CN102249436A - Method for concentrating CMP (chemi-mechanical pulp) waste liquid by using membrane process - Google Patents
Method for concentrating CMP (chemi-mechanical pulp) waste liquid by using membrane process Download PDFInfo
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- CN102249436A CN102249436A CN2011101976934A CN201110197693A CN102249436A CN 102249436 A CN102249436 A CN 102249436A CN 2011101976934 A CN2011101976934 A CN 2011101976934A CN 201110197693 A CN201110197693 A CN 201110197693A CN 102249436 A CN102249436 A CN 102249436A
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Abstract
The invention relates to the field of industrial waste water treatment, particularly relates to and discloses a method for concentrating CMP (chemi-mechanical pulp) waste liquid by using a membrane process. The method comprises the following steps: (1) heat exchange for cooling; (2) microfiltration treatment; (3) ultrafiltration pretreatment; and (4) membrane preconcentration. In the CMP waste liquid treatment method provided by the invention, the CMP waste liquid with initial concentration by mass percentage of 1-2% is concentrated to 7-10% by a membrane concentration system, and penetration liquid can be directly discharged or reused. Through adopting an immersed ultrafiltration and reverse-osmosis/nanofiltration preconcentration process and a series of membrane pollution control techniques, the smoothly continuous operation of the system can be ensured, thereby realizing the zero discharge of the CMP waste liquid. By using the method provided by the invention, the problem that the CMP waste liquid is treated to meet the States discharge standards can be completely solved; and compared with a direct evaporation and concentration mode, the method is characterized by adopting preconcentration of the membrane system, the energy consumption is greatly reduced, and a good deal of produced water can be recycled, therefore, the method provided by the invention has good economic and social benefits.
Description
Technical field
The present invention relates to the Industrial Wastewater Treatment field, particularly the embrane method concentration method of a kind ofization machine pulp waste.
Background technology
Compare with traditional chemical pulp waste water, though the quantity discharged of change machine pulp waste water and pollution load reduce greatly, but because it pollutes the composition complexity, existing residue chemistry medicament, the timber leachable is arranged again, the COD of waste water and BOD5 concentration are higher, methods such as that treatment process at present commonly used mainly contains is aerobic, anaerobic biological treatment method and direct evaporation.Owing to the more polyphenols of chemical impregnation stripping, colourity is also big in the change machine slurry production process, the toxic chemical content height, and biodegradability is relatively poor.May contain higher sulfate ion in the waste water simultaneously, very big to the anaerobic biological treatment influence.Along with the enforcement of " pulp and paper industry pollution discharge standard GB3544-2008 ", adopt traditional obvious intractable of anaerobism+aerobic process up to standard.Some new technology constantly occur, patent (application number) 200910231012.4 discloses change machine pulp waste water and has adopted the spissated technology of distillation to handle, if obviously will change the machine pulp waste directly carries out evaporation concentration, then energy consumption is very big, working cost is higher, does not meet the requirement of national energy-saving and emission-reduction industry policy simultaneously.The patent disclosure of patent (application number) 200810019354.5 adopt the treatment process of ultrafiltration and reverse osmosis that waste water is concentrated, but because it is higher to change machine pulp waste water concentration, water quality is very complicated, adopt the Pollution of Ultrafiltration Membrane of adding pressure type very serious, but the unexposed relevant film groundwater pollution control of this patent.
Summary of the invention
At prior art existence machine pulp waste qualified discharge difficulty, defective and the with serious pollution realistic problem of film that the evaporation concentration energy consumption is big, the invention provides that a kind of investment cost is little, running cost is low, energy consumption is little, can obtain the great lot of water resources reuse, the embrane method concentration method of the change machine pulp waste of realizationization machine pulp waste embrane method pre-concentration.
For achieving the above object, the present invention adopts following technical scheme:
The spissated treatment process of a kind ofization machine pulp waste embrane method comprises the steps:
(1) heat exchange cooling: will change the machine pulp waste and carry out heat exchange process, and be cooled to 25～30 ℃ by heat exchanger; Satisfy the feed liquor temperature requirement of film system.
(2) micro-filtration is handled: will handle through micro-filtration through the change machine pulp waste that cooling is handled, and remove graininess impurity, and protect follow-up hollow-fibre membrane, and prevent graininess impurity scratching film silk.
(3) immersion ultrafiltration pretreatment: the change machine pulp waste that micro-filtration is handled carries out pre-treatment by the immersion ultra-filtration equipment, remove suspended substance, obtain pretreatment fluid, the working pressure of described immersion ultra-filtration equipment is negative 1～3 standard atmospheric pressure, molecular weight cut-off is 5～200,000 dalton, service temperature is 5～45 ℃, and delivery turbidity is less than 0.5NTU, and the pH value is 6～8;
(4) the film pre-concentration is handled: pretreatment fluid is input to reverse osmosis or nanofiltration membrane system carries out pre-concentration and handle, obtain concentrated solution, permeate water is for cyclically utilizing or discharging, the working pressure of described reverse osmosis or nanofiltration equipment is 5～20 standard atmospheric pressures, ratio of desalinization is 80%～95%, service temperature is 5 ℃～40 ℃, and the mass percent concentration of the concentrated solution that obtains is 7%～10%; Further concentrate through pretreated feed liquid, moisture is separated cyclically utilizing or discharging.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, the described heat exchanger of step (1) is the stainless steel spiral heat exchanger.Heat-exchange capacity is strong, can drop to temperature required effectively with changing the machine pulp waste.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, the described micro-filtration filtering accuracy of step (2) is the 50-200 micron.Can effectively remove graininess impurity.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, the ultra-filtration membrane of the described immersion ultra-filtration equipment of step (3) adopts hollow fiber film assembly, and material is polypropylene, polyvinylidene difluoride (PVDF), polyethersulfone or polyvinyl chloride.Adopt submerged ultrafiltration, not only saved the preceding complicated pretreatment of film system, and utilize the swing of immersion hollow-fibre membrane silk, the pollution that has alleviated ultra-filtration membrane greatly.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, described reverse osmosis of step (4) or nanofiltration equipment adopt the rolling composite membrane, and mould material is a polymeric amide.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, the described immersion ultra-filtration equipment of step (3) adopts line pulse formula backwash technology, and the flow of backwash water is at 0-20L/m
2H, backwash pressure is pulsed at 0-0.15MPa and changes.Effectively avoided the deposition of pollutent on the film surface.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, the described immersion ultra-filtration equipment of step (3) adopts air water mixing flushing membrane silk surface, and gas-water ratio is 10-20: 1, effectively avoided the deposition of pollutent on the film surface.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste; described reverse osmosis of step (4) or nanofiltration equipment are provided with automatic low-pressure washing device; described automatic low-pressure washing device can wash reverse osmosis or nanofiltration equipment automatically by program control PLC; displace the dense water in reverse osmosis or the nanofiltration equipment before the system-down, described automatic low-pressure washing device comprises water pump, water tank, pipe valve.Effectively avoided the deposition of pollutent on the film surface.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, described reverse osmosis of step (4) or nanofiltration equipment are divided into first section and second section, reverse osmosis or nanofiltration equipment are provided with the segmentation chemically-cleaning device, be used for carrying out matting to first section and second section, described segmentation chemically-cleaning device comprises water pump, water tank, chemicals dosing plant, pipe valve.Segmentation is cleaned with two sections mixing cleanings and is compared, and has significant advantage, avoids the membrane module pollution of the pollutent of leading portion to the rear end, and the flux restorability of film is improved.
In the embrane method concentration method of above-mentioned a kind ofization machine pulp waste, described reverse osmosis of step (4) or nanofiltration equipment washing pipeline are provided with the air purge mouth, during matting, can carry out the air water mixing and wash, and intake pressure is 0.1-0.2MPa.Reverse osmosis or nanofiltration equipment have strict requirement to water inlet, but practical engineering project can not guarantee fully, such as pre-treatment handle inadequately fully or variation water quality bigger, all colloid and suspended substance might be brought in rolling reverse osmosis or the nanofiltration device.Adopting pharmaceutical chemistry to clean obviously separately can not adopt air water to mix the method for washing fully with colloid and suspended substance removal, has aggravated the turbulence state of water, colloid and suspended substance effectively can be removed, and the flux restorability of film is improved, and prolong work-ing life.
The embrane method concentration method of a kind ofization machine pulp waste of the present invention adopts the membrane concentration system will change the machine pulp waste and is concentrated into 7%～10% from initial mass percentage concentration 1%～2%, by adopting a series of film Pollution control technology, but assurance system stable and continuous operation, this technology is the thorough qualified discharge difficult problem of solution machine pulp waste water not only, and concentrate with direct evaporation and to compare, because pre-concentration by the film system, its energy consumption reduces greatly, and the reuse of big volume production water cycle is arranged, have good economic and social benefit.
Description of drawings
Fig. 1 is the process flow diagram of the embrane method concentration method of a kind ofization machine pulp waste of the present invention.
Fig. 2 is the technological process device sketch of the embrane method concentration method of a kind ofization machine pulp waste of the present invention.
Specific embodiment
Below in conjunction with accompanying drawing 1-2 and embodiment the present invention is described in further detail:
Embodiment 1
As shown in Figure 1, the process flow diagram for the embrane method concentration of a kind ofization machine pulp waste of the present invention comprises: the heat exchange cooling, and micro-filtration is handled, and immersion ultrafiltration pretreatment and film pre-concentration are handled.
As shown in Figure 2, be the technological process device sketch of the embrane method concentration method of a kind ofization machine pulp waste of the present invention, comprise the former pond 1, first topping-up pump 2, stainless steel spiral heat exchanger 3, micro-filtration 17, submerged ultrafiltration equipment 4, vacuum primingpump 5, backwashing pump 6, intermediate pool 7, second topping-up pump 8, security personnel's filter 9, high-pressure pump 10, reverse osmosis or nanofiltration equipment 11, the flushing arrangement 12 that connect successively, produce pond 13, dense pond 14, the 3rd topping-up pump 15, follow up device 16.
First topping-up pump 2 is extractionization machine pulp waste from former pond 1, extracted amount is 100 tons/hour, pressure 0.3MPa, enter stainless steel spiral heat exchanger 3, the temperature of this momentization machine pulp waste is 1% at 50 ℃, mass percent concentration, by the processing of lowering the temperature of 3 pairs of waste liquids of spiral heat exchanger, the leaving water temperature(LWT) after over-heat-exchanger is handled is 25 ℃.Enter microfiltration equipment 17 afterwards, the micro-filtration filtering accuracy is 50 microns, enter submerged ultrafiltration equipment 4 again, submerged ultrafiltration equipment 4 is totally 4 covers (wherein 1 cover is standby), every cover produces 92 tons/hour in water, immersion ultrafiltration apparatus 4 working pressures are negative 2 standard atmospheric pressures, and molecular weight cut-off is 100,000 dalton, and service temperature is 25 ℃, during works better, vacuum primingpump 5 is drawn into intermediate pool 7 with pretreatment fluid, and one hour at interval, vacuum primingpump 5 cut out, backwashing pump 6 is opened, submerged ultrafiltration equipment 4 was carried out counterflush about 2 minutes, adopt line pulse formula backwash technology, the flow of backwash water is 20L/m
2H, backwash pressure is pulsed at 0-0.15MPa and changes, open vacuum primingpump 5 again after the flushing and carry out work, the delivery turbidity of described immersion ultrafiltration apparatus 4 is 0.4NTU, the pH value is 6, the ultrafiltration apparatus rate of recovery is 90%, the liquid that sees through of ultrafiltration enters security personnel's strainer 9 by second topping-up pump 8, enters reverse osmosis or nanofiltration equipment 11 by high-pressure pump 10, and reverse osmosis or nanofiltration equipment 11 is totally two covers, 40 tons/hour of every cover water production rates, produce water and enter product pond 13, ratio of desalinization 95%, working pressure is at 5 standard atmospheric pressures, the concentrated solution mass percent concentration of reverse osmosis or nanofiltration equipment is 7%, and concentrated solution is input to dense pond 14.Respectively reverse osmosis membrane was carried out automatic low-pressure washing by flushing arrangement 12 in per 4 hours, the flux performance recovery rate is more than 99%, and concentrated solution is input to follow up device 16 by the 3rd topping-up pump 15, further handles.
Technical process and device sketch such as embodiment 1.
First topping-up pump 2 is extractionization machine pulp waste from former pond 1, extracted amount is 100 tons/hour, pressure 0.3MPa, enter stainless steel spiral heat exchanger 3, the temperature of this momentization machine pulp waste is 2% at 48 ℃, mass percent concentration, by the processing of lowering the temperature of 3 pairs of waste liquids of spiral heat exchanger, the leaving water temperature(LWT) after over-heat-exchanger is handled is 27 ℃.Enter microfiltration equipment 17 afterwards, the micro-filtration filtering accuracy is 200 microns, enter submerged ultrafiltration equipment 4 again, submerged ultrafiltration equipment 4 is totally 4 covers (wherein 1 cover is standby), every cover produces 92 tons/hour in water, immersion ultrafiltration apparatus 4 working pressures are negative 3 standard atmospheric pressures, and molecular weight cut-off is 200,000 dalton, and service temperature is 45 ℃, during works better, vacuum primingpump 5 is drawn into intermediate pool 7 with pretreatment fluid, and one hour at interval, vacuum primingpump 5 cut out, backwashing pump 6 is opened, submerged ultrafiltration equipment 4 was carried out counterflush about 2 minutes, adopt air water mixing flushing membrane silk surface, gas-water ratio is 10: 1.Open vacuum primingpump 5 again after the flushing and carry out work, the delivery turbidity of described immersion ultrafiltration apparatus 4 is 0.3NTU, the pH value is 7, the ultrafiltration apparatus rate of recovery is 90%, the liquid that sees through of ultrafiltration enters security personnel's strainer 9 by second topping-up pump 8, enter reverse osmosis or nanofiltration equipment 11 by high-pressure pump 10, reverse osmosis or nanofiltration equipment 11 is totally two covers, 40 tons/hour of every cover water production rates, produce water and enter product pond 13, ratio of desalinization 80%, working pressure is at 10 standard atmospheric pressures, the concentrated solution mass percent concentration of reverse osmosis or nanofiltration equipment is 10%, and concentrated solution is input to dense pond 14.Carried out primary chemical cleaning to first section and second section respectively by flushing arrangement 12 in per 15 days, the flux performance recovery rate is more than 99%.
Embodiment 3
Technical process and device sketch such as embodiment 1.
First topping-up pump 2 is extractionization machine pulp waste from former pond 1, extracted amount is 100 tons/hour, pressure 0.3MPa, enter stainless steel spiral heat exchanger 3, the temperature of this momentization machine pulp waste is 1.5% at 45 ℃, mass percent concentration, by the processing of lowering the temperature of 3 pairs of waste liquids of spiral heat exchanger, the leaving water temperature(LWT) after over-heat-exchanger is handled is 30 ℃.Enter microfiltration equipment 17 afterwards, the micro-filtration filtering accuracy is 100 microns, enter submerged ultrafiltration equipment 4 again, submerged ultrafiltration equipment 4 is totally 4 covers (wherein 1 cover is standby), every cover produces 92 tons/hour in water, immersion ultrafiltration apparatus 4 working pressures are negative 1 standard atmospheric pressure, and molecular weight cut-off is 150,000 dalton, and service temperature is 10 ℃, during works better, vacuum primingpump 5 is drawn into intermediate pool 7 with pretreatment fluid, and one hour at interval, vacuum primingpump 5 cut out, backwashing pump 6 is opened, submerged ultrafiltration equipment 4 was carried out counterflush about 1 minute, adopt line pulse formula backwash technology, the flow of backwash water is 10L/m
2H, backwash pressure is pulsed at 0-0.15MPa and changes, open vacuum primingpump 5 again after the flushing and carry out work, the delivery turbidity of described immersion ultrafiltration apparatus 4 is 0.2NTU, the pH value is 8, the ultrafiltration apparatus rate of recovery is 90%, the liquid that sees through of ultrafiltration enters security personnel's strainer 9 by second topping-up pump 8, enters reverse osmosis or nanofiltration equipment 11 by high-pressure pump 10, and reverse osmosis or nanofiltration equipment 11 is totally two covers, 40 tons/hour of every cover water production rates, produce water and enter product pond 13, ratio of desalinization 90%, working pressure is at 20 standard atmospheric pressures, the concentrated solution mass percent concentration of reverse osmosis or nanofiltration equipment is 8%, and concentrated solution is input to dense pond 14.Respectively reverse osmosis membrane was carried out matting and carbonated drink by flushing arrangement 12 in per 15 days and mix flushing, the flux performance recovery rate is more than 99%, and concentrated solution is input to follow up device 16 by the 3rd topping-up pump 15, further handles.
At last, it needs to be noted that what more than enumerate only is concrete case study on implementation of the present invention.Obviously, the invention is not restricted to above-mentioned case study on implementation, can also many combinations.The all scenario that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (10)
1. an embrane method concentration method of changing the machine pulp waste is characterized in that, comprises the steps:
(1) heat exchange cooling: will change the machine pulp waste and carry out heat exchange process, and be cooled to 25～30 ℃ by heat exchanger;
(2) micro-filtration is handled: will handle through micro-filtration through the change machine pulp waste that cooling is handled, and remove graininess impurity;
(3) immersion ultrafiltration pretreatment: will carry out pre-treatment by the immersion ultra-filtration equipment through the change machine pulp waste that micro-filtration is handled, remove the suspended substance in the feed liquid, obtain pretreatment fluid, the working pressure of described immersion ultra-filtration equipment is negative 1～3 standard atmospheric pressure, molecular weight cut-off is 10～200,000 dalton, service temperature is 5～45 ℃, and delivery turbidity is less than 0.5NTU, and the pH value is 6～8;
(4) the film pre-concentration is handled: pretreatment fluid is input to reverse osmosis or nano-filtration membrane equipment carries out pre-concentration and handle, obtain concentrated solution, enter follow-up vapo(u)rization system, permeate water is for cyclically utilizing or discharging, the working pressure of described reverse osmosis or nanofiltration equipment is 5～20 standard atmospheric pressures, ratio of desalinization is 80%～95%, and service temperature is 5 ℃～40 ℃, and the mass percent concentration of the concentrated solution that obtains is 7%～10%.
2. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: the described heat exchanger of step (1) is the stainless steel spiral heat exchanger.
3. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: the described micro-filtration filtering accuracy of step (2) is the 50-200 micron.
4. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1, it is characterized in that: the ultra-filtration membrane of the described immersion ultra-filtration equipment of step (3) adopts hollow fiber film assembly, and material is polypropylene, polyvinylidene difluoride (PVDF), polyethersulfone or polyvinyl chloride.
5. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: described reverse osmosis of step (4) or nanofiltration equipment adopt the rolling composite membrane, and mould material is a polymeric amide.
6. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: the described immersion ultra-filtration equipment of step (3) adopts line pulse formula backwash technology, and the flow of backwash water is at 0-20L/m
2H, backwash pressure is pulsed at 0-0.15MPa and changes.
7. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: the described immersion ultra-filtration equipment of step (3) adopts air water mixing flushing membrane silk surface, and gas-water ratio is 10-20: 1.
8. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1, it is characterized in that: described reverse osmosis of step (4) or nanofiltration equipment are provided with automatic low-pressure washing device, described automatic low-pressure washing device can wash reverse osmosis or nanofiltration equipment automatically by program control PLC, displace the dense water in reverse osmosis or the nanofiltration equipment, described automatic low-pressure washing device comprises water pump, water tank, pipe valve.
9. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1, it is characterized in that: described reverse osmosis of step (4) or nanofiltration equipment are divided into first section and second section, reverse osmosis or nanofiltration equipment are provided with the segmentation chemically-cleaning device, be used for carrying out matting to first section and second section, described segmentation chemically-cleaning device comprises water pump, water tank, chemicals dosing plant, pipe valve.
10. the embrane method concentration method of a kind ofization machine pulp waste according to claim 1 is characterized in that: described reverse osmosis of step (4) or nanofiltration equipment washing pipeline are provided with the air purge mouth, during matting, carry out the air water mixing and wash.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215838A (en) * | 2013-03-11 | 2013-07-24 | 中国地质大学（武汉） | Process of wood pulp papermaking black liquor resourceful treatment |
| CN104229941A (en) * | 2014-09-28 | 2014-12-24 | 王建军 | Device and method for recycling treatment of amino containing waste water |
| CN104341054A (en) * | 2014-10-16 | 2015-02-11 | 衢州市鼎盛化工科技有限公司 | Reclaimed water recycling intelligent integrated device capable of implementing zero sewage discharge and application thereof |
| CN106186485A (en) * | 2016-07-07 | 2016-12-07 | 广州优华过程技术有限公司 | Boiler blow-off water treatment system and method |
| CN109970273A (en) * | 2018-10-26 | 2019-07-05 | 中国林业科学研究院林业新技术研究所 | A kind of reducing rules wastewater membrane separation coupling evaporation treatment process and device |
| CN113087079A (en) * | 2021-03-31 | 2021-07-09 | 山东润泰环保技术有限公司 | Device for treating supersaturated solution by membrane technology |
| CN115434178A (en) * | 2022-08-23 | 2022-12-06 | 天津科技大学 | Chemical alkali recovery treatment process for chemi-mechanical pulp waste liquid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215838A (en) * | 2013-03-11 | 2013-07-24 | 中国地质大学（武汉） | Process of wood pulp papermaking black liquor resourceful treatment |
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| CN104229941A (en) * | 2014-09-28 | 2014-12-24 | 王建军 | Device and method for recycling treatment of amino containing waste water |
| CN104341054A (en) * | 2014-10-16 | 2015-02-11 | 衢州市鼎盛化工科技有限公司 | Reclaimed water recycling intelligent integrated device capable of implementing zero sewage discharge and application thereof |
| CN106186485A (en) * | 2016-07-07 | 2016-12-07 | 广州优华过程技术有限公司 | Boiler blow-off water treatment system and method |
| CN109970273A (en) * | 2018-10-26 | 2019-07-05 | 中国林业科学研究院林业新技术研究所 | A kind of reducing rules wastewater membrane separation coupling evaporation treatment process and device |
| CN109970273B (en) * | 2018-10-26 | 2024-06-21 | 中国林业科学研究院林业新技术研究所 | Membrane separation coupling evaporation treatment process and device for chemi-mechanical pulp wastewater |
| CN113087079A (en) * | 2021-03-31 | 2021-07-09 | 山东润泰环保技术有限公司 | Device for treating supersaturated solution by membrane technology |
| CN115434178A (en) * | 2022-08-23 | 2022-12-06 | 天津科技大学 | Chemical alkali recovery treatment process for chemi-mechanical pulp waste liquid |
| CN115434178B (en) * | 2022-08-23 | 2023-09-01 | 天津科技大学 | Chemical alkali recovery treatment process for chemical mechanical pulp waste liquid |
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| CN102249436B (en) | 2013-01-09 |
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