for automation control.
Four, it is concentrated using crystallisation by cooling, again, the multistage recovery process of crystallisation by cooling again, recycling sodium sulphate adds as resource
To utilize, compared to the recovery process of evaporative crystallization, a large amount of steam are not necessarily to, are not necessarily to high power load, cost of investment and operating cost
80% or more is all reduced, energy-saving benefit is obvious.
Five, using the nanofiltration of dish tubular type (dish tubular membrane component) technology, special runner design, special water conservancy diversion dish structure,
The water flow of high speed scrubs film surface, is resistant to certain colloidal solid object aggregation, therefore improve anti-pollution and block up ability, can be resistant to
Raw water SDI > 15, therefore in low pH, it can prevent silicon dioxide colloid dirt in raw water from blocking up nanofiltration membrane.New process is with emphasis on without useless
Water discharge, all production water reuses greatly save technique rate of water make-up.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of silica gel waste water treatment system in embodiment 1 in the present invention；
Fig. 2 is the structural schematic diagram of silica gel waste water treatment system in embodiment 2 in the present invention.
It is as shown in the figure:
1, wastewater equalization pond, 2, pre-processing device, 3, level-one dish tubular nanofiltration membrane group, 4, sedimentation basin, 5, tubular ultra-filtration membrane
Group, 6, second level dish tubular nanofiltration membrane group, 7, crystallizing pond, 8, production water reuse tank, 9, device for dehydrating sladge waste, the 10, first return pipe,
11, intermediate water tank, the 12, second return pipe, 13, second level disc tube reverse osmosis (dt-ro) film group.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Embodiment 1:
A kind of zero-emission of silica gel waste water and recycling treatment process, comprising the following steps:
The first step, impurity concentration, produce water recycling: waste water is preprocessed filter out suspended matter after, be passed through level-one dish tubular type and receive
Simultaneously sulfate radical, calcium ions and magnesium ions and part of silica are concentrated in concentrated water by level-one dish tubular nanofiltration membrane group 3 for filter membrane group 3,
The production water recycling of level-one dish tubular membrane group 3 is used for silica gel acid cleaning process water.
Waste water carries out homogeneous adjusting and pretreatment before being passed through level-one dish tubular nanofiltration membrane group 3, to the waste water of different periods,
For removing the suspended particulate in waste water.
Second step, flocculation sedimentation, circulating filtration: the concentrated water of level-one dish tubular nanofiltration membrane group 3 is passed through in sedimentation basin 4, first
PH is adjusted to neutrality, flocculant is added afterwards, so that calcium ions and magnesium ions and silica in water is formed precipitating, by solid-liquid in sedimentation basin point
From sedimentation basin solution is passed through tubular membrane group, forms circulating filtration in the concentrate recirculation to sedimentation basin 4 of tubular membrane group.In this implementation
In example, tubular membrane group is tubular ultra-filtration membrane group 5.
The concentrated water of level-one dish tubular nanofiltration membrane group 3 is passed through sedimentation basin 4, and alkaline matter is first added in sedimentation basin 4 and adjusts pH,
Wherein alkali used, which can be caustic soda, soda ash, quick lime, magnesia etc., can be improved the medicament of pH, and flocculant is added afterwards, used
Flocculant include calcium chloride, magnesium chloride, aluminium polychloride, PAM etc., calcium and magnesium hardness and silicon dioxide colloid can be made to convert
It is precipitated at sediment.
In second step, when calcium ions and magnesium ions concentration is lower than 1mmol/L in solution in sedimentation basin 4, silica concentration is lower than
When 20mg/L, the production water of tubular ultra-filtration membrane group 5, which is passed through in next step, to be handled.
Third step, sodium sulphate concentration, crystallisation by cooling: the production water of tubular ultra-filtration membrane group 5 is passed through second level dish tubular nanofiltration membrane group 6
Sodium sulphate is concentrated, carrying out cooling down to the concentrated water of second level dish tubular nanofiltration membrane group 6 analyses sulfate crystal therein
Out, the temperature of the concentrated water cooling down of second level dish tubular nanofiltration membrane group 6 is 0~10 DEG C, and the solution after crystallization is back to second level
30~40 DEG C are heated to the solution after crystallization in dish tubular nanofiltration membrane group 6 and in reflux course, makes it for sodium sulphate
, to concentrated water crystallisation by cooling, concentrated water is realized after second level dish tubular nanofiltration membrane group 6 further concentration in undersaturated condition
The production water recycling of multistage concentration, crystallisation by cooling, the second level dish tubular nanofiltration membrane group 6 is used for silica gel acid cleaning process water.
4th step recycles solid sodium sulfate.
This technique is used for a kind of silica gel waste water treatment system, including wastewater equalization pond 1, further includes level-one dish tubular type nanofiltration
Film group 3, second level dish tubular nanofiltration membrane group 6, sedimentation basin 4 and tubular membrane group；Tubular membrane group is that tubular ultra-filtration membrane group or tubular type are micro-
Filter membrane group.In the present embodiment, using tubular ultra-filtration membrane group 5.
It is also connected between the water inlet end of the wastewater equalization pond 1 and level-one dish tubular nanofiltration membrane group 3 for waste water
At least one of pretreated multi-medium filtering, micro-filtration and ultra-filtration filters or and combinations thereof.
The concentrated water end of level-one dish tubular nanofiltration membrane group 3 is connected by reaction settling basin 4 and the water inlet end of tubular ultra-filtration membrane group 5
It connects, the concentrated water end of tubular ultra-filtration membrane group 5 is connect by the first return pipe 10 with reaction settling basin 4；The reaction settling basin 4 is set
There is sewage draining exit and device for dehydrating sladge waste 9 is connected with by sewage draining exit.
The water inlet end of second level dish tubular nanofiltration membrane group 6 is connect by intermediate water tank 11 with the production water end (W.E.) of tubular ultra-filtration membrane group 5,
The concentrated water end of second level dish tubular nanofiltration membrane group 6 is connected with crystallizing pond 7, and the cooling device that can cool down to concentrated water is equipped in crystallizing pond 7,
Crystallizing pond 7 is also connect by the second return pipe 12 with the water inlet end of second level dish tubular nanofiltration membrane group 6, is equipped in the second return pipe 12
The heat riser that can be heated up to phegma.
The production water end (W.E.) for producing water end (W.E.) and second level dish tubular nanofiltration membrane group 6 of the level-one dish tubular nanofiltration membrane group 3 with production
Water reuse tank 8 connects.
Implementation method is as follows:
Raw water enters in wastewater equalization pond 1, homogeneous adjusting is carried out to the waste water that different periods enter, then by pretreatment
Equipment 2, into level-one dish tubular nanofiltration membrane group 3.For dish tubular membrane component technology, pre-processing device 2 can be multimedium mistake
Filter or micro-filtration, ultra-filtration filters can all meet water inlet and require.
Level-one dish tubular membrane component 3 produces water and enters production water reuse tank 8, due to the operational characteristic of dish tubular membrane component, produces water
99% or more sulfate radical is eliminated, while having also been removed calcium ions and magnesium ions and part of silica, fully meets silica gel pickling work
Skill is required with water.
The concentrated water of level-one dish tubular membrane component 3 enters sedimentation basin 4, and sedimentation basin 4 and tubular ultra-filtration membrane group 5 form circulation point
From system.Sodium hydroxide is added in sedimentation basin 4, adjusts pH, sodium carbonate, magnesia mixture is added, makes the hardness and silica shape in water
At crystalline deposit；Be discharged above sedimentation basin 4, into tubular ultra-filtration membrane group 5, by 5 separating and filtering of tubular ultra-filtration membrane group, produce water into
Enter after intermediate water tank 14 buffers and enters second level dish tubular nanofiltration membrane group 6.The concentrated water of tubular ultra-filtration membrane group 5 passes through the first return pipe 10
It is back to reaction settling basin 4,4 lower part of reaction settling basin is sludge condensation area, and the sludge of concentration squeezes into device for dehydrating sladge waste 9, is taken off
Sludge after water sends landfill disposal outside, and the overflowing liquid of dehydration is back to sedimentation basin 4.
Tubular ultra-filtration membrane group 5 is discharged, and the easily foulant such as hardness and silica is removed, into second level dish tubular type nanofiltration
Film group 6 carries out concentration.Water inlet eliminates fouling components at this time, although salt content is higher than level-one water inlet, by second level dish pipe
After the processing of formula nanofiltration membrane group 6, one times or more of concentration rate still can reach, be no more than the dish tubular membrane component operating pressure limit
Under the conditions of, the sodium sulphate content of concentrate can be concentrated into 20% or more.The concentrate enters crystallizing pond, passes through cooling device
10 DEG C are cooled to hereinafter, sulfate crystal is precipitated, obtains sodium sulphate finished product.
It is precipitated through supercooling, the supernatant after eliminating sulfate crystal is saturated solution.Crystallizing pond 7 also passes through second time
Flow tube 12 is connect with the water inlet end of second level dish tubular nanofiltration membrane group 6, and the liter that can be heated up to phegma is equipped in the second return pipe 12
Warm device, phegma heat up after the second return pipe 12, and sodium sulphate solubility increases, and are in undersaturated condition, pass through
Second return pipe 12 is back to the water inlet end of second level dish tubular membrane component 6, carries out concentration again.
The heat riser used in the present invention can be the devices such as electric heating tube and heat exchanger, meet and carry out to treatment fluid
Heat up function；And cooling device can also use other cooling systems such as heat exchanger, meet and carry out cooling function to treatment fluid
.The cooling device and heat riser that the present invention uses are prior art products, and specific structure repeats no more.
Embodiment 2:
A kind of zero-emission of silica gel waste water and recycling treatment process, comprising the following steps:
The first step, impurity concentration, produce water recycling: waste water is preprocessed filter out suspended matter after, be passed through level-one dish tubular type and receive
Simultaneously sulfate radical, calcium ions and magnesium ions and part of silica are concentrated in concentrated water side by level-one dish tubular nanofiltration membrane group 3 for filter membrane group 3,
The production water recycling of dish tubular membrane component is used for silica gel acid cleaning process water.
Waste water carries out homogeneous adjusting and pretreatment before being passed through level-one dish tubular nanofiltration membrane group 3, to the waste water of different periods.
Second step, flocculation sedimentation, circulating filtration: the concentrated water of level-one dish tubular nanofiltration membrane group 3 is passed through in sedimentation basin 4, first
PH is adjusted to neutrality, flocculant is added afterwards, so that calcium ions and magnesium ions and silica in water is formed precipitating, liquid solution is passed through tubular type
Film group, the concentrate recirculation of tubular membrane group produce water and enter intermediate water tank 11, to form circulating filtration to sedimentation basin 4.In this implementation
In example, tubular membrane group is tubular ultra-filtration membrane group 5.
The concentrated water of level-one dish tubular nanofiltration membrane group 3 is passed through sedimentation basin 4, and alkaline matter is first added in sedimentation basin 4 and adjusts pH,
Wherein alkali used, which can be caustic soda, soda ash, quick lime, magnesia etc., can be improved the medicament of pH, and flocculant is added afterwards, used
Flocculant include calcium chloride, magnesium chloride, aluminium polychloride, PAM etc., calcium and magnesium hardness and silicon dioxide colloid can be made to convert
It is precipitated at sediment.
In second step, when calcium ions and magnesium ions concentration is lower than 1mmol/L in solution in sedimentation basin 5, silica concentration is lower than
When 20mg/L, the production water of tubular ultra-filtration membrane group 5, which is passed through in next step, to be handled.
Third step, sodium sulphate concentration, crystallisation by cooling: the production water of tubular ultra-filtration membrane group 5 is passed through second level disc tube reverse osmosis (dt-ro) film
13 pairs of sodium sulphate of group are concentrated, and carrying out cooling down to the concentrated water of second level disc tube reverse osmosis (dt-ro) film group 13 makes sodium sulphate therein
Crystallization is precipitated, and the temperature of the concentrated water cooling down of second level disc tube reverse osmosis (dt-ro) film group 13 is 0~10 DEG C, and the solution after crystallization is returned
It flow in second level disc tube reverse osmosis (dt-ro) film group 13 and 30~40 DEG C is heated to the solution after crystallization in reflux course, make it
Undersaturated condition is in for sodium sulphate, it is cooling to concentrated water to tie after second level disc tube reverse osmosis (dt-ro) film group 13 further concentration
Crystalline substance, realizes multistage concentration, the crystallisation by cooling of concentrated water, and the production water recycling of the second level disc tube reverse osmosis (dt-ro) film group 13 is used for silica gel
Acid cleaning process water.
4th step recycles solid sodium sulfate.
A kind of silica gel waste water treatment system, including wastewater equalization pond 1 further include level-one dish tubular nanofiltration membrane group 3, second level dish
Tubular type reverse osmosis membrane group 13, sedimentation basin 4 and tubular ultra-filtration membrane group 5；
It is also connected between the water inlet end of the wastewater equalization pond 1 and level-one dish tubular nanofiltration membrane group 3 for waste water
At least one of pretreated multi-medium filtering, micro-filtration and ultra-filtration filters or and combinations thereof.
The concentrated water end of level-one dish tubular nanofiltration membrane group 3 is connect by sedimentation basin 4 with the water inlet end of tubular ultra-filtration membrane group 5, is managed
The concentrated water end of formula ultrafiltration membrane group 5 is connect by the first return pipe 10 with sedimentation basin 4；The sedimentation basin 4 is equipped with sewage draining exit and leads to
It crosses sewage draining exit and is connected with device for dehydrating sladge waste 9.
The water inlet end of disc tube reverse osmosis (dt-ro) film group 13 is connect by intermediate water tank 11 with the production water end (W.E.) of tubular ultra-filtration membrane group 5,
The concentrated water end of second level disc tube reverse osmosis (dt-ro) film group 13 is connected with crystallizing pond 7, and the cooling that concentrated water cools down can be filled by being equipped in crystallizing pond 7
It sets, crystallizing pond 7 is also connect by the second return pipe 12 with the water inlet end of second level disc tube reverse osmosis (dt-ro) film group 13, the second return pipe 12
It is interior to be equipped with the heat riser that heated up to phegma.
The production water end (W.E.) for producing water end (W.E.) and second level disc tube reverse osmosis (dt-ro) film group 13 of the level-one dish tubular nanofiltration membrane group 3 with
Water reuse tank 8 is produced to connect.
Implementation method of the invention is as follows:
Raw water enters in wastewater equalization pond 1, homogeneous adjusting is carried out to the waste water that different periods enter, then by pretreatment
Equipment 2, into level-one dish tubular nanofiltration membrane group 3.For dish tubular membrane component technology, pre-processing device 2 can be multimedium mistake
Filter or micro-filtration, ultra-filtration filters can all meet water inlet and require.
Level-one dish tubular nanofiltration membrane group 3 produces water and enters production water reuse tank 8, due to the operational characteristic of dish tubular membrane component, produces
Water eliminates 99% or more sulfate radical, while having also been removed calcium ions and magnesium ions and part of silica, fully meets silica gel pickling
Process water requirement.
The concentrated water of level-one dish tubular membrane nanofiltration membrane group 3 enters sedimentation basin 4, and sedimentation basin 4 and tubular ultra-filtration membrane group 5, which are formed, to be recycled
Separation system.Sodium hydroxide is added in sedimentation basin 4, adjusts pH, sodium carbonate, magnesia mixture is added, makes the hardness and silica in water
Form crystalline deposit；It is discharged above reaction settling basin 4, into tubular ultra-filtration membrane group 5, by 5 separating and filtering of tubular ultra-filtration membrane group,
It produces water and enters subsequent disc tube reverse osmosis (dt-ro) film group 13.It is heavy that the concentrated water of tubular ultra-filtration membrane group 5 is back to by the first return pipe 10
Shallow lake pond 4,4 lower part of sedimentation basin are sludge condensation areas, and the sludge of concentration squeezes into device for dehydrating sladge waste 9, and dewatered sludge, which is sent outside, to be filled out
Processing is buried, the overflowing liquid of dehydration is back to reaction settling basin 4.
Tubular ultra-filtration membrane group 5 is discharged, and the easily foulant such as hardness and silica is removed, into second level dish tubular type reverse osmosis
Permeable membrane group 13 carries out concentration.Water inlet eliminates fouling components at this time, although salt content is higher than level-one water inlet, by second level dish
After the processing of tubular type reverse osmosis membrane group 13, one times or more of concentration rate still can reach, be no more than dish tubular membrane component work pressure
Under power maximum conditions, the sodium sulphate content of concentrate can be concentrated into 20% or more.The concentrate enters crystallizing pond, passes through drop
Warm device cools to 10 DEG C hereinafter, sulfate crystal is precipitated, and obtains sodium sulphate finished product.
It is precipitated through supercooling, the supernatant after eliminating sulfate crystal is saturated solution.Crystallizing pond 7 also passes through second time
Flow tube 12 is connect with the water inlet end of second level disc tube reverse osmosis (dt-ro) film group 13, and being equipped in the second return pipe 12 can heat up to phegma
Heat riser, phegma heats up after the second return pipe 12, and sodium sulphate solubility increases, and is in undersaturated condition,
It is back to the water inlet end of second level disc tube reverse osmosis (dt-ro) film group 13 by the second return pipe 12, carries out concentration again.
The heat riser used in the present invention can be the devices such as electric heating tube and heat exchanger, meet and carry out to treatment fluid
Heat up function；And cooling device can also use other cooling systems such as heat exchanger, meet and carry out cooling function to treatment fluid
.The cooling device and heat riser that the present invention uses are repeated no more with prior art products, specific structure.
Waste water is in projects index after the processing of the treatment process of the embodiment of the present invention 1 and embodiment 2, contained
Parameters variation is as shown in the table:
In addition, the difference of embodiment 1 and embodiment 2 is that second level dish tubular membrane group uses DTNF in embodiment 1 in this programme
(nanofiltration), operating pressure is lower with DTRO (reverse osmosis) than embodiment 2, can reduce operation energy consumption.
Certainly, above description is also not limited to the example above, technical characteristic of the present invention without description can by or
It is realized using the prior art, details are not described herein；Above embodiments and attached drawing are only used to illustrate the technical scheme of the present invention not
It is limitation of the present invention, is described the invention in detail referring to preferred embodiment, the ordinary skill people of this field
Member is it should be appreciated that variation, remodeling, the addition that those skilled in the art are made within the essential scope of the present invention
Or replacement also should belong to claims of the invention without departure from spirit of the invention.
Claims (10)
1. a kind of no pollution of silica gel waste water discharges and recycling treatment process, it is characterised in that: the following steps are included:
The first step, impurity concentration, produce water recycling: waste water is preprocessed filter out suspended matter after, be passed through level-one dish tubular membrane component
And sulfate radical, calcium ions and magnesium ions and part of silica are concentrated in concentrated water side by level-one dish tubular membrane component, level-one dish tubular type
The production water recycling of membrane module permeate side is used for silica gel acid cleaning process water；
Second step, flocculation sedimentation, circulating filtration: the concentrated water of level-one dish tubular membrane component is passed through in sedimentation basin, first adjust pH to
Flocculant is added in neutrality afterwards, so that calcium ions and magnesium ions and silica in water is formed precipitating, solution in sedimentation basin is separated by solid-liquid separation,
Sedimentation basin solution is passed through tubular membrane group, forms circulating filtration in the concentrate recirculation to sedimentation basin of tubular membrane group；
Third step, sodium sulphate concentration, crystallisation by cooling: the production water of tubular membrane group is passed through second level dish tubular membrane component and carries out to sodium sulphate
Concentration, carrying out cooling down to the concentrated water of second level dish tubular membrane component is precipitated sulfate crystal therein, will be molten after crystallization
Liquid is back in the water inlet of second level dish tubular membrane component and in reflux course to the solution heat temperature raising after crystallization, makes it for sulfuric acid
Sodium is in undersaturated condition, after being further concentrated using second level dish tubular membrane component, to concentrated water crystallisation by cooling, realizes the more of concentrated water
Grade concentration, crystallisation by cooling；
4th step recycles solid sodium sulfate.
2. the no pollution of silica gel waste water according to claim 1 discharges and recycling treatment process, it is characterised in that: described
Level-one dish tubular membrane component be dish tubular nanofiltration membrane group；The second level dish tubular membrane component is dish tubular nanofiltration membrane group or dish
Tubular type reverse osmosis membrane group.
3. the no pollution of silica gel waste water according to claim 1 discharges and recycling treatment process, it is characterised in that: second
In step, when calcium ions and magnesium ions concentration is lower than 1mmol/L in solution in sedimentation basin, when silica concentration is lower than 20mg/L, tubular membrane
The production water of group is passed through the processing of second level dish tubular membrane component.
4. zero-emission and the recycling treatment process of silica gel waste water according to claim 1, it is characterised in that: in third step
In, the concentrated water cooling down of second level dish tubular membrane component is to 10 DEG C or less；Solution after crystallization is back to second level dish tubular membrane group
During part, temperature is heated to 30~35 DEG C.
5. the no pollution of silica gel waste water according to claim 1 or 2 discharges and recycling treatment process, it is characterised in that:
In the third step, the production water recycling of the second level dish tubular membrane component is used for silica gel acid cleaning process water.
6. the no pollution of silica gel waste water according to claim 1 discharges and recycling treatment process, it is characterised in that: described
Tubular membrane group be tubular ultra-filtration membrane group or tube microfiltration membrane group.
7. the no pollution of silica gel waste water according to claim 1 discharges and recycling treatment process, it is characterised in that: the
In two steps, the flocculant is the combination of one or more of calcium chloride, magnesium chloride, aluminium polychloride, PAM.
8. a kind of silica gel waste water treatment system using treatment process described in claim 1, including wastewater equalization pond, feature
It is:
It further include level-one dish tubular membrane component, second level dish tubular membrane component, sedimentation basin and tubular membrane group；
The water inlet end of level-one dish tubular membrane component is connect with wastewater equalization pond, and the concentrated water end of level-one dish tubular membrane component passes through precipitating
Pond is connect with the water inlet end of tubular membrane group, and the concentrated water end of tubular membrane group is connect by the first return pipe with sedimentation basin；
The water inlet end of second level dish tubular membrane component is connect by intermediate water tank with the production water end (W.E.) of tubular membrane group, second level dish tubular membrane group
The concentrated water end of part is connected with crystallizing pond, and the cooling device that can cool down to concentrated water is equipped in crystallizing pond, and crystallizing pond also passes through second time
Flow tube is connect with the water inlet end of second level dish tubular membrane component, and the heat riser that can be heated up to phegma is equipped in the second return pipe.
9. silica gel waste water treatment system according to claim 8, it is characterised in that: the level-one dish tubular membrane component is
Dish tubular nanofiltration membrane group；The second level dish tubular membrane component is dish tubular nanofiltration membrane group or disc tube reverse osmosis (dt-ro) film group.
10. silica gel waste water treatment system according to claim 8, it is characterised in that: the level-one dish tubular membrane component
Production water end (W.E.) and second level dish tubular membrane component production water end (W.E.) with produce water reuse tank connect.
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| CN113429053A (en) * | 2021-07-21 | 2021-09-24 | 山东金汇膜科技股份有限公司 | Silica gel wastewater recycling treatment method |
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