CN106430793A - Zero discharging method and device for vitamin B2 production waste water - Google Patents
Zero discharging method and device for vitamin B2 production waste water Download PDFInfo
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- CN106430793A CN106430793A CN201611045542.6A CN201611045542A CN106430793A CN 106430793 A CN106430793 A CN 106430793A CN 201611045542 A CN201611045542 A CN 201611045542A CN 106430793 A CN106430793 A CN 106430793A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 239000011716 vitamin B2 Substances 0.000 title claims abstract description 64
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 title claims abstract description 57
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 title claims abstract description 57
- 229930003471 Vitamin B2 Natural products 0.000 title claims abstract description 57
- 229960002477 riboflavin Drugs 0.000 title claims abstract description 57
- 235000019164 vitamin B2 Nutrition 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000007599 discharging Methods 0.000 title abstract 4
- 239000012528 membrane Substances 0.000 claims abstract description 153
- 238000001728 nano-filtration Methods 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001953 recrystallisation Methods 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012466 permeate Substances 0.000 claims description 40
- 238000003860 storage Methods 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 18
- 230000014759 maintenance of location Effects 0.000 claims description 16
- 230000004907 flux Effects 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000008016 vaporization Effects 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009834 vaporization Methods 0.000 abstract 1
- 229930003270 Vitamin B Natural products 0.000 description 23
- 235000019156 vitamin B Nutrition 0.000 description 23
- 239000011720 vitamin B Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000012958 reprocessing Methods 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003851 biochemical process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D475/00—Heterocyclic compounds containing pteridine ring systems
- C07D475/12—Heterocyclic compounds containing pteridine ring systems containing pteridine ring systems condensed with carbocyclic rings or ring systems
- C07D475/14—Benz [g] pteridines, e.g. riboflavin
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of waste water treatment, in particular to a zero discharging method and device for vitamin B2 production waste water. The method includes the steps: (1) feeding the vitamin B2 production waste water into an organic tubular membrane system, concentrating the waste water to obtain tubular membrane concentrated solution and tubular membrane permeated solution, and subjecting the tubular membrane concentrated solution to recrystallization and drying to obtain vitamin B2; (2) delivering the tubular membrane permeated solution into a nano-filtration system, performing separation to obtain nano-filtration permeated solution and nano-filtration concentrated solution, vaporizing the nano-filtration permeated solution to obtain recycled inorganic salt, and returning outlet water from vaporization to a production section to be recycled. According to the zero discharging method, an advanced membrane separation technique is introduced into treatment of the vitamin B2 production waste water, the problem of difficulty in treatment of the vitamin B2 production waste water is effectively solved, more importantly, zero discharging of the waste water is really realized, vitamin B2 and the inorganic salt in the waste water are recycled, salty waste water is recycled, final effluent is recycled, and environmental and economic benefits are remarkable.
Description
Technical field
The present invention relates to technical field of waste water processing, especially a kind of method and device of vitamin B2 wastewater zero discharge.
Background technology
Vitamin B2 is widely used in medicine, food additive and feed additive, and with expanding economy and application model
The expansion that encloses, its demand constantly increases.At present, widely used microbe fermentation method commercial production vitamin B2 both at home and abroad, sends out
Using vegetable oil, glucose, molasses or rice etc. as primary carbon source in ferment culture medium.Which produces concentration of organic wastewater height, contains
Salt amount is big, biodegradability is poor, belongs to industrial difficult waste water.With vitamin B2 industry development, how to realize its production waste water and reach
Mark processes the key issue for becoming its development of restriction.
At present, the domestic research report to vitamin B2 wastewater treatment is few, and all with discharged wastewater met the national standard as index.
Wang Shaojun etc. processes high concentration vitamin B2 using the group technology of Fe/C pretreatment+biochemistry+ozone charcoal
Production waste water.Fe/C pretreatment can reach 45% to the clearance of COD, and anaerobism is with aerobic biochemical treatment process to waste water COD
Clearance reaches 92.8%, then is removed COD, water outlet COD further and can be fully achieved by ozone high grade oxidation and biological activated carbon
《Integrated wastewater discharge standard》（GB8978-1996）Three-level discharge standard.
ZL201220493361.0 proposes a kind of handling process based on biochemical process combination Ozonation, vitamin
B2 production waste water enters HAF anaerobic reation pool after entering water distribution regulating reservoir water distribution and enters anaerobic reaction, and reacted waste water is entered
FSBBR biological reaction pool of wandering about as a refugee carries out biological respinse of wandering about as a refugee, and bio-chemical effluent enters ozone oxidation pond and carries out ozone oxidation, ozone oxygen
Dissolving water entrance bis- biological treatment tanks of TBF carries out secondary biochemical treatment, is directly entered sedimentation tank precipitation, finally after reaching standard
Waste water is discharged by outlet.
Above-mentioned report is main process all using biochemical process, but often vitamin B2 waste water salinity is higher, and biochemical process is not
Being suitable for, and all with qualified discharge as index, does not reclaim to composition such as vitamin B2 etc. is worth in waste water, cause resource wave
Take.
Content of the invention
The purpose of the present invention is：Overcoming deficiency of the prior art, one kind is provided and vitamin is realized using membrane separation technique
B2 is concentrated, vitamin B2 is separated with inorganic salt and the method for the vitamin B2 of Sewage advanced treatment production wastewater zero discharge, with
And the equipment that the method is used.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of method of vitamin B2 wastewater zero discharge, the method comprising the steps of：
（1）Vitamin B2 production waste water is sent into organic tubular type film device concentrated, obtain tubular membrane concentrated solution and tubular membrane
Permeate, tubular membrane concentrated solution is carried out recrystallization again, after drying, obtains vitamin B2；
（2）Organic tubular membrane permeate feeding nanofiltration membrane system is carried out separating, obtains NF membrane permeate and nanofiltration membrance concentration
Liquid, after nanofiltration permeate liquid is evaporated again, is recycled inorganic salt, and evaporation water outlet returns production section and recycles.
Preferably, the step（1）Middle waste water first adds alkali to adjust pH to 5-7 before entering organic tubular type membranous system.
Preferably, the step（1）The vitamin B2 concentration of middle waste water is 1.20～3.21g/L.
Preferably, organic tubular type membrane aperture 30-50 nm, membrane material selects Kynoar, polyacrylonitrile, polyethers
Sulfone or polysulfones, 0.3～0.55MPa of operating pressure, film average flux is 86-102L/m2·h.
Preferably, the nanofiltration system includes one-level nanofiltration membrane system and two grades of nanofiltration membrane system, one-level NF membrane dense
Contracting liquid is back in organic tubular membrane carries out filtration treatment, and the concentrated solution of two grades of NF membrane is back to one-level NF membrane to be carried out
Filter is processed.
Preferably, the molecular cut off 800-1000Da of the one-level NF membrane, operating pressure is controlled to 2.0-3.0MPa,
Film average flux is 21.7-25.6L/m2·h.
Preferably, two grades of nanofiltration retaining molecular weights are 100-300Da, control operation pressure 2.0-3.5MPa, film
Average flux is 20.6-23.4 L/m2·h.
A kind of device of vitamin B2 wastewater zero discharge, including the first storage tank, organic tubular type film device, the second storage tank and receives
Filter membrane system, is connected by pipeline between the first storage tank, organic tubular type film device, the second storage tank and nanofiltration membrane system, and described have
Organic tubular membrane is installed in machine tubular type film device, the retention side of organic tubular membrane is connected with crystallization apparatus by pipeline, organic
The per-meate side of tubular membrane is connected with the feed liquid port of nanofiltration membrane system by pipeline, the per-meate side of nanofiltration membrane system by pipeline with
Vaporising device connects.
Preferably, the nanofiltration system includes one-level nanofiltration membrane stack and two grades of nanofiltration membrane stacks, the one-level nanofiltration membrane stack
Permeable formation is connected with the feed liquid port of two grades of nanofiltration membrane stacks, and the retention side of one-level nanofiltration membrane stack is by pipeline and the bottom of the second storage tank
End connection, the retention side of two grades of nanofiltration membrane stacks is connected with the top of the second storage tank by pipeline, the per-meate side of two grades of nanofiltration membrane stacks
It is connected with vaporising device by pipeline.
Preferably, between the one-level nanofiltration membrane stack and two grades of nanofiltration membrane stacks, the 3rd storage tank is connected with by pipeline, the 3rd
The top of storage tank is connected with the permeable formation of one-level nanofiltration heap by pipeline, and the bottom of the 3rd storage tank is by pipeline and two grades of NF membrane
The feed liquid port connection of heap；The retention side of the one-level nanofiltration membrane stack is connected with the first storage tank by pipeline；Two grades of nanofiltrations
The retention side of membrane stack is connected with the second storage tank by pipeline.
Using the beneficial effect of technical scheme it is：
The present invention is incorporated into membrane separation technique in vitamin B2 wastewater treatment, advanced technology, efficiently solves vitamin B2 and gives up
The intractable problem of water, the what is more important present invention is truly realized wastewater zero discharge, not only by the vitamin B2 in waste water,
Inorganic salt is reclaimed, salt cycling utilization of wastewater, and final outflow water is recycled, and environment benefits and economic gains are obvious.
In the present invention, vitamin B2 content can be concentrated into by vitamin B2 crystallization retention by 30g/ using organic tubular membrane
More than L, and a part of colloid, protein impurities transmission can be improve the recovery purity of vitamin B2 by organic tubular membrane, when
Concentrated solution meets recrystallization requirement, vitamin B2 product is obtained through recrystallization.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the method schematic diagram of the vitamin B2 wastewater zero discharge of the present invention.
Fig. 2 is the apparatus structure schematic diagram of the vitamin B2 wastewater zero discharge of the present invention.
In figure：1st, the first basin；2nd, organic tubular type film device；3rd, the second basin；4th, one-level nanofiltration membrane stack；5th, the 3rd storage
Tank；6th, two grades of nanofiltration membrane stacks；7th, vaporising device；8th, crystallization apparatus.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, only with
The basic structure of the illustration explanation present invention, therefore which only shows the composition relevant with the present invention.
As shown in figure 1, the acid waste water for getting off from production workshop section (pH about 1～3) is added alkali to adjust pH5 by the present invention first
～7, the one-level NF membrane trapped fluid for returning with back segment sends into organic tubular type membranous system, organic tubular type membrane aperture 30-50 after mixing
Nm, membrane material selects Kynoar, polyacrylonitrile, polyether sulfone or polysulfones, 0.05～0.6MPa of operating pressure；Using organic pipe
Vitamin B2 content can be concentrated into more than 30g/L by vitamin B2 crystallization retention by formula film, and organic tubular membrane can be by
A part of colloid, protein impurities are passed through, and improve the recovery purity of vitamin B2, when concentrated solution meets recrystallization requirement, through weight
Crystallization is obtained vitamin B2Product；
Organic tubular membrane permeate is sent into one-level nanofiltration system and is separated again, and one-level nanofiltration 800～1000Da of retaining molecular weight is
System 1.0～4.0MPa of operating pressure, one-level NF membrane can retain some vitamin B2, and the concentrated solution being trapped returns organic pipe
Formula film circular treatment, through vitamin B in the waste water of one-level NF membrane2Content ＜ 300mg/L, one-level NF membrane permeate is sent into
Two grades of nanofiltration membrane system are processed further, to reclaim a small amount of vitamin B2 therein, two grades of nanofiltration retaining molecular weights 100～
300Da, 1.0～4.0MPa of operating pressure, through vitamin B in the waste water of two grades of NF membrane2Content ＜ 30mg/L, then warp
Vapo(u)rization system is processed, and is divided into distilled water and inorganic salt（Predominantly Sodium Chloride）, its distilled water recycled as industrial water, chlorine
Change sodium salt to sell as side-product, returned at one-level nanofiltration membrane system circulation by the concentrated solution of two grades of NF membrane retentions
Reason.
Embodiment 1
S1：Vitamin B the acid waste water (pH about 1～3) for getting off from production workshop section2Concentration is 1.20g/L, is first adjusted with liquid caustic soda
PH to 6, vitamin B after mixing with the one-level NF membrane trapped fluid of back segment return2Concentration is 1.25g/L, is then fed into organic pipe
Formula membranous system, organic tubular type membrane aperture 30nm, control operation pressure 0.3MPa, film average flux 102L/m2H, vitamin B2Knot
Crystalline substance is trapped, vitamin B in the concentrated solution of retention2Concentration 32.5g/L, concentrated solution meets recrystallization requirement, is obtained through recrystallization
Vitamin B2Product, product purity is 99.76%, vitamin B in permeate2Concentration 560mg/L；
S2：The permeate of organic tubular type membranous system is sent into one-level nanofiltration system and is separated again, one-level nanofiltration retaining molecular weight
1000Da, control operation pressure 2.0MPa, film average flux 25.6L/m2H, one-level NF membrane can retain some vitamin
B2, vitamin B in permeate2Concentration 151mg/L, vitamin B in the concentrated solution of retention2Concentration 1.32g/L, before trapped fluid is returned
Section sends into organic tubular membrane reprocessing with raw water after mixing；
S3：The permeate of one-level nanofiltration membrane system is sent into two grades of nanofiltration membrane system and is processed further, and two grades of NF membrane retain molecule
Measure as 100Da, control operation pressure 3.5MPa, film average flux 20.6L/m2H, through dimension life in the waste water of organic nanofiltration membrane
Plain B2Content 5mg/L, then process through vapo(u)rization system, it is divided into distilled water and sodium chloride salt, its distilled water is circulated as industrial water
Utilize, sodium chloride salt can sell as side-product, by vitamin B in the waste water of two grades of NF membrane retentions2Content 555mg/
L, returns and sends into one-level nanofiltration membrane system reprocessing after leading portion is mixed with organic tubular membrane permeate.
Embodiment 2
S1：Vitamin B the acid waste water (pH about 1～3) for getting off from production workshop section2Concentration is 3.21g/L, is first adjusted with liquid caustic soda
PH to 7, vitamin B after mixing with the one-level NF membrane trapped fluid of back segment return2Concentration is 3.23g/L, is then fed into organic pipe
Formula membranous system, organic tubular type membrane aperture 50nm, control operation pressure 0.55MPa, film average flux 86L/m2H, vitamin B2Knot
Crystalline substance is trapped, vitamin B in the concentrated solution of retention2Concentration 41.6g/L, concentrated solution meets recrystallization requirement, is obtained through recrystallization
Vitamin B2Product, product purity is 99.85%, vitamin B in permeate2Concentration 756mg/L；
S2：The permeate of organic tubular type membranous system is sent into one-level nanofiltration system and is separated again, one-level nanofiltration retaining molecular weight
1000Da, control operation pressure 3.0MPa, film average flux 25.6L/m2H, one-level NF membrane can retain some vitamin
B2, vitamin B in permeate2Concentration 236mg/L, vitamin B in the concentrated solution of retention2Concentration 3.35g/L, before trapped fluid is returned
Section sends into organic tubular membrane reprocessing with raw water after mixing；
S3：The permeate of one-level nanofiltration membrane system is sent into two grades of nanofiltration membrane system and is processed further, and two grades of NF membrane retain molecule
Measure as 300Da, control operation pressure 2.0MPa, film average flux 23.4L/m2H, through dimension life in the waste water of organic nanofiltration membrane
Plain B2Content 18mg/L, then process through vapo(u)rization system, it is divided into distilled water and sodium chloride salt, its distilled water is circulated as industrial water
Utilize, sodium chloride salt can sell as side-product, by vitamin B in the waste water of two grades of NF membrane retentions2Content 738mg/
L, returns and sends into one-level nanofiltration membrane system reprocessing after leading portion is mixed with organic tubular membrane permeate.
Embodiment 3
S1：Vitamin B the acid waste water (pH about 1～3) for getting off from production workshop section2Concentration is 1.89g/L, is first adjusted with liquid caustic soda
PH to 5, vitamin B after mixing with the one-level NF membrane trapped fluid of back segment return2Concentration is 1.93g/L, is then fed into organic pipe
Formula membranous system, organic tubular type membrane aperture 30nm, control operation pressure 0.4MPa, film average flux 98L/m2H, vitamin B2Knot
Crystalline substance is trapped, vitamin B in the concentrated solution of retention2Concentration 35.4g/L, concentrated solution meets recrystallization requirement, is obtained through recrystallization
Vitamin B2Product, product purity is 99.85%, vitamin B in permeate2Concentration 632mg/L；
S2：The permeate of organic tubular type membranous system is sent into one-level nanofiltration system and is separated again, one-level nanofiltration retaining molecular weight
800Da, control operation pressure 2.5MPa, film average flux 21.7L/m2H, one-level NF membrane can retain some vitamin
B2, vitamin B in permeate2Concentration 185mg/L, vitamin B in the concentrated solution of retention2Concentration 2.01g/L, before trapped fluid is returned
Section sends into organic tubular membrane reprocessing with raw water after mixing；
S3：The permeate of one-level nanofiltration membrane system is sent into two grades of nanofiltration membrane system and is processed further, and two grades of NF membrane retain molecule
Measure as 200Da, control operation pressure 2.5MPa, film average flux 24.2L/m2H, through dimension life in the waste water of organic nanofiltration membrane
Plain B2Content 10mg/L, then process through vapo(u)rization system, it is divided into distilled water and sodium chloride salt, its distilled water is circulated as industrial water
Utilize, sodium chloride salt can sell as side-product, by vitamin B in the waste water of two grades of NF membrane retentions2Content 603mg/
L, returns and sends into one-level nanofiltration membrane system reprocessing after leading portion is mixed with organic tubular membrane permeate.
As shown in Fig. 2 a kind of device of vitamin B2 wastewater zero discharge, including the first storage tank, organic tubular type film device,
Two storage tanks and nanofiltration membrane system, between the first storage tank, organic tubular type film device, the second storage tank and nanofiltration membrane system by pipeline even
Connect, organic tubular membrane be installed in organic tubular type film device, the retention side of organic tubular membrane is connected with crystallization apparatus by pipeline,
The per-meate side of organic tubular membrane is connected with the feed liquid port of nanofiltration membrane system by pipeline, and the per-meate side of nanofiltration membrane system is by pipe
Road is connected with vaporising device.
Operation principle：Waste water during use, is first sent into organic tubular type in the first storage tank by vitamin B2 production storage of waste water
Concentrated in film device, tubular membrane concentrated solution and tubular membrane permeate is obtained, tubular membrane concentrated solution is carried out recrystallization again, is done
After dry, vitamin B2 is obtained；By organic tubular membrane permeate feeding nanofiltration membrane system carry out separate, obtain NF membrane permeate and
NF membrane concentrated solution, after nanofiltration permeate liquid is evaporated again, is recycled inorganic salt, and evaporation water outlet returns production section circulation profit
With.
Nanofiltration system in the present invention includes one-level nanofiltration membrane stack and two grades of nanofiltration membrane stacks, the permeable formation of one-level nanofiltration membrane stack
It is connected with the feed liquid port of two grades of nanofiltration membrane stacks, the retention side of one-level nanofiltration membrane stack is by the top of pipeline and the first storage tank even
Connect, the retention side of two grades of nanofiltration membrane stacks is connected with the top of the second storage tank by pipeline, and the per-meate side of two grades of nanofiltration membrane stacks passes through
Pipeline is connected with vaporising device, and the concentrated solution of one-level NF membrane is back in the first storage tank and stores, and then enters back into organic tubular type
Filtration treatment is carried out in film, and the concentrated solution of two grades of NF membrane is back to one-level NF membrane carries out filtration treatment, using this structure,
Process can be circulated to waste water, substantially increase treatment effeciency.
Between one-level nanofiltration membrane stack in the present invention and two grades of nanofiltration membrane stacks, the 3rd storage tank, the 3rd storage are connected with by pipeline
The top of tank is connected with the permeable formation of one-level nanofiltration heap by pipeline, and the bottom of the 3rd storage tank is by pipeline and two grades of nanofiltration membrane stacks
Feed liquid port connection, the 3rd storage tank is used for storing the permeate of one-level nanofiltration membrane stack, and the permeate of one-level nanofiltration membrane stack is first stored up
Exist in the 3rd storage tank, a cushioning effect can be played, it is ensured that whole processing procedure persistently can be carried out, while greatly improving
Treatment effeciency.
PH regulator device is connected with pipeline between the first storage tank in the present invention and organic tubular type film device, adopts this
Structure, in that context it may be convenient to which pH value regulation, more convenient operation are carried out to pending waste water.
Crystallization apparatus in the present invention are connected with the top of the first storage tank by pipeline, and the waste water after crystallization returns to the first storage
In tank, continue following cycle operation.
With the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
In the range of without departing from this invention technological thought, various change and modification can be carried out entirely.The technology of this invention
Property scope is not limited to the content in description, it is necessary to determine its technical scope according to right.
Claims (10)
1. a kind of method of vitamin B2 wastewater zero discharge, it is characterised in that the method comprising the steps of：
（1）Vitamin B2 production waste water is sent into organic tubular type film device concentrated, obtain tubular membrane concentrated solution and tubular membrane
Permeate, tubular membrane concentrated solution is carried out recrystallization again, after drying, obtains vitamin B2；
（2）Organic tubular membrane permeate feeding nanofiltration membrane system is carried out separating, obtains NF membrane permeate and nanofiltration membrance concentration
Liquid, after nanofiltration permeate liquid is evaporated again, is recycled inorganic salt, and evaporation water outlet returns production section and recycles.
2. the method for a kind of vitamin B2 wastewater zero discharge according to claim 1, it is characterised in that：The step（1）
Middle waste water first adds alkali to adjust pH to 5-7 before entering organic tubular type membranous system.
3. the method for a kind of vitamin B2 wastewater zero discharge according to claim 1, it is characterised in that：The step（1）
The vitamin B2 concentration of middle waste water is 1.20～3.21g/L.
4. the method for a kind of vitamin B2 wastewater zero discharge according to claim 1, it is characterised in that：Organic tubular type
Membrane aperture 30-50 nm, membrane material selects Kynoar, polyacrylonitrile, polyether sulfone or polysulfones, operating pressure 0.3～
0.55MPa, film average flux is 86-102L/m2·h.
5. the method for a kind of vitamin B2 wastewater zero discharge according to claim 1, it is characterised in that：The nanofiltration system
Including one-level nanofiltration membrane system and two grades of nanofiltration membrane system, the concentrated solution of one-level NF membrane is back in organic tubular membrane and carried out
Filter is processed, and the concentrated solution of two grades of NF membrane is back to one-level NF membrane carries out filtration treatment.
6. the method for a kind of vitamin B2 wastewater zero discharge according to claim 5, it is characterised in that：The one-level nanofiltration
The molecular cut off 800-1000Da of film, operating pressure is controlled to 2.0-3.0MPa, and film average flux is 21.7-25.6L/m2·
h.
7. the method for a kind of vitamin B2 wastewater zero discharge according to claim 5, it is characterised in that：Two grades of nanofiltrations
Retaining molecular weight is 100-300Da, control operation pressure 2.0-3.5MPa, and film average flux is 20.6-23.4 L/m2·
h.
8. a kind of device of vitamin B2 wastewater zero discharge, it is characterised in that including the first storage tank, organic tubular type film device,
Two storage tanks and nanofiltration membrane system, between the first storage tank, organic tubular type film device, the second storage tank and nanofiltration membrane system by pipeline even
Connect, organic tubular membrane is installed in organic tubular type film device, the retention side of organic tubular membrane is by pipeline and crystallization apparatus
Connection, the per-meate side of organic tubular membrane is connected with the feed liquid port of nanofiltration membrane system by pipeline, the per-meate side of nanofiltration membrane system
It is connected with vaporising device by pipeline.
9. the device of a kind of vitamin B2 wastewater zero discharge according to claim 1, it is characterised in that：The nanofiltration system
Including one-level nanofiltration membrane stack and two grades of nanofiltration membrane stacks, the permeable formation of the one-level nanofiltration membrane stack is entered with the feed liquid of two grades of nanofiltration membrane stacks
Mouth connection, the retention side of one-level nanofiltration membrane stack is connected with the bottom of the second storage tank by pipeline, the retention side of two grades of nanofiltration membrane stacks
It is connected with the top of the second storage tank by pipeline, the per-meate side of two grades of nanofiltration membrane stacks is connected with vaporising device by pipeline.
10. the device of a kind of vitamin B2 wastewater zero discharge according to claim 9, it is characterised in that：The one-level is received
Between filter membrane heap and two grades of nanofiltration membrane stacks, the 3rd storage tank is connected with by pipeline, the top of the 3rd storage tank is received with one-level by pipeline
The permeable formation connection of filter heap, the bottom of the 3rd storage tank is connected with the feed liquid port of two grades of nanofiltration membrane stacks by pipeline；The one-level
The retention side of nanofiltration membrane stack is connected with the first storage tank by pipeline；The retention side of two grades of nanofiltration membrane stacks passes through pipeline and second
Storage tank connects.
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| CN113583070A (en) * | 2021-08-05 | 2021-11-02 | 安徽普朗膜技术有限公司 | Separation and purification method for extracting vitamin VB12 from fermentation liquor |
| CN114314994A (en) * | 2022-02-17 | 2022-04-12 | 上海师范大学 | Device system and method for treating vitamin B6 production wastewater through membrane separation |
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Application publication date: 20170222 |