CN105110504A - Equipment and method for recycling membrane-process printing and dyeing wastewater - Google Patents
Equipment and method for recycling membrane-process printing and dyeing wastewater Download PDFInfo
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- CN105110504A CN105110504A CN201510528614.1A CN201510528614A CN105110504A CN 105110504 A CN105110504 A CN 105110504A CN 201510528614 A CN201510528614 A CN 201510528614A CN 105110504 A CN105110504 A CN 105110504A
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Abstract
The invention relates to equipment and method for recycling membrane-process printing and dyeing wastewater. The method comprises the following steps: mechanically filtering secondary biochemical effluent of printing and dyeing wastewater, and introducing into an ultrafiltration system; leading produced water which is obtained by filtering of an ultrafiltration membrane in the ultrafiltration system into one side of a membrane contact reactor, and introducing an ozone-containing gas to the other side of the membrane contact reactor; diffusing the ozone through the membrane, reacting ozone with organic matters in the wastewater, and removing residual colors, organic matters and the like in the wastewater to realize deep treatment. Equipment for the method comprises a mechanical filter, the ultrafiltration membrane system and the membrane contact reactor, wherein the molecular weight cutoff of the ultrafiltration membrane is optimally selected, and is 30kDa-50kDa. The defects of low mass transfer efficiency and low ozone utilization in the existing ozone mass transfer process, and complicated process, large floor area and high recycling cost of printing and dyeing wastewater recycling can be overcome by utilizing the membrane-process combined method, and deep treatment and recycling of printing and dyeing wastewater can be realized.
Description
[technical field]
The present invention relates to the Apparatus and method for of a kind of embrane method printing-dying wastewater recycling process, be specifically related to a kind ofly apply ultrafiltration system and film contact reactor carries out the Apparatus and method for of advanced treatment and Treatment for Reuse to dyeing waste water secondary biochemical effluent, belong to field of waste water treatment.
[background technology]
Dyeing waste water complicated components, colourity, COD equal size are higher.Especially along with the development of dye chemical industry, dye component is increasingly sophisticated, and its process becomes difficulty all the more.Meanwhile, dyeing has strict restriction to residual in reuse water COD, colourity etc.Dyeing waste discharge amount is huge, and reclamation rate is very low.The advanced treatment and the reuse that realize dyeing waste water are significant.Dyeing waste water is after secondary biochemical treatment, and water outlet is residual comparatively high chroma generally, forms primarily of the hardly degraded organic substance and a large amount of microbial metabolites with color development functional group.Microbial metabolites divides subspan large, microbial polymer (> 10kDa), protein and polysaccharide, humic-like substance (1-10k), low molecular organic acids and neutral substance (< 1kDa). and macromole content in waste water is more, biodegradable performance is poor, and intractability is large.
Ozone oxidation is very competent, do not produce mud and peculiar smell, non-secondary pollution, and source of the gas is easy to get, is usually used in wastewater deep treatment process.But ozone solubleness in water is not high, less stable, need suitable gas liquid contacting technology to realize ozone short mix, reduce the power loss in mass transfer process.Traditional ozone contact mode is mostly packing tower, spray tower, bubble tower etc.The ozone rate of mass transfer of these equipment is not high enough, and easily occurs that liquid flooding, emulsion, foam, aerosol such as to carry secretly at the problem.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, utilizing ultra-filtration membrane and film contact reactor to carry out advanced treatment and reuse to dyeing waste water secondary biochemical effluent.
The object of the invention is to realize in the following manner:
The invention provides the equipment of a kind of embrane method printing-dying wastewater recycling process, comprise raw water box, topping-up pump, filtered water tank, source of the gas, ozonizer, ozone concn detector, ozone decomposed device, this equipment also comprises mechanical filter, ultrafiltration system, film contact reactor.
Described mechanical filter adopt in grid, filter screen filter cloth, sand filtration, gac, active cotton, micro-filtration one or more.
Present invention also offers the method for a kind of embrane method printing-dying wastewater recycling process, the method comprises the following steps:
1) pending dyeing waste water is introduced raw water box after secondary biochemical treatment, under topping-up pump effect, waste water is introduced in mechanical filter;
2) by above-mentioned 1) in waste water after mechanical filter filters to introduce containing molecular weight cut off be the ultrafiltration system of the ultra-filtration membrane of 3kDa-100kDa, the dense water produced after described ultrafiltration system filters is arranged outward, obtains ultrafiltration simultaneously and produces water;
3) by 2) in ultrafiltration produce the side that water introduces film contact reactor, pass into containing ozone gas at the opposite side of film contact reactor simultaneously;
4) control 3) in film contact reactor gas phase side pressure be less than bubbling pressure and liquid phase pressure sum, ozone gas is made to be undertaken spreading by film in still mode and react with the useless Organic substance in water of opposite side, by the removal such as residual chroma, organism in waste water, realize the advanced treatment of waste water;
5) tail gas fully produced after reaction is emptying after decomposing, organic waste water through fully oxidized up to standard after discharge.
Above-mentioned steps 1) in the mechanical filter silt removed in raw wastewater, suspended substance and be partly dissolved state organism.This step can membrane module in available protecting subsequent step from the physical abrasion of impurities in water, reduce the organic loading of subsequent disposal simultaneously;
Step 2) utilize preposition ultra-filtration membrane to tackle further macromole in water, to alleviate the organic loading of subsequent oxidation process.In secondary biochemical effluent, organism has residual dye, microbial decomposition product etc., and molecular weight distribution is wider.Ultra-filtration membrane can remove the larger partial organic substances of its middle-molecular-weihydroxyethyl, to the reduction Be very effective of total organic matter in water;
Step 3) to utilize film contact reactor to carry out ozonation aerated, and be less than liquid phase pressure and transmembrane pressure sum by controlling gaseous pressure, aeration process is carried out in still mode.This aeration mode pressure-losses is little, and mass transfer process energy consumption is little.By non-vesicular forms aeration, the mass transfer coefficient of ozone is large, and mass-transfer efficiency is high.The film contact reactor used is made up of hollow-fibre membrane, and this membrane module provides very large specific surface area.The volume of ozone contact device can be reduced by film contact reactor.The problems such as meanwhile, in film contact reactor, gas phase and liquid phase independently flow, and the operation of two-phase does not interfere with each other, the liquid flooding that can effectively avoid traditional reactor easily to occur.
On the basis of technique scheme, present device can also do following improvement:
Preferably, the molecular weight cut off of the film of described ultrafiltration membrane system is 30kDa-50kDa.
Further, in described film contact reactor, gas phase side force value is 1kPa-10kPa.
Further, the film of described film contact reactor adopts sludge proof Hollow-fibre membranes material to form.
Further, described Hollow-fibre membranes material is one or more in polyvinylidene difluoride (PVDF), tetrafluoroethylene, poly-(vinylidene-copolymerization-R 1216), poly-(vinylidene-copolymerization-tetrafluoroethylene), poly-(vinylidene-copolymerization-trifluoro-ethylene), poly-(vinylidene-copolymerization-chlorotrifluoroethylene).
Further, described hollow-fibre membrane is dewatering microporous film, and pore size is 0.1-1 micron, and porosity is 40-90%, and wall thickness is 0.1-0.4mm.
The invention has the beneficial effects as follows:
The inventive method utilizes preposition ultra-filtration membrane to tackle to alleviate the load in follow-up ozone oxidation stage to larger molecular organics in dyeing waste water bio-chemical effluent.Then film contact reactor is utilized to realize the short mix of ozone and waste water in the mode of bubble-free aeration.Utilize this embrane method combination process to realize advanced treatment and the reuse of dyeing waste water, and to overcome in prior art ozone mass transfer process that mass-transfer efficiency is low, ozone utilization rate is low and printing-dying wastewater recycling process complicated, floor space is large, the defect that reuse cost is high.
[accompanying drawing explanation]
Fig. 1 is the process flow diagram of a kind of embrane method printing-dying wastewater recycling process
Fig. 2 is a kind of embrane method printing-dying wastewater recycling method ozone mass transfer principle schematic
In accompanying drawing, the list of parts representated by each label is as follows:
1, raw water box, 2, mechanical filter, 3, ultrafiltration system, 4, film contact reactor, 5, topping-up pump, 6, filtered water tank, 7, source of the gas, 8, ozonizer, 9, ozone concn detector, 10, ozone decomposed device.
[embodiment]
Be described principle of the present invention and feature with the following Examples, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Experimental example
With the secondary biochemical effluent of certain printing and dyeing enterprise waste discharge for object, investigate the impact of ultra-filtration membrane on oxidation effectiveness of different molecular weight cut off in preposition ultrafiltration system.There is provided with the ultra-filtration membrane optimized choice of this experimental study to this invention and further illustrate.
The water quality of waste water after secondary biochemical treatment of this enterprise discharge is: chemical oxygen demand (COD) 85.3mg/L, biochemical oxygen demand (BOD) 8.2mg/L, colourity 60, turbidity 15, total suspended solid 15.6mg/L, pH=8.3.
Former water is after sand filtration is filtered, be 100kDa respectively by molecular weight cut off, 30kDa, 10kDa, ultra-filtration membrane (the Millipore of 3kDa and 1kDa, USA), the ultrafiltration cup (Amicon, Model8400) of use be furnished with stir original paper make stoste be tending towards homogeneous with anti-pollution too fast.Pressure source is adopted as nitrogen (99.5%), cross film pressure to be respectively: 1bar (100kDa ultra-filtration membrane), 2bar (30kDa ultra-filtration membrane), 3bar (10kDa ultra-filtration membrane), 4bar (3kDa ultra-filtration membrane), 5bar (1kDa ultra-filtration membrane).
The product water at different levels obtained enter the side of film contact reactor, the ozone gas of 60mg/L is introduced at reactor opposite side, flow is that the film contact reactor that 200ml/min. uses is made up of Pvdf Microporous Hollow Fiber Membrane, membrane module is containing hollow-fibre membrane 20, useful length 10cm, effective surface area 0.00854m
2, film mean pore size 0.13 micron, porosity 78%. ozone gas is in the flowing of hollow-fibre membrane tube side, and waste water is at hollow-fibre membrane shell fluid flow.
The chemical oxygen demand value of waste water after the different oxidization time of film contact reactor through the preposition ultra-filtration membrane of difference sees the following form (unit: mg/L):
| Filter water outlet | 100kDa | 30kDa | 10kDa | 3kDa | 1kDa | |
| 0min | 76.4 | 61.7 | 54.7 | 51.1 | 49.5 | 48.9 |
| 30min | 77.2 | 56.5 | 49.0 | 43.9 | 42.0 | 42.2 |
| 60min | 69.2 | 45.8 | 38.2 | 35.7 | 32.4 | 33.1 |
| 90min | 60.1 | 39.8 | 32.9 | 32.6 | 26.0 | 26.2 |
| 120min | 55.2 | 32.1 | 23.7 | 24.6 | 23.4 | 22.1 |
Upper example illustrates that the secondary biochemical effluent molecular weight distribution of dyeing waste water is comparatively wide, and ultra-filtration membrane can remove partial organic substances in water effectively, is conducive to follow-up ozone oxidation.Along with the reduction of molecular weight cut off, ultra-filtration water chemical oxygen demand (COD) diminishes.From the situation of ultra-filtration water change of water quality, 100kDa and 30kDa ultra-filtration membrane to organic matter removal successful, 10kDa and following ultra-filtration membrane not obvious to organic further rejection effect.After preposition ultra-filtration membrane pre-treatment, secondary biochemical effluent more easily processes reuse and requires (chemical oxygen demand (COD) < 30mg/L).Present example demonstrates the beneficial effect of preposition ultra-filtration membrane, for the selection of ultra-filtration membrane provides real case.
Embodiment
With the secondary biochemical effluent of certain printing and dyeing enterprise waste discharge for object, the example that application the present invention carries out Treatment for Reuse is described further.
The water quality of waste water after secondary biochemical treatment of this enterprise discharge is: chemical oxygen demand (COD) 85.3mg/L, biochemical oxygen demand (BOD) 8.2mg/L, colourity 60, turbidity 15, total suspended solid 15.6mg/L, pH=8.3.
Technical process as shown in Figure 2, by above-mentioned pending waste water with 1m
3/ h flow introduces raw water box, is forced into after 2atm enters the mechanical filter that weighting material is quartz sand through pump.Producing water water quality is: chemical oxygen demand (COD) 78.4mg/L, biochemical oxygen demand (BOD) 8.6mg/L, colourity 50, turbidity 3, total suspended solid 5.7mg/L, pH=8.3.
Above-mentioned filtration is produced water and is introduced hyperfiltration membrane assembly side, and hyperfiltration membrane assembly is Hydranautics HUF-8040, useful area 15.8m
2, molecular weight cut-off 50kDa. working pressure 2atm.Obtain producing water with ultra-filtration membrane opposite side, dense water is arranged outward, producing water ratio 80%.Producing water water quality is: chemical oxygen demand (COD) 57.3mg/L, biochemical oxygen demand (BOD) 8.7mg/L, colourity 31, turbidity 3, total suspended solid 0.3mg/L, pH=8.3.
Above-mentioned ultrafiltration is produced water and is introduced film contact reactor side, passes into ozone gas at film contact reactor opposite side.The ozone membrane reactor group used totally 8, each reactor is containing assembly 10, and each membrane module is containing hollow-fibre membrane 100, film silk useful length 25cm. is for each membrane reactor, wastewater flow is 10L/h, and ozone concn is 10mg/L, and gas flow is 200ml/min.Hollow-fibre membrane used is polyvinylidene fluoride material preparation, mean pore size 0.13 micron, and porosity 78%. adopts sequence batch (reactive mode, after 2h reaction, waste water quality is: chemical oxygen demand (COD) 20.3mg/L, biochemical oxygen demand (BOD) 11.2mg/L, colourity 2, turbidity 3, total suspended solid 0.3mg/L, pH=8.3., after 5h reaction, waste water quality is: chemical oxygen demand (COD) 12.4mg/L, biochemical oxygen demand (BOD) 7.6mg/L, colourity 2, turbidity 3, total suspended solid 0.3mg/L, pH=8.3.
Dyeing waste water secondary biochemical effluent handled by above-described embodiment reaches dyeing reuse water quality requirement.Illustrate that the present invention can carry out advanced treatment to difficult for biological degradation trade effluent effectively.
Claims (8)
1. an equipment for embrane method printing-dying wastewater recycling process, comprises raw water box, topping-up pump, filtered water tank, source of the gas, ozonizer, ozone concn detector, and ozone decomposed device, is characterized in that, this equipment also comprises mechanical filter, ultrafiltration system, film contact reactor.
2. the equipment of a kind of embrane method printing-dying wastewater recycling process according to claim 1, is characterized in that, described mechanical filter adopt in grid, filter screen filter cloth, sand filtration, gac, active cotton, micro-filtration one or more.
3., based on a method for the embrane method printing-dying wastewater recycling process of the equipment described in claim 1 or 2, it is characterized in that, the method comprises the following steps:
1) pending dyeing waste water is introduced raw water box after secondary biochemical treatment, under topping-up pump effect, waste water is introduced in mechanical filter;
2) by above-mentioned 1) in waste water after mechanical filter filters to introduce containing molecular weight cut off be the ultrafiltration system of the ultra-filtration membrane of 3kDa-100kDa, the dense water produced after described ultrafiltration system filters is arranged outward, obtains ultrafiltration simultaneously and produces water;
3) by 2) in ultrafiltration produce the side that water introduces film contact reactor, pass into containing ozone gas at the opposite side of film contact reactor simultaneously;
4) control 3) in film contact reactor gas phase side pressure be less than bubbling pressure and liquid phase pressure sum, ozone gas is made to be undertaken spreading by film in still mode and react with the useless Organic substance in water of opposite side, by the removal such as residual chroma, organism in waste water, realize the advanced treatment of waste water;
5) tail gas fully produced after reaction is emptying after decomposing, organic waste water through fully oxidized up to standard after discharge.
4. the method for printing-dying wastewater recycling according to claim 3, is characterized in that, the molecular weight cut off of the film of described ultrafiltration membrane system is 30kDa-50kDa.
5. the method for printing-dying wastewater recycling according to claim 3, is characterized in that, in described film contact reactor, gas phase side force value is 1kPa-10kPa.
6. the method for printing-dying wastewater recycling process according to claim 3, is characterized in that, the film of described film contact reactor adopts sludge proof Hollow-fibre membranes material to form.
7. the method for printing-dying wastewater recycling process according to claim 6, it is characterized in that, described Hollow-fibre membranes material is one or more in polyvinylidene difluoride (PVDF), tetrafluoroethylene, poly-(vinylidene-copolymerization-R 1216), poly-(vinylidene-copolymerization-tetrafluoroethylene), poly-(vinylidene-copolymerization-trifluoro-ethylene), poly-(vinylidene-copolymerization-chlorotrifluoroethylene).
8. the method for the printing-dying wastewater recycling process according to claim 6 and 7, is characterized in that, described hollow-fibre membrane is dewatering microporous film, and pore size is 0.1-1 micron, and porosity is 40-90%, and wall thickness is 0.1-0.4mm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967318A (en) * | 2016-07-21 | 2016-09-28 | 上环保科技（杭州）有限公司 | Membrane contact oxidation device and method for advanced treatment of wastewater |
| CN109052712A (en) * | 2018-08-17 | 2018-12-21 | 广东溢达纺织有限公司 | A kind of system and method handling simultaneously reuse textile industry qualified discharge water |
| CN109231417A (en) * | 2018-09-20 | 2019-01-18 | 河海大学 | A method of the ozonisation disinfection of water is carried out using membrane contactor and bromination minimizes |
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
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| KR100864587B1 (en) * | 2007-05-25 | 2008-10-20 | 호서대학교 산학협력단 | Method and apparatus for disposing wastewater in digital textile printing |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967318A (en) * | 2016-07-21 | 2016-09-28 | 上环保科技（杭州）有限公司 | Membrane contact oxidation device and method for advanced treatment of wastewater |
| CN109052712A (en) * | 2018-08-17 | 2018-12-21 | 广东溢达纺织有限公司 | A kind of system and method handling simultaneously reuse textile industry qualified discharge water |
| CN109231417A (en) * | 2018-09-20 | 2019-01-18 | 河海大学 | A method of the ozonisation disinfection of water is carried out using membrane contactor and bromination minimizes |
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
| CN113772843B (en) * | 2021-09-15 | 2023-09-08 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by utilizing special ceramic membrane separation integration technology |
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Application publication date: 20151202 |