CN101628771A - Method with zero discharge of waste water - Google Patents
Method with zero discharge of waste water Download PDFInfo
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- CN101628771A CN101628771A CN200810071425A CN200810071425A CN101628771A CN 101628771 A CN101628771 A CN 101628771A CN 200810071425 A CN200810071425 A CN 200810071425A CN 200810071425 A CN200810071425 A CN 200810071425A CN 101628771 A CN101628771 A CN 101628771A
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Abstract
The invention discloses a method for zero discharge of waste water, which comprises the following steps that: the industrial waste water is subjected to anaerobic decomposition treatment and aerobiotic decomposition treatment in a waste water treating field in sequence, and 70 to 90 percent of organic matters in the waste water are decomposed; water discharged from the waste water treating field is treated by a hardness removing device, a filter, a residue hardness removing device, a degassing device and a multi-segmental reverse osmosis membrane set so as to obtain the concentrated water with TDS more than 80,000ppm; and the concentrated water is subjected to evaporation concentration by an evaporation crystallizer and a pressure filter, so that the waste solid with the water content of less than 15 percent is prepared. The method has the advantages of recycling over 99 percent of the waste water for reutilization, reducing environmental pollution, and reducing waste of water resources.
Description
Technical field
The present invention relates to a kind of method that reduces discharge of wastewater, relate to a kind of method of wastewater zero discharge particularly.
Background technology
A large amount of trade effluents that the high speed development of modern industry produces have caused serious pollution to environment, have destroyed the eubiosis of the Nature.In order to strengthen the protection to ecotope, the trade effluent that industry is produced must be through recycling, to reach emission standard.
Traditional process for treating industrial waste water, only by biochemical treatment, organism in the waste water is formed mud by the microbiological degradation sedimentation, the part metals ion also is adsorbed in the mud by microorganism, bury with mud, discharge after waste water quality after the biochemical treatment reaches country-level discharge water standard, apparatus for recovering recovery part water in maybe can adopting is used for the occasion not high to water quality requirement.In the recyclable part waste water of water reuse, but still caused the significant wastage of water resources; Though the waste water quality that discharges after biochemical treatment has reached discharging standards, but because its organism and heavy metals emission amount there is no minimizing, heavy metal in the sewage etc. also can enter environment with mud, environment is caused damage, and the ecology of fragility is impacted; In addition, use traditional treatment process to be difficult to handle and reclaim high rigidity, high basicity, high organic trade effluent.
In pure terephthalic acid (PTA) manufacturing processed, contain terephthalic acid (TA), phenylformic acid (BA), p-methylbenzoic acid (PT) in the waste water by the discharging of oxidation section and purifying workshop section, to metal ions such as carboxyl benzaldehyde (4-CBA), acetic acid (HAC) organism of etc.ing and cobalt, manganese, directly discharge and pollute the environment.Existing method is the waste water that is discharged by oxidation section and purifying workshop section in the PTA production process, drain into the waste water processing station via cobalt, the processing of manganese recovery system again after reclaiming cobalt, manganese metal, PTA waste water is after the anaerobism and aerobic treatment of waste water processing station, organism such as 70%～90% TA, BA, PT acid, 4-CBA and HAC are decomposed in the waste water, form carbonic acid gas (CO
2) and water, waste water processing station chemical oxygen demand (COD) (the COD)＜60ppm in the water that releases, suspended substance (SS)＜80ppm.This waste water can mix with cooling tower draining, water treatment system draining after waste water processing station anaerobism and aerobic treatment disaggregating treatment, dual disposal water COD is 15～60ppm, hardness (Ca-H) is 20～1000ppm, basicity (M-Alk.) is 200～2000ppm, TDS is 2000～3000ppm, the pH value is 8～14, reaches national grade one discharge standard and directly discharges, and has caused the great amount of water resources waste.And along with society improves day by day to environmental requirement, water saving, reducing sewage discharge is the trend of industrial development.
Summary of the invention
The method that the purpose of this invention is to provide a kind of wastewater zero discharge is to solve the above-mentioned problems in the prior art.The waste water that the method for the wastewater zero discharge among the present invention can reclaim more than 99% utilizes again, reduces discharge of wastewater, reduces the pollution to environment, reduces water resource waste.
The technical solution used in the present invention is as follows:
A kind of method of wastewater zero discharge comprises steps A～C:
A, trade effluent is carried out anaerobic digestion and aerobic disaggregating treatment in the wastewater treatment field sequence, decompose in the waste water 70% ~ 90% organism;
B, current are banished in the waste water processing station that obtains in the steps A handle through removing hardness device, filtration unit, removal alkalinity apparatus, de-gassing vessel and 1～N section reverse osmosis membrane group, obtain total dissolved solidss (TDS)＞80, the condensed water of 000ppm and total dissolved solidss (TDS) clean water that accounts for waste water total amount 95～99% below 60ppm;
C, flow through evaporative crystallization device and filter-pressing device of condensed water carried out evaporation concentration, make water content＜15% solid slag;
Wherein, N is an integer, 3≤N≤5.
Among the step B current being banished in the waste water processing station that obtains in the steps A handles through removing hardness device, filtration unit, removal alkalinity apparatus, de-gassing vessel and multistage reverse osmosis membrane group (RO or HERO) group, can obtain TDS＞80, the condensed water of 000ppm and total dissolved solidss (TDS) clean water that accounts for waste water total amount 95～99% below 60ppm, clean water is further handled purifying through the zwitterion resin bed, can be used as the water of productive use of factory again, as the cooling tower make up water, the water inlet of desalted water station etc.
In the method for aforementioned wastewater zero discharge, described removal hardness device is fluidized-bed crystallizer (FBC) or lime softening method (LIME), preferably uses fluidized-bed crystallizer, to remove the calcium magnesium hardness in the water; Described filtration unit is a high efficiency filter, to remove the suspended substance in the water, avoids stopping up follow-up multistage reverse osmosis membrane group; Described removal residual harness device is that Weak-acid cation exchange bed (WAC) is the hardness of further removing in the waste water, and basicity is changed into carbonic acid gas (CO
2); Described de-gassing vessel is acidification degassing tower (Degas), removes the carbonic acid gas in the waste water; Described 1 ~ N section reverse osmosis membrane group is reverse osmosis membrane group (RO) or efficient reverse osmosis membrane group (HERO), preferably uses HERO, sewage can be concentrated into higher concentration, and save the concentrating unit treatment capacity, reduces investment cost.
Concentrate back TDS＞80, the condensed water of 000ppm flow through evaporative crystallization device and filter-pressing device evaporation concentration are made the solid slag of water content＜15%, can not pollute water resources and environment, can bury safely.Can get back in the system through the steam condensate of evaporative crystallization device and filter-pressing device evaporative condenser among the step C and recycle, with further conserve water resource, final Wastewater Recovery rate can reach more than 99%.
In the method for aforementioned wastewater zero discharge, described evaporative crystallization device is flasher or evaporative crystallization jar; Described filter-pressing device is belt filter press or centrifuge.
In the method for aforementioned wastewater zero discharge, the middle water reuse factory that water can be flowed through earlier and be made up of simple reverse osmosis membrane group is banished in the waste water processing station, reclaims and obtains the junior relatively clear water of water quality.
In the method for aforementioned wastewater zero discharge, described waste water is the waste water of terephthalic acid factory discharging, comprises the waste water of discharging in wastewater treatment workshop treat effluent, desalted water station ion exchange regenerant waste water, cooling water recirculation system discharge water and/or the PTA production.
In the method for aforementioned wastewater zero discharge, drain into the waste water processing station again after the terephthalic acid plant effluent handle reclaimed cobalt and manganese via cobalt manganese recovery system.Waste water (COD) content that discharges in terephthalic acid (PTA) production process is 4500ppm～6000ppm, and cobalt, manganese metal ion total amount reach 8～25ppm in the waste water; The ionic radius of cobalt, manganese metal is bigger, if the obstruction of reverse osmosis membrane group in the wastewater zero discharge system can be caused in the not treated waste water processing station that directly is disposed to, after cobalt, manganese recovery system are handled recovery cobalt, manganese metal, cobalt contents is less than 0.5ppm in the waste water, and manganese content is less than 0.5ppm in the waste water.
In the method for aforementioned wastewater zero discharge, described organism is TA, BA, PT acid, 4-CBA and/or HAC.After the wastewater treatment field sequence was carried out anaerobic digestion and aerobic disaggregating treatment, organism such as 70% ~ 90% TA, BA, PT acid, 4-CBA and HA were decomposed in the waste water, formed carbonic acid gas (CO
2), the methane G﹠W, waste gas is sent into heat power plant burning, waste water processing station chemical oxygen demand (COD) (the COD)＜60ppm in the water that releases, suspended substance (SS)＜60ppm.
In the method for aforementioned wastewater zero discharge, can also comprise PTA mother liquor solids recovery system, the waste water of discharging was flowed through earlier and is flowed into cobalt manganese recovery system again after the PTA mother liquor solids recovery system during PTA produced.The PTA powder that contains higher concentration in the PTA mother liquor increases waste water COD, and after PTA mother liquor solids recovery system was handled, waste water COD reduced by 70%～80%, greatly reduces the aerobic decomposition at waste water workshop and the load of anaerobic digestion workshop section.
The waste water that the method for the wastewater zero discharge among the present invention can reclaim more than 99% utilizes again, reduces discharge of wastewater, reduces the pollution to environment, and reduces water resource waste, has alleviated the increasingly serious environmental protection pressure and the pressure of water resources; Solid slag mainly is made up of salts such as chlorate, vitriol, and water content can not pollute water resources and environment less than 15%, can bury safely; The meeting that contains in the also recyclable terephthalic acid of the present invention factory waste discharge not only can be eliminated heavy metal contamination, and have important economic value the cobalt manganese heavy metal ion that environment pollutes
Embodiment
Can further understand the present invention by embodiment given below; following examples only are several specific embodiment of the present invention; but design concept of the present invention is not limited thereto; allly utilize this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Embodiment 1
Trade effluent is flowed into the waste water processing station, and after order was carried out anaerobic digestion and aerobic disaggregating treatment, 70% ~ 90% organism was decomposed in the waste water, and chemical oxygen demand (COD) in the water (COD)＜60ppm is banished in the waste water processing station, suspended substance (SS)＜60ppm.
The middle water reuse factory that current are formed via simple reverse osmosis membrane group is banished in the waste water processing station that obtains, reclaim and obtain the junior relatively clear water of water quality, can be used as the cooling tower make up water and utilize again.In the dense water section of water reuse factory and cooling tower draining and the water treatment system inorganic wastewater fluidized-bed crystallizer (FBC) of flowing through, be filled with silica sand in the fluid bed crystallizer, by adding acid or alkali or Na
2CO
3Regulate pH value to 9.0 ~ 12.0, calcium, magnesium plasma be at the silica sand surface crystallization, will grow up and be precipitated to the crystallizer bottom along with crystal with calcium magnesium salts crystalline silica sand, and be discharged by the bottom; Filter through crystal filter, filtered water flows into the fluidized-bed crystallizer water inlet again, and the crystal of low moisture percentage then reclaims or buries, to remove the calcium magnesium hardness in the water; The water purification that overflows from the fluidized-bed crystallizer water outlet flows into high efficiency filter, and the suspended substance in the trap water avoids stopping up follow-up multistage reverse osmosis membrane group; The water that comes out from high efficiency filter flows into weak acid ion exchange bed (WAC), and the hardness with remaining in the further replacing water of hydrogen ion makes hardness less than 0.5ppm; After the water that comes out from the weak acid ion exchange bed adds acid, regulate the pH value and be about 4～5, flow into acidification degassing tower (Degas), carbonate and hydrocarbonate are converted to carbonic acid gas, by removing contained carbonic acid gas in the waste water in the degassing tower, make gas concentration lwevel be reduced to 5 ~ 10ppm.Collect the degassing tower water outlet with degassing water pot, and adjust the water inlet of multistage HERO film.
The water that comes out from degassing water pot adds alkali, regulates HERO influent quality pH value to 10.0 ~ 11.0, makes the SiO in the dense water of HERO
2Keep high solubleness, avoid SiO
2Stop up the film group.The water inlet pH value of HERO film is higher than the RO film, and is more less scaling, and cycles of concentration is higher.
The water that adds alkali flows into first section efficient reverse osmosis membrane group (producing water ratio 65%～75%), obtain hardness below 2ppm, basicity is below 2ppm, and dioxide-containing silica is below 0.5ppm, and conductivity is below 100 μ s/cm and the clean water of total dissolved solidss (TDS) below 60ppm; The clean water that obtains is flowed through behind the zwitterion resin bed, further removes the ion in the water, obtains silicone content less than 0.02ppm, conductivity＜0.2 μ s/cm, and total iron is less than the pure water of 0.02ppm; The waste water of zwitterion resin bed resin regeneration flows into fluidized-bed crystallizer as the water treatment system inorganic wastewater and circulates again;
First section middle efficient reverse osmosis membrane group of multistage (producing water ratio 40%～75%) of condensed water inflow that efficient reverse osmosis membrane group obtains, pass back into degassing water pot from the effusive clear water of the efficient reverse osmosis membrane group of middle multistage, the effusive condensed water of the efficient reverse osmosis membrane group of middle multistage flows into the efficient reverse osmosis membrane group water inlet of terminal section jar and enters the efficient reverse osmosis membrane group of terminal section (producing water ratio 30%～45%);
The efficient reverse osmosis membrane group of terminal section can be concentrated into waste water TDS＞80, and 000ppm is to reduce the load of concentration and evaporation operation; Account for plant effluent cumulative volume 3% from the efficient reverse osmosis membrane group of terminal section water inlet jar effusive TDS＞80, the waste water condensed water of 000ppm enters dense water charging stock tank high in salt; Flow into the efficient reverse osmosis membrane group water inlet of terminal section jar from the effusive condensed water of the efficient reverse osmosis membrane group of terminal section, clear water flows into degassing water pot and circulates again.
The concentrated waste water that enters dense water charging stock tank high in salt enters the evaporative crystallization jar behind steam heater, then enter belt filter press again, the water content that obtains is less than 15% solid slag and account for the filtered liquid of plant effluent cumulative volume 2.5%, filtered liquid is got back in the fluidized-bed crystallizer as the inorganic wastewater of water treatment system again, the steam condensate of evaporative crystallization jar and belt filter press evaporative condenser can be got back in the system and recycle, and the waste water overall recovery reaches 99%.
The also available reverse osmosis membrane group of above-mentioned efficient reverse osmosis membrane group replaces, when using the reverse osmosis membrane group, the concentrated waste water that the enters dense water charging stock tank high in salt flasher of need flowing through earlier, with dense water flash concentration to TDS＞80,000ppm, flash-off steam is recovered in the degassing water pot again, remaining high salinity condensed water enters the evaporative crystallization jar after steam heating, then flow into bag filter again, the water content that obtains is less than 15% solid slag and account for the filtered liquid of plant effluent cumulative volume 2.5%, filtered liquid is got back in the fluidized-bed crystallizer as the inorganic wastewater of water treatment system again, the steam condensate of evaporative crystallization jar and bag filter evaporative condenser can be got back in the system and recycle, filtered liquid reenters the evaporative crystallization jar and carries out evaporative crystallization, and the waste water overall recovery reaches 99%.
Embodiment 2
Embodiment 2 is further comprising the steps of with the difference of embodiment 1: will comprise that the waste water (PTA mother liquor) that discharges in the PTA production of pure terephthalic acid (PTA), crude terephthalic acid (CTA), BA, PT acid, 4-CBA and HAC flows into PTA mother liquor recovery system, the major part that contains in the PTA mother liquor is filtered by the strainer of PTA mother liquor solids recovery system, and waste water COD reduces by 70%～80%; Add acetic acid,, reclaim the PTA solid the dissolving of the PTA slurry in the strainer.Then waste water is flowed into PTA mother liquor metal recovery system, add regenerating acid, regenerating acid can be hydrochloric acid, bromic acid or sulfuric acid, reclaims heavy metal ion such as cobalt, manganese.Waste water and CTA processing wastewater through PTA mother liquor metal recovery system handles together flow into the waste water processing station.Then continue to handle according to the step of implementing 1, after all operation is finished, the water content that obtains less than 15%, the solid slag security landfill mainly formed by salts such as chlorate, vitriol, the waste water overall recovery reaches 99%.
Description of drawings
Fig. 1 is the industrial flow chart of Industrial Wastewater Treatment;
Fig. 2 is the industrial flow chart of PTA production wastewater treatment.
Claims (9)
1, a kind of method of wastewater zero discharge comprises steps A～C:
A, trade effluent is carried out anaerobic digestion and aerobic disaggregating treatment in the wastewater treatment field sequence, remove in the waste water 70% ~ 90% organism;
B, current are banished in the waste water processing station that obtains in the steps A handle through removing hardness device, filtration unit, removal residual alkalinity device, de-gassing vessel and 1～N section reverse osmosis membrane group, obtain TDS＞80, the condensed water of 000ppm and the TDS clean water that accounts for waste water total amount 95～99% below 60ppm;
C, flow through evaporative crystallization device and filter-pressing device of condensed water carried out evaporation concentration, make water content＜15% solid slag;
Wherein, N is an integer, 3≤N≤5.
2, according to the method for the wastewater zero discharge described in the claim 1, it is characterized in that: described removal hardness device is fluidized-bed crystallizer or lime softening method; Described filtration unit is a high efficiency filter; Described removal residual harness device is a Weak-acid cation exchange bed; Described de-gassing vessel is the acidification degassing tower.
3, according to the method for the wastewater zero discharge described in the claim 2, it is characterized in that: described evaporative crystallization device is flasher or evaporative crystallization jar; Described filter-pressing device is belt filter press or centrifuge.
4, according to the method for the wastewater zero discharge described in the claim 3, it is characterized in that: the middle water reuse factory that water is flowed through earlier and is made up of simple reverse osmosis membrane group is banished in the waste water processing station, reclaims and obtains the junior relatively clear water of water quality.
5, according to the method for the wastewater zero discharge described in the claim 1, it is characterized in that: described waste water is the terephthalic acid plant effluent.
6, according to the method for the wastewater zero discharge described in the claim 5, it is characterized in that: drain into the waste water processing station again after the terephthalic acid plant effluent is handled recovery cobalt and manganese via cobalt manganese recovery system.
7, according to the method for the wastewater zero discharge described in the claim 5, it is characterized in that: described terephthalic acid plant effluent comprises the waste water of discharging in wastewater treatment workshop treat effluent, desalted water station ion exchange regenerant waste water, cooling water recirculation system discharge water and/or the PTA production.
8, according to the method for the wastewater zero discharge described in the claim 5, it is characterized in that: described organism is PTA, TA, BA, PT acid, 4-CBA and/or HAC.
9, according to the method for the wastewater zero discharge described in the claim 5, it is characterized in that: also comprise PTA mother liquor solids recovery system, the waste water of discharging is flowed through earlier and is flowed into cobalt manganese recovery system again after the PTA mother liquor solids recovery system from PTA produces.
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| CN103896443A (en) * | 2012-12-26 | 2014-07-02 | 王炜 | Reusing treatment technology for wastewater and recycled water generated during production process of purified terephthalic acid |
| CN103910459A (en) * | 2012-12-31 | 2014-07-09 | 北京清大国华环保科技有限公司 | Method and device for coal chemical sewage reuse and zero emission |
| CN104370394A (en) * | 2013-08-15 | 2015-02-25 | 北京紫光益天环境工程技术有限公司 | Surface water desalting apparatus by-producing saline waste water treatment method |
| CN107176745A (en) * | 2016-03-09 | 2017-09-19 | 王仲甫 | The method for biologically treating wastewater of polybasic carboxylic acid residue |
| CN109205717A (en) * | 2018-10-29 | 2019-01-15 | 国家能源投资集团有限责任公司 | A kind of non-crystal seed method evaporation process method and processing system of waste water |
| CN112142259A (en) * | 2020-09-25 | 2020-12-29 | 中蓝连海设计研究院有限公司 | Comprehensive treatment method of PTA-containing wastewater |
| CN113735353A (en) * | 2020-05-29 | 2021-12-03 | 天华化工机械及自动化研究设计院有限公司 | PTA (pure terephthalic acid) oxidized tail gas treatment and recovery system and method |
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| CN100400432C (en) * | 2004-10-29 | 2008-07-09 | 中国石油化工股份有限公司 | Terephthalic acid production waste water disposal method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896443A (en) * | 2012-12-26 | 2014-07-02 | 王炜 | Reusing treatment technology for wastewater and recycled water generated during production process of purified terephthalic acid |
| CN103896443B (en) * | 2012-12-26 | 2015-12-23 | 上海洗霸科技股份有限公司 | Water from refined p-benzene dicarboxylic acid production Treated sewage reusing treatment process |
| CN103910459A (en) * | 2012-12-31 | 2014-07-09 | 北京清大国华环保科技有限公司 | Method and device for coal chemical sewage reuse and zero emission |
| CN103910459B (en) * | 2012-12-31 | 2017-09-01 | 北京清大国华环境股份有限公司 | A kind of coal chemical sewage recycling and the method and apparatus of zero-emission |
| CN104370394A (en) * | 2013-08-15 | 2015-02-25 | 北京紫光益天环境工程技术有限公司 | Surface water desalting apparatus by-producing saline waste water treatment method |
| CN104370394B (en) * | 2013-08-15 | 2016-08-31 | 北京紫光益天环境工程技术有限公司 | A kind of processing method of surface water desalter by-product brine waste |
| CN107176745A (en) * | 2016-03-09 | 2017-09-19 | 王仲甫 | The method for biologically treating wastewater of polybasic carboxylic acid residue |
| CN109205717A (en) * | 2018-10-29 | 2019-01-15 | 国家能源投资集团有限责任公司 | A kind of non-crystal seed method evaporation process method and processing system of waste water |
| CN109205717B (en) * | 2018-10-29 | 2022-10-04 | 国家能源投资集团有限责任公司 | Amorphous seed method evaporation treatment method and treatment system for wastewater |
| CN113735353A (en) * | 2020-05-29 | 2021-12-03 | 天华化工机械及自动化研究设计院有限公司 | PTA (pure terephthalic acid) oxidized tail gas treatment and recovery system and method |
| CN113735353B (en) * | 2020-05-29 | 2024-02-09 | 天华化工机械及自动化研究设计院有限公司 | PTA oxidation tail gas treatment and recovery system and method |
| CN112142259A (en) * | 2020-09-25 | 2020-12-29 | 中蓝连海设计研究院有限公司 | Comprehensive treatment method of PTA-containing wastewater |
| CN112142259B (en) * | 2020-09-25 | 2023-03-14 | 中蓝连海设计研究院有限公司 | Comprehensive treatment method of PTA-containing wastewater |
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