CN102765839A - Method for treating wastewater by sodium saccharin acidification and technology thereof - Google Patents
Method for treating wastewater by sodium saccharin acidification and technology thereof Download PDFInfo
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- CN102765839A CN102765839A CN2011101149556A CN201110114955A CN102765839A CN 102765839 A CN102765839 A CN 102765839A CN 2011101149556 A CN2011101149556 A CN 2011101149556A CN 201110114955 A CN201110114955 A CN 201110114955A CN 102765839 A CN102765839 A CN 102765839A
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Abstract
The invention belongs to the technical field of industrial water treatment and especially relates to a method for treating wastewater by sodium saccharin acidification and a technology thereof. The technology comprises two workshop sections of pretreatment and a two-stage membrane distillation system. Firstly, neutralization by addition of alkali and scale inhibition pretreatment are carried out so as to avoid wetting of a hydrophobic membrane during wastewater membrane distillation and concentration process and alleviating deposition of scale on the membrane surface. The two-stage membrane distillation system can be utilized to simultaneously realize wastewater desalination and organic matter removal. Pretreated wastewater enters a primary membrane distiller to carry out desalination and concentration on the wastewater. Due to the existence of volatile organic compounds in water, the primary membrane distiller produced water contains volatile organic compounds. The primary membrane distiller produced water enters a secondary membrane distiller (vacuum-type membrane distillation), and the volatile organic compounds are removed through adjustment of technological parameters. The method provided by the invention can be adopted to effectively solve problems of lengthy process, high energy consumption, severe secondary pollution and the like during the wastewater treatment process by sodium saccharin acidification and is helpful for standard discharge of wastewater and resource reclamation.
Description
Technical field:
The invention belongs to the Treatment of Industrial Water technical field, particularly relate to a kind of soluble saccharin acid out wastewater treatment method and technology.
Background technology:
Soluble saccharin production is generally processed through amidation, Hofmann degradation esterification, diazotization, displacement, chlorination, ammonification, acid out, alkalization and decoloring reaction.Wherein acid out waste water is strongly-acid, high organism, high saliferous.And such waste water output is big, 7 tons of one ton of soluble saccharin average emission of every production acid out waste water.It is 6000～15000mg/L that waste liquid contains COD, saltiness 7～15g/L, pH=1～3.The contribution margin of COD is main with the organic components of difficult degradation in the waste water, and mostly wherein topmost organism is aromatic compounds such as toluene, o-amino benzoyl ester, methyl o-aminobenzoate and verivate thereof etc., and contains methyl alcohol.Also having the inorganic salt of high density simultaneously, mainly is Na
+, SO
4 2-, Cl
-, and contain Ca
2+, SiO
3 2-Deng.
Traditional treatment process is carried out the biochemical process comprehensive treating process after generally adopting the reduction of iron aeration, coagulating sedimentation, Fenton reagent oxidation-pre-treatment such as flocculation again, and part enterprise adopts the directly discharging of neutralization dilution back.There are shortcomings such as technology is tediously long, expense is high, treatment effect is not good in traditional treatment process.And the not in addition reuse of inorganic salt that can utilize in the waste water and organism is so not only wasted resource and is increased production cost, and also can cause certain pollution to environment behind this discharging of waste liquid, is unfavorable for environment protection.
The present invention is intended to propose a kind of efficiently feasible and investment and all lower soluble saccharin acid out waste water reclaiming treatment process and the technology of working cost, has wherein mainly adopted film distillation technology.
Membrane distillation, be a kind ofly utilize hydrophobic microporous membrane, be the membrane sepn process of motivating force with the vapor pressure difference of film both sides.The operating method of membrane distillation mainly contains following form: four kinds of direct contact type membrane distillation, vacuum type membrane distillation, GAP TYPE membrane distillation, gas flow purging formula membrane distillations etc.The membrane distillation process need not be heated to boiling point with solution, as long as the suitable temperature difference is kept in the film both sides, this process just can be carried out.Compare the advantage highly significant of membrane distillation with other embrane method water technology: (1) membrane distillation process is almost carried out under normal pressure, and equipment is simple, and is easy to operate; (2) ratio of desalinization is up to 100% (in theory); (3) can handle the brackish water of high concentration, even can solution concentration be formed to hypersaturated state and be so-called membrane distillation crystallization technique; (4) film distillation technology is low to the requirement of mechanical strength of mould material.
Principal character of the present invention is: utilize membrane distillation technique realize to the desalination and concentration of such highly salt containing organic waste water with remove volatile organic matter, inorganic salt and organism in the reuse water help soluble saccharin industry standard wastewater discharge.The present invention is not only applicable to the wastewater treatment of soluble saccharin acid out, is applicable to other highly salt containing organic waste water processing yet.
The present invention utilizes film distillation technology that soluble saccharin acid out waste water is carried out desalination, removes organism, has overcome the existing deficiency of existing treatment process.Technology of the present invention is simple, and method is practical, technical feasibility, and its advantage applies exists: one, turn harm into good, turn waste into wealth.Adopt the present invention to handle soluble saccharin acid out waste water, through desalination, remove organism and help discharged wastewater met the national standard; Inorganic salt and organism can be recycled in the water; Two, technical process is simple, floor space is little, investment is less, widely applicable, convenient operating maintenance; Three, processing cost reduces.The membrane distillation sepn process has higher vaporization efficiency, can make full use of enterprise's low-grade exhaust heat and realize the film evaporation concentration, compares with evaporation concentration method with roasting method, and energy consumption obviously reduces; Four, technology is integrated flexibly.Can be different with processing requirements according to water quality, technical process is adjusted.Five, significantly reduce the environmental pollution degree.Membrane distillation has alleviated the contaminated degree of environment as a kind of green treatment technology, has tangible environmental benefit and social benefit.
In sum, utilizing film distillation technology to handle soluble saccharin acid out waste water is the original innovation to existing tupe, will reduce the processing cost of soluble saccharin acid out waste water, helps to realize soluble saccharin industry standard wastewater discharge.
Summary of the invention:
The present invention proposes a kind of soluble saccharin acid out wastewater treatment method, explains as follows:
The present invention mainly comprises two workshop sections of pre-treatment and twin-stage membrane distillation system, respectively shown in workshop section 1, workshop section 2 among the figure.
At first waste water gets into pre-treatment workshop section (abbreviating workshop section 1 as); In this workshop section, waste water is added alkali neutralization, scale inhibition pre-treatment, thereby avoid the wetting of hydrophobic membrane in wastewater membrane distillation (MD) desalination and concentration process; Also can suppress the deposition of dirt, slow down The decline of membrane flux on the film surface.Waste water is neutralized to pH=5～7, and nitrogenous organic multicomponent phosphoric acid class Scale inhibitors addition is 0.01～0.1g/L.
Workshop section 2 is a twin-stage membrane distillation system, can realize simultaneously to the desalination and concentration of waste water with remove volatile organic matter.Utilize film distillation technology that pending waste water is carried out desalination earlier, this membrane distillation demineralising process is a motivating force with the both sides vapour pressure deficit of hydrophobic membrane, and feed liquid side water vapour pressure arrives through fenestra and produces the water side greater than producing water side vapor pressure, and waste water is by desalination and concentration.
Because organism is main with aromatics in the saccharin sodium wastewater, and contains methyl alcohol.Volatile organic matters such as methyl alcohol, aromatics can see through fenestra to producing the water side simultaneously with water vapor in the membrane distillation process, so one-level membrane distillation device produces in the water and contains volatile organic matter.In the present invention, adopt membrane distillation degassing technology to remove one-level membrane distillation device and produce volatile organic matter in the water: one-level membrane distillation device produces water and gets into secondary membrane distillation device (vacuum type membrane distillation), realizes volatile organic matter in the water is removed.Volatile organic matter concentration is far above the inlet side organic concentration in the secondary membrane distillation feed liquid.Because the volatile organic matter volatility is higher than water, its separation factor is much larger than 1, thereby volatile organic matter is very easily striden film entering inlet side, after the inlet side condensation, becomes the strong solution that contains volatile organic matter; Feed liquid side organism reduces, and aqueous solution COD descends.Desalination, the product water that removes volatile organic matter are derived as total system in good time and are produced water.
One-level membrane distillation device belongs to direct contact type membrane distillation device among the present invention, and its mass transfer motivating force is the steam pressure difference of both sides solution, and its steady running need keep the solution-stabilized temperature head in both sides; Secondary membrane distillation device belongs to vacuum type membrane distillation device, and its mass transfer motivating force is the concentration difference of both sides volatile organic matter.Because the membrane distillation process is a synchronous mass-and heat-transfer process; Membrane distillation device feed temperature can progressively reduce; One-level membrane distillation device cold side solution temperature can progressively raise; Therefore establishing well heater in the hot side of one-level membrane distillation keeps the constant of feeding temperature, and one-level membrane distillation device cold side solution temperature is kept steady temperature through the heat transfer effect of secondary membrane distillation device, thereby guarantees that one-level membrane distillation device both sides solution temperature difference is constant.One-level membrane distillation device feed liquid flow velocity remains on 0.2～1.2m/s, and temperature remains between 40～70 ℃; Liquid (cold side solution) flow velocity that sees through of membrane distillation remains on 0.2～0.6m/s, and temperature remains between 20～30 ℃.Through adjustment secondary membrane distillation device structural parameter, the control flow velocity is at 0.2～1.2m/s, and cold side vacuum tightness maintains between 40～80kPa.
Water cooler 9 is set among the present invention, and the adjustment of visual processing parameter opens and closes, thereby the temperature that keeps getting into the cold cycle fluid of one-level membrane distillation device is between 20～30 ℃.
Description of drawings:
Workshop section 1 and workshop section 2 are as shown in the figure.1 is that pre-treatment jar, 2 is that whisking appliance, 3 is that lift pump, 4 is that brine tank, 5 is that valve, 6 is that well heater, 7 is that recycle pump, 8 is that one-level membrane distillation device, 9 is that water cooler, 10 is that desalination water pot, 11 is that secondary membrane distillation device, 12 is that prolong, 13 is a vacuum pump.
Embodiment:
Below set forth the present invention through specific embodiment, purpose is to help the reader to understand essence of the present invention better, but not as the qualification of practical range of the present invention.Embodiment is following:
Soluble saccharin acid out waste water quality is following: COD is 7850mg/L, and specific conductivity is 19.2mS/cm, and TDS is 7.22g/L, UV
254Be 31.52cm
-1, pH is 1.2.
1, soluble saccharin acid out waste water is neutralized to pH=6.0, adds the nitrogenous organic multicomponent phosphoric acid class Scale inhibitors of 0.03g/L then, be stirred to evenly.
2, with in the above-mentioned waste liquid adding one-level membrane distillation device waste water being carried out desalination and concentration.One-level membrane distillation process operation parameter is following: hot side temperature remains on 50 ± 1 ℃, and hot effluent speed is at 0.5m/s; Cold-side temperature remains on 20 ± 1 ℃, and flow velocity is at 0.3m/s.One-level membrane distillation device membrane flux is stabilized in 14.7～15.7kg/m in the operational process
2H produces water conductivity and is stabilized in below the 100 μ S/cm, and COD is at 2000～2500mg/L.One-level membrane distillation device produces water and gets into secondary membrane distillation device, and volatile organic matter is removed.The feed liquid flow velocity remains on 1.0m/s, and cold side vacuum tightness maintains 40kPa.For containing the strong solution of volatile organic matter, feed liquid side water outlet COD reduces to 280-330mg/L to inlet side after condensation.
Claims (6)
1. soluble saccharin acid out wastewater treatment method and technology, it is characterized in that: treatment process is made up of pre-treatment, two workshop sections of twin-stage membrane distillation system.
2. like said a kind of soluble saccharin acid out wastewater treatment method of claim 1 and technology; It is characterized in that: workshop section 1 is through neutralization, scale inhibition pre-treatment; Not only can prevent the wetting of membrane distillation desalination and concentration process hydrophobic membrane; Also can slow down the decay of membrane distillation process flux, improve membrane distillation process operation efficient; In this workshop section, waste water is added alkali neutralization, scale inhibition pre-treatment, waste water is neutralized to pH=5～7, nitrogenous organic multicomponent phosphoric acid class Scale inhibitors addition is 0.01～0.1g/L.
3. like said a kind of soluble saccharin acid out wastewater treatment method of claim 1 and technology, it is characterized in that: workshop section 2 is twin-stage membrane distillation system, can realize the desalination of waste water simultaneously and remove organism.Waste water is introduced into one-level membrane distillation device, carries out the membrane distillation desalination; Because the existence of volatile organic matter in the waste water, it is actual in containing organic solution to produce water after the desalination; This solution gets into secondary membrane distillation device, and it is the vacuum type membrane distillation, through the adjusting process parameter, realizes that volatility organically removes in the solution.
4. like said a kind of soluble saccharin acid out wastewater treatment method of claim 1 and technology; It is characterized in that: the hot side feed liquid of one-level membrane distillation device flow velocity remains on 0.2～1.2m/s; Temperature remains between 40～70 ℃; Liquid (cold side solution) flow velocity that sees through of membrane distillation remains on 0.2～0.6m/s, and temperature remains between 20～30 ℃; Secondary membrane distillation device structural parameter are adjusted into flow velocity at 0.2～1.2m/s, and cold side vacuum tightness maintains between 40～80kPa.
5. like said a kind of soluble saccharin acid out wastewater treatment method of claim 1 and technology; It is characterized in that: be provided with water cooler 9; The adjustment of visual processing parameter opens and closes, thereby the temperature that keeps getting into the cold cycle fluid of one-level membrane distillation device is between 20～30 ℃.
6. like said a kind of soluble saccharin acid out wastewater treatment method of claim 1 and technology, it is characterized in that: secondary membrane distillation device can adopt the vacuum type membrane distillation, also can adopt other membrane distillation types such as GAP TYPE membrane distillation, sweeping type membrane distillation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104973658A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Concentrating method of low-concentration phosphoric acid waste liquid |
| CN105906026A (en) * | 2016-06-08 | 2016-08-31 | 浙江奇彩环境科技股份有限公司 | Treatment method for wastewater containing small-molecular organic matter |
| CN106495404A (en) * | 2016-11-29 | 2017-03-15 | 湖南平安环保股份有限公司 | A kind of processing method of the high salinity cupric organic wastewater of highly acidity |
| CN110746052A (en) * | 2019-11-19 | 2020-02-04 | 河南省高新技术实业有限公司 | Method for treating saccharin production wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104973658A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Concentrating method of low-concentration phosphoric acid waste liquid |
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| CN110746052B (en) * | 2019-11-19 | 2021-11-02 | 河南省高新技术实业有限公司 | Method for treating saccharin production wastewater |
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Application publication date: 20121107 |