CN1253461C - Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique - Google Patents
Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique Download PDFInfo
- Publication number
- CN1253461C CN1253461C CN 03125471 CN03125471A CN1253461C CN 1253461 C CN1253461 C CN 1253461C CN 03125471 CN03125471 CN 03125471 CN 03125471 A CN03125471 A CN 03125471A CN 1253461 C CN1253461 C CN 1253461C
- Authority
- CN
- China
- Prior art keywords
- glucose
- hydrochloric acid
- diosgenin
- membrane
- waste water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 52
- 235000002722 Dioscorea batatas Nutrition 0.000 title 1
- 235000006536 Dioscorea esculenta Nutrition 0.000 title 1
- 235000003416 Dioscorea oppositifolia Nutrition 0.000 title 1
- 240000001811 Dioscorea oppositifolia Species 0.000 title 1
- 108010084592 Saporins Proteins 0.000 title 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 claims abstract description 74
- 239000008103 glucose Substances 0.000 claims abstract description 63
- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 claims abstract description 48
- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 claims abstract description 48
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 230000000149 penetrating effect Effects 0.000 claims abstract description 19
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 13
- 244000062245 Hedychium flavescens Species 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 238000001728 nano-filtration Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 18
- 238000001223 reverse osmosis Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 3
- 240000006365 Vitis vinifera Species 0.000 claims description 3
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 235000017008 Dioscorea nipponica Nutrition 0.000 abstract description 3
- 241000908494 Dioscorea nipponica Species 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 230000004907 flux Effects 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 244000281702 Dioscorea villosa Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000004879 dioscorea Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a wastewater treatment technology for extracting diosgenin by using yellow ginger or dioscorea nipponica, particularly to a method for treating diosgenin wastewater and recovering glucose and hydrochloric acid by a membrane integrated technology. The present invention is characterized in that the technology comprises the following steps: 1. pretreatment: after the diosgenin wastewater is pre-filtered, suspended substances or macromolecule impurities in the diosgenin wastewater are removed to obtain filtering liquid; 2, the recovery of the glucose and the hydrochloric acid: the pre-filtered filtering liquid is treated by acid-proof polyamide nano-filtering membrane, wherein the water solution of the hydrochloric acid penetrates the membrane to obtain the hydrochloric acid under the conditions of the pressure of 1.6 to 2.5MPa and the temperature of 20 to 40 DEG C, the glucose is intercepted, and the concentration of the intercepted glucose solution is concentrated to more than 10% from 2 to 7%; when the quantity of the concentrated solution accounts for below 40% of material feeding quantity, water is replenished in the concentrated solution, residual acid in the concentrated solution is removed, and the concentrated solution is evaporated and concentrated for preparing the glucose; 3, advanced treatment: after neutralized, penetrating liquid reaches standards to be discharged or recycled. The wastewater treatment technology of the present invention reaches one-level discharge standards established by China, and the glucose and the hydrochloric acid in the wastewater can be effectively utilized.
Description
Technical field
The present invention relates to utilize yellow ginger or Dioscorea nipponica Mak. Ningpo Yam Rhizome to extract the waste water treatment process of diosgenin.Be specifically related to the hydrolysising original liquid and washing lotion or their mixed solution that produce in the diosgenin leaching process, reclaim wherein glucose and hydrochloric acid.
Background technology
Diosgenin waste water is the waste water that produces in yellow ginger or Dioscorea nipponica Mak. Ningpo Yam Rhizome processing diosgenin process, mainly from acid hydrolysis, and the filtration of hydrolyzate and washing process.Diosgenin content is 1.8-3.2% in the dried yellow ginger, the starch that wherein also contains 40% left and right sides Mierocrystalline cellulose and about 50%, diosgenin content is 0.6-0.8% in the cadmium yellow ginger, wherein also contain 20% left and right sides Mierocrystalline cellulose and 18% above starch, add hydrochloric acid or the sulfuric acid of 0.8-2N during hydrolysis usually, at 115-125 ℃ of following hydrolysis 2-4 hour, hydrolyzed solution after filtration, be washed to neutrality, after centrifugal, the drying, hydrolyzate, use the non-polar solvent extract diosgenin.Hydrolyzate filters in the filtrate that produces and contains the glucose of 4-7% and hydrochloric acid or the sulfuric acid of 0.6-1.5N, its COD value is 90000-110000mg/l, contain the glucose of 2-4% and hydrochloric acid or the sulfuric acid of 0.02-0.5N in the wash water, its COD value is 40000-50000mg/l, one ton of diosgenin of every production produces about 500 tons of waste water approximately, and wherein 180 tons of hydrolysising original liquids and washing lotion are 320 tons.
The improvement method that diosgenin waste water is commonly used is a biochemical process.This method requires to transfer PH to neutral with lime diosgenin waste water earlier.The sulfuric acid process hydrolyzed waste water in and the time produce calcium sulfate precipitation and separated, the chlorion in the salt acid system hydrolyzed waste water then is difficult to remove.This has not only consumed a large amount of alkali, has increased running cost, has also wasted useful matter glucose and hydrochloric acid in the diosgenin waste water.And because organic concentration height in the diosgenin waste water, saltiness is big, has strengthened the difficulty of biochemical treatment, often is difficult to reach the first discharge standard of national regulation through the waste water of biochemical process processing.
Ceng Youyong trialkylamine (as Tributylamine, trioctylamine) extracting-back extraction obtains glucose after getting and separating hydrochloric acid, the more biochemical treatment process of utilizing in addition.But this method also exists extraction agent consumption big, complex technical process, and the shortcoming that cost is too high is difficult to implement in full scale plant.
Patent of invention CN1316523A has proposed to be applied to extract the method for glucose from the diosgenin waste water of sulphuric acid hydrolysis technology, this invention propose sulphuric acid hydrolysis waste water in lime with after desalting method be respectively:
1, adopts two-stage two-segment electrodialysis → resin cation (R.C.) → resin cation (R.C.);
2, two sections reverse osmosis → resin cation (R.C.) → resin anion(R.A)s of one-level;
3, resin cation (R.C.) → resin anion(R.A) → resin cation (R.C.) → resin anion(R.A).
This method exists energy consumption big, shortcomings such as resin regeneration expense height.
Summary of the invention
The objective of the invention is to overcome first discharge standard, the glucose in the waste water and hydrochloric acid that existing diosgenin wastewater biochemical treatment technology is difficult to reach national regulation and can not get the shortcoming effectively utilized, provide a kind of membrane integrating technique to handle diosgenin waste water and reclaim glucose and the method for hydrochloric acid.
To achieve these goals, technical scheme of the present invention is: membrane integrating technique is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that may further comprise the steps:
1, pre-treatment:
Diosgenin waste water is removed suspended substance or macromole impurity through pre-filtering, gets filtrate.Diosgenin in recyclable suspended substance or the macromole impurity.Pre-filtering comprises following method:
1) with molecular weight cut-off 10000-100000 dalton's (Daltons) hollow fiber ultrafiltration membrane, under 0.2-0.5MPa pressure and 20-50 ℃ of temperature, filters;
2) adopting the aperture is the inorganic micro filtering membrane (comprising aluminum oxide or zirconium oxide film) of 0.1-0.45 micron, and filter pressure is 0.2-0.6MPa, and filtration temperature is 15-60 ℃;
3) press filtration of polypropylene sheet frame or vacuum filtration, process be at the pressure of 0.3-0.6MPa, or under the vacuum tightness of 500-700mmHg, carry out in 20-50 ℃ temperature;
2, reclaim glucose and hydrochloric acid:
Filtrate after the pre-filtering is handled with the acid proof polyamide nanofiltration membrane, and aqueous hydrochloric acid wherein is to see through film under the temperature of 1.6-2.5MPa and 20-40 ℃ at pressure, obtain hydrochloric acid, and glucose is trapped.Hydrochloric acid is purified, thereby satisfies the requirement that is back to the yellow ginger hydrolysis process.Glucose solution is concentrated simultaneously, and its concentration is concentrated to more than 10% by 2-7%.When the amount of concentrated solution (glucose) reaches 40% when following of charging capacity, beginning make up water in concentrated solution removes remaining acid in the concentrated solution, and the concentrated solution after the depickling is through evaporation concentration system glucose, and penetrating fluid is through the advanced treatment qualified discharge.
3, advanced treatment:
Keeping the skin wet through the penetrating fluid pH value behind the film in concentrated solution during the nanofiltration membrane operation is more than 2.5, and the COD value is below the 6000mg/l, still can not directly discharge, and need carry out the primary standard that advanced treatment reaches country's " integrated wastewater discharge standard ".The deep treatment method that the present invention takes is as follows:
1), penetrating fluid is at the pressure of 1.6-2.5MPa, uses the one-level nanofiltration membrane treatment under 20-40 ℃ of temperature.Concentrated solution continues evaporation concentration system glucose, pass through penetrating fluid behind the one-level film in lime and after, handle under the temperature of the pressure of 1.2-1.8MPa and 20-40 ℃ with the two-pass reverse osmosis film, reach first discharge standard.
2), penetrating fluid is with the lime PH7-9 that neutralizes, under the pressure of 1.4-2.5MPa, under 20-40 ℃ temperature, hold back the anti-pollution reverse osmosis membrane second-stage treatment with ultralow pressure reverse osmosis membrane and height and reach the first discharge standard (see figure 1).
3), penetrating fluid neutralizes after the neutrality with lime, handle through anaerobism, aerobic biochemical to reach first discharge standard.(see figure 2).
4), penetrating fluid is as the wash water direct reuse (see figure 3) first time of hydrolyzate.
Reclaim the refining of grape liquid glucose:
The pH value of concentrated solution reaches more than 2.5, and wherein the concentration of glucose rises to 10-12%, is neutralized to PH5-6 with sodium hydroxide, and every 100L liquid glucose adds the gac of 0.5-2kg, 70-90 ℃ of heating 20-40 minute, filters.Filtrate is through evaporation concentration, and the evaporation condensed water direct reuse washs in hydrolyzate, obtains the glucose product that concentration is 40-45%.
Reclaim the utilization of hydrochloric acid:
Handle the hydrochloric acid that obtains with the acid proof polyamide nanofiltration membrane, fixed by accurate PH instrumentation, the pH value that reclaims hydrochloric acid is 0.05-0.5, concentration is 0.3-0.85N, be made into the hydrochloric acid of 2N with 30% mixed in hydrochloric acid, be added in pulverizing, pre-fermented yellow ginger, the concentration of hydrochloric acid that makes the acidolysis material is 0.8-1.5N.
The present invention has overcome the shortcoming that existing diosgenin wastewater biochemical treatment technology is difficult to reach the first discharge standard of national regulation, and the material in the waste water is utilized effectively.The present invention realizes qualified discharge when reclaiming glucose in the diosgenin waste water and hydrochloric acid, and a kind of method of handling diosgenin waste water with membrane integrating technique is provided.The Glucose Liquid that reclaims can be used for the carbon source in the biochemical products production through concentrating the product that obtains containing sugar＞40%.Concentration of hydrochloric acid＞the 0.6N that reclaims is back to yellow ginger hydrolytic process or other processes.The maximum characteristics of this method are to state in realization not need many chemical reagent in the purpose process, and technology is simple, and is easy to operate, and working cost is low, does not produce secondary pollution, and bring more benefit for manufacturing enterprise.Waste water after treatment reaches the primary standard of country's " integrated wastewater discharge standard ".
Description of drawings
Fig. 1 is first kind of process flow sheet of the present invention
Fig. 2 is second kind of process flow sheet of the present invention
Fig. 3 is the third process flow sheet of the present invention
Embodiment
Use embodiment below, the present invention is done detailed explanation
Embodiment 1:
1), pre-treatment as shown in Figure 1, membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (hydrolyzed solution) 100L, COD105000mg/L, pH value 0.16,36 ℃ of temperature; Via hole diameter is the aluminum oxide micro-filtrate membrane filtration of 200nm, and filter pressure is 0.41MPa, average flux 197L/m
2H removes suspended substance or macromole impurity, gets filtrate 93L.2), reclaim glucose and hydrochloric acid: using the nanofiltration membrane depickling, is average flux 6.5L/m under the 1.8MPa at pressure
2H, aqueous hydrochloric acid see through film, obtain hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: the nanofiltration concentrated solution adds water 40L depickling, penetrating fluid with in the lime and after the one-level advanced treatment be the low pressure reverse osmosis film, be that average flux under the 1.8MPa is 16.8L/m at pressure
2H; The secondary advanced treatment is that height is held back anti-pollution reverse osmosis membrane, is the average flux 22.4L/m of 1.6MPa at pressure
2H, water outlet COD64mg/L.
Reclaim hydrochloric acid 54.5L, concentration is 0.76N; Hydrolyzed solution glucose content 5.67%, be concentrated into 11.26% through nanofiltration membrane, get Glucose Liquid 38.5L, NaOH solution neutralization with 20%, the gac that every 100L liquid glucose adds 1kg decolours under 80 ℃ temperature, and final evaporation concentration obtains 40.62% Glucose Liquid.
Embodiment 2:
1), pre-treatment membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (hydrolyzed solution) 100L, COD96000mg/L, pH value 0.18,32 ℃ of temperature; Through 100nm zirconium white micro-filtrate membrane filtration, filter pressure is 0.41MPa, and average flux 247L/m2h removes suspended substance or macromole impurity, gets filtrate.2), reclaim glucose and hydrochloric acid: filtrate is through the nanofiltration membrane depickling, and pressure is 1.8MPa, average flux 6.0L/m
2The h aqueous hydrochloric acid sees through film, obtains hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: concentrated solution adds water 80L depickling must concentrate liquid glucose 35L, and the one-level advanced treatment of the penetrating fluid of depickling is a nanofiltration membrane, is that average flux under the 1.8MPa is 18.1L/m at pressure
2H; The secondary advanced treatment is that height is held back anti-pollution reverse osmosis membrane, and the average flux under pressure 1.6MPa is 24.2L/m
2H, water outlet COD are 82mg/L.
The concentration of hydrochloric acid that reclaims is 0.70N; Hydrolyzed solution glucose content 4.62% is concentrated into 11.72% through nanofiltration membrane, and final evaporation concentration obtains 42.36% Glucose Liquid 36.2L.The process for purification of liquid glucose is with embodiment 1.
Embodiment 3:
1), pre-treatment membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (hydrolyzed solution) 100L, COD88000mg/L, 34 ℃ of pH value 0.21 temperature; Through vacuum filtration, get filtrate.2), reclaim glucose and hydrochloric acid: gained filtrate is used the nanofiltration membrane depickling, is average flux 11.8L/m under the 1.8MPa at pressure
2H; Aqueous hydrochloric acid sees through film, obtains hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: get concentrated solution 36L, add the further depickling of water 60L, penetrating fluid carries out the two-stage advanced treatment through neutralization with the low pressure reverse osmosis film, and the average flux under pressure 1.8MPa is respectively 9.3L/m
2H and 25.4L/m
2H, water outlet COD78mg/L.
The concentration of hydrochloric acid that reclaims is 0.65N; Hydrolyzed solution glucose content 6.58% is concentrated into 10.48% through nanofiltration membrane, and final evaporation obtains 45.4% Glucose Liquid.The process for purification of liquid glucose is with embodiment 1.
Embodiment 4:
1), pre-treatment membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (wash water) 200L, COD45000mg/L, pH value 0.88,38 ℃ of temperature; Pellumina through 500nm filters the average flux 216L/m under pressure 0.42MPa
2H gets filtrate.2), reclaim glucose and hydrochloric acid: filtrate is used the nanofiltration membrane depickling, at 1.8MPa, average flux 5.9L/m
2H; Aqueous hydrochloric acid sees through film, obtains hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: dope adds water 30L depickling, the pressure 1.6MPa of first-stage reverse osmosis, average flux 17L/m
2H; The pressure 1.0MPa of two-pass reverse osmosis, flux 22L/m
2H, water outlet COD64mg/L.
The concentration of hydrochloric acid that reclaims is 0.35N; Hydrolyzed solution glucose content 4.2% is concentrated into 10.48% through nanofiltration membrane, and final evaporation obtains 45.4% Glucose Liquid.The process for purification of liquid glucose is with embodiment 1.
Embodiment 5:
1), pre-treatment as shown in Figure 2, membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (mixed solution) 200L, COD56000mg/L, pH value 0.32,40 ℃ of temperature, press filtration under the pressure of 0.3MPa.2), reclaim glucose and hydrochloric acid: filtrate is used the nanofiltration membrane depickling, the flux 14.2L/m under 1.8MPa pressure
2H; Aqueous hydrochloric acid sees through film, obtains hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: dope adds water 50L depickling, and penetrating fluid is used in the lime and pre-treatment, again by prior art anaerobism, aerobic technical finesse, water outlet COD＜100mg/L.
The recovery concentration of hydrochloric acid is 0.32N, and hydrolyzed solution glucose content 3.05% is concentrated into 9.26% through NF, and final evaporation obtains 41.57% Glucose Liquid.The process for purification of liquid glucose is with embodiment 1.
Embodiment 6:
1), pre-treatment as shown in Figure 3, membrane integrating technique is handled diosgenin waste water and is also reclaimed glucose and the method for hydrochloric acid, is realized by following steps:: diosgenin waste water (hydrolyzed solution) 100L, COD86000mg/L, pH value 0.16,36 ℃ of temperature; Via hole diameter is the aluminum oxide micro-filtrate membrane filtration of 200nm, and filter pressure is 0.41MPa, average flux 197L/m
2H removes suspended substance or macromole impurity, gets filtrate 93L.2), reclaim glucose and hydrochloric acid: using the nanofiltration membrane depickling, is average flux 6.5L/m under the 1.8MPa at pressure
2H, aqueous hydrochloric acid see through film, obtain hydrochloric acid, and be trapped be the glucose concentrated solution.3), advanced treatment: the nanofiltration concentrated solution adds water 40L depickling, and penetrating fluid is as the wash water direct reuse first time of hydrolyzate.
Claims (9)
1. membrane integrating technique is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that may further comprise the steps:
1). pre-treatment:
Diosgenin waste water is removed suspended substance or macromole impurity through pre-filtering, gets filtrate;
2). reclaim glucose and hydrochloric acid:
Filtrate after the pre-filtering is handled with the acid proof polyamide nanofiltration membrane, and aqueous hydrochloric acid wherein is to see through film under the temperature of 1.6-2.5MPa and 20-40 ℃ at pressure, obtain hydrochloric acid, and glucose is trapped; The glucose solution that is trapped is concentrated, its concentration is concentrated to more than 10% by 2-7%, when the amount of concentrated solution reaches 40% when following of charging capacity, beginning is make up water in concentrated solution, remove remaining acid in the concentrated solution, concentrated solution continues evaporation concentration system glucose, and penetrating fluid is through the advanced treatment qualified discharge;
3). advanced treatment:
The penetrating fluid pH value that acid proof polyamide nanofiltration membrane when operation make up water in concentrated solution sees through behind the film is more than 2.5, and the COD value is below the 6000mg/l, to neutralize, qualified discharge or reuse after the advanced treatment.
2. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: the pre-filtering in the described preprocessing process is: with the daltonian hollow fiber ultrafiltration membrane of molecular weight cut-off 10000-100000, filter under 0.2-0.5MPa pressure and 20-50 ℃ of temperature.
3. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: the pre-filtering in the described preprocessing process is: adopting the aperture is the inorganic micro filtering membrane of 0.1-0.45 micron, aluminum oxide or zirconium oxide film filter under 0.2-0.6Mpa pressure and 15-60 ℃ of temperature.
4. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: the pre-filtering in the described preprocessing process is: with polypropylene sheet frame press filtration or vacuum filtration, filtration is at the pressure of 0.3-0.6MPa, or under the vacuum tightness of 500-700mmHg, carry out in 20-50 ℃ temperature.
5. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, and it is characterized in that: described advanced treatment: penetrating fluid is used the one-level nanofiltration membrane treatment at the pressure of 1.6-2.5MPa under 20-40 ℃ of temperature; Through the penetrating fluid behind the one-level film in lime and after, handle under the temperature of the pressure of 1.2-1.8MPa and 20-40 ℃ with the two-pass reverse osmosis film, reach first discharge standard.
6. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: described advanced treatment: penetrating fluid is with the lime PH7-9 that neutralizes, under the pressure of 1.4-2.5MPa, under 20-40 ℃ temperature, hold back the anti-pollution reverse osmosis membrane second-stage treatment with ultralow pressure reverse osmosis membrane and height and reach first discharge standard.
7. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: described advanced treatment: penetrating fluid neutralizes with lime after the neutrality, handles through anaerobism, aerobic biochemical to reach first discharge standard.
8. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: described recovery grape liquid glucose, the pH value of grape liquid glucose concentrated solution reaches more than 2.5, wherein the concentration of glucose rises to 10-12%, be neutralized to PH5-6 with sodium hydroxide, every 100L liquid glucose adds gac 0.5-2kg, 70-90 ℃ of heating 20-40 minute, filters; Filtrate is through evaporation concentration, and the evaporation condensed water direct reuse washs in hydrolyzate, obtains the glucose product that concentration is 40-45%.
9. membrane integrating technique according to claim 1 is handled diosgenin waste water and is reclaimed glucose and the method for hydrochloric acid, it is characterized in that: handle the hydrochloric acid that obtains with the acid proof polyamide nanofiltration membrane, its pH value is 0.05-0.5, concentration is 0.3-0.85N, be made into the hydrochloric acid of 2N with 30% mixed in hydrochloric acid, be added in pulverizing, pre-fermented yellow ginger, the concentration of hydrochloric acid that makes the acidolysis material is 0.8-1.5N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125471 CN1253461C (en) | 2003-09-29 | 2003-09-29 | Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125471 CN1253461C (en) | 2003-09-29 | 2003-09-29 | Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528768A CN1528768A (en) | 2004-09-15 |
| CN1253461C true CN1253461C (en) | 2006-04-26 |
Family
ID=34285932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03125471 Expired - Fee Related CN1253461C (en) | 2003-09-29 | 2003-09-29 | Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253461C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318323C (en) * | 2005-12-23 | 2007-05-30 | 北京盖雅环境科技有限公司 | Method for highly efficient treatment of yellow ginger-processing wastewater and uses thereof |
| CN108911390B (en) * | 2018-07-18 | 2021-10-15 | 荆楚理工学院 | A kind of treatment method for comprehensive utilization of turmeric saponin wastewater |
| CN111268840B (en) * | 2020-02-25 | 2023-01-31 | 苏州翔铭化工设备有限公司 | Method for recycling and treating salt in waste water of yeast drum |
| CN111268841B (en) * | 2020-02-25 | 2022-11-22 | 苏州翔铭化工设备有限公司 | Method for desalting yeast drum wastewater |
| CN114805207A (en) * | 2022-04-14 | 2022-07-29 | 山东华鲁恒升化工股份有限公司 | Method for removing sulfuric acid in rearrangement solution by using membrane separation technology |
-
2003
- 2003-09-29 CN CN 03125471 patent/CN1253461C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1528768A (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108249646A (en) | Can resource recycling power plant desulfurization wastewater Zero-discharge treating process and device | |
| CN115784503A (en) | A system and method for extracting lithium from salt lake brine and preparing battery-grade lithium carbonate | |
| CN102060861B (en) | Desalination concentration method for cephalo mother liquor | |
| CN204588908U (en) | A new landfill leachate treatment system | |
| CN104276709A (en) | Coal chemical industry concentrated brine zero discharge technique and special equipment thereof | |
| CN102745836A (en) | Processing method of orange-can production wastewater | |
| CN102597253A (en) | Process for economically manufacturing xylose from hydrolysate using electrodialysis and direct recovery method | |
| CN208120896U (en) | Can resource recycling power plant desulfurization wastewater zero discharge treatment device | |
| CN103172212A (en) | Treatment method of lignin production waste water | |
| CN109970274B (en) | Method for treating acid wastewater and alkaline wastewater in viscose industry | |
| CN105585195A (en) | Coal chemical high-salinity wastewater treatment and recycling system | |
| CN112876429A (en) | Recovery method and recovery system of N-methylmorpholine-N-oxide | |
| CN112939281A (en) | Method and system for recovering N-methylmorpholine-N-oxide | |
| CN112758957A (en) | Process for purifying sodium hydroxide concentration by electrodialysis | |
| CN102476880A (en) | Treatment method of vanadium precipitation wastewater | |
| CN114988438A (en) | Lithium carbonate circulation lithium extraction process | |
| CN1253461C (en) | Method for treating waste water of chinese yam saporin and recovering gluocose and hydrochloric acid by membrane integrating technique | |
| CN1554773A (en) | Method for extracting fermentikve macrolide antibiotics using membrane | |
| CN107500464B (en) | Method for treating acid wastewater of viscose fiber factory | |
| CN113912236A (en) | Method for recovering glycolic acid from CMC wastewater | |
| CN106995398A (en) | L proline novel technology for extracting | |
| CN204111506U (en) | A kind of Coal Chemical Industry strong brine technique of zero discharge specific equipment | |
| CN1197785C (en) | Method for treating waste water containing low concentration ammonium chloride | |
| CN101870639A (en) | Production method of kelp mannitol with low energy consumption | |
| CN111875094B (en) | Comprehensive treatment process of beryllium-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20110929 |